7.

1 Using the (E)-(Z) designation [and in parts (e) and (f) the (R-S) designation as well], give IUPAC names for each of the following.
Br H C Cl C CH2CH2CH3
H3C CH2CH(CH3)2 C H C CH3

(a)
Cl

(b)
Br

Cl

(c)
I

CH3 C C CH2CH3
Cl C C

C CH2 CH3
H CH3

(d)
I
Br

H3 C

(f)
C C CH3
H

(e)
H

H3C

Answer:

(a) (Z)-1-Bromo-1-chloro-1-pentene (b) (Z)-3,5-Dimethyl-2-hexene (c) (E)-2-Bromo-1-chloro-1-iodo-1-butene (d) (Z)-1-Chloro-1-iodo-2-methyl-1-butene

(e) (2Z,4S)-3,4-Dimethyl-2-hexene (f) (1Z,3R)-1-Bromo-2-chloro-3-methyl-1-hexene 7.2 Heats of hydrogenation of three alkenes are as follows: 2-methyl-1-butene (-119kJ/mol) 3-methyl-1-butene (-127kJ/mol) 2-methyl-2-butene (-113kJ/mol) (a) Write the structure of each alkene and classify it as to whether its doubly bonded atoms are monosubstituted, disubstituted, trisubstituted, or tetrasubstituted. (b) Write the structure of the product formed when each alkene is hydrogenated. (c) Can heats of hydrogenation be used to relate stabilities of these three alkene? (d) If so, what is the predicted order of stability? If not, why not? (e) What other alkene isomers are possible for these alkenes? Write their structures. (f) What data would be necessary to relate the stabilities of all these isomers? Answer: (a)

2-methyl-1-butene

disubstituted

3-methyl-1-butene

monosubstituted

2-methyl-2-butene

trisubstituted

(b)

2-methyl-butane

(c) Yes. Because the products are the same. (d) stability: 3-methyl-1-butene<2-methyl-1-butene<2-methyl-2-butene (e)
1-pentene

2-pentene
(f) heats of combustion and heats of hydrogenation. 7.3 Predict the more stable alkene of each pair. (a) 2-Methyl-2-pentene or 2,3-dimethyl-2-butene, (b) cis-3-hexene or trans-3-hexene, (c) 1-hexene or cis-3-hexene, and (d) trans-2-hexene or 2-methyl-2-pentene. Answer: (a) 2,3-dimethyl-2-butene , (b) trans-3-hexene , (c) cis-3-hexene , (d) 2-methyl-2-pentene are more stable alkenes of each pair. 7.4 Consider the pairs of alkenes, for which pairs could you use heats of hydrogenation to determine their relative stabilities? For which pairs would you be required to use heats of combustion? (a) 2-methyl-2-pentene or 2,3-dimethyl-2-butene, (b) cis-3-hexene or trans-3-hexene, (c) 1-hexene or cis-3-hexene, (d) trans-2-hexene or 2-methyl-2-pentene Answer: To both (b) and (c), we could use heats of hydrogenation to analysis their relative stability, to (a) and (d), we need to use heats of combustion to analysis their relative stabilisty. 7.5 List the alkenes that would be formed when each of the following alkyl halides is subjected to dehydrohalogenation with potassium ethoxide and use Zaitsevs rule to predict the major product of each reaction: (a) 2-bromo-3-methylbutane and (b) 2-bromo-2,3-dimethylbutane. Answer: (a) 2-bromo-3-methylbutane
Br

KOCH2CH3 CH3CH2OH

major

minor

(b) 2-bromo-2,3-dimethylbutane.
Br

KOCH2CH3 CH3CH2 OH
major

minor

7.6 Consider a simple molecule such as ethyl bromide and show with Newman projection formulas how the anti periplanar state would be favored over the syn periplanar one. Answer

BH H

H H H Br

Anti periplanar transition state is staggered, therefore, its lower energy.

