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Advanced Higher Chemistry Unit 3 - Organic Chemistry PERMEATING ASPECTS & REACTION MECHANISMS Learning Outcomes Questions & Answers
page 1
Advanced Higher
Reaction Types
3.1.1 Equations can be written for the following reaction types and, given equations, these reaction types can be identified. hydrolysis substitution addition oxidation elimination reduction
condensation
3.1.2 The following reaction mechanisms can be described in terms of electron shifts. ( i)
Reaction Mechanisms
( ii)
(iii)
3.2.4 Alkanes undergo substitution reactions with chlorine and bromine by a chain reaction mechanism. 3.2.5 The chain reaction includes the following steps ( i) initiation by homolytic fission to produce radicals ( ii) propagation (iii) termination dehydration of alcohols using aluminium oxide, concentrated sulphuric acid or orthophosphoric acid base-induced elimination of hydrogen halides from monohalogenoalkanes.
( i) catalytic addition with hydrogen to form alkanes ( ii) addition with halogens to form dihalogenoalkanes (iii) addition with hydrogen halides according to Markownikoffs rule to form monohalogenoalkanes ( iv) acid-catalysed addition with water according to Markownikoffs rule to form alcohols. 3.2.9 The mechanisms of the above reactions involve ( i) for halogenation cyclic ion intermedate ( ii) for hydrohalogenation carbocation intermediate (iii) for acid catalysed hydration carbocation intermediate
page 2 Permeating Aspects & Reaction Mechanisms
Advanced Higher
3.2.12 Monohalogenoalkanes undergo nucleophilic substitution reactions. 3.2.13 Monohalogenoalkanes undergo elimination reactions to form alkenes. 3.2.14 Monohalogenoalkanes react with: ( i) alkalis to form alcohols ( ii) alcoholic alkoxides to form ethers (iii) ethanolic cyanide to form nitriles which can be hydrolysed to carboxylic acids(chain length increased by one carbon atom) ( iv) ammonia to form amines via alkyl ammonium salts. Alcohols and ethers 3.2.17 Alcohols can be prepared from
3.2.19 Alcohols react with some reactive metals to form alkoxides . 3.2.20 Alcohols can be dehydrated to alkenes. 3.2.21 Alcohols undergo condensation reactions slowly with carboxylic acids and more vigorously with acid chlorides to form esters. 3.2.27 Ethers can be prepared by the reaction of halogenoalkanes with alkoxides. Aldehydes, ketones & carboxylic acids 3.2.31 Aldehydes and ketones can be reduced to primary and secondary alcohols, respectively, by reaction with lithium aluminium hydride in ether. ( i) (ii) 3.2.32 Aldehydes and ketones undergo addition reactions in which the carbon atom in the polar carbonyl group submits to nucleophilic attack. condensation reactions with derivatives of ammonia (XNH2) which proceed by nucleophilic addition of XNH2 followed by elimination of a water molecule.
( i) oxidising primary alcohols and aldehydes ( ii) hydrolysing nitriles, esters or amides
( i) formation of salts by reactions with metals, carbonates and alkalis ( ii) condensation reactions with alcohols to form esters (iii) reaction with ammonia or amines and subsequent heating of the ammonium salt to form amides ( iv) reduction with LiAlH4 to form primary alcohols.
KHS Chemistry Jan 2007 page 3
Advanced Higher
Aromatics
3.2.49 Most reactions of benzene involve attack of an electrophile on the cloud of delocalised electrons, that is electrophilic substitution. 3.2.50 Benzene resists addition reactions but undergoes electrophilic substitution reactions. These include: ( i) chlorination and bromination to produce chlorobenzene and bromobenzene ( ii) nitration to produce nitrobenzene (iii) sulphonation to produce benzene sulphonic acid ( iv) alkylation to produce alkylbenzenes.
page 4
Advanced Higher
(carbocation intermediate)
Electrophilic Addition
(carbocation intermediate)
Electrophilic Addition
H H | | H C = C H H + O H H H
Though water is polar, the presence of H+ ions makes this reaction easier (catalyst).
electrons from the C=C bond come out to form a new bond with the H+ ion
H H | | C C H | H :Br The carbocation is then attacked by the lone pair of the bromide ion, a
neucleophile.
