Chapter 7

7.1 One problem with elimination reactions is that mixtures of products are often formed. For example, treatment of 2-bromo-2-methylbutane with KOH in ethanol yields a mixture of two alkene products. What are their likely structures? Solution:

major product Br

7.2 How many alkene products, including E,Z isomers, might be obtained by dehydration of 3-methyl-3-hexanol (3-methyl-3-hydroxyhexane) with aqueous sulfuric acid? Solution:

dehydration OH

7.3 What product would you expect to obtain from addition of Cl2 to 1,2-dimethylcyclohexene? Show the stereochemistry of the product. Solution:

Cl
Cl H3C H3C CH3 Cl Cl Cl CH3 H3 C Cl CH3

Cl

H3C H3C Cl Cl CH3

Cl

CH3

7.4 Addition of HCl to 1,2-dimethylcyclohexene yields a mixture of two products. Show the stereochemistry of each, and explain why a mixture is formed. Solution:

Cl
Cl CH3 H3C CH3 H Cl H3C H3 C CH3

H3C

CH3

CH3

Cl
H3 C Cl

7.5 What product would you expect from the reaction of cyclopentene with NBS and water? Show the stereochemistry. Solution:

H H O H Br Br H H Br H H Br H

OH

OH Br

Br

Br H H OH OH

7.6 When an unsymmetrical alkene such as propene is treated with NBS in aqueous DMSO, the major product has the bromine atom bonded to the less highly substituted carbon atom. Is this Markovnikov or non-Markovnikov orientation? Explain.

OH H3C
Solution:

C H

CH2

NBS,H2O DMSO

H3C

C H

CH2Br

H H3C

Br

Br CH2

vs
CH2

H3C

H 2O
The product is Markovnikoff product.

H 2O

7.7 What products would you expect from oxymercuration of the following alkenes? Solution: (a)
H3C H2 C H2 C C H CH2 Hg(OAc)2 H2O OH H3C H2 C H2 C H C CH3

2-pentanol
(b)
OH H3C C CH3 C H H2 C CH3 Hg(OAc)2 H2O H3C C CH3 H2 C H2 C CH3

2-methyl-2-pentanol

7.8 What alkanes might the following alcohols have been prepared from? Solution: (a)
H3C C CH3 C H H2 C H2 C CH3 Hg(OAc)2 OH H2O H3C Hg(OAc)2 H2 C H2 C H2 C H2O C OH H2 C H2 C H2 C CH3

2-methyl-2-hexene

H2C

C CH3

CH3

2-methyl-1-hexene

(b)
OH Hg(OAc)2 H2O

cyclohexylethylene
1.BH3
2.H2O2 OH

ethylidenecyclohexane
7.9 Show the structures of the products you would obtain by hydroboration/oxidation of the following alkenes: (a)
CH3

(b)
CHCH2CH3

CH3

CH3C

Solution: (a)

CH3

OH CHCH2CH3
OH

CH3CH

(b)

CH3

7.10 What alkenes might be used to prepare the following alcohols by hydroboration/oxidation? (a) (CH3)2CHCH2CH2OH

(b)

OH

(CH3)2CHCHCH3

(c)
CH2OH

Solution: (a)

(CH3)2CHCH CH2
(b) (c)
CH2

(CH3 )2C

CHCH3

7.11 The following cycloalkene gives a mixture of two alcohols on hydroborotion followed by oxidation, Draw the structures of both, and explain the result.

H H3C CH3 H
Solution: The structure of the two cycloalcohols:
H H3C H H3C CH3 H H3C H H CH3 H OH CH3 H

1. BH3 / THF 2. OH-, H2O

H OH

7.12 What products would you expect from the following reactions?

CH2
(a)

Cl Cl C Cl H

KOH

Zn(Cu)
(b)

(H3C)2HCH2CHC CHCH3

CH2I2

Solution:

CH2
(a)

Cl Cl Cl C Cl H
Zn(Cu)
KOH

Cl C
HCl

(b)

(H3C)2HCH2CHC CHCH3

CH2I2

ZnI2

7.13 What product would you obtain from calalytic hydrogenation of the following alkenes? CH3

(a) H3C (b)

C H CH3

H2 C

CH3

CH3

Solution
CH3 H2 C CH3 H2 C

(a) H3C (b)