B-

Br H H H H

Syn periplanar transition state is eclipsed, therefore, it has higher energy. So, the anti periplanar state would be favored over the syn periplanar one. 7.7 When cis-1-bromo-4-tert-butylcyclohexane is treated with sodium ethoxide in ethanol, it reacts rapidly; the product is 4-tert-butylcyclohexene, under the same condition, transbromo-4-tert-butylcyclohexane reacts very slowly. Write conformational structures and explain the difference in reactivity of these cis-trans isomers. Answer:
Br

EtONa / EtOH

EtOH Br

EtO-

Br

7.8 (a) When cis-1-bromo-2-methylcyclohexane undergoes an E2 reaction, two products (cycloalkenes) are formed. What are these two cycloalkenes, and which would you expect to be the major product? Write conformational structures showing how each is formed. (b) When trans-1-bromo-2methylcyclohexane reacts in an E2 reaction, only one cycloalkene is formed. What is this product? Write conformational structures showing why it is the only product. Answer: (a)
Br

+
CH3

CH3

is the major product.

Br

(b)

To
H H H Br

CH3
Br H H H H H CH3
CH3

H3C

CH3

Therefore, stereoselective.

should be the only product, because the reaction is

7.9 Dehydration of 2-propanol occurs in 75% H2SO4 at 100oC. (a) Using curved arrows write all steps in a mechanism for the dehydration. (b) Explain the essential role performed in alcohol dehydrations by the acid catalyst. (Hint: Consider what would have happen if no acid were present.) Answer: (a) Step1

CH3 H3C C H O H

CH3 H3C C H

H O H

O H

O H

Step 2
CH3 H3C C H H O H H3C CH3 CH H

Step 3
H H C CH H3C H H CH2 H H3C CH H

(b) In step1, an acid-base reaction, a proton is rapidly transferred from the acid to one of the unshared electron pairs of the alcohol. So step1 will not be occurred without a strong acid; and so do the following steps. 7.10 Acid-catalyzed dehydration of neopentyl alcohol, (CH3 )3CCH2 OH , yields 2-methyl-2butene as the major product. Outline a mechanism showing all steps in its formation. Answer: Step 1

CH3

H CH2 O

CH3

H3C

C CH3

+ H
H

O+ H

H 3C

C CH3

CH2 OH2

H2 O

Step 2
CH3

CH3 CH2 OH2

H 3C

C CH3

H3 C

C CH3

CH2 +

H2 O

Step 3

CH3

H3 C CH2

H3 C

C CH3

H 3C

CH2

CH3

+ H 3C
C CH3 CH2

CH3

Step 4

A(a) + H
CH2 C

(b)
H CH

(a)

CH2

C CH3

H2 C

CH3

minor product

(b)
CH3 CH3

CH3

C CH3

C H

CH3

major product

7.11 Acid-catalyzed dehydration of either 2-methyl-1-butanol or 3-methyl-1-butanol gives 2-methyl-2-butene as the major product. Write plausible mechanisms that explain these results. Because the stability of carbocations is tertiary>secondary>primary, the mechanisms of the results can be explain in the following way:

OH

OH2

OH

OH2

7.12 When the compound called isoborneol is heated with 50% sulfuric acid, the product of the reaction is the compound called camphene and not bornylene as one might expect. Using models to assist you, write a step-by-step mechanism showing how camphene is formed. Solution: Mechanism:

OH

H3O+ heat

7.13 Outline all steps in a synthesis of propyne from each of the following: (c) CH3CHBrCH2Br (a) CH3COCH3 (d) CH3CH=CH2 (b) CH3CH2CHBr2 Answer: (a)
O Cl

