Fs fe}to my studentsCHAPTER 1 SPECIAL TOPIC I CHAPTER 2 CHAPTER 3 SPECIAL TOPIC IL SPECIAL TOPIC III CHAPTER 4 SPECIAL TOPIC IV CHAPTER 5 TABLE OF CONTENTS Electronic Structure and Bonding + Acids and Bases Important Terms Solutions to Problems Practice Test pH, pKa, and Buffers Problems Solution to Problems ‘An Introduction to Organic Compounds: Nomenclature, Physical Properties, and Representation of Structure Important Terms Solutions to Problems Practice Test 34 47 49 58 62 82 Alkenes: Structure, Nomenclature, and an Introduction to Reactivity * ‘Thermodynamics and Kinetics Important Terms Solutions to Problems Practice Test Exercise in Drawing Curved Arrows Problems Answers Kinetics Problems Solutions to Problems Reactions of Alkenes Important Terms Solutions to Problems Practice Test Exercise in Model Building Stereochemistry: The Arrangement of Atoms in Space. The Stereochemistry of Addition Reactions Important Terms Solutions to Problems Practice Test 84 87 9 104 106 5 122 122 123 124 127 149) 151 152 158 192TO THE STUDENT {As you study organic chemistry, make certain you fully understand each new fact that you encounter. While studying the material, you should be continuously asking yourself "why?": Why does that reaction occur? Why is that product formed? Why is that compound more stabie? If you truly understand each new piece of information, you will be creating a foundation upon which to lay subsequent information. A strong foundation will allow you to master a great deal of material with much less effort than you would have to put out if you were memorizing your way through the material Often it is the new vocabulary that you encounter when you are first exposed to a discipline that can be the biggest hurdle to mastering the material. For that reason I have included a list of the important terms and their definitions at the beginning of cach chapter in the Study Guide. Reading these is a good way to review some of the important aspects of the chapter. ‘There are two kinds of problems in the textbook. The problems at the end of each section within a chapter are designed to let you see if you have understood the material presented in that section, and to reinforce the material. You should do these problems as you encounter them. The problems at the end of each chapter integrate the concepts in the Chapter and sometimes include concepts that were mastered in previous chapters. Try to do as many of these as possible. The more problems you do, the more comfortable you will become with organic chemistry, and the more you Will enjoy it. Organic chemists use curved arrows to show the bonds that break and the bonds that form in an organic reaction. When you start studying organic reactions in Chapter 3, take time to do the exercise on drawing curved arrows that you will find on page 101. There is also an exercise in model building (page 151) that will help you with the material in Chapter 5. Good luck in your study. If you have any comments or suggestions about how the ‘Study Guide could be improved for those students who will follow you, I would be very happy to hear from you. Paula Yurkanis Bruice Department of Chemistry and Biochemistry University of California, Santa Barbara Santa Barbara, CA 93106 pybruice @chem.ucsb.eduCHAPTER 6 Reactions of Alkynes * Introduction to Multistep Synthesis Important Terms 194 Solutions to Problems 196 Practice Test 2u CHAPTER 7 Electron Delocalization, Resonance, and Aromaticity * More About Molecular Orbital Theory Important Terms 213 Solutions to Problems 215 Practice Test 234 CHAPTER 8 Reactions of Dienes * Ultraviolet/Visible Spectroscopy Important Terms 237 Solutions to Problems 240 Practice Test 262 CHAPTER 9 Reactions of Alkanes * Radicals Important Terms 265 Solutions to Problems 266 Practice Test 218 CHAPTER 10 Substitution Reactions of Alkyl Halides Important Terms 280 Solutions to Problems 282, Practice Test 300 CHAPTER 11 Elimination Reactions of Alkyl Halides + Competition Between Substitution and Elimination Important Terms 302 Solutions to Problems 303 Practice Test 330 CHAPTER 12 Reactions of Alcohols, Ethers, Epoxides, and Sulfur-Containing Compounds * Organometallic Compounds Important Terms 332 Solutions to Problems 334 Practice Test 367 CHAPTER 13 Mass Spectrometry and Infrared Spectroscopy Important Terms 369 Solutions to Problems 371 Practice Test 392 CHAPTER 14 NMR Spectroscopy Important Terms 394 Solutions to Problems 397 Practice Test 420CHAPTER 15 CHAPTER 16 CHAPTER 17 CHAPTER 18 CHAPTER 19 CHAPTER 20 CHAPTER 21 CHAPTER 22 CHAPTER 23 ‘Aromaticity + Reactions of Benzene Important Terms Solutions to Problems Practice Test Reactions of Substituted Benzenes Important Terms Solutions to Problems Practice Test Carbonyl Compounds I: Nucleophilic Acyl Substitution Important Terms Solutions to Problems Practice Test 422 424 437 439 441 477 479 482 514 Carbonyl Compounds Il: Nucleophilic Acyl Addition, Nucleophilic Acyl Substitution, and Nucleophilic Addition-Elimination + Reactions of o,B- Unsaturated Compounds Important Terms Solutions to Problems Practice Test Carbonyl Compounds III: Reactions at the a-Carbon Important Terms Solutions to Problems Practice Test More About Oxidation-Reduction Reactions Important Terms Solutions to Problems Practice Test More About Amines * Heterocyclic Compounds Important Terms Solutions to Problems Practice Test Carbohydrates Important Terms Solutions to Problems Practice Test Amino Acids, Peptides, and Proteins Important Terms Solutions to Problems Practice Test 516 519 552 554 556 596 598 600 626 628 630 657 659 662 678 680 683 703CHAPTER 24 CHAPTER 25 CHAPTER 26 (CHAPTER 27 CHAPTER 28 CHAPTER 29 CHAPTER 30 Answers to Practice Tests Catalysis Important Terms Solutions to Problems ‘The Organic Mechanisms of the Coenzymes ‘Important Terms Solutions to Problems Lipids Important Terms Solutions to Problems Nucleosides, Nucleotides, and Nucleic Acids Imporant Terms Solutions to Problems Synthetic Polymers Important Terms Solutions to Problems Pericyclic Reactions Important Terms Solutions to Problems ‘The Organic Chemistry of Drugs: Discovery and Design ‘Important Terms Solutions to Problems 705 707 726 28 144 741 164 167 782 785 804 806 824 826 832CHAPTER 1 Electronic Structure and Bonding Acids and Bases Important acid acid-base reaction acid dissociation constant acidity antibonding molecular orbital atomic number atomic orbital atomic weight aufbau principle base basicity bond dissociation energy bonding molecular orbital bond length Bronsted acid Bronsted base buffer solution carbanion carbocation condensed structure conjugate acid conjugate base a substance that donates a proton, a reaction in which an acid donates a proton to a base. a measure of the degree to which an acid dissociates. ‘a measure of how easily a compound gives up a proton. a molecular orbital that results when two atomic orbitals with opposite signs interact. Electrons in an antibonding orbital decrease bond strength. tells how many protons (or electrons) the neutral atom has. an orbital associated with an atom. the average mass of the atoms in the naturally occurring element. states that an electron will always go into the available orbital with the lowest energy. ‘a substance that accepts a proton. describes the tendency of a compound to share its electrons with a proton. the amount of energy required to break a bond homolytically (each of the atoms retains one of the bonding electrons) or the amount of energy released when a bond is formed. ‘a molecular orbital that results when two atomic orbitals with the same sign interact. Electrons in a bonding orbital increase bond strength. the internuclear distance between two atoms at minimum energy (maximum stability). a substance that donates a proton. a substance that accepts a proton. solution of a weak acid and its conjugate base. a compound containing a negatively charged carbon. a compound containing a positively charged carbon. a structure that does not show some (or all) of the covalent bonds. the compound formed when a base accepts a proton. the compound formed when an acid loses a proton.2 Chapter 1 core electrons electrons in filled shells. covalent bond a bond created as a result of sharing electrons. degenerate orbitals orbitals that have the same energy. delocalized electrons electrons that do not belong to a single atom nor are they shared in a bond between two atoms. dipole a positive end and a negative end. dipole moment (4) a measure of the separation of charge in a bond or in a molecule. double bond composed of a sigma bond and a pi bond, electron affinity the energy given off when an atom acquires an electron. electronegative describes an element that readily acquires an electron electronegativity the tendency of an atom to pull electrons toward itself. electropositive describes an element that readily loses an electron. electrostatic attraction _an attractive force between opposite charges. electrostatic potential map a map that allows you to see how electrons are distributed in a molecule. equilibrium constant the ratio of products to reactants at equilibrium (or the ratio of the rate constants for the forward and reverse reactions). excited-state electronic the electronic configuration that results when an electron in the ground configuration state has been moved to a higher energy orbital. formal charge the number of valence electrons - (the number of nonbonding electrons + 1/2 the number of bonding electrons). free radical a species with an unpaired electron. (radical) ground-state electronic a description of which orbitals the electrons of an atom occupy when they configuration are all in their lowest energy orbitals. Heisenberg uncertainty states that both the precise location and the momentum of an atomic principle particle cannot be simultaneously determined. Henderson-Hasselbalch pK, = pH + log(HAJ/[A"] equation Hund's rule states that when there are degenerate orbitals, an electron will occupy an empty orbital before it will pair up with another electron, hybrid orbital an orbital formed by hybridizing (mixing) atomic orbitals. hydride ion a negatively charged hydrogen.hydrogen ion (proton) inductive electron withdrawal ionic bond ionic compound ionization energy isotopes Kekulé structure Lewis acid Lewis base Lewis structure lone-pair electrons mass number molecular orbital molecular orbital (MO) theory node nonbonding electrons nonpolar covalent bond octet rule orbital orbital hybridization organic compound Pauli exclusion principle pH pi (m) bond Chapter! 3 a positively charged hydrogen. the pull of electrons through sigma bonds by an atom or a group of atoms. abond formed through the attraction of two ions of opposite charges. a compound composed of a positive ion and negative ion. the energy required to remove an electron from an atom. atoms with the same number of protons but a different number of neutrons. a model that represents the bonds between atoms as lines. a substance that accepts an electron pair. a substance that donates an electron pair. a model that represents the bonds between atoms as lines or dots and the rnonbonding electrons as dots. valence electrons not used in bonding. the number of protons plus the number of neutrons in an atom, an orbital associated with a molecule. describes a model in which the electrons occupy orbitals as they do in atoms but the orbitals extend over the entire molecule. a region within an orbital where there is zero probability of finding an electron. valence electrons not used in bonding. a bond formed between two atoms that share the bonding electrons equally. states that an atom will give up, accept, or share electrons in order to achieve a filled shell. Because a filled second shell contains eight electrons, this is known as the octet rule. the volume of space around the nucleus where an electron is most likely to be found. mixing of atomic orbitals. ‘a.compound that contains carbon. states that no more than two electrons can occupy an orbital and that the ‘two electrons must have opposite spin. the pH scale is used to describe the acidity of a solution (pH = -log{H*)). a bond formed as a result of side-to-side overlap of p orbitals.4 Chapter 1 PKa polar covalent bond potential map describes the tendency of a compound to lose a proton (pKa = -log Ka, where Ka is the acid dissociation constant). bond formed between two atoms that do not share the bonding electrons equally. a map that allows you to see how electrons are distributed in a molecule, (electrostatic potential map) proton proton transfer reaction quantum mechanics radical (free radical) resonance resonance contributors resonance hybrid sigma (6) bond single bond tetrahedral bond angle tetrahedral carbon trigonal planar carbon triple bond valence electrons valence shell electron pair repulsion (VSEPR) model wave equation wave functions 4 positively charged hydrogen; a positively charged atomic particle. reaction in which a proton is transferred from an acid to a base, the use of mathematical equations to describe the behavior of electrons in atoms or molecules, a species with an unpaired electron. having delocalized electrons. structures with localized electrons that approximate the true structure of a compound with delocalized electrons. the actual structure of a compound with delocalized electrons. a bond with a symmetrical distribution of electrons about the internuclear axis. a single pair of electrons shared between two atoms. the bond angle (109.5°) formed by an sp’ hybridized central atom an sp? hybridized carbon; a carbon that forms covalent bonds using four sp? hybrid orbitals. an sp? hybridized carbon, composed of a sigma bond and two pi bonds. an electron in an outermost shell. a model that combines the concepts of atomic orbitals and shared electron pairs with minimization of electron repulsions an equation that describes the behavior of each electron in an atom or a molecule. a series of solutions of a wave equation.Chapter] 5 Solutions to Problems 1, The mass number = the number of protons + the number of neutrons The atomic number = the number of protons. All isotopes have the same atomic number; in the case of oxygen itis 8. ‘Therefore: ‘The isomer of oxygen with a mass number of 16 has 8 protons and 8 neutrons. The isomer of oxygen with a mass number of 17 has 8 protons and 9 neutrons. The isomer of oxygen with a mass number of 18 has 8 protons and 10 neutrons. 2. Using the aufbau principle (electrons go into available orbitals with the lowest energy) and the Pauli exclusion principle (no more than 2 electrons in each atomic orbital), and remembering that the relative energies of the atomic orbitals are: Is<2s<2p <3s<3p<4s<3d<4p<5s<4d Clr. relative strengths of the bonds are: Clz > Br2. b. relative lengths: HBr > HCl > HF relative strengths: HF > HC] > HBr ‘We know the o bond is stronger than a 7 bond because the o bond in ethane has a bond dissociation energy of 88 kcal/mol, whereas the bond dissociation energy of the double bond (@ +n) in ethene is 152 kcal/mole, which is less than twice as strong. Because the bond is stronger, we know that it has more effective orbital-orbital overlap. The carbon-carbon sigma bond formed by sp’—sp” overlap is stronger because an sp? orbital has 33.3% s character, whereas an sp orbital has 25% s character. Because electrons in an s orbital are closer on average to the nucleus than those in a p orbital, the greater the s character in the interacting orbitals, the stronger (and shorter) bond. APO @ CH\CHCH=CHCH,C=CCH, an ce J sp10 Chapter 1 a, BeH, Because beryllium does not have any unpaired electrons in its ground state, it cannot form any bonds unless it promotes an electron. After promotion, hybridization of the two orbitals (an + orbital and a p orbital) that contain unpaired electrons results in two sp hybrid orbitals. 1s 2sp 2sp as 2s Each sp orbital of beryllium overlaps with the s orbital of a hydrogen. The two sp orbitals orient themselves to get as far away from each other as possible, resulting in a bond angle of 180°. eee HC)> we CO )a bond angle = 180° 7 promotion Wr 7 hybridization Notice that because beryllium does not have an electron in ap orbital, it cannot form am bond. b. BH, Without promotion, boron could form only one bond because it has only one unpaired clectron. Promotion gives it three unpaired electrons, When the three orbitals (one s orbital and ‘two p orbitals) containing the unpaired electrons are hybridized, three sp? orbitals result. 2x By 1s 2s 2px 2py 1s 2sp? 2sp? HON fp pp inten Each sp? hybrid orbital overlaps with the s orbital of hydrogen. The three sp? orbitals orient themselves to get as far away from each other as possible, resulting in bond angles in of 120°, 2p t— : Chapter AL bond angles = 120° CCl, ‘The carbon in CCl4 is bonded to four atoms, so it uses four sp3 hybrid orbitals. Each carbon-chlorine bond is formed by the overlap of an sp3 orbital of carbon with a p orbital of chlorine. Because the four sp3 orbitals orient themselves to get as far away from each other as possible, the bond angles are all 109.5°. a ® aNd a ‘ca bond angles = 109.5° 4. CO, The carbon in CO3 is bonded to two atoms, so it uses two sp hybrid orbitals. Bach carbon- ‘oxygen bond is a double bond. One of the bonds of each double bond is formed by the overlap of an sp orbital of carbon with an sp? orbital of oxygen. The second bond of the double bond is formed as a result of side-to-side overlap of a p orbital of carbon with a p orbital of oxygen. Because the two sp orbitals orient themselves to get as far away from each other as possible, the bond angle in CO is 180°, ©. The double-bonded carbon and the double-bonded oxygen in HCOOH use sp? hybrid orbitals. The single-bonded oxygen uses sp? hybrid orbitals and each hydrogen uses an s orbital. the o bond is formed by sp?-sp? overlap the % bond is formed by p-p overlap :p2-s overlap )12 26. 27. Chapter 1 £. The triple bond consists of one c bond and two m bonds. Each nitrogen uses an sp hybrid orbital to form the o bond and a p orbital to form each of the two m bonds. N=N The electrostatic potential map of ammonia is not symmetrical in the distributior three hydrogens, ‘The electrostatic potential map of the ammonium ion symmetrical in the distribution of the charg atom forms a bond with each ae, g,h a— Because Be is sp hyridized, the bond angle in BeCl, is 180° the 6 bond is farmed by sp-sp overlap each 7 bond is formed ry p-p overlap symmetrical in shape because it is not mn of the charge—the nitrogen end is more electron rich than the is symmetrical in shape because it is e. Its symmetry results from the fact that the nitrogen of the four hydrogens and the four bond angles are all the same. ‘Be—Cl H I Con weve cl and the compound does not have a dipole mome; Because C is sp° hyridized, the bond angles in CHCl, are 109.5* and the compound has a dipole moment. a (1)*NHy (2) HCI b. ()"NH2 (2) Br (3) H20 (3) NO" if the lone pairs are not shown: a. CH,OH asanacid CH,OH as abase b. NH as anacid NHg asa base CH,OH + NH; CH,OH + HCI NH; + HOT NH, + HBr (4) H30*+ (4) Ho- = cHo + NH, = cada + cr H == WH + 0 == NK + BFChapter! 13 if the lone pairs are shown: a. CHjOH as an acid CH3OH asa base D. NH asan acid NHg as a base 28. a. The lower the pXa, the stronger the acid, so the compound with pKa = 5.2 is the stronger acid. b. The greater the dissociation constant, the stronger the acid, so the compound with dissociation constant = 3.4 x 10°3 is the stronger acid. 29. Ka = Keq[H20] Ky 4.53x10~% 3 Keq = = ——— = 8.16 x 10 <4 [20] 35.5 30. ee that in each case, the equilibrium goes away from the ‘strong acid and toward the weak acid. = HCl + HO —™ ca + H0* pK, =-7 pKg=-L7 1 a a : CH;COH + HO ~<=— CHO + 4H,0' pKy=48 pKy=-17 CH;NH, + HO == cH,NH + H,0 PKq=40 PKg= 15.7 CH;NH, + H,O* —=™ CH,NH; + HO PKg=-1.7 PKq=10.74 31. 32. 33. Chapter 1 b. HCl + HO —--~—s 0 eet: PKa PKg=-17 NH; + H,0 = ‘My + HO pKy= 15.7 pKqy=94 a. CH;COO™ is the stronger base Because HCOOH is the stronger acid, it has the weaker conjugate base, b, “NED is the stronger base. Because HO is the stronger acid, it has the weaker conjugate base. €. HO is the stronger base. Because CH3OH," is the stronger acid, it has the weaker. conjugate base. The conjugate acids have the following relative strengths: 9 + i * CH;OH, > CH,;COH > CH3NH,; > CH,OH > CH,NH, ‘The bases, therefore, have the following relative strengths: = tl CH;NH > CH,O” > CH;NH; > CH;CO” > CH,OH Ka_of the reactant acid Kg of the product acid For a the reactant acid is HCI and the product acid is Hj0+ For b the reactant acid is CH3COOH and the product acid is HjOt Fore the reactant acid is HO and the product acid is CH,NH, For d the reactant acid is CHNVH and the product acid is HjOtChapter] 15 | ee 107 107-17 4953) = 2.0% 105 | eq 1017 ; 4.8 q hee aa = 14ST ig65 = 32x 10-7 I 15.7 eke Aaa = 101574107 = 195 = 10x 10-5 107 10.7 - ie 10° 2 1017-17 _ ps = 4.0% 10-13 101-7 34, a. CH;OCH,CH,OH __ because of the CH,O group that withdraws electrons inductively b. CHjCH,CH,OH, _because oxygen is more electronegative than nitrogen and, therefore, is better at withdrawing electrons inductively ©. CH;CH,0CH,CH,OH because the electron-withdrawing oxygen is closer to the OH group 9 tl 4, CH;CH,COH because the electron-withdrawing C=0 is closer to the OH group 38. CHsCHCH,OH > CHsCHCH,OH > CH,CH;CH;0H > CH;CH;CH,0H F a a ‘The first two compounds are the most acidic because they have the electron-withdrawing substituent closest to the O—H bond. The first compound is more acidic than the second because fluorine is more electronegative than chlorine, ‘The second listed compound is a stronger acid than the third listed compound because the chlorine in the third compound is farther away from the O—H bond. ‘The last-listed compound does not have a substituent that withdraws electrons inductively, 80 it is the least acidic of the compounds. 