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4.

1 Write condensed structural formulas for all of the constitutional isomers with the molecular formula
C7H16 (There is a total of nine constitutional isomers).

Answer:

Heptane
2-methylhexane 3-methylhexane

2,2-dimethylpentane 2,3-dimethylpentane 2,4-dimethylpentane

2,2,3-trimethylbutane 3,3-dimethylpentane 3-ethylpentane

4.2 (a) In addition to the 2,2-dimethylpropyl (or neopentyl) group just given, there are seven other
five-carbon groups. Write their structures and give each structure its systematic name. (b) Provide
IUPAC names for the nine C7H16 isomers that you gave as answers to problem 4.1.

Answer:
CH3 H2 H2
H2 H2 H2 C C
C C CH C H3C CH
H3C C C H3C C
H2 H2 H2
CH3

Pentyl 3'-methylbutyl 2'-methylbutyl

CH3
CH3 CH3
H2
H2 CH C
C CH H3C CH H3C C
H3C C
H2
CH3 CH3

1'-methylbutyl 1',2'-dimethylpropyl 1',1'-dimethylpropyl

CH3
H2C

H3C CH
C
H2

1'-ethylpropyl
4.3 Give IUPAC substitutive names for all of the isomers of (a) C4H9Cl and (b) C5H11Br
Answer:
Cl
(a) Cl
Cl
Cl

1-Chlorobutane
2-Chlorobutane 1-Chloro-2-methylpropane 2-Chloro-2-methylpropane

Br
(b) Br

Br

1-Bromopentane 2-Bromopentane 3-Bromopentane

Br Br

Br
1-Bromo-3-methylbutane 1-Bromo-2-methylbutane 2-Bromo-2-methylbutane

Br

Br
2-Bromo-3-methylbutane 1-Bromo-2,2-dimethylpropane

4.4 Give IUPAC substitutive name for all of the isomeric alcohols with the formulas
(a) C4H10O and (b) C5H12O.

Answer:
(a) CH3CH2CH2CH2OH 1-Butanol
H2
H3C C CH CH3

OH 2-Butanol

CH3
H2
H 3C C C OH
H 2-methyl-1-propanol

CH3

H 3C C CH3

OH 2-methyl-2-propanol
(b) CH3CH2CH2CH2CH2OH 1-pentanol
H2 H2 H
H 3C C C C CH3

OH 2- pentanol

H2 H H2
H 3C C C C CH3

OH 3- pentanol

CH 3
H2 H2
H 3C C C C OH
H 2-methyl-1-butanol
CH 3
H2
H 3C C C CH 3

OH 2-methyl-2-butanol
CH 3

H
H 3C C C CH 3
H

OH 3-methyl-2-butanol
CH 3
H2
H 2C C C CH 3
H

OH 3-methyl-1-butanol
CH 3

H3C C CH 3

CH 2

OH 2,2-dimethyl-1-propanol

4.5 Give names for the following substituted alkanes :


Cl

CH3

(d)
(a)
(H3C)3C

CH(CH3 )2
CH3

Cl
(H3C)2HCH2C
OH
(b) (e)

H3C

OH

(c) H3C(H2C)2H2C (f)

C(CH3)3

Answer:

(a) 1-t-butyl-2-isopropylcyclopentane
(b) 1-isobutyl-2-methylcyclohexane
(c) butylcyclohexane
(d) 1-chloro-2,4-dimethylcyclohexane
(e) 2-chlorocyclopentanol
(f) 3-t-butylcyclohexanol

4.6 Give names for each of the following bicyclic alkanes:

Cl
(a) (b) (c)

Cl

(d) (e)

(f) Write the structure of a bicyclic compound that is an isomer of bicycl0[2,2,0]hexane and give its
names.

Answer:
(a) 2-Chlorobicyclo[1,1,0]butane
(b) Bicyclo[3,2,1]octane
(c) Bicyclo[2,1,1]hexane
(d) 2-Methylbicyclo[2,2,2]octane]
(e)

Bicyclo[3,1,0]hexane bicyclo[2,1,1]hexane

4.7 Give IUPAC names for the following alkenes:

(a) (b) (c)

OH OH

(d) (e) (f)

Cl

Answer:
(a) trans-3-Heptene
(b) 2,5-Dimethyl-2-octene
(c) 4-Ethyl-2-methyl-1-hexene
(d) 3,5-Dimethylcyclohexene
(e) 4-Methyl-4-pentene-2-ol
(f) 2-Chloro-3-methyl-3-cyclohexen-1-ol