PCl5
Cl

NaNH2 mineral oil heat H+

(b)
Br

NaNH2
Br

Br

NaNH2

(c)
Br Br Br Br

NaNH2

NaNH2

(d)
Br Br

Br2

Br

NaNH2
Br

NaNH2

7.14 Predict the products of the following acid-base reactions. If the equilibrium would not result in the formation of appreciable amounts products, you should so indicate. In each case label the stronger acid, the stronger base, the weaker acid, and the weaker base. (a) CH3CH=CH2 + NaNH2 (b) CH3CCH + NaNH2 (c) CH3CH2CH3 + NaNH2 (d) CH3CC:- + CH3CH2OH (e) CH3CC:- + NH4Cl Answer: (a) CH3CH=CH2 (Weaker acid) + NaNH2 (Weaker base) CH3CH=CH:- (Stronger base) + Na+ + NH3 (Stronger acid) (no appreciable amounts products) (b) CH3CCH (Stronger acid) + NaNH2 (Stronger base) CH3CC:- (Weaker base) + Na+ + NH3 (Weaker acid) (c) CH3CH2CH3 (Weaker acid) + NaNH2 (Weaker base) CH3CH2CH2:- (Stronger base) + Na+ + NH3 (Stronger acid) (no appreciable amounts products) (d) CH3CC:- (Stronger base) + CH3CH2OH (Stronger acid) CH3CCH (Weaker acid) + CH3CH2O:- (Weaker base) (e) CH3CC:- (Weaker base) + NH4Cl (Weaker acid) CH3CCH (Stronger acid)+ NH2:(Stronger base) + HCl (no appreciable amounts products)

7.15 Your goal is to synthesize 4,4-dimethyl-2-pentyne. You have a choice of beginning with any of the following reagents.
CH3 CH3 Br

H3C

CH

H3C

C CH3

H3C

C CH3

CH

H3C

Assume that you also have available sodium amide and liquid ammonia. Outline the best synthesis of the required compound. Answer: The best way is that:
CH3 CH3 C CH

H 3C

C CH3

+ N aN H 2

liq.NH 3

H3C

C CH3

C : -- N a +

+ NH 3

Then:
CH3 CH3 C C:--Na+

H3C

C CH3

+ H3C

nucleophilic substitution SN2 H3C

C CH3 C C CH3

+ NaI

There is another way to synthesize 4,4-dimethyl-2pentyne,

H3C

CH

+ NaNH2

liq.NH3

H3C

C:--Na+

+ NH3

CH3

CH3

H3C

C:--Na+

+ H3 C

nucleophilic
C CH3 Br

substitution

H3C

C CH3

CH3

+ NaBr

But this synthesis fails when the alkynide ion acts as a base rather than as a nucelophile, and the major result is an E2 elimination. The products of the elimination are alkene and the alkyne from which the sodium alkynide was originally formed.
CH3 CH3 Br

H3C

C:--

+ H3 C

C CH3

E2

H3C

CH

+ H2C

CH3

+ Br--

7.16 What is the index of hydrogen deficiency of 2-hexene? (a) Of methylcyclopentane? (b) Does the index of hydrogen deficiency reveal anything about the location of the double bond in the chain? (c) About the size of the ring? (d) What is the index of hydrogen deficiency of 2-hexyne? (e) In general terms, what structural possibilities exist for a compound with the molecular formula C10H16?

Answers: (a) 1 (b) 1 (c) No, it doesnt. (d) No, either. (e) 2 (f) The index of hydrogen deficiency of C10H16 equals 3. So there must be six structural possibilities for a compound. (1) It has three double bonds. (2) It has one triple bond and one double bond. (3) It has two double bonds and a ring. (4) It has one triple bond and a ring. (5) It has one double bond and two rings. (6) It has three rings. (Perhaps this possibility cannot exist very stably, but I think we can consider it as well.)