36. The weaker acid has the stronger conjugate base i 4 4 b % CHCHCO —b. CHTHCH,CO—& CHCH,COd.CHCCH,CH,S Br a 37. Solved in the text.16 38. 39. 40. 41. Chapter 1 a. Because HF is the weakest acid, F~ is the strongest base. b. Because HI is the strongest acid, I” is the weakest base. a. oxygen b, HyS ¢. CH3SH ‘As you saw in Problem 37, the size of an atom is more important than its electronegativity in determining stability. So even though oxygen is more electronegative than sulfur, H2S is a stronger acid than HO and CHSH is a stronger acid than CH3OH because the sulfur atom is larger—therefore, the electrons in the its conjugate base are spread out over a greater volume of causing it to be a more stable base. The more stable the base, the stronger its conjugate acid. a, CH;C=NH 8 HNO3 is more acidic than HNO}. ‘When the structure of the conjugate base of ‘each acid is drawn out, you can see that NO3 has a positively charged nitrogen and NO3 does b. CH;CH; or CH, «. F,CCOH not. The positive charge decreases the electron density on the oxygen by inductive electron withdrawal, thereby stabilizing it 4, an sp? hybridized oxygen A stable base is a weak base. Therefore, it has the stronger conjugte acid. e. sp > sp? > sp? bs a Ni) f. sp > sp2 > sp ee When a sulfonic acid loses a proton, the electrons left behind are shared by three oxygen atoms. In contrast, when a carboxylic acid loses a proton, the electrons left behind are shared by only two oxygen atoms, The sulfonate ion, therefore, is more stable than the carboxylate ion. The more stable the base, the stronger is its conjugate acid. Thus the sulfonic acid is a stronger acid than the carboxylic acid. <> a carboxylate ionChapter] 17 42, 43, greater than pH 10.4 As long as the pH is greater than the pK, of the compound, the majority of the compound will be in its basic form, 44, a, 10.4 (two log units more basic than the pK) b. 2.7 (one log unit more acidic than the pK) ¢. 4.9 Af 10% is in its basic form, 90% will be in its acidic form, so the pH needs to be one log unit more acidic than the pK, ) 4. 73 (pH=pK,) . 9.3 if 1% is in its acidic form, 99% will be in its basic form, so the pH needs to be two log units more basic than the pK.) 45, a. 1, neutral . charged ¢. 1. neutral 2. neutral charged 2. neutral 3. equal amounts of both . charged 3, neutral 4. charged |. charged 4, neutral 5. charged 5. equal amounts of both neutral 6. charged neutral 6. neutral 7. charged neutral 7, neutral18 47. 48. 49, ‘Chapter 1 a. 1. pH=49 2. pH= 107 be 1. pH>6.9 Because the basic form is the form in which the compound is charged, the pH needs to be more than two units more basic than the pKy. 2.pH<87 Because the acidic form is the form in which the compound is charged, the pH needs to be more than two units more acidic than the pK, a.CH;COO” —¢ H,0 €.CH;CH,OH g. HCEN i, NO} b.CH,CH,NH, 4.CHCH,OH NH, h.NOy | j.Br> & 2h + CHOH === CHOH “ZnCl, b. FeBr; + Bro =— _—sBr—FeBr, e AIC, + cr =—-~—s al—-Aic, ° “O-BF; a BF; + HCH =— onc 3, by cand h are Bronsted acids (protonating-donating acids). Therefore, they react with HO” by donating a proton to it 4, ef, and g are Lewis acids. They react with HO” by accepting a pair of electrons from it. & CHOH + HO b. NH, + HOT © CH;NH, + HO" on. a BF; + HOM CHO” + HO NH; + H,0 CH;NH, + H,0 HO—BF,$1. 52, e CH + HOM = f FeBr; + HO" — g AIC + HOM =— h. CH;COOH + HO™ Chapter 1 CH,OH HO—FeBr, HO—AICI; CH,COO + H,0 19 a. sp3, tetrahedral 4. sp?, trigonal & sp, linear Db. sp?, trigonal . sp3, tetrahedral h. sp3, tetrahedral ©. sp3, tetrahedral f. sp?, trigonal i, sp3, tetrahedral a. CH;CH,CH; —b, CHj;CH=CH, © CH,C=CCH, or CH,CH,C=CH20 53, Chapter 1 a.107.3° ©. 109.5% e104.5° —-g.109.5° i. 109.5° b, 107.3° d. 104.5°° £. 120° h, 180° *104.5° is the correct prediction based on the bond angle in water. However, the bond angle is actually somewhat larger (111.7°) because the bond opens up to minimize the interaction between the electron clouds of the relatively bulky CH groups. formal charge = the number of valence electrons ~ (the number of lone-pair electrons + 1/2 the number of bonding electrons) a formal charge = 6 - (6+ 1) = 6-7 = -1 b. formal charge = 6 -(5+1) = 6-6 =0 ¢. formal charge = 5 ~ (4) = +1 es cHs—-N—cHy CH, d. formal charge = 5 - (242) = 5-4 =41 H-N-H , formal charge =4 ~(2+2) = 4-4 = H-¢-H f, Nhas a formal charge =5 - (4) = +1 B has a formal charge = 3 - (4) = - 1 HH H-N-B2H HHChapter 1 1 g. formal charge=4 -(2+3) = 4-5 =- H iH H 1 h, formal charge = 6 = (2+3) = 6-5 =+ S Soe oe o> * m-O-n pele t E-0-0-0-2! z | = = m-O-z | z 5 | m=O g E-O-0-m _— cae m-0-0-b-x ETP mU-0- [eo fos jz moe =O-m mp = = = a a pas i. 7 7 ay, me ae Pan ee era x = = a 4 322 37. 58, 59, Chapter 1 a, CHy «. HO-NH, e. CH;—OH < > <_< b. CH,—Li da. I—Br f. (CH3))N—H sp sp i a. CH,CH=CH, . CH;CH,OH . CHyCH=NCH; a sp os w 4 |) b. CHjCCH; 4. CHyCEN f. CHOCH,CH; ‘The open arrow points to the shorter of the two indicated bonds in each compound. For 1,2, and 3: a triple bond is shorter than a double bond which is shorter than a single bond. For 4and5: Because an s orbital is closer to the nucleus than a p orbital, the greater the s character in the hybridized orbital, the shorter is the bond. Therefore, the bond formed by a hydrogen and an sp hybridized carbon is shorter than the bond formed by a hydrogen and an sp? hybridized carbon, which is shorter than the bond formed by a hydrogen and an sp? hybridized carbon. (See Table 1.7 on page 37 of the text.) sw sp sp Ah 1. CH,CH=CH SP sp Osp? Sn” 2. CH,;CCH,;OH we bse 5. sp? CH,NHCH,CH,N=CHCH; sp3 sp} sp3 sp? sp? sp? sp?1 Chapter! 23 60, If the solution is more acidic than the p&‘, of the compound, the compound will be in its acidic form (with the proton). If the solution is more basic than the pK, of the compound, the compound will be in its basic form (without the proton). a. atpH=3 CH,COH —b. atpH=3 CHjCH,NH; —« atpH=3 CF,CH,OH 9 + at pH=6 cut atpH=6 CH,CH,NH; atpH=6 CF,CH,OH 1 R at pH = 10 CH;CO™ at pH =10 CH3CH,NH; at pH=10 CF,CH,OH a at pH= 14 CH,CO™ at pH=14 CH;CH,NH, at pH= 14 CF,CH,O7 61, If the central atom is sp” hybridized, the molecule will have tetrahedral bond angles, ‘Therefore, the following have tetrahedral bond angles. 0, H,0*, NH;, *NH,, CH; 62, In an alkene, six atoms are in the same plane: the two sp” hybridized carbons and the two atoms that are bonded to each of the two sp” hybridized carbons. The other atoms in the molecule will not be in the same plane with these six atoms, no q ce CH; a CH; iH ‘CH, CH; C=C. C=C AL, . H CH; He ‘CH,CH, ee VC Ww Ww yes no. yes If you put stars next to the six atoms that lie in a plane in each molecule, you might be able to see | more clearly whether the indicated atoms lie in the same plane. * _ CH;24 Chapter 1 6. a. CH,COOH + CH,O ==" CH;COO + CH,OH b. CH;CH,OH + NH, —<=" CH;CH,O + NH ¢. CH;COOH + CH;NH, ==" CH,COO + CHSNH; 4. CH;CH,OH + HCl —==" CH,CH,OH, + Cl 64, 1 The 3 carbons are all sp3 hybridized. i All the bond angles are 109.5°. ra = mm 65. Thelog of 10°4 =~ 4, the log of 10°° = — 5, the log of 10°° = ~ 6, ete. Because the pKa =~ logKa, the pKq of an acid with a Ka of 10° = is - (4) = ‘An acid with a Kg of 4.0 10 is a stronger acid than one with a Ka of 1.0 10" ‘Therefore, the pKa can be estimated as being between 3 and 4. between 3 and 4 D. 1. pK 1 2, between -2 and -1 2. pKa 3. between 10 and 11 3. pK; 4, between 9 and 10 4, pK, 5. between 3 and 4 5. pK, c. Because the lower the pKa the stronger the acid, nitric acid is the strongest acid.67. Chapter 125 a CH;CH,CHCOOH > CH;CHCH,COOH > CICH,CH,CH,COOH > CH,CH,CH,COOH a a b. The electron-withdrawing substituent makes the carboxylic acid more acidic, because it stabilizes its conjugate base by decreasing the electron density around the oxygen atom, ¢. The closer the electron-withdrawing Cl is to the acidic proton, the more it can decrease the electron density around the oxygen atom, so the more it stabilizes the conjugate base. i or H-C-Nent H or Hes H The reaction with the most favorable equilibrium constant is the one with the greatest difference between the strengths of the reactant acid and the product acid. (i.e. the one that has the strongest reactant acid and the weakest product acid. a. 1, CH3OH is a stronger reactant acid (pa = 15.5) than CHyCH2OH (pKa = 15.9), and both reactions form the same product acid (+NH4). Therefore, the reaction of CH3OH with HG has the more favorable equilibrium constant. 2. Both reactions have the same reactant acid (CH3CH2OH). The product acids are different: *NHG4 is a stronger product acid (pKa = 9.4) than CH3NH3* (pKa = 10.7). Therefore, the reaction of CH3CH2OH with CH3NHp has the more favorable equilibrium constant. b. Now we have to compare “apples” and “oranges” because the reaction with the most favorable equilibrium constant in 1 and the reaction with the most favorable equilibrium constant in 2 do not have any species in common: I has the stronger reactant acid, whereas 2 has the weaker product acid, Therefore, the equilibrium constants have to be calculated. ‘The reaction of CH3OH with NH3 has an equilibrium constant = 7.9 x 10-7 (Keg = K-15 5/K-94 = K-61 = 7.9 x 10-7). The reaction of CH3CH2OH with CH3NHp has an equilibrium constant = 6.3 x 10-6 (Req = K-15 9/K-107 = K-52 = 63 x 10°), Therefore, the reaction of CH3CH2OH with CH3NH» has the greatest equilibrium constant of the four reactions,26 © Chapter L 0. He H Nac’ ron a cl a The dipole moment is 2.95 because the two Cl's_ The dipole moment is 0 because the two CIs are withdrawing electrons in the same direction. _are withdrawing electrons in opposite directions. 70. OH} [HO-] i 1,0) Ky = (1x10-7)(1x 107) 55.5 Ky = 1.80x10-16 PKq =~ log 1.80x 10-16 pKa = 15.7 The answer can also be obtained in the following way: — ETLHO} 7 1,0] K, (H,0] = (H'] [HO] take the log of both sides log, + log[H,O] = log(H"] + log (HO) multiply both sides by -1 a ~logKa - log(H,0] = ~ logfH"] - log [HO] pH + pOH pKa — log[H,0] pK, — log[H,0] = 14 pK, = 14 + log[H,0] PK, = 14 + log 555 pKy = 14 + 17 pKy = 15.7n Chapter 127 From the following equilibria you can see that a carboxylic acid is neutral when it is in its acidic form and charged when it is in its basic form, An amine is charged when it is in its acidic form and neutral when it is in its basic form, RCOOH === Rcod + i’ RNH, <== RNH, + H* Charged species will dissolve in water and neutral species will dissolve in ether. In separating compounds you want essentially all (100:1) of each compound in either its acidic form or its basic form. From the Henderson-Hasselbalch equation it can be calculated that in order to obtain a 100:1 ratio of acidic form:basic form, the pH must be two pH units lower than the pKa of the ‘compound; and in order to obtain a 100:1 ratio of basic form:acidic form, the pH must be two pH units greater than the pXa of the compound. a. If both compounds are to dissolve in water, they both must be charged. Therefore, the carboxylic acid must be in its basic form, and the amine must be in its acidic form. To accomplish this, the pH will have to be at least two pH units greater than the pK of the carboxylic acid and at least two pH units less than the pKa of the ammonium ion. In other words, it must be between pH 6.8 and pH 8.7. b. For the carboxylic acid to dissolve in water, it must be charged (in its basic form), so the pH. will have to be greater than 6.8. For the amine to dissolve in ether, it will have to be neutral Gin its basic form), so the pH will have to be greater than 12.7 to have essentially all of it in the neutral form. Therefore, the pH of the water layer must be greater than 12.7, ¢. To dissolve in ether, the carboxylic acid will have to be neutral, so the pH will have to be less than 2.8 to have essentially all the carboxylic acid in the acidic (neutral) form. To dissolve in water, the amine will have to be charged, so the pH will have to be less than 8.7 to have essentially all the amine in the acidic form. Therefore, the pH of the water layer must be less than 2.8,28 Chapter 1 72. Charged compounds will dissolve in water and uncharged compounds will dissolve in ether. The acidic forms of carboxylic acids and alcohols are neutral and the basic forms are charged. ‘The acidic forms of amines are charged and the basic forms are neutral. a09 9 9 pKg=4.17 pK, = 4.60 pKq= 10.00 pKq = 10.66 ether water at pH=2.0 ether layer +NH; — +NH; coon OH a add ether add H,0 at pH adjust pH of H,O to between 7 and 8 between 7 and 8 ether layer ‘water layer ether layer +NH, NH, coo” oH Od add ether, adjust pH of H,0 to 12.7 d x 713. If light is shone on a molecule of Hy or Bra, one of the two electrons in a bonding MO can be promoted to an empty antibonding MO. The electron in the antibonding MO will cancel out the electron that is left in the bonding MO, so overall there will be no bonding, In other words, Hy ‘or Bry will have been broken up into hydrogen atoms or bromine atoms. The energy difference between the bonding and antibonding MO’s is greater in the case of H, than in the case of Bra. Therefore, less energy is required to break Bry into bromine radicals.Chaptert 29 74. Using the following reaction as an example: CH,OH + NH, == CHO" + NH, a & " z K, reactant acid = ust [cx,07 . © [con] K,, product acid. = t Jix4s) NH, [H°][CH,O- x. = Kqttasamscid _ _(CHOH eq K, product acid [H*][NH,] [hn] [cH,07 _ [CH.OH] = Ny Nu, [cHo][ NH, ~ [NA,][CH.OF] 75. For adiscussion of how to do problems such as Problems 75-77, see Special Topic I (pH, pKa, and Buffers) on p. 34. pKq = pH + log ™1. When the value of the pH is equal to the value of the PK. the concentration of buffer in the acidic form equals the concentration of buffer in the basse form, 2. When the solution is more acidic than the PK,, more buffer species is in the acidic form than in the basic form 3. When the solution is more basic than the PK,, more buffer species is in the basic form than in the acidic form. THA] Ka = pH + log PKa = pi +e Because the pH of the blood (~7.4) is greater than the PK, of the buffer (6.1), more buffer Species is in the basic form than in the acidic form, Therelore, the buffer is better at neutralizing excess acid, a amount in the acidic form amount in the acidic form amount in the basic fom fHA] (HA) + [A] Because there are two unknowns, we must define one in terms of the other. By using the definition of the acid dissociation constant, we can determine [A ~] in terms of [HA]. fraction present in the acidic form = kK, = 21a THA] [A] = (HA) ty Substituting the value of [A’} into the equation gives the fraction that is present in the acidic form (HA) (Hay 1 i) —— = e (HA) + [A7] quay + XalHAl pa Kal fH] +K, 1) wy Therefore, the percent that is present in the acidic form is given by: au J x 100 fH] + K, Because the pH of the solution is given as 5.7, we know that [H") is 2.0 x 10° ~log(H*)), Sttuting into the equation that gives the percent that is present in the acidic form:Chapier1 oa 2.0 x 10% See «10 2.0 x 10% + 5.0 x 107 6 2.0 x10" 100 = 29% 7.0 x 10 : (H') D._ percent present in the acidic form = ———— = 80 (H'] + Ky [H) = 80 (fH) + Ky) [H*] = 800] + 80K, 20H] = .80 Ky (HY) = 4K, fH] = 4 x 50x 106 (H] = 20 x 106 pH = 47 7. nite 1H) [A a x, = 24d b. ew (HA] HA] 1m x 10S = —% 2.00 x 1011 = 10 - 1 174x105 = x 2.00 x 10-12 = x2 x = 416x103 x = 141x106 pH = 238 pH = 5.85 ‘¢. This question can be answered by plugging the numbers into the Henderson-Hasselbalch equation. 3.76 3.76 3.76 pH = 3.76 - 0.48 = 3.2832 1h Chapter 1 Answer the following: a, Which is a stronger acid, HCI or HBr? b. Which is a stronger base, NH3 or HO? €. Which bond has a greater dipole moment, a carbon-oxygen bond or a carbon-fluorine bond? 4. Which has a dipole moment of zero, CHCI3 of CCl4? What is the hybridization of the carbon atom in each of the following compounds? CH; CH, cus Draw the Lewis structure for HCO3”. The following compounds are drawn in their acidic forms, and their pKa's are given. Draw the form in which each compound would predominantly exist at pH = 8. CH;COOH CH,CH,OH cH,08 CH,CH,NH; pky=48 pkg =15.9 pKg=-25 PKq= 11.2 ‘Which compound has greater bond angles, H30* or *NH4? ‘What is the conjugate base of NH3? Give the structure of a compound that contains five carbons, two of which are sp? hybridized and three of which are sp? hybridized. ‘a, What products would be formed from the following reaction? CHOH + NH, === b. Does the reaction favor reactants or products?10. 1. 12. ‘Chapter 1 33 a, What orbitals do carbon's electrons occupy before promotion? b. What orbitals do carbon’s electrons occupy after promotion? Which of the following compounds is a stronger acid? CHjFHCH,COOH — or CH,CH,CHCOOH a a For each of the following compounds indicate the hybridization of the atom to which the arrow is pointing: I O=C=0 HCOH HC=N CH;0CH; CH;CH=CH, A le L Indicate whether each of the following statements is true or false: a, A pi bond is stronger than a sigma bond. T OF b. A triple bond is shorter than a double bond. T OF ‘¢. The oxygen-hydrogen bonds in water are formed by the overlap of an sp? orbital of oxygen with an s orbital of hydrogen. Teer 4d, HO™is a stronger base than “NH. T OF €. A double bond is stronger than a single bond. T OF f. A tetrahedral carbon has bond angles of 107.5°, T OF & A Lewis acid is a compound that accepts a share in a pair of electrons T OF ANSWERS TO ALL THE PRACTICE TESTS CAN BE FOUND AT THE END OF THE SOLUTIONS MANUAL.SPECIAL TOPIC I pH, pKa , and Buffers This is a continuation of the discussion on acids and bases found in Section 1.16 - 1.21 on pages 39 - 55 of the text. Now we will see how the pH of solutions of acids and bases can be calculated. We will lock at three different kinds of solutions, 1. A solution made by dissolving a strong acid or a strong base in water. 2. A solution made by dissolving a weak acid or a weak base in water. 