C H

CH3

CH3

7.14 What alkene would you start with to prepare each of the following compounds?
H OH OH OH C CH3 CH3 OH CH3 OH OH C H H2 C OH

(a)

(b)

H3C

H2 C

C H

(c) HO

H2 C

C H

olution:
H

(a)

(b)

H3C

H2 C

C H

C CH3

CH3

(c)

H2C

C H

C H

CH2

CH3

7.15 What products would you expect? Solution: (a) Aqueous acidic KMnO4 Product CH3COCH2CH2CH2CH2COOH

(b) O3 Product CH3COCH2CH2CH2CH2CHO 7.16 Propose structure for alkenes. Solution: (a): (CH3) 2C=O and H2C=O Structure Structure (CH3) 2C =CH2 CH3CH2CH=CHCH2CH3 (b): 2 equiv CH3CH2CH=O

7.17 Show the monomer units you would use to prepare the following polymers:
OCH3 H2 C C H H2 C OCH3 C H H2 C OCH3 C H

(a)
OCH3

Solution: The monomer unit is H2C

CH

Cl C H

Cl C H

Cl C H

Cl C H

Cl C H

Cl C H

(b) Solution: The monomer unit is ClHC

CHCl.

7.18 One of the chain-termination steps that sometimes occurs to interrupt polymerization is the following reaction between two radicals:

2
Solution:

CH2CH2

CH2CH3

C H

CH2

Propose a mechanism for this reaction, using fishhook arrows to indicate electron flow.

H C H H2 C

CH2 C H CH2 + CH2CH3

CH2

7.19 tert-Butyl vinyl ether is polymerized commercially for use in adhesives by a cationic process.

Draw a segment of poly(tert-butyl vinyl ether), and show the mechanism of the chain-carrying step.

tert-butyl vinyl ether

Solution:
Acid catalyst H
O

O O O O

Repeat many times

*

O C H H2 C *

7.20 Name the following alkenes, and predict the products of their reaction with (i) KMnO4 in aqueous acid and (ii) O3, following by Zn in acetic acid:

(a) Solution: (a)2,5-dimethyl-2-heptene

(b)

O O OH

and
(i)
O O H

and
(ii) (b)3,3-dimethylcyclopentene

HO

O OH

(i)
H O

(ii)

7.21 Draw the structures of alkenes that would yield the following alcohols on hydration (red=O). Tell in each case whether you would use hydroboration/oxidation.

Solution: (a)

CH2

I would use oxymercuration in this case.

(b) Both oxymercuration / demercuration and hyboration / oxidation reactions could be used. 7.22 The following alkene undergoes hydroboration/oxidation to yiele a single product rather than a mixture. Explain the result, and draw the product showing its stereochemistry. Solution: The reactant is symmetrical, so
OH adding to either of the carbon that is double bonded

will yield the same product. The single product is:

OH

7.23 Predict the products of the following reactions (the aromatic ring is unreactive in all cases). Indicate regiochemistry when relevant.
(a) H2/Pd CH CH2 (b) (c) (d) Br2 HBr

1.OsO4 2.NaHSO4 (e) D2/Pd

CH

CH2 H2/Pd

H H C

H C H H

Solution: (a)
CH CH2 Br2 H Br C H C Br H

(b)
CH CH2 HBr H Br C H C H H

(c)
HO H CH CH2 1.OsO4 2.NaHSO4 C C OH H H

(d)
CH CH2

D H D2/Pd

D H H

(e) 7.24 Suggest structures for alkenes that give the following reactions products. There may be more than one answer for some cases.
CH3

CH3 CH3

(a) ?
? Br 2

CH3CHCH2CH2CH2CH3

(b)
Cl ? HCl CH3CHCHCH2 CH2CH2CH3 CH3

Br

CH3 Br

CH3CHCHCH2CHCH3

(c)

(d)

OH 1.Hg(OAc)2,H2O ? CH3CH2CH2CHCH3 (e) 2.NaBH4

CH3CHCH2CH2CH CH2

H3C H3CHCH2CHC CHCH3

Solution: (a)

CH3

H3C H3CHCHC CHCH2CH3 CH3

H2C

CH3 H3CC CHCH2CH2CH3

CCH2CH2CH2CH3 CH3 CH3 CH3 CH3

CH3

(b) (c) H3CHC

CHCH2 CHCH3

H2C

CHCHCH2CH2CH2CH3 CH3

(d)