7.17 Zingiberene, a fragrant compound isolated from ginger, has the molecular formula C15H24 and is known not to contain any triple bonds. (a) What is the index of hydrogen deficiency of zingiberene? (b) When zingiberene is subject to catalytic hydrogenation using an excess of hydrogen, 1 mol zingiberene absorbs 3 mol of hydrogen and produce a compound with the formula C15H30. How many double bonds does a molecule of zingiberene have? (c) How many rings? Answer: (a) Index of hydrogen deficiency = 4 (b) It has 3 double bonds. (c) It has 1 ring. 7.18 Each of the following names is incorrect. Give the correct name and explain your reasoning. (a) trans-3-Pentene (d) 4-Methylcyclobutene (b) 1,1-Dimethylethene (e) (Z)-3-Chloro-2-butene (c) 2-Methylcyclohexene (f) 5,6-Dichlorocyclohexene Answer: (a) thans-2-pentene Because IUPAC rules that number the main chain beginning with the end of the chain nearer the double bond when alkenes are named. (b) 2-Methyl-1-propene Because IUPAC rules that locate the longest continuous chain of carbon atoms when alkenes are named (c) 1-Methylcyclohexene Because IUPAC rules that number the longest chain beginning with the end of the chain nearer the substituent when alkenes are named (d) 3-Methylcyclobutene Because IUPAC rules that number the longest chain beginning with the end of the chain nearer the substituent when alkenes are named (e) (Z)-2-chloro-2-butene Because IUPAC rules that number the longest chain beginning with the end of the chain nearer the substituent when alkenes are named (f) 1,2-Dichlorocyclohexene Because IUPAC rules that number the longest chain beginning with the end of the chain nearer the substituent when alkenes are named 7.19 Write a structural formula for each of the following: (a) 3-Methylcyclobutene (g) (Z,4R)-4-Methyl-2-hexene (b) 1-Methylcyclopentene (h) (E,4S)-4-Chloro-2-pentene

(c) 2,3-Dimethyl-2-pentene (d) (Z)-3-Hexene (e) (E)-2-Pentene (f) 3,3,3-Tribromopropene Answer: (a)

(i) (Z)-1-Cyclopropyl-1-pentene (j) 5-Cyclobutyl-1-pentene (k) (R)-4-Chloro-2-pentyne (l) (E)-4-Methyl-4-hexen-1-yne

(g)

3-Methylcyclobutene
(b)

(Z,4R)-4-Methyl-2-hexene
(h)

Cl

1-Methylcyclopentene
(c)

(E,4S)-4-Chloro-2-pentene
(i)

2,3-Dimethyl-2-pentene
(d)

(Z)-1-Cyclopropyl-1-pentene
(j)

(Z)-3-Hexene
(e) (k)

5-Cyclobutyl-1-pentene

Cl

(E)-2-Pentene
(f)
Br

(R)-4-Chloro-2-pentyne
(l)

Br Br

3,3,3-Tribromopropene

(E)-4-Methyl-4-hexen-1-yne

7.20 Write three-dimensional formulas for and give names using (R-S) and (E)-(Z) designations for the isomers of: (a) 4-Bromo-2-hexene (b) 3-Chloro-1, 4-hexadiene (c) 2, 4-Dichloro-2-pentene (d) 2-Bromo-4-chloro-2-hexen-5-yne Answer:
Br

(a) 4-Bromo-2-hexene 4-Bromo-2-hexene

Cl

(S) - 4-Bromo-2-hexene (Z) -

(b) 3-Chloro-1, 4-hexadiene 4-hexadiene (Z) 4-hexadiene

Cl Cl

(R) -3-Chloro-1, 3-Chloro-1,

(c) 2, 4-Dichloro-2-pentene 4-Dichloro-2-pentene (E) 4-Dichloro-2-pentene

Cl Br

(S) - 2, 2,

(d)

2-Bromo-4-chloro-2-hexen-5-yne (E)

(R)

2-Bromo-4-chloro-2-hexen-5-yne -2-Bromo-4-chloro-2-hexen-5-yne
7.21 Give the IUPAC names for each of the following:

(a)

(c)

(e)

Cl

(b)

Cl

(d)

(f)

Answer: (a) 3,5-Dimethyl-2-hexene (b) 4-Chloro-3-methyl-cyclopentene (c) 6-Methyl-3-heptyne (d) 1-sec-Butyl-2-methyl-cyclohexene (e) R-3-chloro-hept-4-en-1yne (f) 6-Methylene-undecane