3. A solution made by dissolving a weak acid and its conjugate base in water. Such a solution is known as a buffer solution. Before we start, we need to review a few terms. ‘An acid is a compound that donates a proton, and a base is a compound that accepts a proton. ‘The degree to which an acid (HA) dissociates is described by its acid dissociation constant (Ka). HA == H+ A Ka CHAT [HA] ‘The strength of an acid can be indicated by its acid dissociation constant or by its pK value. PKa =~ log Ka ‘The stronger the acid, the larger its dissociation constant and the smaller its pKg value. For example, an acid with a dissociation constant of 1 x 10-2 (pKa = 2) is stronger than an acid with a dissociation constant of 1 x 10-4 (pKa = 4). While the pKa scale is used to describe the strength of an acid, the pH scale is used to describe the acidity of a solution. In other words, the pH scale describes the concentration of hydrogen ions in a solution. PH =~ log [H"] The smaller the pH, the more acidic the solution. Acidic solutions have pH values <7; a neutral solution has a pH = 7; basic solutions have pH values > 7, A solution with a pH is more acidic than a solution with a pH = 4. A solution with a pH 2 is more basic than a solution with a pH = 8, LESpecial Topic 35 Determining the pH of a Solution To determine the pH of a solution, the concentration of hydrogen ion [H*] in the solution must be determined. Strong Acids A strong acid is one that dissociates completely in solution. Strong acids have pKa values < 1. Because a strong acid dissociates completely, the concentration of hydrogen ions is the same as the concentration of the acid: a 1.0 M HC solution contains 1.0 M [HI*J, a 1.5 M HCI solution contains 1.5 M [H+]. Therefore, to determine the pH of a strong acid, the [H+] value does not have to be calculated; it is the same as the molarity of the strong acid. solution be) pH 1.0MHCL 10M 0 1.0x 102M HC] 1.0x 102M 2.0 64x104MHCl 64x104M 3.2 Strong Bases Strong bases are compounds such as NaH or KOH that dissociate completely in water. Because they dissociate completely, the [HO™] is the same as the molarity of the strong base. The pOH scale describes the basicity of a solution. The larger the pOH, the more basic the solution. pOH = log [HO7] {HO-] and [H+] are related by the water ionization constant (Ki). Ky = (H*] [HO7] = 10-14 pH+pOH = 14 solution [Ho"] pou pH 1.0 M NaOH 10M 0 LOx10*MNaOH = -1L0x10*M 4.0 7.8x107MNaOH = 7.8x107M LE 140-11 =12.936 Special Topic 1 Weak Acids A weak acid does not dissociate completely in solution, This means that [H*] must be calculated before the pH can be determined. Acetic acid (CH3COOH) is an example of a weak acid. It has an acid dissociation constant of 1.74 X 10°5 (pKa = 4.76). The pH of a 1.00 M solution of acetic acid can be calculated as follows: CH;COOH === H* + CH,COO™ x ~ Et ][ex,coo ‘a [cH,CooR] Each molecule of acetic acid that dissociates forms one proton and one molecule of acetate ion. Thus the concentration of protons in solution equals the concentration of acetate ions. Each has a concentration that can be represented by x. The concentration of acetic acid therefore is whatever we started with minus x. L74xio# = OG) e 1.00-x ‘The denominator (1.00 — x) can be simplified to 1.00 because 1.00 is much greater than x. (When we actually calculate the value of x, we see that it is 0.004. And 1.00 ~ 0.004 = 1.00.) a 5 x Lt4x10% = 7 x = 417x107 pH = ~log4.17x107 pH = 238 Formic acid (HCOOH) has a pK, value of 3.75. The pH of a 1.50 M solution of formic acid can be calculated as follows: A compound with a pKg = 3.75 has an acid dissociation constant of 1.78 x 10-4, HCOOH == # + HCO” _ [H'][Hcoo"] ‘a ~ "THCOOH] OeSpecial TopicI 37 Lsxit = OO - fe 1L50-x 1.50 x= 267x10~ x = 163x107 pH = ~log!.63x 107 pH = 179 Weak Bases ‘When a weak base is dissolved in water, it accepts a proton from water, creating hydroxide ion. Determining the concentration of hydroxide allows the pOH to be determined, and this in turn allows the pH to be determined. ‘The pH of a 1.20 M solution of sodium acetate can be calculated as follows: CH,COo + H,0 == * CH;COOH + HO" Ky _ [Ho"}IcH,coon] K, [cH,CoO 1,00 x10" @)@) 14x10? ~ 120-x 5.75x10% = 120 ¥ 6.86 x10" x = 262x10° ~log 2.62 x 10° 458 14.00 - 4.58 9.42 Notice that by setting up the equation equal to Ky/Ka, we can avoid the introduction of a new term (Kp).38 Special Topic I Buffer Solutions A buffer solution is a solution that maintains nearly constant pH in spite of the addition of small amounts of H* or HO”. That is because a buffer solution contains both a weak acid and its conjugate base. The weak acid can donate a proton to any HO™ added to the solution, and the conjugate base can accept any H* that is added to the solution, so the addition of HO” or H* does not significantly change the pH of the solution. (In oder to maintain approximately constant pH, the amount of H* or HO added to the solution cannot ‘exceed the concentration of the conjugate acid or base in the solution.) A buffer can maintain nearly constant pH in a range of one pH unit on either side of the pK, of the conjugate acid. For example, an acetic acid/sodium acetate mixture can be used as a buffer in the pH range 3.76 — 5.76 because acetic acid has a pKa = 4.76; methylammonium ion/methylamine can be used as a buffer in the pH range 9.7 ~ 11.7 because the methylammonium ion has a pK = 10.7. ‘The pH of a buffer solution can be determined from the Henderson-Hasselbalch equation. This equation ‘comes directly from the expression defining the acid dissociation constant. Its derivation is found on page 52 of the text. ‘Henderson-Hasselbalch equation {HA] pk, = pH +08 Fo) ‘The pH of an acetic acid/sodium acetate buffer solution (pKa of acetic acid = 4.76) that is 1.00 M in acetic acid and 0.50 M in sodium acetate is calculated as follows: a [Ha] pk, = pH log ry 1.00 4.76 = pH+ log = pH i°8 050 4.76 = pH+log2 476 = pH+0.30 pH = 4.46 Remember from Section 1.20 that compounds exist primarily in their acidic forms in solutions that are more acidic than their pK,'s and primarily in their basic forms in solutions that are more basic than their pKz's. Therefore, it could have been predicted that the above solution will have a pH less than the pKa of acetic acid because there is more conjugate acid than conjugate base present in the solution,Special Topic} 3 ‘There are three ways a buffer solution can be prepared: 1d We ‘A buffer solution can be prepared by mixing a solution of a weak acid with a solution of its conjugate base ‘The pH of a formic acid/sodium formate buffer (pKa of formic acid = 3.75) solution prepared by mixing 35 mL of 0.10 M formic acid and 15 mL. of 0.20 M sodium formate is calculated as follows: moles, _ millimoles liters milliliters molarity = “The number of millimoles (mmol) of each of the buffer components can be determined by multiplying the number of milliliters (mL) by the molarity (M) - 25 mLx0.10M = 2.5 mmol formic acid 15mLx0.20M = 3.0 mmol sodium formate = {HA} pKa = pH + log 25 HH + log —— pH Te “3.0 3.15 = pH + log 0.83 3.75 3.15 = pH - 0.08 pH = 3.83 1 It-could have been predicted thatthe above solution would have a pH greater than the pK, of formic ee because there 4s more conjugate base than conjugate acid present in the solution 2 ci e ‘A buffer solution can be prepared by mixing a solution of a weak acid with a strong ase such as NaOH. Aone sation cat apletely with the weak acid, thereby creating the conjugate base. For ‘example, if Fee NaOH react aeicmnd 5 mmol of a strong base are added to a solution, the S mmol of song base par) et with 3 mmol of weak acid, creating 5 mmol weak base and leaving behind 15 mmol of weak acid. ‘The pH of a solution prepared by mixing 10 mL of a 2.0 M solution of weak acid with a pK, of 5.86 with's O mL. of a 1.0 M solution of sodium hydroxide can be calculated as follows:42 Special Topic I ‘The formulas describing the fraction present in the acidic or basic form are obtained from the definition of the acid dissociation constant. [Ha] [HA]+[A~ x, = EJ) «> Taal K, (Ha) oe fraction present in the acidic form = mery ~ Bla ' “, THA] ~ Wale tey 1+78 - | +H] fraction present in the acidic form = fH] 4 fraction present in the base form = —/ = [HA]+[A x He [HA] = tel] ‘a fraction present in the basic form =Special Topicl 43 preparing Buffer Solutions The type of calculations discussed on pages 39-42 can be used to determine how to make a buffer solution. For example, how can 100 mL of a 1.00 M buffer solution of pH = 4.24 be prepared if you have available to you 1.50 M solutions of acetic acid, sodium acetate, HCI, and NaOH? acetic acid has a pKa = 4.76 fraction present in the acidic form at pH= 4.24 = wh, _ 5.75x 10° K, +[H"'] 174x107 + 5.75 x 10% 5.75107 7.49 x107 0.77 5.75x10° 7.49 x 10% = 0.77 Ifa 1.00 M buffer solution is desired, the buffer must be 0.77 M in acetic acid and 0.23 M in sodium acetate. Recalling that42 Special Topic T ‘The formulas describing the fraction present in the acidic or basic form are obtained from the definition of the acid dissociation constant, fraction present in the acidic form ] fraction present in the acidic form fraction present in the basic form = [wa] = fraction present in the basic form eS HA] © [RA] +[A>44 Special Topic I There are three ways such a buffer solution can be prepared: 1, By mixing the appropriate amounts of acetic acid and sodium acetate in water, and adding water to obtain a final volume of 100 mL. The amount of acetic acid needed: [cH,cooH] = 0.77M xmmol = 0.77 100mL = x = 77mmol ‘Therefore, we need to have 77 mmol of acetic acid in the final solution. To obtain 77 mmol of acetic acid from a 1.50 M solution of acetic aci The amount of sodium acetate needed: [cH,coo"] = 023m xmmol 100 mL x = 23mmol To obtain 23 mmol of sodium acetate from a 1.50 M solution of sodium acetate: 23 mmol ym y w 150M 15.3 mL, The desired buffer solution can be prepared using: 51.3 mL 1.50 M acetic acid 15.3 mL 1.50 M sodium acetate 33.4 mL H30Special Topic! 45 2, By mixing the appropriate amounts of acetic acid and sodium hydroxide, and adding water to obtain a final volume of 100 mL. ‘Sodium hydroxide is used to convert some of the acetic acid into sodium acetate. ‘This means that acetic acid will be the source of both acetic acid and sodium acetate The concentrations needed are: {CHjCOOH] = 1.00M [NaOH] = 0.23M ‘The amount of acetic acid needed: [CH,COOH] = 1.00M zmmol 2 190M 100 mL. x = 100mmol To obtain 100 mmol of acetic acid from a 1.50 M solution of acetic acid: 100 mmol ymL y = 66.7 mL = 150M The amount of sodium hydroxide needed: [NaOH] = 023M xmmol = 023M loom ~ ° x = 2%3mmol To obtain 23 mmol of sodium hydroxide from a 1.50 M solution of NaOH: 23 mmol = 150M ymL " y = 133mL ‘The desired buffer solution can be prepared using: 66.7 mL 1.50 M acetic acid 15.3 mL 1,50 M NaOH 18.0 mL Hj046 Special Topic I 3. By mixing the appropriate amounts of sodium acetate and hydrochloric acid, and adding water to obtain a final volume of 100 mL. Hydrochloric acid is used to convert some of the sodium acetate into acetic acid. This means that sodium acetate will be the source of both acetic acid and sodium acetate. The concentrations needed are: [CHsCOONa] = 1.00M {HCl] = 0.77M The amount of sodium acetate needed: [CH,COONa] = 1.00M xmmol = i 100 mL me x = 100mmol To obtain 100 mmol of sodium acetate from a 1.50 M solution of sodium acetate: 100 mmol = 15 ymb = y = 66.7mL The amount of hydrochloric acid needed: [acl] = 077M xmmol = 077M 100 mL x = 77mm To obtain 77 mmol of hydrochloric acid from a 1.50 M solution of HCI: immo _ som ymL y = S13mL 100 mL. of a 1.00 M acetic acid/acetate buffer cannot be made from these reagents, because the Yolumes needed (66.7 mL + 51.3 mL) add up to more than 100 mL. To make this buffer using Sodium acetate and hydrochloric acid, you would need to use a more concentrated solution of sodium acetate or a more concentrated solution of HCI.* Special Topic. 47 problems on pH, pKa, and Buffers 1 5. 1. Calculate the pH of each of the following solutions. a. 1x103M HCI b. 0.60 M HCI c. 140x102 M HCL d. 1x10 MKOH e, 3.70x 10-4 M NaOH f. 1.20 M solution of an acid with a pKa = 4.23 g. 1.60 x 10-2 M sodium acetate (pK, of acetic acid = 4.76) Calculate the pH of each of the following buffer solutions: ‘a. A buffer prepared by mixing 20 mL of 0.10 M formic acid and 15 mL of 0.50 M sodium formate (pK; of formic acid = 3.75). b. A butfer prepared by mixing 10 ml. of 0.50 M aniline and 15 mL of 0.10 M HCI (pK of the anilinium ion = 4.60). ¢. A buffer prepared by mixing 15 mL of 1.00 M acetic acid and 10 mL of 0.50 M NaOH (pKa of acetic acid = 4.76). ‘What fraction of a carboxylic acid with pK, = 5.23 would be ionized at pH = 4.982 ‘What would be the concentration of formic acid and sodium formate in a 1.00 M buffer solution with a pH = 3.12? You have found a bottle labeled 1.00 M RCOOH. You want to determine what carboxylic acid itis, so you decide to determine its pKa. How would you do this? ‘a. How would you prepare 100 mL of a buffer solution that is 0.30 M in acetic acid and 0.20 M in sodium acetate using a 1.00 M acetic acid solution and a 2.00 M sodium acetate solution? b. The pK; of acetic acid is 4.76. Would the pH of the above solution be greater or less than 4.16? You have 100 mL of a 1,50 M acetic acid/sodium acetate buffer solution that has a pH = 4.90. How could you change the pH of the solution to 4.50?48 10. 11. Special Topic T You have 100 mL of a 1.00 M solution of an acid with a pK, = 5.62 to which you add 10 mL of 1.00 M sodium hydroxide. What fraction of the acid will be in the acidic form? How much more sodium hydroxide will you need to add in order to have 40% of the acid in the acidic form? Describe three ways to make a 1.00 M acetic acid/sodium acetate buffer solution with a pH! = 4.00. You have available to you 1.50 M solutions of acetic acid, sodium acetate, sodium hydroxide, and hydrochloric acid. How would you make 50 mL of each of the buffers described in the preceding problem? ‘How would you make a 1.0 M buffer solution with a pH = 3.30? ‘You are planning to carry out a reaction that will produce protons. In order for the reaction to take place at constant pH, it will be carried in a solution buffered at pH = 4.2. Would it be better to use a formic acid/formate buffer or an acetic acid/acetate buffer?Special Topicl 49 Answers to Problems on pH, pK,, and Buffers 1 a. pH = -log1x 10° 4. pOH = -log1x10° pH =3 poH = 3 pH = 14-3 = 11 b. pH = ~ log 0.60 e. pOH = ~1og3.70x 10 pH = 0.22 pOH = 3.43 pH = 10.57 2 ¢. pH = —log 140x 10 pH = 185 f. pKa = 4.23, Ky = 589x105 841x107 2.08 & Lyaxlo® ~ Teoxlo™ (Ky = 10476 = 1.74x 105 2 0 x 5.75x10" = —— > . 160x107 2 = 9.20x10* x = 3.03x10° pOH = 5.52 pH = 14.00-5.52 = 8.4850 Special Topic 1 2. a, formic acid: 20 mL x0.10M = 2.0 mmol sodium formate: 15 mL x 0.50M = 7.5 mmol mK, = sit Al 2.0 3.75 = pH+log—— eens 3.75 = pH+10g0.27 3.75 = pH+(-0.57) pH = 432 b, aniline: 10 mL x 0.50 HCE 15mL x 0.10 5.0mmol —* 3.5 mmol aniline (RN) 1.5 mmol —* 1.5 mmol anilinium hydrochloride (RNH3) [HA] pK, = PAL Toe Ta Ls 4.60 = pH + log = 4.60 = pH + log 0.43 4.60 = pH+(-037) pH = 4.97 © aceticacid: 15 mL x 1.00 = 15 mmol — 10 mmol acetic acid NaOH: 10 mL x 0.50 = 5.0mmol —» 5.0 mmol sodium acetate x [HA] PK, = PH Tos Tay 4.76 = pH + og 22 4.76 = pH+log2 4.76 = pH+0.30 pH = 4.46 ‘The ionized form is the basic form. 5.89 x10 5.89 x 10% ~ 5.89x10% +10.47x10% ~ 16.36x10 = 0.36Special Topicl 51 4 pK, = 375 = 0.63 = 427 = [Ha] = 4.27[A"] [HA] +[47] = LOM 42[A]+[A] = LOM s.27[A] = LOM {A ] = 019M [sodium formate] = 0.19M [formic acid] = 0.81M 5 pK, = artes when [HA] [a] pH pete Preparing a solution of x mmol of RCOOH and 1/2 x mmol NaOH will give a solution in which [RcooH] = [Rcoo"}. For example: 20 mL of 1,00 MRCOOH = 20 mmol 10 mL of 1.00 M NaOH = 10 mmol ‘This will give a solution that has 10 mmol RCOOH and 10 mmo! RCOO™ ‘The pH of this solution is the pKa of RCOOH. TTT {52° Special Topic I 6B om xmmel _ 930M xmmol _ 020M 100 mL. 100 mL x = 30mmol of acetic acid x = 20:mmol of sodium acetate 30mm! = 100M 20mmol = 200M ymL ym Y= 30miL of 1,00 M acetic acid y= 10mL of 2.00 M acetic acid ‘The buffer solution could be prepared by mixing: 30 mL of 1.00 M acetic acid 10 mL of 2.00 M sodium acetate 60 mL of water b. Because the concentration of buffer in the acidic form (0.30 M) is greater than the concentration of buffer in the basic form (0.20 M), the pH of the solution will be less than 4.76. HA PK, = pit og original solution7 Special Topic! 53 desired solution 4.76 = 4.50+1og SHA] a] [HA] 0.26 = "8 Ta] A _ [HA 1.82 = if [HA] = 182[A7] {HA]+[A>] = 150M 182[A-]+[A] = 150M 2.82[A"] = 150M [A] = 053M [HA] = 097M The original solution contains 87 mmol of A~ (100 mL x 0.87 M). ‘The desired solution with a pH = 4.50 must contain 53 mmol of A. Therefore, 34 mmol of A~ (87 - 53 = 34) must be converted to HA. This can be done by adding 34 mmol of HCI to the original solution. If you have a 1.00 M HCI solution, you will necd to add 34 mL to the original solution in order to change its pH from 4.90 t0 4.50. 34 mmol 24mmol 1.00 : M x = 34mL Note that after adding HCI to the original solution, it will no longer be a 1.50 M butter; it will be more dilute (150 mm/134 mL = 1.12 M), ‘The change in the concentration of the buffer solution will be less if a more concentrated solution of HCI is used to change the pH. If you have a 2.00 M HC! solution: 34 mmol amm = 200M xmL ” x = I7mL You will need to add 17 mL to the original solution, and the concentration of buffer species will be 1.28 M (150 mm/117 mL = 1.28 M). certr mm 54 Special Topic I acid: 100 mL x 1.00 = 100 mmol = 90 mmol HA NaOH: 10mL x 1.00 = 10mmol —* 10 mmol A Therefore, 90% is in the acidic form. For 40% to be in the acidic form you need: 40 mmol HA 60 mmol A~ You need to have 60 mmol rather than 10 mmol in the basic form. To get the additional 50 mmol in the basic form, you would need to add 50 mL of 1.0 M NaOH. PK, = pH+log raf 4.76 = 4.00 + on Fe 0.76 = SIS = fe now take the antilog of both sides (Ha] = 5.75[a"] [Ha]+[A-] = Lom 5.73[A-]+[A"] = LOM 6.75[A-] = LOM [A] = osm [HA] = 085M a © [acetic acid] = 0,85M [sodium acetate] = 1.00 M [sodium acetate] = 0.15M [HCl] = 085M [acetic acid] = 1.00M [NaOH] = 015M10. 2% x mmol 50 mL 42.4 mmol Special Topic I = 085M 42.5 mmol of acetic acid 150M 28.3 mL of 1.50 M acetic acid = 015M 7.5 mmol of sodium acetate 150M. 5.0 mL of 1.50 M sodium acetate 28.3 mL of 1.50 M acetic acid 5.0 mL of 1.50 M sodium acetate 16.7 mL of H20 = 100M 50 mmol of acetic acid 1.50M 33.3 mL of 1.50 M acetic acid = 015M 7.5 mmol of NaOH 150M 5.0 mL of 1.50 M NaOH 33.3 mL of 1.50 M acetic acid 5.0 mL of 1.50 M NaOH 11.7 mL of HzO 35556 Special Topic I c x mmol = 100M 50 mL x = 50 mmol of sodium acetate 5O0mmol_ = 150M ymL Y = 33.3 mL of 1.50 M sodium acetate x mmol = 085M 50 mL x = 425mm 42.5 mmol = 15M ymL. y = 283ml of 1.5 MHCI We cannot make the required buffer with these solutions, because 33.3 mL + 28.3 mL > 50 mL. JI, Because formic acid has a pK, .75, a formic acid/formate buffer can be a buffer at pH = 3. pK, = pH+log ie 375 = 20 +toe i} A (HA) 0.45 = | og Fa [HA] a] [HA] = 2.82[A"] [HA]+[a-] = Lom 2.82[A]+[A] = LOM 3.82[A"] = LOM 2.82 =Special Topic 57 [a] = 026M [HA] = 0.74M ‘The solution must have [formic acid] = 0.74 M and [sodium formate] = 0.26 M. 12. At pH = 4.20, 74% of the formate buffer will be in the basic form. pH = 4.20, [H+] =6.31 x 105 Formic acid has a pKg = 3.75, Ka = 1.78 x 10-4. 1.78 x10* ttt 1.78 x10 1.78x10% + 631x10* ~ 178x107" + 0.63x10" — 478x10* ~ 241x10* = 0.74 At pH = 4.20, 22% of the acetate buffer will be in the basic form. pH=4.20, [H+] =6.31 x 10-5 Acetic acid has a pKa 1L74x10% 1.74x10* + 6.31x 107 1.78x10 8.05 x 10 = 0.22 1.76, Ka = 1.74x 10°, ‘The reaction to be carried out will generate protons that will react with the basic form of the buffer in order to keep the pH constant. Therefore, the formate buffer is preferred because it has 4 greater percentage of the buffer in the basic form.CHAPTER 2 An Introduction to Organic Compounds: Nomenclature, Physical Properties, and Representation of Structure nt Terms alcohol alkane alkyl halide alkyl substituent amine angle strain anti conformer axial bond banana bonds boat conformation boiling point chair conformation cis fused cis isomer cls-trans stereoisomers (geometric isomers) common name conformation conformational analysis a compound with an OH group in place of one of the hydrogens of an alkane (ROH). @ hydrocarbon that contains only single bonds, @ compound with a halogen in place of one of the hydrogens of an alkane 4 substituent formed by removing a hydrogen from an alkane. ® compound in which one or more of the hydrogens of NH is replaced by an alkyl substituent (RNHo, RoNH, R3N). the strain introduced into a molecule as a result of its bond angles being distorted from their ideal values. the staggered conformer in which the largest substituents bonded to the tw carbons are opposite each other. It is the most stable of the staggered conformers. a bond of the chair form of cyclohexane that is perpendicular to the plane in which the chair is drawn (an up-down bond). the bonds in small rings that are slightly bent as a result of orbitals overlapping at an angle rather than overlapping head-on, the conformation of cyclohexane that roughly resembles a boat. the temperature at which the vapor pressure of a liquid equals the atmospheric pressure, the conformation of cyclohexane that roughly resembles a chair. It is the most stable conformation of cyclohexane {wo rings fused together in such a way that ifthe second ring were considered to be two substituents of the first ring, the two substituents would be on the same side of the first ring, the isomer with both hydrogens on the same side of the double bond, geometric (or E, Z) isomers. nonsystematic nomenclature. the three-dimensional shape of a molecule at a given instant the investigation of vatious conformations of a compound and their relative stabilities,Chapter2 59 conformers different conformations of a molecule. constitutional isomers molecules that have the same molecular formula but differ in the way the (Gtructural isomers) atoms are connected. an alkane with its carbon chain arranged in a closed sing. the interaction between an axial substituent and the other two axial substituents on the same side of the cyclohexane ring, dipole-dipole interaction an interaction between the dipole of one molecule and the dipole of another. eclipsed conformation a conformation in which the bonds on adjacent carbons are parallel to each other as viewed looking down the carbon-carbon bond, equatorial bond a bond of the chair form of cyclohexane that juts out from the ring in approximately the same plane that contains the chair. ether ‘8 compound in which an oxygen is bonded to two alkyl groups (ROR). flagpole hydrogens the two hydrogens in the boat conformation of cyclohexane that are closest to each other. functional group the center of reactivity of a molecule. gauche conformer a staggered conformer in which the largest substituents bonded to the two carbons are gauche to each other; i., they have a dihedral angle of approximately 60°. x x ‘The substituents are gauche to each other. gauche interaction the interaction between two atoms or groups that are gauche to each other. geometric isomers cis-trans (or E, Z) isomers. (cis-trans stereoisomers) half-chair conformer the least stable conformation of cyclohexane. : homolog a member of a homologous series. homologous series a family of compounds in which each member differs from the next by one methylene group. hydrocarbon a compound that contains only carbon and hydrogen. hydrogen bond an unusually strong dipole-dipole attraction (5 kcal/mol) between a hydrogen bonded to O, N, or F and the lone pair of a different O, N, or F. induced dipole-induced _an interaction between a temporary dipole in one molecule and the dipole dipole interaction that the temporary dipole induces in another molecule. Di60 Chapter 2 TUPAC nomenclature melting point, methylene group Newman projection packing parent hydrocarbon perspeetive formula polarizability primary alcohol primary alkyl halide primary amine primary carbon primary hydrogen quaternary ammonium salt ring-flip (chair-chair interconversion) sawhorse projection secondary alcohol secondary alkyl halide secondary amine secondary carbon secondary hydrogen skeletal structure skew-boat conformer systematic nomenclature. the temperature at which a solid becomes a liquid. 