(e) H3CH2CH2CHC

CH2

7.25 Predict the products of the following reactions, indicating both regiochemistry and stereiochemistry when appropriate:

CH3

1. O3 2.Zn, H3O+
(a)

H
O CH3 CH3

1. O3 2.Zn, H3O+
H
Solution:
KMnO4 H3 O+

H O

(b)
O OH

KMnO4 H3O+
OH

Solution:
CH3

1. BH3 2. H2O2,- OH

(c)
CH3 H CH3 CH3 H

1. BH3 2. H2O2,- OH
OH H

+
H OH

Solution:
CH3

50%

50%

1. Hg(OAc)2,H2 O 2. NaBH4

(d)

CH3

CH3

OH

1. Hg(OAc)2,H2O 2. NaBH4
H OH H CH3

Solution:

50%

50%

7.26 How would you carry out the following transformations? Indicate the reagents you would use in each case.
H OH

?
OH

(a)

H OH OH H
OH

1.OsO4 2.NaHSO3 ,H2O

Solution:

(b)
OH

1. Hg(Ac)2 2. NaBH4

Solution:
H Cl

?
Cl

(c)
1. CHCl3 2. KOH

H Cl

Cl

Solution:
CH3

CH3 OH

(d)

CH3 OH 1. H2SO4, H2 O 2. THF, 50

CH3

Solution:
CH3 H3CHC CHCHCH3 O CH3

CH3CH

+ CH3CHCH
O

(e)
CH3 H3CHC CHCHCH3 O

CH3

1. O3 2. Zn/H3 O+
CH3

CH3CH + CH3 CHCH

O

Solution:
CH3

(f)

H3CC

CH2

CH3CHCH2 OH
CH3

CH3 H3CC CH2

Solution:

1. BH3 , THF 2. H2O2,OH-

CH3 CHCH2OH

7.27 What product will result from hydroboration/oxidation of 1-methylcyclopentene with deuterated borane, BD3? Show both the stereochemistry (spatial arrangement) and the regiochemistry (orientation) of the product.
H CH3 H

D D B

CH3

H
-

CH3

OH H2O2
HO D

D2B

BD3
H CH3 D D B D D2B D
-

HO

CH3 H CH3

OH H2O2
H CH3

7.28 Draw the structure of an alkene that yield only acetone, (CH3)2C=O, on ozonolysis followed by treatment with Zn.

O3 Zn/H3O+

+ O

7.29 Draw the structure of a hydrocarbon that react with 1 molar equivalent of H2 on catalytic hydrogenation and gives only pentanal , CH3CH2CH2CH2CHO, on the ozonolysis followed by treatment with Zn. Write the reaction involved.

Solution: The structure of the hydrocarbon is showed in the following picture:

The reactions are showed as follow:

Catalyst H2
O3 H

2
Zn/H3O O

7.30 Draw the structure of alkenes that give the following products on oxidative cleavage with KMnO4 in the acidic solution:

+
(a).
O O

+
CO2
(b).

(c). Solution:

(a).

(b).

(c).

7.31 Compound A has the formula C10H16. On catalytic hydrogenation over palladium, it reacts with only 1 molar equivalent of H2. Compound A also undergoes reaction with ozone, followed by zinc treatment, to yield a symmetrical diketone, B (C10H16O2). (a) How many rings does A have? A have two rings. (b) What are the structures of A and B?

(c) Write the reactions.

+H2 palladium
O

+O3

Zn

O 7.32 An unknown hydrocarbon A, with formula C6H12, reacts with 1molar equivalent of H2 over a

palladium catalyst. Hydrocarbon A also reacts with OsO4 to give a diol, B. When oxidized with KMnO4 in acidic solution, A gives two fragments. One fragment is propanoic acid, CH3CH2CO2H, and the other fragment is a ketone. C. What are the structures of A, B, and C? Write all reactions, and show your reasoning.