7.22 Outline a synthesis of propene from each of the following a Propyl chloride b Isopropyl chloride c Propyl alcohol d Isopropyl alcohol e 12-Dibromopropane f Propyne Answer a
Base Cl (-HCl) heat

b
Cl C2H5O Na heat

C2H5OH

or
Cl Base (-HCl) heat

c
OH H+, heat (-HOH)

d
OH H+, heat (-HOH)

e 1
Br

Zn, CH3COOH (-ZnBr2) Br

2
Br

+2NaI Br

acetone +I2+2NaBr

f
H2,Pd/CaCO3 (Lindlar's catalyst) quinoline (syn addition)

7.23 Outline a synthesis of cyclopentene from each of the following: (a) Bromocyclopentane (b) 1,2-Dichlorocyclopentane (c) Cyclopentanol Answer: (a)
Br

(b)
Cl Cl

(c)
OH

7.24 Starting with ethyne, outline syntheses of each of the following. You may use any other needed reagents, and you need not show the synthesis of compounds prepared in earlier parts of this problem. (a) Propyne (b) 1-Butyne (c) 2-Butyne (d) cis-2-Butyne (e) trans-2-Butyne (f) 1-Pretyne (g) 2-Hexyne (h) (Z)-2-Hexene (i) (E)-2-Hexene (j) 3-Hexyne CD (k) H3CH2CC

H3C D CH3
(l)
ANSWER: (a)

+ Cl2
Cl
(b)

Cl

HCl

CH3MgCl

Cl

CH3CH2MgCl

(c)

+ 2Cl2

Cl

Cl + 2HCl

Cl
(d)
H3C

Cl + CH3MgCl

H 3C

CH 3

CH3

H2

Pd/BaSO4

H3C

CH3

(e)

CH3CH2MgCl

H3C

CH3

H2

Na/NH3

H3C

CH3

(f)
Cl

CH3CH2CH2MgCl

(g)

Cl2
Cl

Cl

+ CH CH CH MgCl 3 2 2

(h)

+
(i)

H2

Pd/BaSO4

H2

Na/NH3

(j)

+
(k)

CH3CH2MgCl

Na
Na

Na

D2 O

CD

(l)

Pd/BaSO4 D2

H3C

CH3

7.25 Starting with 1-methylcyclohexene and using any other needed reagents, outline a synthesis of the following deuterium-labeled compound.
D

CH3 D H

+ D2

Ni
D H

CH3

7.27 Outline a synthesis of phenylethyne from each of the following: (a) 1,1-Dibromo-1-phenylethane (b) 1,1-Dibromo-2-phenylethane (c) phenylethene (styrene) (d) Acetophenone (C6H5COCH3) Answer:
Br
(1) 3 NaNH2

C
heat

CH

C Br

CH3
mineral oil (2)H+

(a)

Br H2 C
(1) 3 NaNH2

C
heat

CH

CH Br
mineral oil (2)H+

(b) (c)
C H CH2
Br2 CCl 4

CH Br

CH2Br

(1) 3 NaNH 2 mineral oil (2) H + heat

CH

(d)
Cl O C CH3
PCl5 0 .C

C Cl

CH3

(1) 3 NaNH 2 mineral oil (2) H+ heat

CH

7.29 Match the following heats of combustion (3375 kJ mol-1, 3369 kJ mol-1, 3365 kJ mol-1, 3361 kJ mol-1, 3355 kJ mol-1) with the following alkenes: cis-2-pentene, trans-2-pentene, 2-methyl-2-butene, 1-pentene, 2 -methyi-1-butene. Answer: cis-2-pentenecombustion is 3369 kJ mol-1 trans-2-pentenecombustion is 3361 kJ mol-1 2-methyl-2-butenecombustion is 3355 kJ mol-1 1-pentenecombustion is 3375 kJ mol-1 2-methyl-1-butenecombustion is 3365 kJ mol-1 7.30 Without consulting tables, arrange the following compounds in order of decreasing acidity. Pentane 1-pentene 1-pentyne 1-pentanol Answer: pentane <1-pentene<1-pentyne<1-pentanol 7.31 Write structural formulas for all the products that would be obtained when each of the following alkyl halides is heated with sodium ethoxide in ethanol. When more than one product results you should indicate which would be the major product and which would be the minor product(s). You may neglect cis-trans isomerism of the products when answering this question. (a) 2-Bromo-3-methylbutane (b) 3-Bromo-2, 2-dimethylbutane (c) 3-Bromo-3-methylpentane (d) 1-Bromo-1-methylcyclohexane (e) Cis-1-Bromo-2-ethylcyclohexane (f) trans-1-Bromo-2-ethylcyclohexane Answer: (a) Structural formulas for all the products of (a).