H H | | C C H | H H :O H
H H | | C C H | | H Br
C2H5Br
page 5
H | C | H
H | C H | O H | H
A monohaloalkane is prduced and overall the reaction can be represented by the equation:
A hydrogen ion is reformed (catalyst) and an alkanol is produced. Overall the reaction can be represented by the equation:
C2H4 + HBr
C2H4 + H2O
C2H5OH
Addition
Addition, Hydration
Advanced Higher
Electrophilic Addition
UV radiation is absorbed
Cl : Cl 2 Cl
Propagation
Instead of a carbocation being formed, the positive charge is shared between the 2 carbon atoms and the bromine atom. The Bromide ion (nucleophile) will then attack from the other side. A TRANS arrangement.
:Br H H C C H H Br
Cl CH3
A series of reactions between a free radical and a molecule keep the reaction going. Because each step makes another free readical, the reaction is a chain reaction.
Br H | | H C C H | | H Br
A dihaloalkane is prduced and overall the reaction can be represented by the equation:
Termination
Cl
CH3 CH3Cl
A mixture of haloalkanes will be produced but the first stage can be represented by the equation:
C2H4 + Br2
C2H4Br2
CH4
page 6
+ Cl2 CH3Cl +
HCl
Addition
Substitution
Advanced Higher
R' | Nu C Br R R''
As the nucleophiles' electron pair moves in, the electons of the CBr bond move onto the bromine Even if R , R' and R'' are all different (assymetric carbon), only one possible isomer can be produced. Nucleophiles include:
If R , R' and R'' are all different (assymetric carbon), then a mixture of optical isomers will be produced. Nucleophiles include:
HO alcohols : : RO ethers
HO alcohols : : RO ethers
: :
(Ammonia)
(Ammonia)
(Alcoholic cyanides)
(Alcoholic cyanides)
A variety of products can be made by this reaction but overall the reaction can be represented by the equation:
A variety of products can be made by this reaction but overall the reaction can be represented by the equation:
RHal
+ Nu
The first step is the rate determining step and, since it only involves one substance, the reaction is first order
Sn1 or Sn2 ?
Substitution
RNu +
Hal
RHa + Nu
: :
The rate determining step involves both chemicalss so the reaction is second order
Substitution
RNu + Hal
Can depend on the polarity of the CHal bond. Can depend on the polarity of the solvent used. Can depend on the size of the R , R' and R'' groups. No easy answer. Just need to be aware of the the two possibilities.
page 7
Advanced Higher
H | HO C | H + H : :
H | C H | H
A lone pair from the hydroxyyl oxygen forms a new bond with the H+ ion. The alcohol ibecomes protonated.
H | H C H HO: :
H | C Br | H
HO | H
The electrons of the CO bond move onto the oxygen and a water molecule is eliminated
H | C | H
H | C H | H
The OH ion acts like a base by removing a Hydrogen from the molecule as an H+ ion.
The electrons move from the CH bond to form a bond between the 2 carbon atoms. The electrons move from the CBr bond to form a bromide ion which is eliminated.
H | C | H
H A carbocation is formed. | C H Electrons move from the | CH bond to form a bond H between the 2 carbon atoms
H H | | H C = C H
A hydrogen atom and a bromine atom have been eliminated from the molecule to form an alkene. Overall the reaction can be represented by the equation:
C2H5Br
C2H4
HBr
Elimination
H H | | H C = C H
An alkene is prduced and overall the reaction can be represented by the equation:
C2H5OH
C2H4
+ H2O
page 8 Permeating Aspects & Reaction Mechanisms
Elimination (Dehydration)
Advanced Higher
This is the main reaction of benzene rings. Though they have even more electrons than the C = C bond in alkenes, they resist addition because the loss of the delocalised ring is too destabilising. Alkylation - using alkyl halides/AlCl3 Halogenation - using Halogens/AlCl3
Electrophilic Substitution
H H C Cl : H
The production of the electrophile requires the presence of AlCl3 . (The Al make use of its empty 4th orbital).
AlCl3
CH3
The production of the electrophile is helped by the presence of AlCl3 . The reaction would be very slow otherwise.
Cl Cl :
AlCl3
electrons move from the ring to form a new bond with the methyl ion.
Cl
electrons move from the ring to form a new bond with the chlorine ion, Cl+.
CH3
Cl
CH3
Cl
The production of the electrophile , NO2 is a result of a reaction between these two strong acids.
+
The electrophile is a molecule of SO3. The 3 oxygen atoms are more electronegative; a large + forms on the sulphur.