A
H2 C CH3

B H3C
H HO O CH3 OH

H2

palladium

H2 C

CH3

OsO4

H3C H HO O CH3 OH O

KMnO4

+ H3C

C C H2 O

7.33 Using an oxidative cleavage reaction explain how you would distinguish between the following two isomeric dienes:

and Solution: When they react with KMnO4 in acid, the first one will yield two products and the second one will only yield one product. 7.34 Compound A, C10H18O, undergoes reaction with dilute H2SO4 at 2500C to yield a mixture of two alkenes, C10H16. The major alkene product, B, gives only cyclopentanone after ozone treatment followed by reduction with zine in acetic acid. Identify A and B, and write the reaction. Solution: A:
HO

B:

Reaction:
HO

H2SO4 2500C major

O3
O

Zn/H3O

7.35 Which reaction would you expect to be faster, addition of HBr to cyclohexene or to 1-methylcyclohexene? Explain. Solution: The intermediates of the two reactions are not equal in stability. Judge by Hammond postulate, the more stable intermediate forms faster, so addition of HBr to 1-methylcyclohexene may be faster.

7.36 Predict the products of the following reactions, and indicate regiochemistry if relevant:
Br

(a)

HBr

(c)

CH2I2 , Zn-Cu
H H

(d)

CH2I2 , Zn-Cu
H H

7.37 Iodine azide, IN3, adds to alkenes by an electrophilic mechanism similar to that of bromine. If a monosubstituted alkene such as 1-butene is used, only one product results:
N H3CH2CHC CH2 N N

CH3CH2CHCH2 I

(a)

Add lone-pair electrons to the structure shown for IN3, and draw a second resonance form for the molecule.
I N N N I N N N

(b)

Calculate formal charges for the atoms in both resonance structures you drew for IN3 in part For the iodine: Iodine valence electrons Iodine bonding electrons Iodine nonbonding electrons Formal charge = 7 - 2/2 6 = 0 For the left nitrogen: Nitrogen valence electrons Nitrogen bonding electrons Nitrogen nonbonding electrons Formal charge = 5 6/2 2 = 0 For the middle nitrogen: Nitrogen valence electrons Nitrogen bonding electrons =5 =8 =5 =6 =2 =7 =2 =6

Nitrogen nonbonding electrons Formal charge = 5 8/2 0= 1 For the right nitrogen: Nitrogen valence electrons Nitrogen bonding electrons Nitrogen nonbonding electrons Formal charge = 5 4/2 4= - 1 (c)

=0

=5 =4 =4

In light of the result observed when IN3 adds to 1-butebe, what is the polarity of the I-N3bomd? Propose a mechanism for the reaction using curved arrows to show the electron flow in each step.

H3CH2CHC

CH2

N H3CH2CHC CH2I N N N

CH3CH2CHCH2I
7.38 Draw the structure of a hydrocarbon that absorbs 2 molar equivalents of H2 on catalytic hydrogenation and gives only butanedial on ozonolysis.
O HC H2 C H2 C O CH

Butanedial

Solution: 7.39 SimmonsSmith reaction of cyclohexene with diiodomethane gives a single cycloproprane product, but the analogous reaction of cyclohexene with 1,1-diiodoethane gives (in low yield) a mixture of two isomeric methylcyclopropane products. What are the two products, and how do they differ? Solution: The reaction occurs as below:

H + I2HC CH3 Zn(Cu) Ether

CH3 +

H3C

7.40 In planning the synthesis of one compound from another, its just as important to know what not to do as to know what to do. The reactions all have serious drawbacks to them. Explain the potential problems of each. Solution: (a)

CH3 H3C C CHCH3

HI

CH3 H3 C C CHCH3 H I
CH3 H3C C CH2CH3 I

According to Markovnikovs rule the reaction should be:

CH3 H3C C CHCH3 HI

(b)
H 1.OsO4 2.NaHSO3 OH H OH

Actually it should be syn addition as below:

H 1.OsO4 2.NaHSO3 H OH OH

(c)
CHO 1.O3 CHO 2.Zn Actually the reaction should be: H2 1.O3 2 OHC C CHO 2.Zn (d)

CH3

H 1.BH3 2.H2O2 , OH H

CH3 OH

Actually the reaction should be:

CH3 1.BH3 2.H2 O2, OH

CH3

H OH

7.41 Which of the following alcohols could be made selectively by hydroboration/oxidation of an alkene? Explain.
H CH3 OH CH3

OH

OH

OH

(a)

CH3CH2 CH2CHCH3

(b)