1.

2.

3.

4.

OEt

EtO

The second structure is major product. The third and forth structure just very little. (b) Structural formulas for all the products of (b). 1. 2. 3.
OEt

OEt

The first structure is major product. (c) Structural formulas for all the products of (c). 1. 2.
OEt

The first structure is major product. (d) Structural formulas for all the products of (d). 1. 2.

3.

OEt

The first structure is major product. (e) Structural formulas for all the products of (e). 1. 2.

3.

4.

OEt

OEt

The first structure is major product. (f) Structural formulas for all the products of (f) 1. 2.

3.

4.
OEt

OEt

The second structure is major product. 7.32 Write structural formulas for all the products that would be obtained when each of the following alkyl halides is heated with potassium tert-butoxide in tert-butyl alcohol. When more than one product results you should indicate which would be the major product and which would be the minor product(s). You may neglect cis-trans isomerism of the products when answering this question. (a) 2-Bromo-3-methylbutane (b) 4-Bromo-2,2-dimethylbutane (c) 3-Bromo-3-methylpentane (d) 4-Bromo-2,2-dimethylpentane (e) 1-Bromo-1-methylcyclohexane Answer: According to the Hofmann rule, when potassium tert-butoxide reacts with alkyl halides as an E2 reaction, the products are mainly the less substituted alkenes rather than the more substituted alkene which is more stable. Therefore the solution to this problem is as follows: (a) Major product
H 2C C H H C CH3 CH3

3-methyl-1-butene

Minor product
H3C C H C CH3 CH3

2-methyl-2-butene

(b) Only one product

CH3 H2C C H C CH3 CH3

3, 3-dimethyl-1-butene

(c) Major product

3-Methylene-pentane Minor product

3-methyl-2-pentene (d) Major product

2, 2-dimethyl-4-pentene

Minor product

2, 2-dimethyl-3-pentene (e) Main product 1-methylene-cyclohexane Minor product 1-Methyl-cyclohexene 7.33 Starting with an appropriate alkyl halide and base, outline syntheses that would yield each of the following alkenes as the major (or only) product. (a) 1-Pentene (b) 3-Methyl-1-butene (c) 2,3-Dimethyl-1-butene (d) 4-Methylcyclohexene (e) 1-Methylcyclopentene

Answer:
C2H5ONa Cl 1-Chloro-pentane C2H5OH Pent-1-ene

C2H5ONa Cl 1-Chloro-3-methyl-butane C2H5OH 3-Methyl-but-1-ene

C2H5ONa Cl C2H5OH 2,3-Dimethyl-but-1-ene

1-Chloro-2,3-dimethyl-butane

CH3 CH3

C2H5ONa C2H5OH

Cl 1-Chloro-4-methylcyclohexane
CH3 Cl C2H5ONa C2H5OH 1-Chloro-1-methyl-cyclopentane

4-Methyl-cyclohexene

CH3

1-Methyl-cyclopentene

7.34 Arrange the following alcohols in order of their reactivity toward acid-catalyzed dehydration (with the most reactive first): 1-pentanol 2-methyl-2-butanol 3-methyl-2-butanol

Answer: 2-methyl-2-butanol 3-methyl-2-butanol 1-pentanol Because the ease with which alcohols undergo dehydration is in the following order: (R)3COH(R)2CHOHRCH2OH