+
NO2
electrons move from the ring to form a new bond with the nitro ion, NO2+.
O electrons move from the O ring to form a new bond with Othe sulphur trioxide, SO3. O O O
NO2
NO2
OH O The H+ ion that is eliminated from O the benzene ring attaches itself to the
oxygen ion. Overall, a HSO3 group takes the place of a hydrogen atom, Substitution.
page 9
Ethers
LiAlH4
alc oh
c oli
CH3CH2NH2
CH3CH2CN
CH3CH2COOH
Advanced Higher
alcoholic
con
Cl2 or Br2
Cl2 or Br2
CH3COOC2H5 Dihalogenoalkanes Halogenoalkanes Esters Nucleophilic O4 S 2 Substitution c.H l/ o oh Electrophilic Addition CH3CH2Cl CH3CH2OH Radical CH3COOCl alc alkali, OH(cyclic ion (carbocation Halogenoalkanes Alcohols Substitution Acid chlorides intermediate) intermediate) l C H H O Elimination ic K hol o c l a C racking Dehydration Oxidation Oxidation CH2=CH2 CH3CH2OH CH3CHO CH3COOH CH3CH3 Al2O3 / heat K2Cr2O7 / dil H2SO4 Al2O3(400C) or c.H2SO4 or H3PO4 K2Cr2O7 / dil H2SO4 Alkanes Alkenes Aldehydes Acids Primary Alcohols
Addition
H2 / Ni
Hydration
H2O / c.H2SO4
Reduction Oxidation
LiAlH4
Reduction
LiAlH4
alcohol / c.H2SO4
CH3CH2Cl
CH2ClCH2Cl
c. N H 3
Alkoxide, -OR
CN
H2O (H+/OH-)
Benzene
Halobenzene
page 10
NaOH HCl
reforming
alkylation
Secondary Alcohols
CH3CH(OH)CH3
CH3COCH3
Reduction
LiAlH4
Ketones
CH3COONa+
Salts
Alkylbenzenes AlCl3 / RHal R Electrophilic ni tra Substitution tio NO n Nitrobenzene + 2 NO2 CH3C(CH3)(OH)CH3
Nucleophilic Addition
sulp
halogenation
Cl2 / Br2
Tertiary Alcohols
No Oxidation
Derivatives
OH
Cl
Advanced Higher
steam
hydrogenation
tha no l
l no tha me s e
Alkenes Primary
H
oxidation
Haloalkanes Alkanals
O
oxidation
H H
R C O H
hydroxyl group
addition
C C
R C
gi v e
se
hydration
hydrogenation
reforming
R
hydroxyl group
condensation
Aromatic Compounds
reforming
Unsaturated Polymers
O
condensation
H C C H
Alkynes
addition polymerisation
Diamines
H N X N H
Polyamides
O H H C N H
HC C C H
H H Hn
ad
ion dit
fermentation
Alkanols
H C C H
O
H
reduction reduction
H
H
Alkanoic Acids
R C
diacid
condensation polymerisation
Cl Cl
dehydration
ion ion d it a d e r is a t m ly po
aldehyde group
O H carboxyl group
Secondary
H
oxidation reduction
page 11
Alkanones
O R C R
Alkanes
H
H H
H H H
H C C H
-Amino Acids
H N H H X C H Y C OH O
Proteins
condensation polymerisation
O H
HC C C H
H H
carbonyl group
H C N H
H H H
Tertiary
R R C O
Fats
Cycloalkanes
Glycerol
H H H H C C C H O O O H H H
Oils
condensation
= = =
Notes
Higher Still
www.hsn.uk.net
HSN14290
Advanced Higher
Q1
Br |
Mg ethoxyethane
MgBr |
H | RCOH |
Using bromobenzene above and treating with propanone at (i), subsequent hydrolysis would result in the formation of A
H | CH 3COH |
CH3 | CH 3CH2COH |
OH | CH 3CCH3 |
H | CH3COCH3 |
Q2
Which of the following does not involve a nucleophilic substitution of the organic compound? A B + Cl2 CH3CH2Br + OH- CH3CH2OH + Br-
C D
Cl
+ HCl
page 12
Advanced Higher
Q3 Q4
C2H5NH2 HSNH3
NO2+
In each of the following compounds, the bonding shown is between carbon and one other element. In which compound is the bond polarised such that the carbon has a partial negative charge? A
H3CBr
CH3CH O
Q5
B C D
H3SiCH3
CH3C N
Q6
In the above two reactions, which two substances are acting as electrophiles? A B C D
OH- and C2H4 CO2 and Br2 CO2 and C2H4 C2H5Br + C2H5O-Na+ C2H5OC2H5 + Na+Br-
This reaction is an example of A B C D a condensation reaction to form an ether a condensation reaction to form an ester a nucleophilic substitution to form an ether an electrophilic substitution to form an ether
page 13 Permeating Aspects & Reaction Mechanisms
Q7
Advanced Higher
The reaction scheme shown below is an example of a chain reaction. a) b) c) C2H6 + T + + Br2 Br2 C2H5* X 2Br* + U
initiation step W
V Br*
C2H5* + C2H5* +
C2H5* Z
Br*
C2H5Br
C2H5Br 3 1 1 1 1 (7)
Write down the species represented by the letters T to Z in the reaction scheme. In step , the initiation step, explain if the process is exothermic or endothermic. i) ii) What name is given to the process represented by steps and ? What name is given to the process represented by steps to ?