2.CHp group. a way to represent the three-dimensional spatial relationships of atoms by looking down the length of a particular carbon-carbon bond. the property that determines how well individual molecules fit into a crystal lattice. the longest continuous carbon chain in a molecule. a way to represent the three-dimensional spatial relationships of atoms using two adjacent solid lines, one solid wedge and one hatched wedge. the ease with which an electron cloud of an atom can be distorted. an alcohol in which the OH group is bonded to a primary carbon. ‘an alkyl halide in which the halogen is bonded to a primary carbon, an amine with one alkyl group bonded to the nitrogen. a carbon bonded to only one other carbon. a hydrogen bonded to a primary carbon. a nitrogen compound with four alkyl groups bonded to the nitrogen. the conversion of a chair conformer of cyclohexane into the other chair conformer Bonds that are axa none chair conformer are equatorial in th a way to represent the three-dimensional spatial relationships of atoms by looking at the carbon-carbon bond from an oblique angle. an alcohol in which the OH group is bonded to a secondary carbon, an alkyl halide in which the halogen is bonded to a secondary carbon. an amine with two alkyl groups bonded to the nitrogen. a carbon bonded to two other carbons. a hydrogen bonded to a secondary carbon. a structure that shows the carbon-carbon bonds as lines and does not show the carbon-hydrogen bonds. one of the conformations of a cyclohexane ring,solubi solvation staggered conformation steric hindrance steric strain straight-chain alkane structural isomers (constitutional isomers) symmetrical ether systematic nomenclature tertiary alcohol tertiary alkyl halide tertiary amine tertiary carbon tertiary hydrogen torsional strain trans-fused trans isomer twist-boat conformer unsymmetrical ether van der Waals forces Chapter2 61 the extent to which a compound dissolves in a solvent. the interaction between a solvent and another molecule (or ion). conformation in which the bonds on one carbon bisect the bond angle on the adjacent carbon when viewed looking down the carbon-carbon bond. hindrance due to groups occupying a volume of space the repulsion between the electron cloud of an atom or group of atoms and the electron cloud of another atom or group of atoms, an alkane in which the carbons form a continuous chain with no branches. molecules that have the same molecular formula but differ in the way the atoms are connected. an ether with two identical substituents bonded to the oxygen. TUPAC nomenclature. an alcohol in which the OH group is bonded to a tertiary carbon. an alkyl halide in which the halogen is bonded to a tertiary carbon, ‘an amine with three alkyl groups bonded to the nitrogen, carbon bonded to three other carbons. ‘a hydrogen bonded to a tertiary carbon. the repulsion felt by the bonding electrons of one substituent as they pass close to the bonding electrons of another substituent. two rings fused together in such a way that if the second ring were considered to be two substituents of the first ring, the two substituents ‘would be on opposite sides of the first ring. the isomer that has the hydrogens on opposite sides of the double bond. one of the conformations of a cyclohexane ring. an ether with two different substituents bonded to the oxygen. induced dipole-induced dipole interactions.62 Chapter 2 Soh s to Problems Notice that each carbon forms fours bonds and each hydrogen and bromine forms one bond. CH; CH;CH,CH,CH,Br CH; CHCH,CH; CH GHCH,Br CHG CH Br CH; Br n-butyl bromide sec-butyl bromide isobutyl bromide —_ tert-butyl bromide or butyl bromide 2, Dibromomethane does not have constitutional isomers. If carbon were flat, the two structures shown below would be different, because the Br's would ‘be 90° apart in one compound and 180° apart in the other compound. Because carbon is tetrahedral, the two structures are identical. H Br H—G-Br u-¢-H Br br 3 ie ® CH,CHOH © CH;CH,GHIe CHy¢NH2 CH CH, CH, Gs b. CHyCHCH,CH,F — . CH,CCH,Cl_—_f. CH,CH,CHyCH,CH;CH,CH,CH,Br CH; CH; 4, gis is GaGa a. (CHyGHCHCH,CH,CH, b. CHjCHCH,¢—CHCH,CH3 CH; CHCH; CHy© CH CH:CH,¢CH,CH,CH,CH,CH,CH, a. #1 #2 8 #4 45 CH,CH, CH,CH, gis CHy¢CH,CHCH,CH,CH,CH, CH CH pe CH; CH,CH,CH,CH,CH,CH,CH,CH; octane CH;CHCH,CH,CH;CH,CH, CH; 2-methylheptane CH,CH,CHCH,CH,CH,CH, CH; 3-methytheptane CH,CH,CH,CHCH,CH,CH, CH; 4-methylheptane a CH,CCH,CH,CH,CH CH; 2,2-dimethyihexane es CH CH,CCH,CH,CH, CH, 3,3-dimethylhexane Chapter 2 ei € CHjCHCH,CHCHCH,CH,CH, ae CHCH, CH; ©. CH,CH)CH,CHCH,CH,CH,CH, CHAGCH, CH, gh #7 CHj;CH—CHCH,CH,CH, 23-dimethylhexane gi gi #8 | CHsCHCH,CHCH,CH, 2,4-dimethylhexane ge #9 CHCHCH,CH,CHCH, 2,5-dimethylhexane th #10 CHsCH)CH-CHCH,CH, 3,4-dimethylhexane ges Gh #11 CH;C—CHCH,CH, CH; 2,2,3-trimethylpentane CH, CH; To #12 CH,GCH,CHCH, CH, 2,2,4-trimethylpentane 664 Chapter 2 gi #13 CH,CH—¢CH;CH, #16 CH,CH,CHCH,CH,CH, CH; CH,CH; 2,3,3-trimethylpentane 3-ethylhexane Gls Hs CH Hs #14 CH,CH-CH-CHCH,, #17 CH,CH,CHCHCH, 23 4-trimethylpentane CHCH; 3-ethyl-2-methylpentane CHSCH; CH #15 CHG—CCH; #18 CH,CH,GCH,CH, CH;CH; CH,CH; 2,2,3,3-tetramethylbutane 3-ethyl-3-methylpentane b. The systematic names are under the compound. ¢. Only #1 (n-octane) and #2 (isooctane) have common names. di. #2, #7, #8, #9, #12, #13, #14, #17 e. #3, #8, #10, #11 f. #5, #11, #12, #15 a, 2,2,4-trimethylhexane €. 3,3-diethyl-4-methyl-5-propyloctane b, 2,2-dimethylbutane £, 3-methyl-4-propylheptane ¢. 3,3-diethylhexane g S-ethyl-4,4-dimethyloctane d. 2,5-dimethylheptane h, 4-isopropyloctane CHy CH CH 4. CH3CH;CH,CH,CH, b. CH3CCH; —& CHsCHCH,CH, 4. CH,CHCH,CH, CH, pentane 2,2-dimethylpropane 2-methylbutane _2-methylbutaneChapter2 65 8. tee On © AW Br b. es a ANNO 9. a, L-ethyl-2-methyleyclopentane ¢. 2-cyclopropylpentane b. ethyleyclobutane f. L-ethyl-3-isobutyloyclohexane ¢. 4-ethyl-1,2-dimethyleyclohexane & S-isopropylnonane 4. 3,6-dimethyldecane hi. 1-sec-butyl-4-isopropyleyclohexane 10. a. sec-butyl chloride ¢. cyclohexyl bromide 2-chlorobutane bromocyclohexane secondary secondary b. _isohexyl chloride 4. isopropyl fluoride 1-chloro-4-methylpentane 2-fluoropropane primary secondary | : 1. cH,CI a f Note that the name of a “CHC be OL Hs substituent is "chloromethyl, because a Clis in place of one of the 1 Hs of a methyl substituent chloromethylcyclohexane 1-chloro-1-methyleyclohexane i CH; CH; CH3 cl a 1-chloro-2-methyleyclohexane 1-chloro-3-methylcyclohexane _1-chloro-4-methylcyclohexane66 12, 13, 14, 15. Chapter 2 a, 1. methoxyethane 2. ethoxyethane 3. 4-methoxyoctane b. No. ¢ Leethyl methyl ether 2. diethyl ether 3. no common name CH,OH comimon = methyl alcohol systematic = methanol CH;CH,OH common. = ethyl alcohol systematic = ethanol CH,CH,CH,OH ‘common = propyl alcohol or n-propyl alcohol systematic = 1-propanol 4. 1-propoxybutane 5. 2-isopropoxypentane opropoxy-3-methylbutane 4, butyl propyl ether 5. no common name 6. isopentyl isopropyl ether CHCH,CH,CH,OH common’ = “butyl alcohol or n-butyl alcohol systematic = 1-butanol ‘CH3CH,CH,CH,CH,OH common = ‘pentyl alcohol or n-pentyl alcohol systematic = 1-pentanol (CHCH,CH)CH,CH)CH,OH common = hexy! alcohol or n-hexyl alcohol systematic = 1-hexanol a, 1-pentanol d. 5-methyl-3-hexanol primary secondary b. 4-methylcyclohexanol . 2,6-dimethyl-4-octanol secondary secondary ¢. 5-chloro-2-methyl-2-pentanol _f. 4-chloro-3-ethyleyclohexanol tertiary secondary OH CH, CH GH CH;CCHCH,CH, CHSCH,CCH;CH, CHsC—CHCH, OH OH OH CH; 2-methyl-2-pentanol 3-methyl-3-pentanol 2,3-dimethyl-2-butanolChapter2 67 16. hexylamine 4. diethylpropylamine L-hexanamine N,N-diethy!-1-propanamine b. butylpropylamine e. cyclohexylamine N-propyl-I-butanamine cyclohexanamine ¢. sec-butylisobutylamine ‘N-isobutyl-2-butanamine (notice that the longest continuous chain has 4 carbons) 17. a. CHCH,CH,NHCH,CHCH, 4. CH,CH,CH,NCH,CH,CH, CH; CH, b, CHjCH,NHCH,CH, & CH,CH,CHCH,CH, Ny, HC” *CH, © | CH,CHCH,CH,CH,CH,NH, t ou C -yenscr, cn, 18, a, 6-methyl-1-heptanamine ¢. N-ethyl-N-methylethanamine ; isooctylamine diethylmethylamine primary tertiary b. 3-methyl-N-propyl-I-butanamine 4, 2,5-dimethyleyclohexanamine ssopentylpropylamine no common name secondary primary 19. a. The bond angle is predicted to be similar to the bond angle in water (104.5°) 'b. The bond angle is predicted to be similar to the bond angle in ammonia (107.3°) ¢. The bond angle is predicted to be similar to the bond angle in water (104.5°) d. The bond angle is predicted to be similar to the bond angle in the ammonium ion (109.5°) 20, a 1,4,and5 b. 1,2,4,5, and 668 2. Chapter 2 a, Each water molecule has two hydrogens that can form hydrogen bonds, whereas each alcoho} molecule has only one hydrogen that can form a hydrogen bond. Therefore, there are more hydrogen bonds between water molecules than between alcohol molecules. H---:0-H b. Each water molecule has two hydrogens that can form hydrogen bonds, whereas each ammonia has three hydrogens that can form hydrogen bonds. However, oxygen is more ¢lectronegative than nitrogen, so the hydrogen bonds between water molecules are stronger than the hydrogen bonds between ammonia molecules. Because the number of hydrogen bonds supports ammonia as having the higher boiling point but the strength of the hydrogen bonds supports water, we could not have predicted which would have the higher boiling Point. However, being told that water has the higher boiling point we can conclude that the greater electronegativity of oxygen compared to nitrogen is more important than the number of hydrogens that can form hydrogen bonds. ¢. Each water molecule has two hydrogens that can form hydrogen bonds, whereas each molecule of hydrogen fluoride has only one hydrogen that can form a hydrogen bond. However, fluorine is more electronegative than oxygen. Again we cannot predict which will have the higher boiling point, but we can conclude from the fact that water has the higher boiling point that in this case the greater number of hydrogens that can form hydrogen bonds is more important than the greater electronegativity of fluorine compared to oxygen, OH On OH NH, wo Lows son 3 SLU >\KL .- 3. CHyCH,CH;CH,CH,CH)Br > CH;CH,CH,CH,CH,Br > CH,CH,CH,CH,Br b. CHjCH,CH,CH,CH;CH;CH,CHCH, > CH,CH,CH,CH,CH,CH;CH,CH, > HG CH, CHsGHCH,CH,CH,CH,CH, > CH3C~CCH, CH, HC CH, © CHsCH;CH,CH,CH,OH > CH;CH,CH,CH,OH > CHjCH,CH)CH,CI > CH;CH,CH,CHCH;Chapter2 69 2A. HOCH,CH,CH,OH > CHCH,CH,0H > CH,CH,CH,CH,OH > CHjCH,CH,CH,Cl b. NH) OH CH; ‘The amine is more soluble in water than the alcohol, because the amine has two > > hydrogens that can form hydrogen bonds with water. 25. — Because cyclohexane is a nonpolar compound it will have the lowest solubility in the most polar solvent, which, of the solvents given, is ethanol. CHCH,CH,CH,CH,OH CH,CH,0CH,CH; CH;CH,OH CH,CH,CH,CH,CH,CH, 1-pentanol diethyl ether ethanol frais 6. a Suu, OF cH, HCH, CH,CH, 74s Ss 3 3 H. .CH,CH;, ® iH H at a ital H A B c CH; HCH; is CH. H H (CHaCHa, H W H H # H H CH,CH, CHCH, H D E F70 Chapter 2 potential ‘energy D 7 t + 0 60 120 180 240 300 360 Degrees of Rotation 2. a. CH, i CH,CH; : H,CH3 H. CH H, H H, H H H H ‘CH; CHy CH; CH,CH, CH,CH; CH,CH 28, a b. 180° — oa 9 180°- 45° = 135° 180"- 40° = 140° 29. Hexethal would be expected to be the more effective sedative because it is more nonpolar than barbital since hexethal has a hexyl group in place of the ethyl group of barbital. Being more nonpolar, hexethal will be better able to penetrate the nonpolar membrane of the cell 30. cH, cH, ; cH. cH. * + be CH; CH; a CH; ‘Hy3 32. 33. 35. 36. Chapter2 71 The “strainless” heat of formation of cycloheptane is 7 (- 4.92) = - 34.4 kcal/mol The actual heat of formation of cycloheptane is - 28.2 kcal/mol (from Table 2.9 on p. 96 of the text.) ‘You can get the total strain energy of cycloheptane by subtracting the strainless heat of formation from the actual heat of formation: - 28,2 - (- 34.4) = 6.2 kcal/mol Two 1,3-diaxial (gauche) interactions cause the chair conformer of fluorocyclohexane to be 0.25 kcal/mol less stable when the fluoro substituent is in the axial position than when it is in the equatorial position. ‘The gauche conformer of 1-fluoropropane has one gauche interaction (See Figure 2.14 on p. 99 the text). Therefore, the gauche conformer is (0.25/2) = 0.13 kcal/mol more stable than the anti conformer that has no gauche interactions. Kay = lesustoalconfored 54 [axial conformer] 1 % of equatorial conformer = ————lequatorialconformer]_ agg [equatorial conformer) + [axial conformer] = —54_ x10 = 54 x 100 = 84% 3441 64 Because bromine has a larger diameter than chlorine, one would expect bromine to have a larger 4G". However, the C—Br bond is longer than the CCl bond, which causes bromine to be farther away than chlorine from the other axial substituents. Apparently, the longer bond more than offsets the larger diameter. Both rrans-1,4-dimethyleyclohexane and cis-1-fert-butyl-3-methyleyclohexane have a conformer with two substituents in the equatorial position and a conformer with two substituents in the axial position. cis-1-tert-Butyl-3-methylcyclohexane will have a higher percentage of the diequatorial- substituted conformer because the bulky fert-butyl substituent will have a greater preference for the equatorial position. acis bcis ecis d.trans e.trans — f. trans72 Chapter 2 31. a. ‘CH,CH; b Low CH; CH, ¢. trans-1-Ethyl-2-methylcyclohexane is more stable because both substituents are in equatorial positions. 38. a. one equatorial and one axial d. one equatorial and one axial b. both equatorial and both axial €. one equatorial and one axial ¢. both equatorial and both axial f. both equatorial and both axial 39, a. One chair conformer of trans-1,4-dimethyleyclohexane has both substituents in equatorial positions, so it does not have any 1,3-diaxial interactions. The other chair conformer has both substituents in axial positions. When a substituent is in an axial position, it experiences two 1,3-diaxial interactions, so this chair has a total of four 1,3-diaxial interactions. Since the 1,3- diaxial interaction between a methyl group and a hydrogen causes a strain energy of 0.9 kcal/mol, the chair conformer with both substituents in axial positions is 4 x 0.9 = 3.6 keal/mol less stable than the chair conformer with both substituents in equatorial positions. b, Each of the chair conformers of cis-1,4-dimethylcyclohexane has one substituent in an equatorial position and one in an axial position. Therefore, the two conformers have the same energy. The difference in energy between them is 0 kcal/mol. 40, Both Kekulé and skeletal structures are shown. CH; I a, CH,CH,CHOCCH, b, CH,CHCH,CH,CH,CH;,0H CH; CH CH; Ox AAAouChapter2 73 gas . CH;CHCHNH, a. CHCCH,Br CH; Se oe HCH, CH, NH, CH; e f, CHyCH,CH,CHCHCH,CHCH;,CH, Hy HCH, Ane » (<<) HCH & CHCHN HCH, NNN Br CHCH,CH,CHCH,CH,CH, J. CHsCHCH,CH¢CH,CH,CH, CHCCH, CH; Br i. bBnAx Br ‘Br CH; CAs k. Cx |. CH,CHCHCH,CH,CH, OH OCH,CH, Kou On74 Chapter 2 CH, 1 m. CH;CH,CH,CH,CHCH,CH,CH,CHs —_. CH,CH,CHCHCH,CH,CH,CH CHCH, CH; CHCA, CH, 41. a. S-bromo-2-methyloctane & 3-cthoxyheptane b, 2,2,6-trimethylheptane h, L-bromo-4-methylcyclohexane ¢. 2,3,5-trimethylhexane i. N,N-dimethyleyclohexanamine 4d, 3,3-diethylpentane j. 3-ethylcyclohexanol ¢. S-bromo-N-ethyl-1-pentanamine k. 1,3-dimethoxypropane £. S-methyl-3-hexanol 42 a3 b.6 «3 43. The first conformer is the most stable because the three substituents are more spread out, so its gauche interactions will not be as large—the Cl in the first conformer is between a CH and an 1H, whereas the Cl in the other two conformers is between two CH groups. 44, gos a ie b. CHyC—CCHs ©. CH CHCH,CHCH, CH, CH, CH; CH;Chapter2 75 45, a. L-ethoxypropane f. 2-bromo-2-methylbutane ethyl propyl ether tert-pentyl bromide b. 4-methyl-1-pentanol @ cyclohexanol isohexyl alcohol cyclohexyl alcohol . 2-butanamine h. —_bromocyclopentane sec-butylamine cyclopentyl bromide d. — 2-chlorobutane 2-propanamine sec-butyl chloride isopropylamine fe. 2-methylpentane J. Neethyl-2-butanamine isohexane sec-butylethylamine 46. a. L-bromohexane i. octane b. pentyl chloride J. isopentyl alcohol ¢. L-butanol ‘(The alcohol has the higher boiling point because it 4. I-hexanol forms stronger hydrogen bonds. If you were asked fe. hexane to compare their solubilities in water, the amine is f. L-pentanol more soluble because it forms more hydrogen £: Lbromopentane bonds) butyl alcohol k, hexylamine (it can form more hydrogen bonds) 47, Ansaid is more soluble in water. It has a fluoro substituent that can hydrogen bond to water. Motrin has a nonpolar isobutyl substituent in place of Ansaid’s fluoro substituent. 48. a, correct g correct b. 4-cthyl-2,2-dimethylheptane h. 2,5-dimethylheptane ¢. 3-methylcyclohexanol i. 5-bromo-2-pentanol 4d, 2,2-dimethyleyclohexanol J 3ethyl-2-methyloctane e. 5-(2-methyipropyl)nonane k. 2,3,3-trimethyloctane £. 1-bromo-3-methylbutane 1. 5:methyl-N,W-dimethyl-3-hexanamine 49, B has the highest energy. They are all diaxial-substituted cyclohexanes, so each one has four 1,3- Giaxial interactions. Only B has a 1,3-diaxial interaction between CH and Cl, which will be greater than a 1,3-diaxial interaction between CH; and H or al,3-diaxial interaction between Cl and H.76 Chapter 2 50. The only one is 2,2,3-trimethylbutane, Gls CHa CHyC—CHCH, CH; 51. b. a. Gren f Lo. 52. CH CH; a CHCH; > cHCH,, CHCH, H. H H H H q H H HCH, most stable least stable ¢. Rotation can occur about all the CC bonds. There are six carbon-carbon bonds in the ‘compound, so there are five other carbon-carbon bonds, in addition to the C3-C bond, about which rotation can occur. CHs—CH—CH)—CH,—CHy—CH CH, 4d. Three of the carbon-carbon bonds have staggered conformers that are equally stable because each is bonded to a carbon with three identical substituents. V CH CH—CH)—CH)—CHy—CH, CH;Chapter2 77 53, Cand D are cis isomers. (In C both substituents are downward pointing; in D both substituents are upward pointing.) 54. CH,CH;CH,CH,CH;Br a. L-bromopentane primary alkyl halide b. pentyl bromide CH;CH,CH,CHCH, a, 2-bromopentane secondary alkyl halide Br b. none CH,CH,CHCH,CHy a, 3-bromopentane secondary alkyl halide Br ‘b. none gi CH;CHCH,CH,Br a, L-bromo-3-methylbutane primary alkyl halide . isopentyl bromide a CH,CH,CHCH,Br a. I-bromo-2-methylbutane primary alkyl halide b. none Br CH,CH,CCH, a, 2-bromo-2-methylbutane tertiary alkyl halide cH, b. terepentyl bromide ir CHjCHCHCH, ‘a, 2-bromo-3-methylbutane secondary alky! halide én, 1b. none gi CH,CCH,Br a, L-bromo-2,2-dimethylpropane _ primary alkyl halide cn, b, neopentyl bromide ¢. Four isomers do not have common names. 4. Four isomers are primary alkyl halides. €. Three isomers are secondary alkyl halides, £. One isomer is a tertiary alkyl halide. 55. a. butane €. 6-chloro-4-ethyl-3-methyloctane b. i-propanol f. 1-methoxy-5-methyl-3-propylhexane © 4-propyl-1-nonanol g. G-isobutyl-2,3-dimethyldecane 4. 5-isopropyl-2-methyloctane or h. 8-methyl-4-decanamine 2-methyl-5-(1-methylethyl)octanere 8 56. 57. Chapter 2 HC more stable CH CH,CH; : CH(CH3), - ‘CH,CH, CH(CH,); more stable CHACHs cH, ® ‘CH,CH; CH, more stable CHLCH, CH, a. : ‘CH,CH, HC. more stable CH,CH; (CH,),CH *2° more stable (CH,),CH CH;CH; a ‘CH)CH, -~T (CH3).CH (CH,),CH more stable CH2CHs Alcohols with low molecular weights are more water soluble than alcohols with high molecular weights because, as a result of having fewer carbons, they have a smaller nonpolar component that has to be dragged into water.Chapter2. 79. 58. * 9 cn Na ; a, \ more stable less stable CH . We know that there is more room for a substituent in the equatorial position, Because we have been told that the more stable conformer has the methyl group in the equatorial position, we can conclude that the methyl group takes up more room than the lone pair. 59, Six ethers have molecular formula = CsH120. (CH,OCH,CH,CH,CH, CH;CHCH,CH; CH,CH,0CH;CH,CH OCH. ed f on 2 1-methoxybutane ee L-ethoxypropane butyl methyl ether ethyl propyl ether ‘2-methoxybutane sec-butyl methyl ether CH; CH;CHCH. } aa CH,COCH,, CH,CHCH,OCH, OCH,CH, 1 1 CH CHs ~o xy Aro 2-ethoxypropane 2-methoxy-2 -methoxy-2-methylpropane _1-methoxy-2-methylpropane ethyl isopropyl ether tert-butyl methyl ether isobutyl methyl ether 60. The most stable conformer has two CH groups in equatorial positions and one in an axial Position. (The other conformer would have two CHs groups in axial positions and one in an equatorial position.) CH80 Chapter 2 61. a. 6-methyl-N-methyl-3-heptanamine 4, 5-(1,1-dimethylpropyl)nonane or S-neopentylnonane b. 3-ethyl-2,5-dimethylheptane ¢. 5-(2-ethylbutyl)-3,3-dimethyldecane 1,4-dichloro-5-methylheptane 62, One chair conformer of trans-1,2-dimethylcyclohexane has both substituents in equatorial positions, so it does not have any 1,3-diaxial interactions. However, Figure 2.12 on p. 98 of the textbook shows that the two meihyl substituents are gauche to one another (as they would be in gauche butane), giving it a strain energy of 0.9 kcal/mol. CH; a gauche L~Le*) <—iec, ‘The other chair conformer of srans-1,2-dimethylcyclohexane has both substituents in axial positions. When a substituent is in an axial position, it experiences two 1,3-diaxial interactions. ‘This chair conformer, therefore, has a total of four 1,3-diaxial interactions. Each diaxial interaction is between a CH; and an H, so each results in a strain energy of 0.9 kcal/mol. ‘Therefore this chair conformer has a strain energy of 3.6 kcal/mol. a1 3-diaxial interaction H------3CH, Thus, one conformer is 2.7 kcal/mole more stable than the other. 