4.8 Write structure formula for the following:


(a) cis-3-octene

(b) trans-2-hexene

(c) 2,4-dimethyl-2-pentene

(d) trans-1-chloro-2-butane

Cl
(e) 4,5-dibromo-1-pentene
Br

Br

(f) 1,3-dimethylcyclohexene

(g) 3,4-dimethylcyclopentene

(h) Vinylcyclopentane

(i) 1,2-dichlorocyclohextene
Cl

Cl

(j) trans-1,4-dichloro-2-pentene

Cl

Cl

4.9 Give the structures and IUPAC names for all the alkynes with the formula C6H10.
Answer:
(1) 1-hexyne

(2) 2-hexyne

(3) 3-hexyne

(4) 3-methyl-1-pentyne
(5) 4-methyl-1-pentyne

(6) 4-methyl-2-pentyne

(7) 3,3-dimethyl-1-butyne

4.10 Sketch a curve similar to that in Fig. 4.8 showing in general terms the energy changes that arise
from rotation the C2-C3 bond of 2-methylbutane. You need not concern yourself with the actural
numerical values of the energy changes, but you should label all maxima and minima with the
appropriate conformations.

H3C H3C
CH3 H CH3 H
H CH3
H
CH3 H
H3C H H H
CH3

H3C H

CH3 CH3 CH3


H CH3 H
H3C H CH3 H3C H
CH3 H CH3 H
H H H
H CH3 H3C CH3
H H

0o 60 o 120 o 180 o 240 o 300 o 360 o

4.11 Show by a calculation (using the formular △G=-2.303 RT Log keq)that a free-energy difference
of 7.6 kJ/mol between the axial and equatorial forms of methyl-cyclohexane at 25 ℃ does
correlate with an equilibrium mixture in which the concentration of he equatorial form is
approximately 95%.
Answer:

CH3 (axial)
5 6 5
1 6 1
CH3
4 3 2 4 3 2 (equatorial)

∆G°=-2.303 RT log Keq


Log Keq= 7600 / -2.303 RT = 7.6 / - 2.303*8.314*298 k ≈ 1.32
Keq = 21.38
Let e = amount of equatorial form
a = amount of axial form
% e = 21.38a / (a+21.38a) * 100% = 95.5 %

4.12 Write structures for the cis and trans isomers of (a) 1,2-dichlorocyclopropane and (b)
1,3-dibromocyclobutane.
Answer:

Cl Cl Cl H H H H Br
H H H H
H H
H Br H H

H H H Cl
Br H Br H
H H

4.13 (a) Write structural formulas for the two chair conformations of
cis-1-isopropyl-4-methylcyclohexane. (b) Are these two conformations equivalent? (c) If not,
which would be more stable? (d) Which would be the preferred conformation at equilibrium?
Answer:
(a).
H3CCHCH3 H

H (H3C)2CH
CH3
H

H CH3

(b) They are not equivalent.


(c) The second conformation in which the isopropyl group is in an equatorial position, would be more
stable.
(d) The second one which has an isopropyl in the equatorial position would be the preferred
conformation at equilibrium.

4.14 (a) Write the two conformations of cis-1,2-dimethylcyclohexane. (b) Would these two
conformations have equal potential energy? (c) What about the two conformations of
cis-1-tert-butyl-2-methylcyclohexane? (d) Would these two conformations of
trans-1,2-dimethylcyclohexane have the same potential energy?
Answer: (a)
CH3
CH3

H3C
H
H3C
H
H
H
(b) They have equal potential energy.
(c)
CH3
H3C CH3

H3C CH3 C
H3C
C
H
H3C H H3C

H
H
(d) The two conformations of trans-1,2-dimethylcyclohexane don’t have the same potential
energy. The following one have lower potential energy.
H3C CH3
H3C
C

H3C H
H

4.15 Show the reactions involved for hydrogenation of all the alkenes and alkynes that would yield
2-methyl butane.

Answer:
CH2=C(CH3)CH2CH3 + H2 CH3CH(CH3)CH2CH3

CH3C(CH3)=CHCH3 + H2 CH3CH(CH3)CH2CH3

CH3 CH(CH3)CH=CH2 + H2 CH3CH(CH3)CH2CH3

CH2 =C(CH3)CHCH2 + H2 CH3CH(CH3)CH2CH3

CH2CH(CH3 )C=CH + H2 CH3CH(CH3)CH2CH3

4.16 Your goal is the synthesis of 2,3-dimethylbutane by treating an alkyl halide with zinc and aqueous
acid. Show two methods (beginning with different alkyl halides) for doing this.
Answer:
Zn / H3+O
Br

Zn / H3+O

Br

4.17 Referring to the retrosynthetic analysis for 2-methylhexane in this section, write reactions for
those synthesis routes that are feasible.

Answers: (1) (CH3)2CHCH2C CH + NaNH2 (CH3)2CHCH2C C Na + NH3 ;

(CH3)2CHCH2C C Na + CH3Br (CH3)2CHCH2C CCH3 + NaBr ;

(CH3)2CHCH2C CCH3 + 2 H2 Pt
(CH3)2CHCH2CH2CH2CH3 .
pressure

(2) HC CH + NaNH2 HC C Na + NH3 ;

HC C Na + BrCH2CH2CH(CH3)2 HC CCH2CH2CH(CH3)2 + NaBr ;

HC CCH2CH2CH(CH3)2 + 2 H2 Pt
pressure CH3CH2CH2CH2CH(CH3)2 .