d) Why is the reaction shown referred to as a chain reaction? Q8 Haloalkanes are extremely versatile organic compounds and are widely used in syntheses and preparations, as indicated in the following flow diagram.
amine
a) b) c)
Name the type of reaction involved in reactions to . Why can haloalkanes take part in the type of reaction in a)? How is the reagent OR obtained from an alcohol?
d) 1-bromopropane was used as the starting material for the preparation of carboxylic acids. Name the carboxylic acid formed: i) via route ii) via route . 2
KHS Chemistry Jan 2007 page 14
nitrile
CN
OR haloalkane OH alcohol
ether
NH3
oxidation
carboxylic acid
R = alkyl group 1 1 1
(5)
Advanced Higher
Q9
Haloalkanes are suitable compounds from which to synthesise other compounds. The flow diagram below shows how different compounds can be prepared from 2-bromopropane. reagent X 2-bromopropane C3H7CN reagent Y
H+(aq)
compound Q
compound R
a) b) c)
Draw the structural formula for 2-bromopropane. Which single term is used to describe reagents X and Y? The equation for the reaction that produces compound Q is: H H | | HCH HCH | | 2 C3H7OH H C O C H | | HCH HCH | | H H
d) e) f)
Q is an ether. What name could be given to the reaction that produces this ether? Draw the structural formula for an isomer of Q that belongs to a different homologous series. Draw the structural formula for compound R. Describe briefly how to distinguish between compounds Q and R.
g) Name the organic compound produced on oxidising compound P with acidified potassium dichromate solution.
page 15
compound P C3H7OH
C3H7COOH
1 1
H 2O
1 1 1 1 1 (7)
Advanced Higher
Q10
an ether
b) Name: Q11 c)
2 1 (4)
CH2 = CH2
C2H5Br
C2H5CN
C2H5COOH
C2H5COOCH3
The reagents necessary to bring about the conversions are numbered. Copy the numbers and alongside each number put: a) the type of reaction occurring 7 7 (14)
C2H5COONH4
C2H5CHO
Advanced Higher
Answers
Q2 B Q3 D Q4 C Q5 C Q6
Q1
Q7 a) b) c)
T Br*; X Br2;
U HBr; Y C4H10;
(any 6 )
3 2 2 1 (8) 1 1 1 2 (5) 1 1 1 1
d) Once the Br* radical is produced, the propagation step produces more of these radicals to keep the reaction going. Q8 a) b) c) Nuclophilic substitution They have a polar CX bond. (X = halogen) React the alcohol with an alkali metal (Na).
d) i) Propanoic acid (1) ii) Butanoic acid (1) Q9 a) b) c) CH3CHBrCH3 as a full structural formula Nucleophile Condensation (Joining together with formation of water)
d) Ethers and alcohols are isomers , so any hexanol isomer, e.g. CH3CH2CH2CH2CH2CH2OH e)
f)
(Use infra-red to detect the presence of C=O in R or its absence in Q); later in course ether has lower boiling point than ester; ester can be hydrolysed with NaOH but ether cannot be. (any one)
1 1 (7)
g) Propanone
KHS Chemistry Jan 2007 page 17
Advanced Higher
Q10
a)
1 2
b) c)
1 (4)
HBr/PBr3/PBr5
Hydrolysis
(14)
page 18