63. 1H,0H HO: 0, HO. OH 1H 64. a, 1-Hexanol has a higher boiling point than 3-hexanol because the alkyl group in I-hexanaol can better engage in van der Waals interactions. The OH group of 3-hexanol makes it more difficult for is 6 carbons to lie close to the 6 carbons of another molecule of 3-hexanol. D. The floppy ethyl groups in diethyl ether interfere with the ability of the oxygen atom to engage in hydrogen bonding with water.65. 66. Chapter2 81 One of the chair conformers of cis-1,3-dimethylcyclohexane has both substituents in equatorial positions, so there are no unfavorable 1,3-diaxial interactions. The other chair conformer has three 1,3-diaxial interactions, two between a CH; and an H and one between two CH; groups. ‘We know that a 1,3-diaxial interaction between a CH, and an His 0.9 kcal/mol. Subtracting 1.8 from 5.4 results in a value of 3.6 kcal/mol for the 1,3-diaxial interaction between the two CH toms. Hy---=22=CH; HC ‘The conformer on the left has a gauche interaction between the two CH groups (0.9 kcal/mol) and two 1,3-diaxial interactions between a CH and an H (2 x 0.9 kcal/mole) for a total strain energy of 2.7 kcal/mol. ‘gauche fs interaction Hy CH; gauche HC CH, ---F CH, interaction ‘The conformer on the right has a gauche interaction between the two CH groups (0.9 kcal/mol) and three 1,3-diaxial interactions, two between a CH and an H (1.8 keal/mole) and one between two CH groups (3.6 kcal/mole; see Problem 65) for a total strain energy of 6.3 kcal/mol. H- The conformer on the left will predominate at equilibrium.82 Chapter 2 Chapter 2 Practice Test Name the following compound: yo Draw the following conformers of hexane considering rotation about the C;—Cy bond: a. the most stable of all the conformers b. the least stable of all the conformers . a gauche conformer Give two names for each of the following compounds: a CH,CH,CHCH, b. CH,CHCH,CH,CH,OH « Gps a CH, ‘Br Label the three compounds in each sct in order of decreasing boiling point. ‘(Label the highest boiling compound #1, the next #2, and the lowest boiling #3.) a, CHyCH,CH,CH,CH,Br CH,CH,CH,Br CH;CH;CH;CH,Br b. CHjCH,CH,CH,CH; CH,CH,CH,CH,OH — CH,CH,CH,CH,Cl pope & CHsC—CCH; CHCH,CH,CH,CH,CH,CH,CH; CHsCHCH,CH,CH,CH,CHs CH; CH; CH Give the systematic name for each of the following compounds: a. CH,CHCH,CH,CHCH,CH, & poe CH oH Br CH a I b, CHsCH,CHOCH,CH, @. CHyCHCHCH,CH,CH,CI CH,CH,CH,CH, CH,CH;Chapter2 83 6. Draw the other chair conformer. H Br 7 CHy 7. Draw the most stable conformer of rrans-1-isopropy!-3-methylcyclohexane 8. Which of the following has: a, the higher boiling point: diethyl ether or butyl alcohol? b. the greater solubility in water: 1-butanol or 1-pentanol? . the higher boiling point: hexane or isohexane? 4. the higher boiling point: pentylamine or ethylmethylamine? e. the greater solubility in water: ethyl alcohol or ethyl chloride? 9. Give two names for each of the following compounds: & CHjCHCH,CH,Br —_b. CH,CHCH,CH,0H CH CHCH;CH.NH CH, CH; CH, 10. Which is more stable: a, A staggered conformer or an eclipsed conformer? b. The chair conformer of methylcyclohexane with the methyl group in the axial position or the chair conformer of methyleyclohexane with the methyl group in the equatorial position? ©. Cyclohexane or cyclobutane? 1. Give the structure of the following: a. a secondary alkyl bromide that has three carbons b. a secondary amine that has three carbons ¢. an alkane with no secondary hydrogens 4. a constitutional isomer of butane . three compounds with molecular formula C3HsO ‘CHAPTER 3 Alkenes: Structure, Nomenclature, and an Introduction to Reactivity ‘Thermodynamics and Kineties Important Terms acyclic noneyelic. addition reaction areaction in which atoms or groups are added to the reactant. alkene a hydrocarbon that contains a double bond. allyl group CH)=CHCH,— allylic carbon an sp? carbon adjacent to a vinyl carbon. Arrhenius equation relates the rate constant of a reaction to the energy of activation and to the temperature at which the reaction is carried out (k = Ae“E,/RT), cis isomer the isomer with the hydrogens on the same side of the double bond. degree of unsaturation _the number of bonds and/or rings in a hydrocarbon. E isomer the isomer with the high-priority groups on opposite sides of the dovble on electrophile an electron deficient atom or molecu electrophilic addition an addition reaction in which the first species that adds to the reactant is an reaction electrophile. endergonic reaction a reaction with a positive AG*. endothermic reaction _a reaction with a positive AH®. enthalpy the heat given off (- AH) or the heat absorbed (+ AH”) during the course of a reaction entropy a measure of the freedom of motion in a system. exergonic reaction a reaction with a negative AG®. exothermic reaction a reaction with a negative AH°. experimental energy of a measure of the approximate energy barrier to a reaction. activation (tis approximate because it does not contain an entropy component.) (Ea = AHt-RT) first-order rate constant the rate constant of a first-order reaction. | first-order reaction a reaction whose rate is dependent on the concentration of one reactant. (unimolecular reaction)froe energy of activation act) functional group metric isomers {cis-trans stereoisomers) Gibbs standard energy change intermediate kinetics Kinetic stability mechanism of the reaction nucleophile rate constant rate-determining step or rate-limiting step reaction coordinate diagram saturated hydrocarbon second-order rate constant second-order reaction (bimolecular reaction) solvation thermodynamics Chapter3 85 the true energy barrier to a reaction. the center of reactivity of a molecule. cis-trans (or E, Z) isomers. the difference between the free energy content of the products and the free energy content of the reactants at equilibrium under standard conditions (1M, 25°C, 1 atm), ‘a species formed during a reaction that is not the final product of the reaction. the field of chemistry that deals with the rates of chemical reactions. is indicated by AGT. If AGT is large, the compound is kinetically stable (not very reactive). If AGT is small, the compound is kinetically unstable (is very reactive). ‘a description of the step-by-step process by which reactants are changed into products. an electron-rich atom or molecule. ‘a measure of how easy it is to reach the transition state of a reaction (to get over the energy barrier of the reaction). the step in a reaction that has the transition state with the highest energy. describes the energy changes that take place during the course of a reaction. a hydrocarbon that is completely saturated with hydrogen (contains no double or triple bonds). the rate constant of a second-order reaction. a reaction whose rate is dependent on the concentration of two reactants, or on the square of the concentration of a single reactant. the interaction between a solvent and another molecule (or ion). the field of chemistry that describes the properties of a system at equilibrium.86 Chapter 3 thermodynamic stability trans isomer transition state unsaturated hydrocarbon vinyl group vinylic carbon Zisomer is indicated by AG®. If AG? is negative, the products are more stable than the reactants, If AG* is positive, the reactants are more stable than the products. the isomer with the hydrogens on opposite sides of the double bond. the highest point on a hill in a reaction coordinate diagram. In the transition state, bonds in the reactant that will break are partially broken and bonds in the product thet will form are partially formed. a hydrocarbon that contains one or more double or triple bonds. CH,=cH— a carbon that is doubly bonded to another carbon. the isomer with the high-priority groups on the same side of the double bond.Solutions to Problems 1. aCsHy Cys =e Cie acuta be 4 el 3 a. CH;CH=CH, —b. CH,C=CH A CH,=C=CH, 4 a CH; CH; ga b. CHjC=CCH,CH,CH,Br CH, 5. 4-dimethyl-3-hexene ¢. L-bromocyclopentene 6. aS be 4 a4 Chapter3 87 d. CsHio © HC=CCH,CH; CH,C=CCH, oA Aa (CH,=CHCH=CH, CH, =C=CHCH, © CHjCH,OCH=CH, d. CH,=CHCH,OH -bromo-4-methyl-3-hexene .5-dimethyleyclohexene -butoxy-1-propene a. eL £1r 88 Chapter3 8 Only Chas dipole moment of zero because the bond dipoles cancel since they are in opposit directions. H. ca XN / arcs 4 cl 4 H 9 1 CHG CH CHCl co z H H H ‘CH Zz E 2 CHG, CH,CH, CHCEh C=C’ C=C a” “a a’ cu,cHy E Zz 3, ge . (CH,CH,CH,CH; eee Nee CHCH;CH;QH —_,CHCH, ZN C=C! HCH, ya CH;CH, — GHCHs CH;CH, CH,CI CH, Zz E 4 HOCHCH, —_,C(CH3); HOCH,CH,, CCH C=C. C=C’ e “N eee: o=CH = CECH o=cu ‘C(CH); Zz E 10. CH, HAC, duce: BCE 5 C=C 7 H (CH,CH,CH,CH3,Chapter3 89 1. nucleophiles: H CH;O CH,C=CH NH, electrophiles: AIC, CHjCHCH 2. — > CHC-0 + HO Br + Be > ‘or a ( +OH © CHC-O-H + 6-H cH,C-0-H + 1,0 1H Cis a. CH—oaG — CHC + 0 cHY cH; 13. a, Because the equilibrium constants for all the monosubstituted cyclohexanes in Table 2.10 on page 99 of the text are positive, they all have negative AG? values. (recall that AG® =~ RT In Keq) by the tert-butyl substituent ‘e. the tert-butyl substituent @. AG°=-RT x InKeq AG? =~ 1.986 x 103 x 298 x In 18 AG?=—0.59 x In 18 AG?=—0.59 x 2.89 AG® = -1.7 kcal/mol (or - 7.1 kJ/mol)90 Chapter 3 14. a. Solved in the text b. AG? = -RT In Key = 2.1 = - 1.986 x 103 x 298 x InKeq 3.56 Lisopropyleyclohexanelequaorial 35. Kea = “Topropyleyelohexanelyia ad lisopropylcyclohexane]equatorial = 35 ‘Tsopropyleyclohexanelequaonin + lisopropyleyclohexanclayay 35+ = 3h 6 = 097 = 91% . Isopropylcyclohexane has a greater percentage of the conformer with the substituent in the ‘equatorial position because the isopropyl substituent is a larger substituent than the fluoro substituent. The larger the substituent, the less stable is the conformer in which the substituent is in the axial position because of the 1,3-diaxial interactions, 15, _AS* is more significant in reactions in which the number of reactant molecules and the number of product molecules are not the same. a LA+B = c 2A+B == Cc b. None of the four reactions has a positive AS*. In order to have a positive AS°, the products must have greater freedom of motion than the reactants, 16. a. (1) AG? = AH? - TAS? AG?=-RTIn Keg (recall that T= °C +273) AG? =~ (1.986 x 10°3) (303) In Keg 12-273 + 30)(.01) -15=-0.60 In Keg AG*=-12-3 = -15keal/mol In Keq = 25 Keg =7.2x 101017. 18. Chapter3 91 a. (2) AG°= AH®— TAS? AG? = -12 — (273 + 150)(.01) AG? =~12-4 = -16 kcal/mol b. For this reaction: the calculations show that increasing the temperature causes AG® to be more negative. ¢. For this reaction: the calculations show that increasing the temperature causes Keq, to be smaller. (Remember that In Keq = AGYRT). bonds broken bonds formed. mbond of ethene 63 101 H-al 103 c-al 85 166 186 AH? = 166 ~ 186 = ~20kcal/mol b. bonds broken bonds formed. bond of ethene c-H 101 HoH ca 164 C-H- _101 ‘167 202.0 AH? «= 167 ~ 202 = ~35 kcal/mol ¢. Both are exothermic, 4. Both reactions have sufficiently negative AH” values to expect that they would be exergonic as well, a. a and b because the product is more stable than the reactant b. b because it has the smallest rate constant (highest hill) leading from the product to the transition state €. ebecause it has the largest rate constant (smallest hill) leading from the product to the transition state92 Chapter 3 19, A thermodynamically unstable product is one that is Jess stable than the reactant. A kinetically unstable product is one that has a large rate constant (reforms reactant rapidly), whereas a kinetically stable product is one that has a small rate constant (reforms reactant slowly). a b. Free energy Progress of the reaction —— Progress of the reaction ——_— 20, a. Solved in the text. b. Decreasing the concentration of methyl chloride will decrease the rate of the reaction to 1x 10° Ms, c. _ Changing the concentration will not affect the rate constant (k) of the reaction, because rate constants do not depend on the concentration or the reactants. 21. The rate constant for a reaction can be increased by decreasing the stability of the reactant or by increasing the stability of the transition state 22, Taking the logarithm of both sides of the Arhenius equation gives the following equation, whic ‘we can use to answer the questions: Ea Ink = nA ~ 3 a. Increasing the experimental activation energy will decrease the rate constant of a reaction (will cause the reaction to be slower). b. Increasing the temperature will increase the rate constant of a reaction (will cause the reactio: to go faster).23. Chapter3 93 a. The first reaction has the greater equilibrium constant. ; 2 ky = AH x0 ky = THE ext 1x 105 1x 103 b. Because both reactions start with the same concentration, the first reaction will form the most product because it has the greater equilibrium constant. D = reactant(s) first transition state Free = intermediate energy = second transition state = product(s) Progress of the reaction —ee ‘a. The first step (in the forward direction) has the greatest free energy of activation. b. The first-formed intermediate is more apt to revert to reactants. ¢. The second step is the rate-determining step because it has the transition state with the highest energy. Notice that the second step is rate-determining even though the first step has the greatest energy of activation (steepest hill to climb). That is because it is easier for the intermediate that is formed in the first step to go back to starting material than to undergo the second step of the reaction. So, the second step is the rate-limiting step.94 Chapter 3 26. B A c a. one b. two . the second step (kz) (In this particular diagram, kp > kif you had made the transition stab for the second step a lot higher, you could have had a diagram in which hy > kz.) 4. the second step (1) £ BoC ce. the second step in the reverse direction (ky) g CtoB 27, a. 3,8-dibromo-4-nonene ¢. 1,5-dimethyleyclopentene b. (Z)-4-ethyl-3,7-dimethyl-3-octene _—_d, 3-ethyl-2-methyl-2-heptene 28. CH, oH &. CHj=CHCH,CH,CH,CH, b. CHy=CHCHCH,CH, — ¢. CH,=CHCCH, ‘Hs 29. 9 CH, Hs (CH:CH,Br © Bh SHCH, . CH; ‘cad \ aN ‘Br Br CH,CH,CH, (CH;CH,CH,CH; d, CH,=CHBr f. CH,=CHCH,NHCH,CH=CB30. 31, CH,=CHCH,CH,CH,CH, Lhexene (CH, =CCH,CH,CH, CH; 2-methyl-1-pentene CHsC=CHCH,CH, CH; 2-methyl-2-pentene a CH,=CCHCH, CH, 2,3-dimethiyl-1-butene CHjCH=CHCH,CH,CH, 2-hexene CH, =CHCHCH,CH, CH 3-methyl-1-pentene CHyCH=CCH,CH, CH; 3-methyl-2-pentene ge CH,¢CH=CH, CH; 3,3-dimethyl-L-butene gis CH3C=CCH, CH; 2,3-dimethyl-2-butene Chapter3 95 CHCH,CH=CHCH,CH, 3-hexene Cl=CHCH,CHCH, CH, 4-methyl-I-pentene CH,CH=CHCHCH, CH; 4-methyl-2-pentene CH;CH,C=CH, CH,CH, 2ethyl-1-butene Of the compounds shown above, the following have E and Z isomers: 2-hexene, 3-hexene, 3-methyl-2-pentene, 4-methyl-2-pentene -methyl-3-hexene . trans-8-methyl-4-nonene or (£)-8-methyl-4-nonene €. trans-9-bromo-2-nonene or (E)-9-bromo-2-nonene d. 2,4-dimethyt-I-pentene €. 2-ethyl-I-pentene £. cis-2-pentene or (Z)-2-penteneChapter 3 AG? = - RT In Keg In Keg = - AGIRT In Keq = ~ 4G0.59 kcal/mol 2.7210.59 kcal/mol 2,72/0.59 kcal/mol 4.6 46 = [BJA] = 0.01 [BY[A] = 100 ~0.65/0.59 keal/mol = 0,65/0.59 keal/mol 1.10 1.10 BY[A] = 0.33 [BIA] = 3.0 If the number of carbons is 40, CnH2n+2 = CoHg2. Therefore, a compound with molecular formula CagHs¢ is missing 26 hydrogens. This means that it has a total of 13 rings and x bonds, since each ring and m bond causes the compound to have two fewer hydrogens. Knowing that it has two rings and no triple bonds, one can conclude that it has 11 double bonds. a Z bE GE a. Z If the number of carbons is 30, CnH2n42 = CsoHe2. A compound with molecular formula CaoHs0 is missing 12 hydrogens. Because it has no rings, squalene has 6 bonds (12/2 = 6). a.-I > -Br > -OH > -CH3 b.-OH > -CH2Cl > -CH=CH2 > ~CH2CH20H ¢. “CH= CH > ~CH(CH3), > ~CH2CH2CH3 > -CH3 .-OH > -NH) > -CH,0H > -CH2NHp @.-Cl > -COCHs > -CN > -CH=CHy a. 2-pentene £, 2-chloro-3-hexene b. correct correct ¢. 3-methyl-I-hexene h, 2-methyl-I-hexene d. 3-heptene |. I-methylcyclopentene or methylcyclopentene e. 4-ethyleyclohexene J. 3-methyl-2-pentene 2 «. CtoD eB & exergonic oP e o f. endergonic41. 42, Chapter3 97 AG? = AH°-TAS? a. AG? = 20~(298)(25 x 10°3) = 20-7.5 AG? = 12.5 kcal/mol AG? = -RT In Keg 12.5 = ~1.986 x 10°3 x 298 In Keg 12.5 = - 0.59 In Keg =21.2 = InKeg 63x 1010 = Keg b. AG? = 20-(398)(25 x 103) = 20-10 AG? = 10.0 kcal/mol 10.0 = -1.986 x 10° x 398 In Keq 10.0 = ~ 0.79 In Keg 12.7 = InKeq 31x 105 = Keg a AG? = -RTInKeg AG? = -RTIn 10 AG? = -1.986 x 10°3 x 298 x 23 AG? = -1.36 kcal/mol b. AG? = AH?-0 1.36 = AH®-0 AH? = ~1.36 kcal/mol «AG? =0~ TAS 1.36 = 0 — 298A5° AS? = 136/298 = 4.56 x 10°3 kcal/mol deg) = 4.56 cal/(mol deg) RT In Keg -AGIRT = AG210.59 kcal/mol ~3.8/0.59 kcal/mol -64 (BYTA] = 0.0017 [BYIAy = 0.00171 = 1.7/1000 ‘The previous calculation shows that for every 1000 molecules in the chair conformation. there are 1.7 molecules in a twist-boat conformation. This agrees with the statement in Section 2.12 that for every thousand molecules of cyclohexane ina chair conformation, there are no more than two molecules in a twist-boat conformation.98 4B. Chapter 3 A step-by-step description of how to solve this problem is given in the box entitled "Calculating Kinetic Parameters", Eq can be determined from the Arrhenius equation (In k = - Ea/RT), because a plot of Ink versus I/T gives a slope = - Ea/R In 2.11 x 10° =- 10.77 7 LT = 3.29 x 10°3 ur T=324.5 VT =3.08x 103 T=3328 © UT= T=3422 0 UT 8290 (slope) R 16.4 kcal/mol ~AG® = RT In khITky From the graph used to determine Za, one can find the rate constant (k) at 30°. (itis 1.84x 10°5 s-1) — AG? = 1.98 x 103 x 303 In (1.84 x 105 x 6.625 x 10-27)/(303 x 1.3805 x 10-10) ~AG? = 1.98x 10-3 x 303 In (1.22 x 10°31V(4.18 x 10°8) 1.98x 10-3 x 303 In2.92x 104 1.98 x 10-3 x 303 x (- 54.2) Eq - RT 64 — 198x103 x 303 16.4 - 06 AH? = 15.8 kcal/mol To find AS*; AS® = (AH°~AG°/T AS? = (15.8 - 32.5303 AS = (16.7303 AS° = 0.055 kcal/(mol deg) = 55 cal/(mol deg)Chapter3 (99) ice 4, Name the following compounds: 8, CH,CH,CHCH,CH=CHy © CHsCH,CH=CHCH,CH,CHCH CH CH,CH; a be a. CH Br 2. Label the following substituents in order of decreasing priority in the E, Z system of nomenclature. Label the highest priority #1. ° 1 —CCH —CH=CH, —cl ‘=N 3. Correct the incorrect names. a, 3-pentene ¢. 2-cthyl-2-butene b. 2-vinylpentane 4, 2-methyleyclohexene 4. Indicate whether each of the following statements is true or false: a, Increasing the energy of activation, increases the rate of the reaction, eee b, Decreasing the entropy of the products compared to the entropy of the reactants makes the equilibrium constant more favorable. Dee ¢. An exergonic reaction is one with a- AG®. d. An alkene is an electrophile. 3 €. The higher the energy of activation, the more slowly the reaction will take place. f. Another name for trans-2-butene is Z-2-butene. & trans-2-Butene has a dipole moment of zero. sans om om hh. A reaction with a negative AG® has an equilibrium constant greater than one.100 10. Chapter 3 Do the following compounds have the E or the Z configuration? CH, $ g a cn,cucH,, ,CH,CH,CH,Br b. CH;CH, _,CCHs ae, cacy cHscH ‘CH,OH HH ‘CH,OH CH; CH; Draw structures for the following: a. allyl alcohol ¢. cis-3-heptene b. 3-methyleyclohexene 4. vinyl bromide How many ™ bonds and/or rings does a hydrocarbon have if it has a molecular formula of CH" ‘Using curved arrows show the movement of electrons in the following reaction: CH;CH=CH, + H~ ——> CH;CH-CH, + :: —> CHsFH—CHy Which of the following have cis-trans isomers? a. L-pentene ¢. 