(CH3)2CHC(CH3)2

(c)

(d)

Solution: (a) No selectivity (b) Selectively synthesized (c)Cant be formed

(d) Cant be formed 7.42 What alkenes might be used to prepare the following cyclopropane?
Cl

(a) Solution:

CH(CH3) 2

(b)

Cl

+ (CH3)2CHCHI2

Zn(Cu)

(a)

Ether

CH(CH3)2

Cl

+ CHCl3

OH Cl

(b)

7.43 Predict the products of the following reactions. Dont worry about the size of the molecule; concentrate on the functional groups.
Br2

CH3

HBr

CH3

1. OsO4 2. NaHSO3
HO

1. BH3, THF 2. H2O2, OH-

CH2I2, Zn (Cu)

Solution:
CH3

CH3
CH3

CH3

Br2

HO Br Br

a)

HO

CH3

CH3

CH3

CH3

HBr

b)

HO

HO

Br

CH3

CH3
CH3

CH3

OsO4 NaHSO3
HO OH OH

c)

HO

CH3

CH3
CH3

CH3

BH3,THF H2O2,OH
HO OH

d)

HO

CH3

CH3

CH3

CH3

CH2I2 Zn(Cu)

e)

HO

HO

7.44 The sex attractant of the common housefly is a hydrocarbon with the formula C23H46. On treatment with aqueous acidic KMnO4, two products are obtained, CH3(CH2)12CO2H and CH3(CH2)7CO2H.Propose a structure. Solution:
H3C H2 C H C H2 C

12

C H

CH3

should be the right structure.

7.45 Compound A has the formula C8H8. It reacts rapidly with KMnO4 to give CO2 and carboxylic acid, B (C7H6O2), but reacts with only 1molar equivalent of H2 on catalytic hydrogenation over a palladium catalyst. On hydrogenation under conditions that reduce aromatic rings, 4 equivalents of H2 are taken up and hydrocarbon C (C8H16) is produced. What are the structure of A, B, and C? Write the reactions. SOLUTION:

C C H

C OH

H2 C CH3

The reactions:
O C

H C C H H C C H H H

KMnO4

OH

CO2

H2 C

1mol H2 palladium catalyst

CH3

H C C H H H2 C

4mol H2

CH3

7.46. Plexiglas, a clear plastic used to make many molded articles, is made by polymerization of methyl methacrylate. Draw a representative segment of Plexiglas.
CH3 H2C C O C OCH3

Methyl methacrylate

SOLUTION:

The segment of Plexiglas: CH3 H2 C C C OCH3 7.47 Poly (vinyl pyrrolidone), prepared from N-vinylpyrrolidone, is used both in cosmetics and as a synthetic blood substitute. Draw a representative segment of the polymer. O O

N-vinylpyrrolidone
Solution:
* H C N H2 C *

7.48 Reaction of 2-methylpropene with CH3OH in the presence of H2SO4 catalyst yields methyl tert-butyl ether, CH3OC(CH3)3, by a mechanism analogous to that of acid-catalyst alkene hydration. Write the mechanism, using curved arrows for each step. Solution:

CH3 H3C C CH2

CH3

H + CH3OH

HSO4 H3C C CH3

CH3OH

CH3 H3C H3C C O CH3 H H3C H3C

CH3 C O CH3

H2SO4

HSO4
7.49 When 4-penten-1-ol is treated with aqueous Br2, a cyclic bromo ether is formed, rather than the expected bromohydrin. Propose a mechanism, using curved arrows to show electron movement. Solution:
H O HO Br

H O CH2Br O Br

7.50 How would you distinguish between the following pairs of compounds using simple chemical tests? Tell what you would do and what you would see. (a) cyclopentene and cyclopentane (b) 2-hexene and benzene Solution: Bromine in carbon tetrachloride solution is reddish-brown color. Using this one to identify the double bond by electrophilic addition reaction.

7.51
Cl Cl C Cl O C O-Na+ Cl Cl C Cl OC O Cl Cl CCl + O C O

Cl
l

O C

a N +

C Cl

They have the same intermediate which is CCl3-.

