Chem 1814: Organic Chemistry

Gen Chem Review & Intro to Organic

Formal Charge = Group # (or Valence electron #) - Lone Pair Electrons - shared electrons
Bond number preference: Carbon wants 4 bonds; Oxygen wants to make 2 bonds and have 2 pairs of
nonbonding electrons; Nitrogen wants to make 3 bonds and have 1 pair of nonbonding electrons.
Types of Bonds:
Sigma Bonds All single bonds are sigma bonds. The sigma bond is cylindrically symmetrical and there
is free rotation of the atoms on either side of the sigma bond. All double and triple bonds have one
sigma bond. An s or a p orbital can create a sigma bond.
Pi bond - A pi bond results from p orbitals that are perpendicular to one another. This overlap occurs in
a parallel fashion, and it not cylindrically symmetrical like a sigma bond. Double bonds have one sigma
and one pi bond. Triple bonds have one sigma and two pi bonds. The pi bond is fixed and there is no
rotation around the bond.
Hybridization General rule of thumb: the number of atoms and unbonded pairs on an atom
= the number of orbitals that are involved in hybridization.
Sp3 = the s and 3 p orbitals combine together to reduce steric hinderances. Only sigma bonds can be
made.
Sp2 = the s and 2 p orbitals combine. The other p orbital is either in a pi bond or contains a nonbonding
pair of electrons.
Sp = the s and p orbitals combine. The other 2 p orbitals form pi bonds.
Atom has 4 boned atoms or sets of lone pairs, then it is sp3 hybridized and tetrahedral.
Atom has 3 bonded atoms or lone pairs, then it is sp2 hybridized and trigonal planar.
Atom has 2 bonded atoms or lone pairs, then it is sp hybridized and linear.
Definitions:
Acid loses a proton (remember a proton is a hydrogen ion)
Base gains a proton; Any substance with a lone pair of electrons can be a base.
Nucleophile (also a Lewis Base) An atom with a lone pair of electrons that will share them to initiate a
reaction
Electrophile (also a Lewis Acid) An atom that will serve as a place where the nucleophile will attack.
pKa measure of how strong of an acid a substance is. The smaller the pKa value, the stronger the acid.
Strong acids have pKas ~ 1, Weak acids have values from 3-5, and very weak acids can be 15 or
greater. In a reaction, the reactant with the smaller pKa will be the acid. This can be affected by
substituents (atoms other than C or H) due to delocalization or stabilizing. The more hybridized the
atom, the less acidic the hydrogen attached to that atom. (sp>sp 2>sp3)
Write an example of each functional group and write down the pKa for each functional group family.

Chem 1814: Organic Chemistry

Organic Structures and Nomenclature
Alkane: contains only Carbon-Carbon single bonds and hydrogen. All Cs are sp3 hybridized. Can
undergo cracking or combustion or be involved in radical reactions. General formula: CnH2n+2. Nonpolar.
Hydrophobic, not soluble in water. Boiling point and melting points increase with increasing molecular
weight.
Cylcoalkanes: named like alkanes but with the prefix cyclo-. CnH2n.
1. In a cycloalkane, the ring is usually the parent group; the exception is when the substituent has more
carbons than the ring. In that case, the ring is the substituent. You do not need to number if there is only
one substituent on a ring.
2. If the ring has two different substituents, they are listed in
alphabetical order and the first substituent listed gets the
number 1.
3. If there are more than two substituents, list them in
alphabetical order, and give the 1 position to the substituent
that results in the second substituent having the lowest number
as possible.

Alkene: contains a carbon-carbon double bond. CnH2n

Alkyne: contains a carbon-carbon triple bond CnH2n-2
Alkyl prefixes 1-Meth, 2-Eth, 3-Prop, 4-But, 5-Pent, 6-Hex, 7-Sept, 8-Oct, 9-Non, 10-Dec
Numerical Prefixes 1-Mono, 2-Di, 3-Tri, 4-Tetra, 5-Penta, 6-Hexa, 7-Hepta, 8-Octa, 9-Nona, 10-Deca
Halogen Prefixes Fluor, Chlor, Brom, Iod
Primary Carbon: Only bonded to one other carbon atom
Secondary Carbon: bonded to two other carbon atoms
Tertiary Carbon: bonded to three other carbon atoms
Common Naming:
Common names are formed by taking the
alkyl group name then following it with the
name of the class of compound

IUPAC Naming:
1. Find the Main Chain aka the parent hydrocarbon - This is the longest continuous chain of
carbon atoms. ane for alkanes, -ene for alkenes, -yne for alkynes
2. Number the Parent Chain - Beginning with the end nearest a substituent, number the
carbons of the main chain. The idea is to have the lowest numbers possible.
3. Name the Substituent Groups - The location and name of each substituent group. Alkyl groups
are named like alkanes but replace the -ane with -yl. For example, methane becomes a methyl
group. When derived from the n-alkane name, the groups can take the "n" to be n-propyl or nbutyl groups to separate them from their branched counterparts.
4. Number the substituents so that the lowest possible numbers are in front of the substituents.
5. Organize Multiple Groups - When there are two or more substituents present, they are listed in
alphabetical order. When there are two or more of the same alkyl substituent, use the prefixes di-,
tri-, tetra- to avoid naming the alkyl group twice. The position number still needs to be
identified, even if that means repeating a position number.