2-bromo-3-hexene b. 4-methyl-2-hexene d. 2-methyl-2-hexene Which of the following has a more favorable equilibrium constant (i.e., favors products over reactants)? . A reaction with a AH® of 4 kcal/mol or a reaction with a AH? of 7 kcal/mol? b. A reaction that takes place at 25 °C or the same reaction that takes place at 35 °C? ¢. A reaction in which two reactants form one product or a reaction in which one reactant form: two products?SPECIAL TOPIC IT An Exercise in Drawing Curved Arrows "Pushing Electrons" ‘This is an extension of what you leamed about drawing curved arrows in Section 3.6 on pages 123-124 of the text, Working through these problems will take just a litle of your time. It will, however, be time well spent, because Curved arrows will be used throughout the course and it is important that you are comfortable with this notation. (You will not encounter some of the reaction steps shown in this exercise for weeks or even months, so don't worry about why the chemical changes take place.) Chemists use curved arrows to show how electrons move as covalent bonds break and/or new covalent bonds form. The tail of the arrow is positioned at the point where the electrons are in the reactant, and the head of the arrow points to where these same electrons end up in the product. In the following reaction step, the bond between bromine and a carbon of the cyclohexane ring breaks and both electrons in the bond end up with bromine in the product. Thus, the arrow starts at the electrons that carbon and bromine share in the reactant, and the head of the arrow points at bromine because this is where the two electrons end up in the product. ‘The carbon of the cyclohexane ring is positively charged in the product because it has lost the two electrons it was sharing with bromine. The bromine is negatively charged in the product because it has gained the electrons that it shared with carbon in the reactant. The fact that two electrons move in this example is indicated by the two barbs on the arrowhead. OF — ©. Notice that the arrow always starts at a bond or at a lone pair. It does not start at a negative charge. CH;CHCH, + — CH,CHCH, sCHCH; SCHCHs Nae Cl: In the following reaction step a bond is being formed between the oxygen of water and a carbon of the other reactant. The arrow starts at one of the lone pairs of the oxygen and points at the atom (the carbon) that will share the electrons in the product. The oxygen in the product is Positively charged because the clectrons that oxygen had to itself in the reactant are now being shared with carbon. The carbon that was positively charged in the reactant is not charged in the product, because it has gained a share in a pair of electrons. CH;CHCH; HQ: —— — cagucH; jee :OH H102 Special Topic II In the next examples, a bond breaks and a bond forms in the same step. As in the previous examples, the arrow starts at the point where the electrons are in the reactant, and the head of the arrow points (0 where these same electrons end up in the product (at the carbon atom in the first example, and between the carbons in the next example). Notice that the atom that loses a share in a pair of electrons (C in the first example, H in the second) ends up with a positive charge. ee re CHCTPHCH; = — CHC —CHCH CH CH Gly uch, — > CH =CHCH, + H* H In the examples that follow, a nucleophile attacks an atom, causing a bond to break, with the result that the bonding electrons move to a positively charged atom. oon OH il 1 CHj;-C-CH, + =H,Qt > CHs—¢—CH OH H — CH,CH,-GH + HO? CH,CH» OH + mS “Bet SNe et an Meas — + HOSpecial Topic I 103 Draw curved arrows to show the movement of the electrons in the following reaction steps. Fyou will find the answers immediately after this exercise.) gs es a. CHsCHAC— — = cHCHc + CH, CH; a. CHj;CH,—MgBr ——> CH,CH, + *MgBr © CH;CH,CHCH, + — > CHACH,CHCH, Brt Frequently chemists do not show the lone-pair electrons when they write reactions. The following are the same reaction steps you just saw except that the lone pairs are not shown. Problem 2. Draw curved arrows to show the movement of the electrons. gs ge & CH;CH,¢—Br — cnc ceeeaeeiBee CH; CH; d. CH,CH,—MgBr_ > CH,CH, +104 Special Topic 11 ‘The lone pairs of Br~ in example e have to be shown in the reactant because an arrow can start only at a bond or at a lone pair. Bromine’s lone pairs do not have to be shown in the product. © CH;CH,CHCH; + Brt — CH;CH,CHCH, Br In the examples in Problems 1 and 2 that show a reaction step in which a bond breaks, both of the bonding electrons end up on one of the atoms that shared the electrons in the bond. Because two electrons move, an arrowhead with two barbs is used to show their movement, In the examples in Problems 1 and 2 that show a reaction step in which a bond is formed, the two electrons that form the bond come from the same atom. Because two electrons move, an arrowhead with two barbs is used to show their movement. ‘Sometimes a bond breaks in such a way that each of the bonded atoms gets one of the bonding electrons. An arrowhead with one barb represents the movement of one electron. Of — ©. « ‘Sometimes a bond is formed using one electron from one atom and one electron from the other atom that forms the bond, Because one electron comes from cach atom, an arrowhead with one barb is used to show the movement of each electron CH,CHCH, — — ca.cHCH Br Problem 3. Draw curved arrows to show the movement of the electrons. a. CHjCH)— — CH,CH, + b. — e — aSpecial Topic 105 ‘The following are the same reaction steps you just saw except that the lone pairs are not shown. Problem.4. Draw curved arrows to show the movement of the electrons. a. CH,CH,—CI —» CHCH, + °C b. D>: pa : cee © CH,O—OCH, — CHO. + -OCH As Gas Gis Hs d. CHG-N=N—CCH; —e CHC CH; CH; CH; CH In many reaction steps, two pairs of electrons move simultaneously. In each of the examples, follow the arrows to see how the electrons move. Notice how the movement of the electrons allows you to determine the structure of the products and the charges on the products. ——— CH,CHCH, + ——> = cHcH,—OH + +GH CH,;—C-—CH, +106 Special Topic II Problem §, Draw curved arrows to show the movement of the electrons that result in the formation of the given product. + b. CH,CH,CH=CH, + H-Cl ——* CH;CH,CH-CH; + C7 © CH;CH,—Br + NH; —> cH,cH,—Nn, eB Problem 6, Draw curved arrows to show the movement of the electrons. a. CH,CH=CHCH, + H-G-H ——» CH,CH-CH,CH, + H,0: b, CHCH;CH,CH;—Cl: + —— _CH,CH,CH,CH,—-C=N + ‘0H +OH & CH ¢“GcH; CH;—C-OH + CH;OH OH i 4d. CH,-C-H = + = CH;—MgBr_ | > CH,—¢-H + CH; MgBrSpecial Topic I 107 Problem_7. Draw curved arrows to show the movement of the electrons. i a a, CH;—C—CH, + CH;CH;—MgBrb ——> CHy—¢—CH, + *MgBr CH,CH; e CH;CH;CH;—Br + CH, — > CH,CH,CH,—OCH, + Br ©. CH;CH=CH, + ——> —cH,CH—-CH,—Br 1 il 4d. CHy—G—-OCHCH, = CHs—C—CHy + CH,CHAT CH; Problem 8, Draw curved arrows to show the movement of the electrons. Br I = + CHACH-CHCH; =——> CH;CH=CHCH, + H,0 + BF H b. CH,CH,C=C—H + NH, ——» CHCH,C=C + NH, gs e © CHC—CHCH,CH, = = CHYC~CHCH,CH, CH, CH, Gis Gs 4a, CHa—GCH CHy=CCH; + HY H108 Special Topic I Problem 9, Draw curved arrows to show the movement of the electrons. os ae, H a CHCHGH + H-G*H === CHCHQH + H,O: H crt, + HO: === CHNH, + 4,0: H Curved arrows are used to show the movement of electrons in each step of a reaction, Problem 10, Draw curved arrows to show the movement ofthe electrons in each step of the following reaction sequences, @. CH;CH=CH, + HJ —~ CH;CH-CH, + CH;CH-CH, + # —> cCH—cH, Hs ois b. CHE ches er CH, CH; Hs Hs CH,C+ + Ne, == =~ cu,c-Na, I I CH, CH,Special Topic M109 Draw curved arrows to show the movement of the electrons in each step of the following reactions. Hy cl + na — RMS HattEE * ou + HG: CH CHy ans cH, + HO CH; H H HOH b. CHyCH,CH=CH) —~ CH;CH,CHCH, ——> CH,CH,CHCH CH,OH 20CH. 10CH, H cH Hf CH,OH, + CH,CH,CHCH, OCH ¢. In the following example, the acid and base are not specified: HB” represents any acid present in the reaction mixture and B: can be any base. CH CH, <> auaanreay Q wf) HC” “CH; BH Oy, CH + HB HC CH,110 Special Topic I Problem 12. Use what the curved arrows tell you about electron movement to determine the product of each reaction step. a. CH,CH, — g b. CH;—C-OCH, + H,Q: ——> © HOF + cxscncrzcn, — Ae i> 4. CH,;CH,—C—NH, — OHSpecial Topic = tron Pus bab CH. CH; a. CH;CHE —— —cHcH+ + Hy CH; 1 a b. OL Ow =O # H a. CH;CH,+MgBr CH,CH, + *MgBr @ CH,CH,CHCH, + — > — CHACH,CHCH, Se Br112 Special Topic II Problem 3 a. ox,cae: — CH,CH, + i cupbcn, — cas + cH, iA & CHC CH, Problem 4 a. cuca ld — “Ow — OD. a © cublocr, —_ CH;0- + -OCH, Hy CH; Cy CH da. cag ON GCs — CHG NSN ‘CCH; CHS CH; CH CH;Special Topic 1 113 Problem $ og “gu a CH:—¢"QH — CH;-C-CH; + H,0 CH; b. CHjCH,CH CH;CH,CH-CH, + I~ c exon, She +/ Ne; —» cHCH,-NH, +0 Br Problem 6 . CH;CHSCHCH, + wan — > cwcr-ca,cH, + HY H114 Special Topic IT Problem 7 9 o I I + a. CHy—C—CH, + CH,CHy7MgBr ——> CH; —CH; + MeBr b. cu,cn,cHy Se + CH, — > CH,CH,CH,-OCH; + Br c. CH;CHECH, + — > = cH,CH-CH,-Br 9 av il 4. CHC HCH; = ——= CH;—C—CH; + © CHCH,O cH) Br CHCHZCHCH; ——> CH,CH=CHCH, + H,0 + Br eos b. cu,cr,caC ly + Na, —» CH,CH,C=C + NE, fe gm — —CH,C—GHCH,CH, CHa © ge 7oCH; CH=CCH, + 4HSpecial Topic II 115 Problem? oe H 7 CH,CH,OH + == cHCHOH + H,0: === CHNH, «+ = HO: &. CH,CH=CH, + iG —> cHCH-cH, + CHsCH—CH, + —> ci CH-cH, CH; one + + 0 CH; CH, — cen, CH; 1 ae cnet ——> CH;—C-OH + cr :QH116 Special Topic It Cs CH; Hi, . ‘ +1H0° == ats — ‘CH; ZA, “OH + HO: \ 7” Hy a CH; CH [> °— Sn, = c + H;0° SH ° HAO; ‘CH; H CH;OH b. CHCH,CH=CH, ——= CHCH,CHCH, ——> CH,CH,CHCH, CHQH 20CH, ne cass CHOH, + CHyCH,CHCH, OCH, © en, \. CHS CHs CH besemernt cote <—_ ss Zs ue H,C’ “CH; HC” “CH; HAC’ “CH, Ft CH, cH; HC)Special Topic 1 117 —— CH,CH,OCH, + Br on b. Hy—-e-OCH, + —> cH, —¢-0CH, +OH H + oaycn,cucon, Or ——> CH;CH,CH=CH, + H,O + Br d. CH;CH,—C-NH, —* CH,CH;—C-NH, + HO’ OH > e CH;CH,—C-H + *MgBr CH; FAy OH f£ CHy—¢ — e+ + #H,0 CH CH, Ba +0H i & om} — = CH,-C-—OH + = CH,OHSPECIAL TOPIC HIT Kinetics ‘This is a continuation of the discussion on kinetics found in Section 3.7 of the text. Note that the rate Jaws are derived in Appendix IIT 1. 2 3. 6. 1 How long would it take for the reactant of a first-order reaction to decrease to one-half its initial concentration if the rate constant is 4.5 x 10°3 s-1 and the initial concentration of the reactant is: a.L0M? — b.0.50M? How long would it take for the reactants of a second-order reaction to decrease to one-half their initial concentration if the rate constant is 2.3 x 10-2 M-1s-l and the initial concentration of both reactants is: a. 1.0M? —_—b. 0.50 M? How many half-lives are required for a first-order reaction to reach > 99% completion? ‘The initial concentration of a reactant undergoing a first-order reaction is 0.40 M. After S minutes, the concentration of the reactant is 0.27 M; after an additional 5 minutes, the concentration of the reactant is 0.18 M; and after an additional 5 minutes, the concentration of the reactant is 0.12 M. ‘a. What is the average rate of the reaction during each five-minute interval? 'b. What is the rate constant of the reaction? ‘What percentage of a compound, undergoing a first-order reaction with a rate constant of 2.7 x 10°5 sl, would have reacted at the end of two hours? How long would it take for a first-order reaction with a rate constant of 5.3 x 10-4 s-! to reach 70% completion? ‘The following data were obtained in a study of the rate of inversion of sucrose at 25°C. ‘The initial concentration of sucrose was 1.00 M. Time (minutes) 0 30 60 90 130 180 Sucrose inverted (M)Q 0.100 0.195 0.277 0.373 0.468 a, What is the order of the reaction? b. What is the rate constant of the reaction? Calculate the activation energy of a first-order reaction that is 20% complete in 15 minutes at 40°C or 20% complete in 3 minutes at 60 °C. ‘Analysis of an aqueous solution of sucrose shows that 80 grams of the original 100 grams of ‘Sucrose remain after 10 hours. At this rate, how much sucrose would be left after 24 hours?Special Topic 119 Solutions to Problems in Special Topic III half-life of a first-order reaction = ty. = = 2 minutes, 34 seconds b. The half-life of a first-order reaction is independent of concentration, so the answer is the same as for a (15.4 seconds). a, half-life of a second-order reaction = ty 1 Iya = 1 23x 102M = 43 seconds 1 Bee tig a 2.3 x 10° M-Is"! (0.50 M) 1 © VAS x 102 6 = 87 seconds One-half of the compound reacts during the first half-life. One half of what is left after the first half-life reacts during the second half-life. One half of what is left after the second half-life reacts during the third half-life, etc. umber of half-lives percentage completion 1 0.50 (100) = 50 50 2 0.50 (50) = 25 75 3 0.50 (25) = 12.5 875 4 0.50 (12.5) = 6.25 93.8 5 0.50 (6.25) = 3.125 96.9 6 0,50 (3.125) = 1.5625 98.4 7 0,50 (1.5625) = 0.78125 99.2 Seven half-lives are required.120 Special Topic IIT change in concentration ‘change in time rate = sae ooo tee eegpeestaeeeeeten sere Or = 2.60x 10M mint Smin and interval: rate = 227M—O.18M _ 008M = 1.805 10?M mint min 5 min 3rd interval: rate = QU8M—O12M _ 006M = 4.29x102M mint min 5 min ‘Thus, the rate of the reaction decreases with decreasing concentration. b. rate = & [reactant], using the average concentration of the reactant during the 5 minute interval. 18t interval: 2.60 x 10°? Mine! = & (0.335 M) k = 78x 10? min! 2nd interval: 1.80 x 102M mine! = k (0.225 M) k = 80x10? min! 3d interval: 1.20x 102M min"! = k (0.15 M) k = 8.0.x 102 mit ‘The rate constant, as its name indicates, is constant during the course of-the reaction the initial concentration the concentration that has reacted at time =# n— = & ax 100, _ In OO = 2:70x81 @ hours) in 100 = 2.70xs"t (7200 seconds) 100. In ae = 0.084 oo 8 jee loo = 121-121 12x = 2 x = 174%9.30x 10s 1 = 4120 5.30 xs"! 1 = 2260 seconds + = 376 minutes 18t order a-x in. fice 7 1.000 - 0.100 ig ee = ——100__ . 30 = 351x10* 1.000 - 0.195 Special Topic 124 1 _ 1£000-0.100 1.000 i 30 LU 1-1.000 30 = 370x107 = 1.000122 Special Topic IN a7! _ 1.000 = 0.468 a 180 4.89 x 107 fa, Because the calculated rate constants are relatively constant when the data are plugged into a first-order equation and vary considerably when the data are plugged {nto a second-order equation, one can conclude that the reaction is first-order. b. 3.59 x 103 min! 8. In —100__ karapec = —H00-020° = 149x102 min 15 min ” ino: 036 kat6o°c = 100-020 = 7.4410? min! 3 min ~ Ea 1 4 Inky-Inky = alt ait R \h Th -E; ae In 744x102 ~ In .49x102 = a (5 - in) 1.986% 10 kcal \?99 313 ie - -(- = — 3 — 0,00300- 0 2.60 - (421) = Tyggeqgal©-00800 - 0.00319) 161 = fb, = LSLx 1986x103 co 0.00019 Eq = 168 kcal/mol9% Special Topic It 123 ‘Sucrose is hydrolyzed to form a mixture of glucose and fructose. Because there is an excess water (it is the solvent), the reaction is a pseudo first-order reaction. First, the rate constant of the reaction must be determined: In In 100 80 a = ht = & x 10hours = 2.23x102hrl = kt 2.23 x 10° (24 hr) T00-« 100 In 10 = 0: n I 535 100 _ Toor = bT 100 = 171 L71x Wx = 71 x = ALS ghave reacted Therefore, 58.5 g would be left,CHAPTER 4 Reactions of Alkenes Important Terms acid-catalyzed reaction alkoxymercuration- demercuration carbene carbocation rearrangement catalyst catalytic hydrogenation concerted reaction constitutional isomers (structural isomers) dimer electrophilic addition reaction free radical halohydrin Hammond postulate heat of hydrogenation heterogeneous catalyst heterolytic bond cleavage (heterolysis) homogeneous catalyst homolytic bond cleavage (homolysis) hormone a reaction catalyzed by an acid. ‘addition of an alcohol to an alkene using mercuric acetate followed by sodium borohydride and sodium hydroxide ancutral carbon with a lone-pair of electrons and an empty orbital. the rearrangement of a carbocation to a more stable carbocation. a compound that increases the rate at which a reaction occurs without being Consumed in the reaction. Because it does not change the equilibrium constant of the reaction, it does not change the amount of product that is formed. the addition of hydrogen to a double or a triple bond with the aid of a metal catalyst. ‘reaction in which all the bond-making and bond-breaking processes take place in a single step. molecules that have the same molecular formula but differ in the way the atoms are connected. amolecule formed by joining together two identical molecules. an addition reaction in which the first species that adds to the reactant is an electrophile. ‘an atom or molecule with an unpaired electron. an organic molecule that contains a halogen atom and an OH group. states that the transition state will be more similar in structure to the species (reactants or products) that itis closer to energetically. the heat (AH?) released in a hydrogenation reaction. a catalyst that is insoluble in the reaction mixture. breaking a bond with the result that both bonding electrons stay with one of the atoms. a catalyst that is soluble in the reaction mixture. breaking a bond with the result that each of the atoms gets one of the bonding electrons. a compound that controls growth and other changes in tissues, eelChapter4 125 hydration addition of water to a compound. L,2-hydride shift the movement of a hydride ion from one carbon to an adjacent carbon hydroboration-oxidation the addition of borane to an alkene (or to an alkyne) followed by reaction E with hydrogen peroxide and hydroxide ion. hydrogenation addition of hydrogen hyperconjugation delocalization of electrons by overlap of carbon-hydrogen or carbon-carbon bonds with an empty p orbital. initiation step the step in which radicals are created, or the step in which the radical needed for the first propagation step is created. Markovnikov's rule the actual rule is: “When a hydrogen halide adds to an asymmetrical alkene, the addition occurs such that the halogen attaches itself to the carbon atom of the alkene bearing the least number of hydrogen atoms.” Chemists use the rule as follows: The hydrogen adds to the sp? carbon that is bonded to the greater number of hydrogens. A more general rule is: The electrophile adds to the sp? carbon that is bonded io the greater number of hydrogens. mechanism of the reaction a description of the step-by-step process by which reactants arc changed into products. 1,2-methyl shift the movement of a methyl group with its bonding electrons from one carbon to an adjacent carbon. oxymercuration- addition of water using a mercuric salt of a carboxylic acid as a catalyst, demercuration followed by reaction with sodium borohydride. pericyclic reaction aconcerted reaction that involves a cyclic rearrangement of electrons. peroxide effect causes the electrophile in an addition reaction of HBr to be a bromine radical instead of a proton. pheromone a chemical substance used for the purpose of communication. Primary alkyl radical an alkyl radical with the unpaired electron on a primary carbon. Primary carbocation a carbocation with the positive charge on a primary carbon. Propagation step in the first of a pair of propagation steps, a radical (or an electrophile or a nucleophile) reacts to produce another radical (or an electrophile or a nucleophile) that reacts in the second propagation step to produce the radical (or the electrophile or the nucleophile) that was the reactant in the first propagation step. Tadical (often called a an atom or molecule with an unpaired electron. free radical)CHAPTER 4 Reactions of ack sacs oh _weuve reaction. secondary alkyl radical secondary carbocation steric effect steric hindrance termination step tertiary alkyl radical tertiary carbocation ‘an addition reaction in which the first species that adds is a radical, a reaction in which radicals are formed and react in repeating propagatin steps. a compound that traps radicals. a compound that creates radicals. ‘reaction that leads to the preferential formation of one constitutional isomer over another. ‘an alkyl radical with the unpaired electron on a secondary carbon a carbocation with the positive charge on a secondary carbon. an effect due to the space occupied by a substituent. refers to bulky groups at the site of a reaction that make it difficult for u reactants to approach one another. two radicals combine to produce a molecule in which all the electrons 2 paired. an alkyl radical with the unpaired electron on a tertiary carbon. ‘a carbocation with the positive charge on a tertiary carbon.Chapter4 127 Solutions to Problems CH, a. CH;CHjCCH, > CHCH,CHCH, > CH,CH,CH,CH, Db. The halogen atoms decrease the stability of the carbocation because, since they are more electronegative than a hydrogen, they are more effective than a hydrogen at withdrawing electrons away from the positively charged carbon. This increases the concentration of positive charge on the carbocation which makes it less stable. Because fluorine is more electronegative than chlorine, the fluorine-substituted carbocation is less stable than the chlorine-substituted carbocation. CHCHCH,CH, > CH,CHCH,CH; > CH,CHCH,CH, CH, a F 2, a, The bond orbitals of the carbon that is adjacent to the positively charged carbon are the bond orbitals that are available for overlap with the vacant p orbital. Because the methyl cation does not have a carbon adjacent to the positively charged carbon, there are no bond orbitals available for overlap with the vacant p orbital. b. An ethyl cation is more stable because it has three carbon-hydrogen bond orbitals available for overlap with the vacant p orbital, while a methyl cation does not have any carbon-hydrogen bond orbitals available for overlap with the vacant p orbital. 3. a. products b. reactants c. reactants 4. products 4 CH; CH; ac . HjCH,CHCH, © Chm e Br Br gh ge b. CHACH,CCH, 4. CHsCCH,CH,CH,CH;—f. CHyCH,CHCH Br Br Br128 Chapter 4 gi a, CH)=CCH; b, (ence, a. Cyrene CH, a, CHjCH,;C=CH, b. CH Inboth a and b, the compound that is more highly regioselective is the ‘where the choice is between forming a tertiary carbocation or a primary carbocation. In the less regioselective compound, the choice is between forming a tert carbocation or a secondary carbocation, so the difference in the stability the two possible carbocations is not as great. ‘As long as the pH is greater than -2.5 and less than about 15, more than 50% of 2-propanol ‘would be in its neutral, nonprotonated form. Because when the pH = pK, half the compound is in its acid form and half is in its basic form, a a pH less than — 2.5, more than half of the compound will be in its positively charge protonated form. Ata pH greater than about 15, more than half of the compound will exist as the negatively charged anion. a, 3 transition states b. 2 intermediates &. CH,CH,CH,CHCH, OH b. co ¢, the neutral alcohol d. the second and third steps in the forward direction © CH,CH,CH,CH,CHCH, and CHyCH,CH,CHCH,CH, OH OH OHChapter 4 129 0. Hs GAs Gus oH 1. CHsCCH, 2. CHSC CHS 3. CHCCH, 4. CHGCH a Br OH ocH, b. The first step in all the reactions is addition of an electrophilic proton (H*) to the carbon of the CH, group. The tert-butyl carbocation is formed as an intermediate in each of the reactions. ¢. The nucleophile that adds to the tert-butyl carbocation is different in each reaction. In reactions #3 and #4, there is a third step—a proton is lost from the group that was the nucleophile in the second step of the reaction. 