7.35 Give the products that would be formed when each of the following alcohols is subjected to acid-catalyzed dehydration. If more than one product would be formed, designate the alkene that would be the major product. (Neglect cis-trans isomerism). (a) 2-Methyl-2-propanol (b) 3-Methyl-2-butanol (c) 3-Methyl-3-pentanol (d) 2,2-Dimethyl-1-propanol (e) 1,4-Dimethylcyclohexanol
(a) OH H+ OH2 H

2-Methyl-2-propanol OH (b)

H+

OH2

1,2-H shift

3-Methyl-2-butanol H

more stable

(c)

OH

H+

3-Methyl-3-pentanol H+ Methyl group transfer rearrangement 2,2-Dimethyl-1-propanol OH H+ H more stable H

(d)

OH

(e) OH

1,4-Dimethylcyclohexanol

7.36 1- Bromobicicyclo [221]heptane does not undergo elimination (below) when heated with base. Explain this failure to react.(construction of models may help.)

Br

don't (heat base)

6 6 P P 90

7.37 When the deuterium-labeled compound shown below is subjected to dehydrohalogenation using sodium ethoxide in ethanol, the only alkene product in 3-methyl-cyclihexene. Provide an explanation for the result. Answer:
Br H H H CH3 D
-

CH3

OEt

7.39 Cholesterol is an important steroid found in nearly all body tissues; it is also the major component of gallstones. Impure cholesterol can be obtained from gallstones by extracting them with an organic solvent. The crude cholesterol thus obtained can be purified by (a ) treatment with Br2 in CCl4 (b ) careful crystallization of the product, and (c) treatment of the latter with zinc in ethanol .What reactions are involved in this procedure?
H3 C CH3 CH H2 C C H2 H2 C CH CH3 CH3 CH3

HO

Cholesterol

(a ) addition reaction

H3C CH CH3

H2 C C H2

H2 C CH

CH3

H3C CH3 CH

H2 C C H2

H2 C CH CH3

CH3

CH3 CH3

Br2 CCl4

CH3

HO

HO Br Br

( c) debromination reaction
H3C CH CH3 H2 C C H2 H2 C CH CH3 CH3 CH3 CH3 CH3 H2 C CH C H2 H2 C CH CH3

H3C

CH3

Zn, EtOH

HO Br Br

HO

7.40 Caryophyllene, a compound found in oil of cloves, has the molecular formula C15H24 and has no triple bonds. Reaction of caryophyllene with an excess of hydrogen in the presence of a platinum catalyst produces a compound with the formula C15H28. How many (a) double bonds, and (b) rings does a molecule of caryophyllene have? Answer: The index of hydrogen deficiency of C15H24 are 4, and the index of hydrogen deficiency of C15H28 is 2. The index of hydrogen deficiency of a double bond is 1, which is the same as that of a ring. The ring will not be destroyed by the addition of hydrogen with platinum acting as catalyst. So there should be two double bonds and two rings in the molecule of caryophyllene. 7.41 Squalene, an important intermediate in the biosynthesis of steroids, has the molecular formula C30H50 and has no triple bonds. (a) What is the index of hydrogen deficiency of squalene? (b) Squalene undergoes catalytic hydrogenation to yield a compound with the molecular formula C30H62. How many double bonds does a molecule of squalene have? How many rings? Answer: (a) 2*30+2=62 62-50=12 12/2=6, so the index of hydrogen deficiency of the molecular are 6. (b) The ring will not be destroyed by adding hydrogen. And the index of hydrogen deficiency of C30H62 is 0. So there is no ring in the molecular. The index of hydrogen

deficiency of a double bond is 1. So there are 6 double bonds. 7.42 Consider the interconversion of cis-2-butene and trans-2-butene. (a) What is the value of Ho for the reaction, cis-2-butene trans-2-butene? (b) Assume Ho Go. What minimum value of G+ would you expect for this reaction? (c) Sketch a free-energy diagram for the reaction and label Go and G+. Answer: (a) 5 KJ / mol. (b) 284 KJ / mol