6. If the same substituent numbers can be listed from either direction, the substituent listed first
(alphabetically) gets the lower number. The "di" or "tri" is included in the alphabetizing.
7. This is the tricky part; branched substituents are numbered from the carbon attached to the
parent hydrocarbon. The name of the branched substituent is placed in parentheses.

Chem 1814: Organic Chemistry

StereoChemistry and Isomers
Isomers: 2 or more compounds with the same chemical formula but different arrangement of atoms in
space
Constitutional Isomers (aka Structural Isomers): same chemical formula but different bonding sequence
(ethanol and dimethyl ether)
Stereoiosmers: Isomers that differ in how their atoms are oriented in space
Cis-Trans Isomers: orientation of atoms around a double bond.
Cis = same side (hydrogen on same side),
Trans = opposite (Hydrogen on opposite sides of the bond)
These need to be named with Cis or Trans in the name.
Compounds with Asymmetric centers: an atom that has four different groups is an asymmetric
center. These compounds need to be named with R or S designations.

The stereocenter is an asymmetric center where changing two of the substituent groups converts
between a cis / trans isomer.
Chiral = nonsuperimposable mirror images (no plane of symmetry)
Achiral = superimposable mirror images
Asymmetric center = atom bonded to four
different groups
Enantiomer = two isomers with an asymmetric center and non-superimposable mirror images

Name compounds with asymmetric centers:

1. Assign priority to the substituents:

The higher the atomic number the higher the priority.

In the event of a tie, for example with 2-bromobutane

there are two carbon groups, the rest of the atoms bonded to the tied atoms are
considered. In the case of 2-bromobutane, there is a methyl and an ethyl group. Methyl
has a mass of approximately 15g/mole and Ethyl has a mass of approximately 29g/mole
therefore ethyl will have a higher priority than methyl. The groups are ranked from 1
through 4.

2. Orient the molecule to point the 4th priority (lowest priority) to the back. (Usually H)
3. Assess the order of priority. Clockwise: (R). Counterclockwise: (S).

Fischer Projection rules for naming:

1. Assign priorities to the atoms around the asymmetric center.
2. IF lowest priority (usually H) is on a vertical bond, then

a. Direction of 1-2-3 is clockwise, name with R

b. Direction of 1-2-3 is counterclockwise, name with S
3. IF lowest priority (usually H) is on a horizontal bond, then
a. Direction of 1-2-3 is clockwise, name with S
b. Direction of 1-2-3 is counterclockwise, name with R
Isomer Logic / Flow Chart
Two compounds
1. Do the compounds have the same or different molecular formulas?
a. Different Not isomeric
b. Same
i. Are the atoms connected in the same order or different?
1. Different Constitutional Isomers
2. Same Stereoisomers
a. Are the molecules mirror images of each other?
i. Yes compounds are enantiomers
ii. No compounds are diastereomers
1. Is there a double bond or ring closing at the point of
difference?
a. Yes Geometric isomer (Cis / Trans)
b. No Configurational (just diastereomers)
Chem 1814: Organic Chemistry
Alkenes, Alkynes, Dienes
Alkenes at least one carbon carbon double bond. CnH2n
The carbons in the double bond are sp2 hybridized.
Degree of unsaturation = 2*#Carbon + 2 + # Nitrogen + #phosphorous - # halogens
CyclicAlkene CnH2n-2
Alkynes at least one carbon carbon triple bond CnH2n-2
The carbons in the triple bond are sp hybridized.
Terminal Alkene or Alkyne multiple bond is at the end of the chain
Internal Alkene or Alkyne multiple bond is anywhere but the end of the chain
Naming:
Follow the same rules as alkanes.
1. Find the parent chain (longest chain that contains the double or triple bond)
2. Number the carbons so that the double or triple bond has the lowest number possible.
a. If there is both a double and a triple bond, there is no numerical priority beyond making
the numbers as small as possible. The name is divided like: 1-hepten-5-yne
3. Cis trans? Or E, Z?
a. If there are 2 hydrogens (one on each of the Cs that make the double bond) then use Cis /
Trans
b. If there are 4 different groups, use E or Z
i. Assign priorities 1 & 2 to the groups on each carbon. If both 1s are on the same
side, name it as Z
ii. If both 2s are on the opposite side, name it as E

The pi bond of an alkene is a nucleophile.

Reactions: Syn (same side of double bond) or Anti (opposite sides of double bond)
Markovnikovs rule when adding HX across an alkene, the H will add to the C with more Hs and the

X will add to the C with fewer Hs.