7.52 (a) 3 (b) double bonds:2

(c)

7.53 Evidence that cleavage of 1,2-diols by HIO4 occurs through a five membered cyclic periodate intermediate is based on kinetic data the measurement of reaction rates. When diols A and B were prepared and the rates of their reaction with HIO4 were measured, it was found that diol A cleaved approximately 1 million times faster than diol B. Make molecular models of A and B and of potential cyclic periodate intermediates, and then explain the kinetic results.
OH

OH

HO H H

H H OH

A cis diol
Solution:
OH

B trans diol

HO H

HIO4
O

O O I O OH O O

A:

In cis diol, two OH are in one plane, so it is easier to form a cyclic periodate inetermediate, while in trans diol, the two OH arent in one plane, there is larger steric strain in the five membered cyclic periodate intermediate, it is less stable, so the rates of A is more faster. 7.54 Reaction of HBr with 3-methylcyclohexene yields a mixture of four products: cis- and trans-1-3-methylbromocyclohexane and cis- and trans-1-2-methylbromocyclohexane. The analogous reaction of HBr with 3-bromocyclohexane trans-1, 2-dibromocyclohexane as the sole product. Draw structures of the possible intermediates, and then Explain why only a single product is formed in the reaction of HBr with 3-bromocyclohexane. Solution:

Br

Br Br

Br

Br

Br H

Br H

7.55 The following reaction takes place in high yield:

CO2 CH3 CO2 CH3

Hg(OAc)2
AcO Hg

Use your general knowledge of alkene chemistry to propose a mechanism, even though youve never seen this reaction before. Solution:

CO2CH3 OAc AcO Hg

OAc
CO2CH3

Hg AcO CO2CH3 CO2CH3 H

OAc

AcO

Hg AcO CO2CH3 Hg

AcO

Hg

7.56 Reaction of cyclohexene with mercury(II) acetate in CH3OH rather than H2O, followed by treatment with NaBH4, yields cyclohexyl methyl ether rather than cyclohexanol. Suggest a mechanism.

1.Hg(OAc)2, CH3OH 2.NaBH4

Solution:
OCH3

OAc Hg Hg OAc

OAc

HO

CH3

HgOAc

HgOAc

O H

CH3 OAc

CH3

NaBH4
OCH3

7.57 Hydroboration of 2-methyl-2-pentene at 25 followed by oxidation with alkaline H2O2 yields 2-methyl-3-pentano, but hydroboration at 160 followed by oxidation yields 4-methyl-1-pentanol. Explain.
CH3

1.BH3,THF,25 2.H2O2,OHCH3

CH3CHCHCH2CH3
OH

2-Methyl-3-pentanol CH3C
CHCH2CH3 CH3

1.BH3,THF,160 2.H2O2,OH-

CH3CHCH2CH2CH2OH 4-Methyl-1-pentanol

Solution: Case 1:
CH3 CH3 CHCH2 CH3 + BH3

3 CH3C

THF,25

3 CH3CH CHCH2CH3
BH2

H2O2,OH-

CH3

3 CH3CHCHCH2CH3
OH

Case 2:

BH2

BH2

H2O2 / OHOH

BH2

7.58 Alkynes undergo many of the same reactions that alkenes do. What products would you expect from each of the following reactions?

CH3
H3C C H

H2 C

H2 C

CH

(1) with 1 equiv Br2; (2) with 2 equiv H2 ,Pd/C (3)with 1 equiv HBr Solutions: (1)

CH3
H3C C H

H2 C

H2 C

1 equiv Br2
C CH H3C

CH3
C H

Br
H2 C H2 C C CH

Br
(2)

CH3
H3C
(3)

C H

H2 C

H2 C

2 equiv H2 ,Pd/C
C CH H3C

CH3
C H

H2 C

H2 C

H2 C

CH3

CH3
H3C C H

H2 C

H2 C

1 equiv HBr
C CH H3C

CH3
C H

Br
H2 C H2 C C CH2

7.59 Explain the observation that hydroxylation of cis-2-butene with OsO4 yields a different product than hydroxylation of trans -2-butene. First draw the structure and show the stereochemistry of each product, and then make molecular models. Solution:

H3C

C H

C H

CH3

H3C HC CH

CH3

H3C C H

H C CH3

cis-But-2-ene

trans-But-2-ene

OH H3C C H OH OH C H H OH CH3 H3C C H C CH3

Butane-2,3-diol meso compound

Butane-2,3-diol enantiomer