3. Fis rs) 4 Cs GAs CH3¢CH, ——> CHACCH, + Hyo* CH¢CH, — CHGCH, + H,0* eon OH | OCH OCH, HOH CH,OH H \f \4 ML. a Ww CY + cHoH te OCH, CH . CH b. CH)=CCH, + CH,OH Ey CH,OCCH, CH, © CH,CH=CHCH, + CH,CH,oH Hy CH,CH,CHCH, or OCH,CH, CH,=CHCH,CH; + CH;CH,OH Hy CH,CH,CHCH, or OCH,CH, CH=CH, + CH;CH,CHCH, Le CH;CH,CHCH, ou OCH,CH,130 Chapter 4 a. CHCH=cHcH, + 1,0 te cHCHCH,CH or on CH,=CHCH,CH, + 1,0 a, CHsCHCH3CHs OH OH a £ CH,CH,CH=cCHCH,CH, + 1,0 b> CH;CH;CHCH,CH,CHs On 12, CH,CHCH,CH,OH om cH,GcH, ices crgcHcH.cH be Gct, a, ba, H CH; BE B: is any base that is | present in the reaction ‘mixture: ge HB’ + CHsCHCH,CH,OCCHs CH; CH; 13. Solved in the text.Chapter4 131 14. 1 2-aydie Br a. CH,CHCH=CH, an creer, CHECH,CH, 4 CH,CCH,CH CH, Gy, cH, cn, secondary tertiary eres rae CH Br. CH; © CHjCHCH,CH=CH, a CH,CHCH,CHCH, ry CH CHCH,CHCH, CH; cH, CH, Br Ca CH Br. CH, OO = CH, Gs eaethyi Crt, Gi Br © CHy=CHCCH, an cu,cagcn, > cHycuccn, BS cHCH~Cer, CH; cH, dn, cH, secondary tertiary KGa 8 1-Bromo-3-methyleyclohexane and 1-bromo-4-1 eile will be obtained in SPproximately equal amounts because in each case the initially formed carbocation is secondary16. v7. 18. Chapter 4 cH; Addition of H* would form a i carbocation that could rearrange. CHCCH,CH; in ‘Addition of Br* forms acyclic ‘bromonium ion rather than a carbocation s0 there is no rearrangement. a. The first step in the reaction of ethene with Br forms a cyclic bromonium ion, whereas the first step in the reaction of ethene with HBr forms a carbocation. b._ If the bromide ion were to attack the positively charged bromine atom, a highly unstable compound (with a negative charge on carbon and a positive charge on bromine) would be formed. CH,-CH,—-Br. —Br Notice that the electrostatic potential maps of the cyclic bromonium ions on p. 158 of the text show that the ring carbons are the least clectron dense (most blue) atoms in the intermediate. ‘The nucleophile that is present in greater concentration is more apt to collide with the carbocation intermediate. Therefore, if the solvent is a nucleophile, the major product will come from reaction of the solvent with the carbocation ot cyclic bromonium (or chloronium) ion intermediate, because the concentration of the solvent is much greater than the concentration of the other nucleophile. (For example, in “a” the concentration of CHOH is much greater than the concentration of CI.) Hs CH 8 CICH:CCHs and CICHECH; —&CH;CH,CHCH; and CHsCH,CHCHs OCH, a OH a major major be CHyCHCH, and CHCHCH, 4. CHCH,CHCH; and CHyCH,CHCHs I Br OCH, Br major major {As elements, sodium and potassium achieve an outer sheil of eight electrons by losing the single electron they have in the 3s (in the case of Na) or 4s (in the case of K) orbital, thereby becoming Na” and K’. In order to form a covalent bond, they would have to regain electrons i" these orbitals, thus losing the stability associated with having an outer shell of eight clectrons and no extra electrons.Chapter4 133, 19, Because chlorine is more electronegative than iodine, iodine will be the electrophile. Therefore, it will become attached to the sp? carbon that is bonded to the greater number of hydrogens. It CH,CH,CH=CH, + ha > CHCH,CH—CH, —= CHCH,CHCH a 2. & CH:CHCH,CHs b. CHyCHCH,CH; ¢ CH;CHCH,CH, , CH,CHCH,CH, Br Br Br OH Br OCH,CH, Br OCH, 21. Notice that the addition of water or the addition of an alcohol to an alkene can be carried out using an acid catalyst (Section 4.5) or by mercuration/demercuration (Section 4.8). Ht OCH,CH; a —— CH;CH,OH ee or 1. Hg(0,CCF;),, CHyCH,OH 2. NaBH, b. ce ie CHs CH; CH; & Oo. O% OS H;0 aed or 1. He(OAc),, H,0, THF 1. Hg(OAc),, H;0, THF BC ACs HO, THE 2, NaBH, 2. NaBHy © cacH=cucH, He cy concn a 3 “CaycHjon — CHSPHCHCHs S OCH,CH, 1. Hg(O,CCP;),, CH;CH,0H 2. NaBH,134 Chapter 4 CH; * GH 4. CH) =CCH;CH; i CH,GCH,CH, OcH, = CH,OH or 1_Hg(O,CCF),, CH;0H 2. NaBH, 2. CH, CH, 1,2-hydride CH, cl i H I shift, 1 H,0. I 8. CHy=CHCHCH, ——> CHsCHCHCH, “> CHsCH,CCH, —*—> CHsCHG 01 TP 1 Hg(OAc)a, HHO, THF ge b. CH)=CHCHCH 1 He(OAc),, HzO, THE CH,CHCHCH; 2. NaBH, T OH Ina, a carbocation rearrangement is required to get the desired product from the given starting 1 In by, the desired product must be obtained from a reaction that will not form a carbocation inte 23. Because one mole of BH reacts with three moles of an alkene, one third of a mole of BH3 is needed to react with each mole of alkene. Therefore, two thirds of a mole of BH3 is needed to react with two moles of an alkene (in this case, 1-pentene). CH; i gis . CH,C=CHCH, CHCHCHCHs OH 1. BH, 2. HO, H,0;, HO CH; b. 1. BH, CH, OH 2. HO, HO), H,0Chapter4 135 25. Addition of a proton to the carbon that is bonded to the greater number of hydrogens forms a carbocation intermediate. The alcohol group in the same molecule is the nucleophile that reacts with the carbocation. (>a ‘Hy HC. 1 st cu,=ccr,cucn, EOB cx,—Ccu,cuch, —> CH, CH me HSC by ee ey Bx | HB’ is any acid present in the solution HC B: is any base present in the solution aici HC" + HB CH, CHy SBT + Bre CHy Hy SBr Br a 27. Because alkene A has the smaller heat of hydrogenation, it is more stable. 28, 7 CH,CH This alkene is the most stable beacause it has the greatest number of alkyl substituents bonded to the sp? carbons ‘CH,CH; i CH,CH; : ‘This alkene is the least stable beacause it has the fewest number of alkyl substituents bonded to the sp? carbons. ‘CH,CH; e CH,CH; This alkene has the smallest heat of hydrogenation because it is the most stable of the three alkenes. ‘CH,CHy,136 Chapter 4 29. CH; HAC, H CH,CH, BON hy \__/ ui c=c > fay / cH,cHf H i 2 tans substituents 2 cis substituents 2.cis substituents that cause greater steric strain (CH;CH,CH,CH, H sCH:CH,CH,, Cc: / a H H one substituent 30. Solved in the text. 31. The reaction of 3-methyleyclohexene with HBr and peroxide would form approximately equal amounts of 1-bromo-2-methylcyclohexane (the desired product) and Lbromo-s-methyl- cyclohexane because the bromine radical could add to either the 1-position or the 2-position of {he alkene since in both cases a secondary radical would be formed. Thus, only half as much of the desired product would be formed from 3-methyleyclohexene than from 1-methyl- cyclohexene. CH3 CH; o a + ‘Br A3, free pes CH CH Br + Br I-bromo-2-methyl- __1-bromo-3-methyl- cyclohexane cyclohexaneChapter4 137 If 3-methyloyclohexene were treated with HBr in the absence of peroxide, little 1-bromo- 2- methylcyclohexane (the desired product) would be formed because the secondary carbocation with a positive charge at the 2-position would rearrange to a more stable tertiary carbocation. 6 6 0 pr pr pr CH; CH; Br. (CH, oa « ‘Br 1-bromo-3-methyl- —_1-bromo-2-methyl- 1-bromo-I-methyl- cyclohexane. cyclohexane. cyclohexane. minor 32. wt a. CH,CH=CH, —4—= — CH,CHCH. es > “CHOH eed OCH, Br b. CHSCH,CH=CHCHs + Bry ——e CH,CH,CHCHCH, Br CH,OH ABH 2HO.H;0;, 1,0 CHO, (CH; 6 ‘O-0 & 6.5 = i138 Chapter 4 7 OC + CHCH,CH,OH —H or OCH,CH,CH; 33. Br CH CH,CH, oH b. CH,CCH,CH, a. CH,CH,C—CH ee ‘CH,CH, CHG CHACHs ‘Br Seen ecay Br Br CH 34. clectrophile nucleophile a. CH;CHCH, + —> caqucty nucleophile lectrophil b. core 9 — electrophile Te CH, nucleophile ——> — CHs¢—“GCHs « cyt + CHOH CH H i CH, 38. Hs oH a. CH\C=CHCH; + HBr ——» — CH,C-CH;CHy Br CHy CH; i i b. CH,C=CHCH; + HBr Peroxige, CH,CH-CHCH, BrChapter4 139 GH CAs c CHC=CHCH; + HI —> CHyC—CHCH, I CH GHs 4. CH,C=CHCH, + HT Petoxidg. CH,¢—CH,CH, I gi gi @ CH,C=CHCH; + Il ——» CH,C-CHCH, at CH CH, £ CH,C=CHCH, a CH,CH-CH,CH, CH CH & CHjC=CHCH; + Bry + excess NaCl ——> CH,¢—CHCH, Gib 1. Hg(O Ac), HO os Tila b. CHC=CHCH, 1HEOA HO oud cHcH, 2. NaBH, OH CH CH |. CH,C=CHCH, + H,0 S%eHCl CHi¢—CH.CH, bu cH Hy 3 CH,C=CHCH, +B = CHC-CHCH, a Hy an Hs ke cHc= =CHCH, + Bn CH¢-CHCH HO Br i CH,OH oe |. cH,C=CHCH, +B, CH,¢-CHCH; CHO Br Gs 1. BH, Gis m. CHyC=CHCH; CHCH-CHCH, —— 2. HO, HO™ OH140 36. 31. 1 n. CH;C=CHCH, Chapter 4 CHy 2. NaBH, cH, 1. Hg(O,CCF)2, CH;0H CH; re CH,G-CHCHy OCH CH, 1 I I CH,CH=CCHCH,CHs CHC=GCH,CHACH; | CHjCH=CHCHGHCHs CH; CH; CH 3,4-dimethyl-2-hexene 2,3-dimethyl-2-hexene 4,5-dimethyl-2-hexene 2,3-Dimethyl-2-hexene is the most stable because it has the greatest number alkyl substituents bonded to the sp? carbons. Because it is the most stable, it has the smallest heat of hydrogenation. 4,5-Dimethyl-2-hexene has the fewest all kyl substituents bonded to the sp? carbons. making it the least stable of the three alkenes. It, therefore, has the greatest heat of hydrogenation. ih H 1,2-hydride shift CHCHCHSCH, + HOBr ——= CH,C~CHCH, "> CH¢CH,CHS CH; ts CH;C=CCH CH ‘This compound is most stable. Ithas 4 alkyl substituents bonded to the sp? carbons. r CH; By \é Br i t CH,CHCHCH, CHGCH,CHs CH; CH; CH;=CHCH,CH,CH,CH, — CH)=CHCH,¢HC cH, Ct CH) =CHCHCH,CHs cuytcn =CH) CH; CH; ‘These compounds are the least stable. Each has only one alkyl substituent bonded to the sp? carbons.Chapter4 141 39. i a — > == CH,—C-cH, + CHO — + INH; — > ~—scH,CH,—OcH, + BF ont CHCHCH,Br CH)CH,CH,0H CH,CH,CH, 1. BH; 5 in cy 2. H,0,, HO [Oe HCl, CHGHCH, H,CH= Cr i be Or CH=CH, ction By 4G, 0H CH,CH)CHBr CH,CHCH, : Bre, aa ee estate OCH 2° CH,CHCH;Br Onter 142 41. 42, 43. Chapter 4 a. CH;—Cl Cluses a 3 sp3 orbital in bond formation, while Br uses 4 sp3 orbital. Cl, therefore, forms a shorter and stronger bond with carbon, b. CH;CH,CH, A primary radical is less stable than a secondary 1 H radical, so it is harder to break a bond that results in the formation of a primary radical than itis to break a bond that results in the formation of a secondary radical, © CHy-CH, ‘A methyl radical is less stable than a primary radical, so it is harder to break a bond that results in the formation of two methyl radicals than itis to break a bond that results in the formation of a methyl radical and a primary radical. a. Br—Br I forms a weaker bond than Br because I uses a 5 sp? orbital in bond formation, while Br uses a 4 sp? orbital. a © no reaction a without an acid catalyst b a. ‘OCH, OH Br b. CH,CH,CH,cH=cH, HCL CH, « HBr peroxide cle ‘Oh “CR *O CH,CH=CH, a. H 1,0" ¢. CH,CH,CH=CHCH,CH, a a f. CHjCH;CH=CHCH,CH, — laBr ie excess CH,CH,CH=CHCH,CH, BR Nach excessChapter4 143 . No. CH, CH)Br + HBr _peroxide CH; CH; ‘1 Br + Her Peexidg Yes. CH) HC. (cl + HC —» CH, ee oe . Peroxide has no effect on the addition of HCI, so both compounds will give the same product (the product shown in ¢). CH, I Gis - CH CCH, & CHjC=CHCH,CH, 7 t CH; . CH;CHCH,CH, . CY - CH,CHCH, & CH,CHCH,CH, |. CH;CH,CH,CHCH, a144 Chapter 4 46, a, To determine their relative rates of hydration, the rate constant of each alkene is divided by the smallest rate constant of the series (3.51 x 10°). propene 4.95 x 10°8/3.51 x 108 = 141 cis-2-butene = 8.32 x 10°8/3.51 x 10% = 2.37 trans-2-butene 51x 10°8/3,51 x 10% = 1 15 x 10-4/3.51 x 10°8 = 6.12 x 103 3.42 x 10-473.51 x 10°8 = 9.74 x 103 2-methyl-2-butene 2,3-dimethyl-2-butene b. Both compounds form the same carbocation, but since (Z)-2-butene is less stable than (6)-2-butene, (Z)-2-butene has a smaller free energy of activation. ¢. 2-Methy!-2-butene reacts faster because it forms a tertiary carbocation in the rate-limiting step, while cis-2-butene forms a less stable secondary carbocation. d. Both compounds form tertiary carbocation intermediates. However, 2,3-dimethyl-2-butene has two sp? carbons that can react with a proton to form the tertiary carbocation whereas 2-methyl-2-butene has only one sp? carbon that can react with a proton to form the tertiary carbocation. Therefore there will be more collisions with the proper orientation that lead to a productive reaction in the case of 2,3-dimethyl-2-butenc. 47. Only a symmetrical alkene will form the same alkyl halide when it reacts with HBr in the presence of peroxides that it forms when it reacts with HBr in the absence of peroxides. a b. There are many more symmetrical alkenes in the case of an alkene with an even number of carbon atoms, CH;CHy, EACH, HAC. eis CH; = C= eae, Poce H H HAC CH; oy CH; CH; CH, cach. OM | ce H ‘CH,CH, ‘CH; cH Das ‘CH;Chapter4 145 49. No, he should not follow the’student’s advice. Markovnikov's rule would indicate that the "secondary carbocation is more stable than the primary carbocation. However because of the electron-withdrawing fluoro substituents in this compound, the primary carbocation is more stable than the secondary carbocation, since in the latter the positive charge is closer to the fluoro substituents. So the major product will be 1,1,1-trifluoro-3-iodopropane, not 1,1, 1-trifluoro-2- iodopropane, the compound that would be predicted to be the major product by Markovnikov's rule. 50. a. CHCH,CH=CH, HS cy.cH,CHcH, —— CHCH,CHCH, CH;OH +ocu. he ce" cH col CH,CH,CHCH, OCH; Dy the first step e. the sec-butyl cation © Ht f. methanol 4, 1-butene 51. a, Both 1-butene and 2-butene react with HCI to form 2-chlorobutane. b. Both alkenes form the same carbocation, but because 2-butene is more stable than I-butene, 2-butene has the greater free energy of activation. Because 1-butene has the smaller free energy of activation, it will react more rapidly with HCl. 4d. Both compounds form the same carbocation, but since (Z)-2-butene is less stable, it will Teact more rapidly with HCI. a CH, 4 alkenes : b, 1-Methylcyclopentene is the most stable. 52. cH, CH, CH; © Because 1-methyleyclopentene is the most stable, it would have the smallest heat of hydrogenation,Chapter 4 CH; CH; 1 i CH; a. C=CH, C—CH; 4 4 ‘CH. eh oo 3 secondary Hs tertiary b. The initially formed carbocation is tertiary. . The rearranged carbocation is secondary, which then undergoes another rearrangement to a more stable tertiary carbocation. 4. The initially formed carbocation rearranges in order to release the strain in the four- membered ring. (A tertiary carbocation with a strained four-membered ring is less stable than a secondary carbocation with an unstrained five-membered ring.) It tells us that the first step of the mechanism is the slow step. If the first step is slow, the carbocation will react with water in a subsequent fast step, which means that the carbocation wi not have time to lose a proton to reform the alkene. + 5 #0 €\-cu=co, a CH-CHD, —2= CH—CHD, slow fast F *OH, «Open OHChapter4 147 If the first step were not the slow step, an equilibrium would be set up between the alkene and the carbocation, and because the carbocation could lose either H* or D* when it reformed the alkene, all the deuterium (D) would not be retained in the alkene. Ht (\-ciren, =— €\-cx-cun, — €¥-cuscnn | +D a. A proton adds to the alkene, forming a secondary carbocation, which undergoes a ring- expansion rearrangement to form a more stable tertiary carbocation. = 7 CH + CH; HAC. CH=CH, jC. CHCH: : e (ane a _ . 1,0. =H — HSL a,c CH; HO, H+ He b. At first glance this appears to be a difficult mechanism, but examination of the reaction shows that the only electrophile available to the alkene adds to the sp? carbon bonded to the most hydrogens (the one that results in the formation of the most stable carbocation). This is followed by the addition of the nucleophilic nitrogen to the other sp2 carbon. ais 2 N = CH,CH,CCH,CHR CH HAC’148 Chapter 4 c. The weak oxygen-oxygen bond breaks homolytically, forming a radical that abstracts a hydrogen atom from HCCI. The radical that is formed adds to the double bond. A x clectron of the other double bond pairs with the unpaired electron, forming a bond that divides the ring. The new radical abstracts a hydrogen atom from HCCI, and the propagation steps are repeated. ie —— > 2R0- 7> Wocy —> Row + «cc CCl, ot + -CC, — O) — os CCl, ae 56.Chapter 4 149 Chapter 4 Practice Test Hf ‘Which member of each pair is more stable? ie a, CH3CHCH,CH, or CH,CCH; b. CHs;CH,CH,CH, or CH;CH,CHCH, ©. CH;CH,CH, or ~CICH,CH,CH, 2. Which would be a better compound to use as a starting material for the synthesis of 2-bromopentane? CH;CH,CH,CH=CH, or —CHCH,CH=CHCH, 3. The addition of Hy in the presence of Pd/C to alkenes A and B results in the formation of the same alkane. The addition of Hg to alkene A has a heat of hydrogenation (-AH®) of 29.7 kcal/mol, while the addition of Hz to alkene B has a heat of hydrogenation of 27.3 kcal/mol. ‘Which is the more stable alkene, A or B? 4, What is the major product of each of the following reactions? CH; a, CHj=CCHjCH; 4 HBr —— ‘ie b, CH;CHCH=CH, + HCL ——> © CHCH,CH=cH, + c, 2 ite 3. CHCCH=CH, = + HBr —= CH; ‘Write out the propagation steps that occur in the addition of HBr to 1-methyleyclohexene in the presence of peroxides.150 Chapter 4 6. Indicate how each of the following compounds could be synthesized using an alkene as one of the starting materials: qs a > cHyCCH,CH, CH; OH b. ci — « CH,CH,CH,Br 7 CH; OH 4a, 7. Indicate the carbocations that you would expect to rearrange to give a more stable carbocation. CH, CH; CH; t + CH,CH,CHCHCH, — CH,CH,CHCH, O O 8 What product would be obtained from the hydroboration-oxidation of the following alkenes? a, 2-methyl-2-butene b. L-cthyleyclopentene 9. Indicate whether each of the following statements is true or false: a. The addition of Bry to I-butene to form 1,2-dibromobutane is a concerted reaction. re b. The reaction of 1-butene with HCI will form 1-chlorobutane as the major product if hydrogen peroxide is added to the reaction mixture. Teer ¢. 2,3-Dimethyl-2-pentene is more stable than 3,4-dimethyl-2-pentene. T OF 4d. The reaction of HBr with 3-methylcyclohexene is more highly regioselective than the reaction of HBr with I-methylcyclohexe. Teese ==othe following exercises using molecular model 9% 10. 1. 2 Special Topic IV Exercise in Model Building Build the enantiomers of 2-bromobutane. a. Try to superimpose them. b. Show that they are mirror images. ¢. Which one is (R)-2-bromobutane? Build the erythro enantiomers of 3-bromo-2-butanol. ‘a, Where are the Br and OH substituents (relative to each other) in the Fischer projection? (Recall that in a Fischer projection, the horizontal lines represent bonds that point out of the plane of the paper toward the viewer, and the dashed lines represent bonds that point back from the plane of the paper away from the viewer.) b. Where are the Br and OH substituents (relative to each other) in the most stable conformer considering rotation about the C-2—C-3 bond? a, Build the compounds labeled “1” and “2” shown on the top of page 201 of the text, b. Build their mirror images, ¢. Show that “1"" is superimposable on its mirror image but ‘2” is not. Build the three stereoisomers of 2,3-dibromobutane. Build the four stereoisomers of 2,3-dibromopentane, Why does 2,3-dibromopentane have four stereoisomers, while 2,3-dibromobutane has only three stereoisomers? Build ($)-2-pentanol. Build (25,3R)-3-bromo-2-butanol. Rotate your model so it is in a Fischer projection. Compare its structure with the structure of (25,3R)-3-bromo-2-butanol shown on page 205 of the text. Build the compounds shown in Problem 33 on page 208 of the text. Name the compounds. Build (S)-1-bromo-2-methylbutane, Substitute the Br~ with an HO to form 2-methyl-1-butanol. ‘What is the configuration of your mode! of 2-methyl-1-butanol? Build ethanol. Which of the hydrogens is the pro-R-hydrogen? Build two models of trans-2-pentene. Add Br2 to opposite sides of the double bond, forming the two enantiomers shown on page 226 of the text. Rotate them so they are Fischer projections. Are they erythro or threo enantiomers? Compare your answer with that given in the text. Build models of the molecules shown in Problem 86 on page 237 of the text. What is the Configuration of the chirality center in each of the molecules?CHAPTER 5 Stereochemistr the Arrangement of Atoms in Space; The Stereochemistry of Addition Reactions Important Terms absolute configuration _the three-dimensional structure of a chiral compound. The configuratio designated by R or S. The configuration is called absolute to distinguis from a relative configuration, achiral a molecule or object that contains an element (a plane or @ point) of (optically inactive) symmetry. amine inversion results when a compound containing an sp hybridized nitrogen with a nonbonding pair of electrons rapidly tums inside out. anti addition an addition reaction in which the two added substituents add to opposit: sides of the molecule. asymmetric carbon a carbon atom that is bonded to four different substituents. biochemistry the chemistry associated with living organisms. chiral a chiral molecule has a nonsuperimposable mirror image. (optically active) chirality center an atom that is bonded to four different substituents. cis isomer the isomer with substituents on the same side of a cyclie structure, or the isomer with the hydrogens on the same side of a double bond. cis-trans isomers geometric (or E, Z) isomers. chromatography a separation technique in which the mixture to be separated is dissolved a solvent and the solution is passed