When the alkene/alkyne is unsymmetrical, the X- will add to the Carbon with the fewest Hs (most
substituted). This is the C that will form the most stable cation. 3 o>2o>>1o
Regioselectivity Alkenes will react to form the product that is created from the most stable carbocation
Electrophilic addition reaction (H+ is the electrophile, X- is the nucleophile) - Syn and anti-addition

(no excess HBr)

Add water (only with acid to catalyze) to make alcohol, ketone, or aldehyde
-OH adds to most substituted (like X)
Add alcohol to make an ether (acid catazlyzed) Syn and anti-addition

Add Borane to form alkylborane or as a concerted reaction

Add Halogen to make Alkyl halide Halogen (Br2 or Cl2; Br+ or Cl+ is electrophile and Br- or Cl- is nucleophile) In
water, -OH is the nucleophile - Anti addition

Add Peroxyacid Syn addition

Add Ozone (One O is electrophile, other O is nucleophile)

Add Hydrogen (Hydrogenation) Syn addition

Chain lengthening

1, 2 and 1,4 addition of conjugated diene

Diels Alder reaction (creates a cyclic molecule)

Mechanism:

Chem 1814: Organic Chemistry

Alkyl Halides: Nucleophilic Substitution Reactions & Elimination
Reactions
Alkyl Halide one hydrogen atom of an alkane is replaced with a halogen. Common Name: alkyl group
+ halogen-ide. (ethyl chloride). IUPAC name: 1-chloroethane. As halogen weight increases, the boiling
point of the alkyl halide increases. R-F and R-Cl are less dense than water. R-Cl 2, R-Br, and R-I are more
dense than water.
Synthesis:
Alkene halogenation to produce dihaloalkane

Alkene halogenation with hydrogen halide

Alkyne halogenation with hydrogen halide excess

Alcohol reaction with a variety of compounds

Nucleophilic Substitution Reactions

Unimolecular = SN2
Halogen is leaving group and carbocation is formed (watch for rearrangement)
Nucleophile attacks carbocation from both sides
Enantiomers are formed
1o and methyl halides will only react via the SN2 mechanism
2o favors SN2 when strong Nu and aprotic solvent (like acetone and DMSO)
Favored by high concentration of a good nucleophile in an aprotic solvent

Good Nucleophiles = R-, RCC-, RO-, HO-, RNH2, NH3

Types of compounds that can be made with SN2 reactions

Bimolecular = SN1
Nucleophile attacks the carbon on the opposite side from the halogen (backside attack)
Product has inverted stereochemistry
3o alkyl halides will only react via the SN1 mechanism (not Sn2. They can still produce
elimination)
2o alkyl halides favor SN1 when protic solvent (H2O, ROH)
Mechanism favored by a poor nucleophile
Poor Nucleophiles: RCOO-, F-, -CN, Cl-, Br-. REALLY weak = H 2O, ROH

Elimination Reactions
Unimolecular = E2
Halogen is leaving group and carbocation is formed (watch for rearrangement)
Product is E & Z alkene. Preference for largest groups in E conformation.
1o, 2o, 3o alkyl halides can react with the E2 mechanism
Favored by a high concentration of a strong base
Strong base: R-, RCC-, RO-, HO-, RNH2, NH3

Bimolecular = E1
Nucleophile removes H from carbon next to C with halogen
Electrons from C-H bond go between C-C bond
Halogen is leaving group as ion
Product is both E & Z alkene (possibly). Preference for largest groups in E conformation.
Only with 3o alkyl halides
Mechanism favored by a weak base
Weak base: RCOO-, F-, -CN, Cl-, Br-. REALLY weak base = H 2O, ROH

Zaitsevs Rule The more substituted alkene is obtained when a hydrogen is removed from the Bcarbon that is bonded to the fewest hydrogens. (reverse the addition reaction of an alkene and hydrogen
halide)
When to predict Substituion or Elimination product
Alkyl halide
Strong base
Weak Nu or Weak base
1o
SN2 unless stericially hindered
No reaction
base then E2 only (like t-BuO-)
2o
SN2 + E2 mixture
SN1 + E1 mixture
Stericially hindered base, E2
only
3o
E2
SN1 & E1 mixture

Chem 1814: Organic Chemistry

Synthesis of Alcohols from Ether

Reactions:
Alcohol to Alkyl Halide

Alcohol to Sulfonate Ester

Activated alcohol to a new group on sp3 carbon

Dehydration of alcohols

Oxidation of alcohols

Alcohols & Ethers

Reactions with Epoxides

Forming diols

Arene Oxide reaction Ring opening and rearrangement

Chem 1814: Organic Chemistry

Aromaticity
Aromatic compound
1. Uninterrupted cyclic cloud of pi electrons (must be planar)
2. Odd number of pi electrons (odd # pi bonds!)
Huckels Rule for a compound to be aromatic it must contain 4n+2 pi electrons or an odd number of
pi bonds
AnitAromatic compound
4n pi electrons, even number of pi electrons
Chem 1814: Organic Chemistry
1.

IR & Mass Spec & NMR