284kj/mol

H3C C H C

CH3

5kj/mol

H3C C H C

(c)

CH3

7.44 Compound I and J both have the molecular formula C7H14. Compounds I and J are both optically active and both rotate plane-polarized light in the same direction. On catalytic hydrogenation I and J yield the same compound K (C7H16). Compound K is optically active. Propose possible structures for I, J, and K.
1
C2H5 I H3C H C H C H CH3 I H3C C2H5

2
H H2 C C H CH2

C2H5 J H3C H H2 C C H CH2 J H3C

H H2 C C2H5 C H CH2

C2H5 K H3C H H2 C H2 C CH3 K H3C

H H2 C C2H5 H2 C CH3

7.45

Compounds Land M both have the molecular formula C7H14. Compounds L and M are

optically inactive , are nonresolvable, and are diastereomers of each other . Catalytic hydrogenation of either L or M yields N. Compound N is optically inactive but can be resolved into separate enantiomers . Propose possible structures for L ,M, and N.

The answer: The possible structures for L, M

H C C2H5 C

C2H5

C2H5 C C

C2H5

CH3

CH3

The possible structure for N:

C 2 H5 H C H C

C2H5 CH3

H H

C2H5 H C C CH3

7.46

(a)

Partial

H dehydrohalogenation

C2H5 of either

(1R,2R)-1,2-dibromo-1,2-diphenylethane

or

(1S,2S)-1,2-dibromo-1,2-diphenylethane enantiomers (or a race mate of the two) produces (Z)-1-bromo-1,2-diphenylethene as the product, whereas (b) partial (1R,2S)-1,2-dibromo-1,2-diphenylethane (the meso dehydrohalogenation of gives only compound)

(E)-1-bromo-1,2-diphenylethene. (c) Treating (1R,2S)-1,2-dibromo-1,2-diphenylethane with sodium iodide in acetone produces only (E)-1,2-diphenylethe. Explain these results. Answer: (a)

B
H H
1R

H
2R

1R

Br

Br Br

(1R,2R)-1,2-dibromo-1,2-diphenylethane

H
(Z)-1-bromo-1,2-diphenylethene

Br

-1

B
H
1S

H H
2S 1S

Br

Br Br

(1S,2S)-1,2-dibromo-1,2-diphenylethane

Br
(Z)-1-bromo-1,2-diphenylethene

(b)

B
H
1R

H
2S

1R

Br

Br Br

(1R,2S)-1,2-dibromo-1,2-diphenylethane

(E)-1-bromo-1,2-diphenylethene

Br

(c)
-

Br
1R

H
2S

H
acetone

Br

(1R,2S)-1,2-dibromo-1,2-diphenylethane

(E)-1,2-diphenylethe

Problem 7.48 Predict the structures of compounds A, B, and C: A is an unbranched C6 alkyne that is also a primary alcohol. B is obtained from A by use of hydrogen and nickel boride catalyst or dissolving metal reduction. C is formed from B on treatment with aqueous acid at room temperature. This compound C has no infrared absorption in either the 1620 to 1680 cm-1 or the 3590 to 3650 cm-1 region. It has an index of hydrogen deficiency of one and has one stereocenter but forms as the race mate. Answer: A: B:

H 3C

H2 C

H2 C

H2 C

OH

H3C
CH2 H2C C H C H

OH CH2

C:

H 3C

H2 C

H2 C

H2 C

H C O

CH2

7.49 what is the index of hydrogen deficiency for: (a) C7H10O2 (b) C5H4N4 Answer: (a) the index is 3 (b) the index is 6 13.24 which diene and dienophile would you employ in a synthesis of each of the following?

O CH3 CH H C O

(a)

(d)
O C H O O CN C O CH3

(b)
C O O CH3

(e)

(c)
C O CH3

(f)

C O

CH3 C O OCH3

answer : (a)
O CH

and

(b) (c)

O COCH3

and

COCH3

(c)

O C O CH3

and

H3C

C O

(d)

O C

and
O C O

(e)

CN

and

(f)

and
COCH3 O