through a column packed with an adsorbent stationary phase. configuration the three-dimensional structure of a chiral compound. The configuratior designated by R or 5. configurational isomers stereoisomers that cannot interconvert unless a covalent bond is broken. Cis-trans isomers and optical isomers are configurational isomers. constitutional isomers molecules that have the same molecular formula but differ in the way th (structural isomers) atoms are connected. dextrorotatory the enantiomer that rotates polarized light in a clockwise direction. diastereomer configurational isomer that is not an enantiomer, diastereotopic hydrogens two hydrogens bonded to the same carbon that will result in a pair of diastereomers when each of them is replaced in um with deuterium. enantiomers nonsuperimposable mirror-image molecules.Chapters 153 enantiomerically pure only one enantiomer is present in an enantiomerically pure sample, enantiomeric excess how much excess of one enantiomer is present in a mixture of a pair of enantiomers. enantiotopic hydrogens —_two hydrogens bonded to a carbon that is bonded to two other groups that are nonidentical, enzyme a protein that catalyzes a biological reaction. erythro enantiomers the pair of enantiomers with similar groups on the same side (in the case of stereoisomers with adjacent asymmetric carbons) when drawn in a Fischer projection. Fischer projection ‘a method of representing the spatial arrangement of groups bonded to an asymmetric carbon. The asymmetric carbon is the point of intersection of ‘two perpendicular lines; the horizontal lines represent bonds that project ut of the plane of the paper toward the viewer, and the vertical lines Tepresent bonds that project back from the plane of the paper away from the viewer. isomers nonidentical compounds with the same molecular formula. isomers that contain these can be enantiomers, diastereomers, and meso compounds. asymmetric carbons levorotatory the enantiomer that rotates polarized light in a counterclockwise direction. meso compound @ compound that possesses asymmetric carbons and a plane of symmetry. observed rotation the amount of rotation observed in a polarimeter. optical purity how much excess of one enantiomer is present in a mixture of a pair of enantiomers. optically active rotates the plane of polarized light. (chiral) optically inactive does not rotate the plane of polarized light. (achiral) Pair of enantiomers 4 pair of nonsuperimposable mirror image molecules. Perspective formula a method of representing the spatial arrangement of groups bonded to a chirality center. Two bonds are drawn in the plane of the paper; a solid wedge is used to depict a bond that projects out of the plane of the paper toward the viewer, and a hatched wedge is used to represent a bond that projects back from the paper away from the viewer. plane of symmetry an imaginary plane that bisects a molecule into a pair of mirror images. Plane-polarized light light that oscillates in a single plane passing through the direction the light travels.154 Chapter 5 polarimeter polarized light prochirality center pro-R-hydrogen pro-S-hydrogen racemic mixture (racemic modification, racemate) R configuration regioselective relative configuration resolution of a racemic mixture S configuration specific rotation stereocenter (stereogenic center) stereochemistry stereoisomers stereoselective stereospecific an instrument that measures the rotation of polarized light. light that oscillates in only one plane. a carbon (bonded to two hydrogens) that will become an asymmetric carbon (a chirality center) if one of the hydrogens is replaced by deuterium replacing this hydrogen with deuterium creates an asymmetric carbon with the R configuration. replacing this hydrogen with deuterium creates an asymmetric carbon with the S configuration. ‘a mixture of equal amounts of a pair of enantiomers. after assigning relative priorities to the four groups bonded to a chirality ‘center, if the lowest-priority group is on a vertical axis in a Fischer projection (or pointing away from the viewer in a perspective formula), an arrow drawn from the highest-priority group to the next highest-priority group goes in a clockwise direction. describes a reaction that leads to the preferential formation of one constitutional isomer over another. the configuration of a compound relative to the configuration of another ‘compound. separation of a racemic mixture into the individual enantiomers. after assigning relative priorities to the four groups bonded to a chirality center, if the lowest-priority group is on a vertical axis in'a Fischer projection (or pointing away from the viewer in a perspective formula), an arrow drawn from the highest-priority group to the next highest-priority ‘Broup goes in a counterclockwise direction. the amount of rotation that will be caused by a compound with a concentration of 1.0 g/ml. in a sample tube 1.0 decimeter long. an atom at which the interchange of two groups produces a stereoisomer. the field of chemistry that deals with the structure of molecules in three dimensions. isomers that differ in the way the atoms are arranged in space. describes a reaction that leads to the preferential formation of one stereoisomer over another. describes a reaction in which the reactant can exist as stereoisomers and each stereoisomeric reactant leads to a different stereoisomeric product.tural isomers Constitutional isomers) synaddition threo enantiomers trans isomer Chapter5 155 molecules that have the same molecular formula but differ in the way the atoms are connected, an addition reaction in which the two added substituents add to the same side of the molecule, the pair of enantiomers with similar groups on opposite sides (in the case of stereoisomers with adjacent asymmetric carbons) when drawn in a Fischer projection, the isomer with substituents on the opposite sides of a cyclic structure, or the isomer with the hydrogens on the opposite sides of a double bond. Do not confuse the terms conformation and configuration, Conformations are different spatial arrangments of the same compound (see page 88 of the text). They result from rotation about single bonds. They cannot be separated. Some conformations are more stable than others. Configurational isomers are different compounds. ‘They do not readily interconvert; bonds have to be en to convert one configurational isomer to another.Different Conformations GoD UnstableDifferent Configurations158 Chapter 5 Solutions to Problems L 8. CH,CH,CH,OH — CHCHOH = CHCH,OCH CH, b. There are seven constitutional isomers with molecular formula C 4H 90. gi CHsCH,CH,CH,OH CH,CHCH,OH_ CH,COH—CH,CHCH,CH, CH; CH, OH CHCH,OCHCH, CH,OCH,CH,CH__CH,OCHCH, CH; 2. 7 a CH HH HC 1 ‘ CY a. Hs H Br Bt CH;CH, CH,CH, H 1 CH. V 5 - cH, a. Ge re Br o CHSCH cH,cH,cH, CHCH oy Br H cq oq cis-1,3-dibromo- trans-1 Ho H CH,CH,CH; cyclobutane ——_eyclobut 3. a. F,G,J,L,N,P,Q,R,S,Z b. A,C,D,H, I, M, 0, T, U, V, W, X,Y ‘Whether B, E, and K are chiral or achiral depends on how they are drawn. For example, if B it drawn with two equal loops, it is achiral; if the loops differ in size, itis chiral. 4, a,¢, and have asymmetric carbons. 5. Solved in the text. 6. a,c, and f, because in order to be able to exist as a pair of enantiomers, the compound must he an asymmetric carbon (except in the case of certain compounds with unusual structures. See Problem 88.)Chapter5 159 raw the first enantiomer with the groups in any order you want. Then draw the second Fhantiomer by drawing the mirror image of the first enantiomer. ete CAs ra CHLCH,Cl CH,CH,Cl 7 Br cHycr CM Hy ~CH,CH; 9° 3. b (CH),CH™ Vis bL CH; CH; 2 CH,CH,Cl CH,CH,Cl Br—-H uber H ‘CH; cHy—Ln CH,OH CH,OH CH,CH, CHCH; 3 CHs CH; H HH CH(CH;), — CH(CH,), a. R BR ¢ To determine the configuration, draw the structure with the fourth bond. Remember that it cannot be drawn between the two solid bonds. 4. Draw the structure with the fourth bond, Switch a pair so that the His on a dotted bond. ‘The configuration of the compound with the switched pair is S. Therefore, the configuration of the compound given in the question is R. a switch a pair SOsi Se of substituents The easiest way to determine whether two compounds are identical or enantiomers is to determine their configurations: If both are R (or both are S), they are identical. If one is R and the other is S, they are enantiomers. 4. enantiomers b. enantiomers c. enantiomers d_ enantiomersr 160 Chapter 5 10. @& —CH,0H —CH; —CH,CH,OH 6 Oo 6 © b. —CH=0 —OH —CH, —CH,OH QO O © © —CH(CH,), —CH,CH,Br —C 2 ‘23 -S_ OB Cattached C attached 2s to3Cs Wo as bR oS as 12, = Observed rotation observed specific otion =e oa x EagE [ol = == EE oe concentration klength 2 a 30 13. a. levorotatory b. dextrorotatory 14 a -24° ob, OPChapters 161 6. ‘a. 50% of the mixture is excess (+)-mandelic acid. : observed specific rotation optical purity = 0.50 = —CCrvedspecific rotation _ specific rotation of the pure enantiomer 0.50 = observed specific rotation + 158° observed specific rotation = +79° b. 0° (tisaracemic mixture.) © 50% of the mixture is excess (—)-mandelic acid, observed specific rotation = 79° 16, a. From the data given, you cannot determine what the configuration of naproxen is. b. 97% of the commercial preparation is (+)-naproxen; 3% is a racemic mixture Therefore, the commercial preparation forms 98.5% (+)-naproxen and 1.5% (~)-naproxen, 17, Solved in the text. 18 Asa result of the double bond, the compound has a cis isomer and a trans isomer, Because the compound also has an asymmetric carbon, the cis isomer can exist as a pair of enantiomers and the trans isomer can exist as a pair of enantiomers, CH,CH Zn H By CHa ey trans enantiomers 19. a. enantiomers b. identical compounds (Therefore, they are not isomers.) ©. diastereomersre 162 20, Chapter 5 a. First find the sp3 carbons that are bonded to four different substituents; these are the asymmetric carbons. Cholesterol has eight asymmetric carbons. They are indicated by arrows. b. 28 = 256 21. q c D CH; CH; a cI-H CH, CH, H H--Cl CH,CH, CH;CH; C Band c diastercomers: A. and A and DB and D enantiomers: A and B C and D 2, cH, Bw oH H, /Olts GAs [ econ c—-# H. Af Scucrce CH,CH,CH. ory a ae H H Pee easter a CH,CH,CH, CH,C H CH; CH H--a i++ HO--H H--0l CH,CH,CH, CHC Hy N\ oC OHCH, CH H--Br Br—-H CH, CH H--c| Ci—+-H CH,CH; CH; H-}-Br CH a—-—-H CH)CH, GH; CH; ath ata ch H H—cl ae CH,CH CH,CH; CH, CH; H-Cl Cl ‘CHCH; CH;CH) a—-# Lo CHCH, CH,CH, a. GHcHe FHLCHBs C, aN ccf, \" or Br Br BrCH,CHy —fcu,crs cH,cH,—[-cu,crpr H gy HOH cr 2 1«) ( ie) Br Br Br Br164 Chapter 5 24. al CH CH, CH, a a 1-chloro-1-methyl- cis-1-chloro-5-methyl- trans-\-chloro-5-methyl- cyclooctane cyclooctane cyclooetane 25. There is more than one diastereomer for a, b, and d. c has only one diastereomer. To draw a diastereomer of a, b, or d, switch any one pair of substituents bonded to one of the asymmetric carbons. Because any one pair can be switched, your diastereomer won't be the same as the one drawn here unless you happened to switch the same pair. CH CH. H . a H—--OH © Sad | ’ HO--H H ‘CH, CH, H , ct a quae Hae CH. pec —c—e Hy L CH,CH, CH; HO” H 26. -b,d,andf € and e do not have a stereoisomer that is a meso compound, because they do not have asymmetric carbons 27. Solved in the text. 28. Se ec Peace CH, cH, Cad : or CH,CH;—[-CH,Br BrcH,—}-cHCHs BrcHy \"H BW Now pr cH, CHfCH,CH, b. I Chapter 5 GrhcHs Aeon, . cicH,cH,~ \"H Hi 165 CH; CH ce or cnc#,— ch, cH,01 cicH,cH,—[-cacn cH, CH: f ‘CHCH,Cl CH; ¢. CH;CHCH,OH_ no stereoisomers because the compound does not have an asymmetric carbon @GH:CH,CHCHy Br Br a or cH,cH,—-cH,0H HOCH;—}-cH,CH, nocHy \"H BY" ScH,on Br Br CH; © CHCH,CCH;CHs_no stereoisomers because the compound does not have an asymmetric carbon a qi Yo—c—Br HO', N H CH G A CH, or wey —C SaBr Bas foe Nek HO ‘CH; CH; ‘OH & CHC a He ae a CHACH; CH)CH; ‘ameso compound a meso compound. CH H CHCH, CH,CH; — CH,CH; NoHo Cho H>-C1 CI—-H HY \ "HL cH of CH,CH; CH;CHy MG Cl CH,CH, CH,CH,] 166 Chapter 5 ho oa oa CH; CH, CH, sso compand « 8a wha ata CH CH, CH ca qa qd ca H . C] ch H H Cl AA AK fae ee meso compound i. a a oa CH, “SO cu, or Hcl so Le CH,CH,CH, CH,CH;CH, CH; CH; H- ‘Cl a H CH CH, cl—+-# Hcl CH,CH,CH, — CH,CH,CH, H H a i aoa a ou Ha Ht cl Gf a a a L a cl a—~a This compound does not have any asymmetric carbons, 80 it has only cis-trans isomers, oh—~H cl Br Br Cl aie H a2. (25,3R)-1,3-dichloro-2-butanol Ch OH cc aye nO cu, (25,35)-1,3-dichloro-2-butanol b. CHCl H-}-0H apa CH, (283 R)-1,3-dichloro-2-butanol CH; Chapter 5 ‘This compound does not have any asymmetric carbons, so it has only cis-trans isomers. cH; OH (2R,35)-1,3-dichloro-2-butanol y, CH,CI cl f —C. CH; OH (2R,3R)-1,3-dichloro-2-butanol QR3 $)-1,3-dichloro-2-butanol CH,CI HO--H Ha CH, QR3R)-1,3-dichloro-2-butanol ON ‘NHCCHCI, 167168 31. 32. 35. Chapter 5 ‘Your answer might be correct yet not look like the answers shown here. If you can get the answer shown here by interchanging two pairs of groups bonded to an asyinmetric carbon, then your answer is correct. If you get the answer shown here by interchanging one pair of groups bonded to an asymmetric carbon, then your answer is not correct, HOCH,CH~ Br. b. Ng Gg SaCH,CH, Hs ch, a, Because there are two asymmetric carbons, there are four possible stereoisomers. b, a. (2R,3R)-2,3-dichloropentane b. (2R,3R)-2-bromo-3-chloropentane ¢. (IR,35)-1,3-cyclopentanediol (naming the compound clockwise) or (15;3R)-1,3-cyclopentanediol (naming the compound counterclockwise) d. (3R,45)-3-chloro-4-methylhexane Solved in the text. We see that the 5-alky! halide reacts with HO to form the S-alcohol. We were told that the product (the S-alcohol) is (+). We can, therefore, conclude that the (-) alcohol has the R configuration, From the structures given on page 210 of the text, you can determine the configuration of the asymmetric carbon in each compound, re \ ‘BrChapters 169 37. Only bis true. 38. Greater than 98% is excess of the S enantiomer. The remainder is a racemic mixture, so greater than 99% is the $ enantiomer 39, aenantiotopic es neither b.diastereotopic _—_d. diastereotopic (remember that cis-trans isomers are diastereomers) 40. Compound A has two stereoisomers because it has a chirality center. ‘Compound B has only one stereoisomer because it does not have a chirality center. ‘Compound C has a chirality center but, because of the lone pair, the two enantiomers rapidly interconvert, 80 it exists as a single compound. 41. a.no b.no eno d. yes eno f.no 42. Only the stereoisomers of the major product of each reaction are shown. % GHCHACH, GHLCHACH, a a Bees, or cHcHcH—}-cu, cH —E-cH,cH.cH, cl ‘CH; b. FRC CHs PRCHCHs OH OH C., c oF CHjCH,CH;—}—CH,CH, CH,CH, +-CH,CH,CI Aen a CH,CH,—}-CH,CHl, cH, cH, —}-cH,cH, cach, Wid ~CH:CHs © GHACHACHs — CHACH,CH, CH(CH3), CH(CH3), G. c. or CH CH,CH,, CH,CH,CH, cog HEN, (CH,),CH ‘GH Zz : 'CH(CH3)3 CH; cH;F 170 Chapter 5 4. This compound does not have any stereoisomers because it does not have an asymimetric carbon. Br OH, e This compound does not have any stereoisomers & CH3OCHCHs because it does not have an asymmetric carbon. Br Br CH(CH;), CH(CH,), + ~\ or Br H Be utr ‘CH(CH3)3 CH, cr, 43. a and 3 CH, CH, CH H b. Hydrogen will be more likely to add to the side of the ring where the hydrogen substituent is than to side of the ring where the methyl substituent is because hydrogen provides less steric hindrance than a methyl group. CH; CH; 4, a oe - 3 ¥ ? + CH, CH; CH, CH; b. a. CH, CH; H OH HO Ht I I io Cong gas, cHcHy \"H HZ cucu, CH,CH,H H_ CH,CH OH a or CH CH, ro—--n +H pou CH,CH, CH,CHChapter$ 171 «6 CH,CH; GACH CHy=CCH,CH,CH, = 2 BrCH,CCH,CH:CH, Br CH,CH; HCH, CH)=CCH,CH,CH; ee CH CHCH,CH,CH, CH,CHS CH,CH; (CH,=CCH,CH,CH; 9 += HOCH, CHCH,CH,CH, 2.HO,H,0, ‘ (* indicates an asymmetric carbon) Each of the reactions forms a compound with one asymmetric carbon from a compound with no asymmetric carbons. Therefore, each of the products is a racemic mixture. 46, Because trans-2-butene forms a cyclic bromonium ion intermediate, it forms only the erythro enantiomers. If the reaction formed a carbocation intermediate, both the erythro pair of enantiomers and the threo pair of enantiomers would be formed because both syn and anti addition could occur. 41. _ CH; CH; or aber + ert CH,CH, CHCH, CH; b. CHyCH,CCH,CH, This compound does not a have an asymmetric carbon. 7 CH, SCH, Baa Ni CH; -H ‘CH,CH, CH,CH, al CH,CH, — CH,CH, : or J CH; CH, i HBr Br—-H | AN Z oH Br CH,CH; CH;CH, on CH;—-H CH; CH,CH CH,CH| 172 Chapter 5 4 GHLCH.CH, — CH,CHCH, CH,CH, CH,CH, oc ee ce o a-tpr + BrtH Hh, VF HD SCHLCH, CH,CH,CH,; CH CH,CH, CH; CH, 1 Br Br "prt * ate 7 Le ‘CH,CH, CHACH, geet rete CH,CH, CH,CH, £ FRCHICH:CHs FACHACHACHs CH,Br CH,Br oa + i. o H-tBr + Br—tH Bich, \ Wid “chBr CH,CH,CH,CH,; — CH;CH,CH,C1 48. Two different bromonium ions are formed because Br* can add to the double bond either from the top of the plane or from the bottom of the plane defined by the alkene, and the two bromonium ions are formed in equal amounts. Attacking the less hindered carbon of ‘one bromonium ion forms one stereoisomer, while attacking the less hindered carbon of the other bromonium ion forms the other stereoisomer. Bry HC. /CHACHCH;CH; perce H H Br 49. a HO and ‘HOHChapter5 173 pb. mechanism of the reaction H Br Br 50, a CH)CH, CHCH, Br CH;—}—Br con, ae cH," CH;—}—Br By fone CH,CH; Br CH b. CH,CH, CH,CH cu—tH , # CHCH, CHG J all H-+-cH, CH Xn noe CH,CH, CH,CH; CH3CH, ‘Br Br ‘CH,CH; « CH; Br Br CH; CH; CH; Br GACH; cHH, B Ley at Br CH; CH; CHjCH; CH;CH, CH;174 51. 52. 53. 54. Chapter 5 8. CH,CHCH,Br b. ‘The R and S enantiomers will be formed in equal amounts, I a CH,Br CH,Br CH,Br CHBr 1-bromo-2-chloropropane be bw ata + ata cay WH BS cH cu. cH. SAG I 3 b a. (R)-malate and (S)-malate (A product with one asymmetric carbon would be formed from ; reactant with no asymmetric carbons. Thus, the product would be a racemic mixture.) b, (R)-malate and (S)-malate (A product with one asymmetric carbon would be formed from. reactant with no asymmetric carbons. Thus, the product would be a racemic mixture.) CH, CH; CH)CH=CHCH,CH CH;=CHCH,CH,CH, CH,C=CHCH, CH,CHCH=CH, 2 stereoisomers no stereoisomers nostereoisomers no stereoisomers [cis and trans) CH,CH;C=CH, CH, ‘CHjCH, HC ‘CH, no stereoisomers no stereoisomers CH; 3 stereoisomers {Cis is a meso compoun (Trans is a pair of enantiome ee no stereoisomers. O no stereoisomers no stereoisomers a H H H Br] Br Br] Br a a H H CH, CH; or =H: ‘Br + Br H CH;CHCH; CH,CHCK I CHy I I CH; CH; CH; CHsChapter5 175 rs H ch GC, a H OH 1 a a 4a. CH; CH; cH, HBr Br—--H HBr CH CH, CH, Ha-C «CHIH CH, CH, CH; ‘CH3CH, /EHQCH:CH; CH3CH, fh e c= c=c Mies 7 H H H \CHyCH,CH; HOH Op Oo Bea BH UNE AS PN CH; CH; CH; H H CH CH, CH \ H CH; cH, CH,CHLCH CH, No isomers are possible for this compound because it does not have an asymmetric carbon. CH;176 55, 56. Chapter 5 i G CH=CH, . + or H+ ZN wren cHach Vg SCHaCH CH; b CH, La ui : a, (R)-2-ethyl-4-methyl-I-hexene b. (£)-1-bromo-2-chloro-2-fluoro-I-iodoethene ¢. (Z)-2-bromo-1-chloro-I-fluoroethene d. (6)-4-(2-chloroethy!)-2,3-dimethyl-3-octene e, 8-bromo-2-ethyl-I-octene £. (E}-1,3-dibromo-4,7-dimethyl-3-octene ® . (S)-2-methyl-1,2,5-pentanetriol Fd . (2R,3R)-3-chloro-2-pentanol Mevacor has eight asymmetric carbons. f CH=CH, cl CH,58. ChapterS 177 ‘a. constitutional isomers J. enantiomers b. enantiomers Kk. constitutional isomers ¢. diastereomers 1. enantiomers d. constitutional isomers (One is 3-chloro-2-pentanol and the other is 2-chloro-3-pentanol.) e. diastereomers m. identical £. constitutional isomers n. diastereomers g. identical (By naming them, you see that they both have the R configuration.) h. identical ©. identical i, diastereomers P. identical 1 PACH CH; CH; c or ca + apa a \uH CH; Gy CH,CH; CH,CH; Both cis and trans give these products. 2 Grice, GuLcH, cH, cH, Conyee Fuint or H-bon + HoH eat tong. oe Ci yt nd CoS CHACH,, CH,CH, Both cis and trans give these products cH, CH, or H Br + Br——-H br HS CH,CH, CH,CH; Both cis and trans give these products.178 Chapter 5 4. Cis gives the threo pair. CH Ri Br cc + \ ‘CH, or 5. Cis gives the threo pair. Cease enc Soc Br Brod, Ba YH HO baie OH is CH, Trans gives the erythro pair. 6 CHCH,CH,CH; Both cis and trans give this product, 7. CH,CH, GACH, CO or CH. HO a 8 or Both cis and trans give these products. CH, CH; HBr Br—-H or Br——-H HBr CH; cH, CH ‘Br ‘Br CH; CH; CH; or HOH HO—-H Br——H HBr CH, CH, CH; CH, HO+-H H--0H 7 Br—-H HBr CH; CH; CH; CH; OH + non CH,CHs CH,CH, CH; CH, u—bocn + CHy H CH,CH, CH;CH;Chapter5 179 b, For the cis and trans isomers to form different products, the reaction must form two new asymmetric carbons in the product. ‘Therefore, the cis and trans alkenes form different products when they react with Bro in (CHClz and when they react with Brz in HO. oe does not have stereoisomers; it is, therefore, achiral. eandh have 2 stereoisomers (cis and trans); both are achiral. a,d,f,i,andj have 3 stereoisomers; 2 are chiral and 1 is achiral. bandg have 4 stereoisomers, all of which are chiral, 00. CH,CH; CH,CH, a Oo Oh b ‘CH2CH3 CH,CH, sCH,CH, 2 OL OC peroxide age , "Be Ce CHCH, Br 7 “pr « Co . CH,CH, 2 — — CH,CH, 4 d. CY 1. BHYTHE ,CH,CH, w(CH,CH, = 2.HO", H,0, : oH ‘OH (the H and OH are added to the same side) (CH)CH i CH,CH, ae

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