(3) (CH3)2CHC CH + NaNH2 (CH3)2CHC C Na + NH3 ;

(CH3)2CHC C Na + CH3CH2Br (CH3)2CHC CCH2CH3 + NaBr ;

(CH3)2CHC CCH2CH3 + 2H2 Pt


(CH3)2CHCH2CH2CH2CH3 .
pressure

4.18 (a) Devise retrosynthetic schemes for all conceivable alkynide anion alkylation syntheses of the
insect pheromones undecane and 2-methylheptadecane (Section 4.16). (b) Write reactions for two
feasible syntheses of each pheromone.
Answer:
(a)
NaNH2 BrCH2(CH2)7CH3 H2
HC CH HC CNa HC C(CH2)8CH3 CH3(CH2)9CH3
(-NH3) (-NaBr) Ni

NaNH2 BrCH2(CH2)6CH3 H2
CH3C CH (-NH ) CH3C Na CH3C C(CH2)7CH3 CH3(CH2)9CH3
3 (-NaBr) Ni

NaNH2 BrCH2(CH2)12CH(CH3)2 H2
HC CH HC CNa HC C(CH2)13CH(CH3)2
(-NH3) (-NaBr) Ni

CH3(CH2)14CH(CH3)2

NaNH2 BrCH2(CH2)11CH(CH3)2
CH3C CH (-NH ) CH3C Na CH3C C(CH2)12CH(CH3)2
3 (-NaBr)

H2
CH3(CH2)14CH(CH3)2
Ni

4.19 Write a structural formula for each of the following compounds:


(a) 1,4-Dichloropentane (i) 4-Methyl-2-pentanol
OH
CH3CHClCH2CH2CH2Cl

(b) sec-Butyl bromide

CH3CHBrCH2CH3
(j) trans-4-Isobutylcyclohexanol
H
(c) 4-Isopropylpentane H H2 C C CH3

CH3
HO H

(k) 1,4-Dicyclopropylhexane
(d) 2,2,3-Trimenthylpentane

(e) 3-Ethyl-2-methylhexane (l) Neopntyl alcohol

OH
(f) 1,1-Dichlorocyclopentane (m) Bicyclo[2.2.2]octane

Cl

Cl

(g) cis-1,2-Dimethylcyclopropane (n) Bicyclo[3.1.1]heptane


H H
C C

H3C C CH3
H2

(h) trans-1,2-Dimethylcyclopropane (o) Cyclopentylcyclopentane

H3 C H

C C

H C CH3
H2

4.20 Give systematic IUPAC names for the each of the following:

Answer:
(a)
CH3CH2C(CH3)2CH(CH2CH3)CH3
3,3,4-trimethylhexane
(b)
CH3CH2C(CH3)2CH2OH
2-2-dimethy-1-buanol
(c)

3,5,7-trimethylnonane
(d)

OH
3-methyl-4-heptanol
(e)

Br

2-bromobicyclo[3.3.1]nonane

(f)
Br

Br

2-5-dibromo-4-ethyloctane

(g)

1-Cyclobutylcyclopentane

(h)
Cl

7-chlorobicvclo[2.2.1]heptane

4.21 The name sec-butyl alcohol defines a specific structure but the name sec-pentyl alcohol is
ambiguous. Explain.
Answer:
The sec-butyl alcohol has only one structure:
H3C CH2 CH CH3

OH
But the sec-pentyl alcohol may has two structures:
CH3

H3C CH2 CH2 CH CH3 CH3 CH CH CH3

OH OH
.
4.22 Write the structure and give the IUPAC systematic name of an alkane or cycloalkane with the
formula: (a) C8H18 that has only primary hydrogen atoms, (b) C6H12 that has only secondary hydrogen
atoms, (c) C6H14 that has only primary and secondary hydrogen atoms, and (d) C8H14 that has 12
secondary and 2 tertiary hydrogen atoms.

Answer:

a b cyclohexane
2,2,3,3-trimethylbutane

c 1,1-dimethylcyclobutane

Bicyclo[3.2.1]octane
Bicyclo[5.1.0]octane
Octahydro-pentalene

Bicyclo[4.1.1]octane
Bicyclo[2.2.2]octane Bicyclo[4.2.0]octane

4.23. Three different alkenes yield 2-methylbutane when they are hydrogenated in the presence of the
reactions involved

Answer:
CH3

H2
H2C C C CH3 H3C CH C CH2 H3C C C CH3
H H

CH3 CH3
4.24 An alkane with the formula C6H14 can be synthesized by treating (in separate reactions) five
different alkyl chlorides (C6H13Cl) with zinc and aqueous acid. Give the structure of the alkane and the
structures of the alkyl chlorides.
Answer:

4.25 An alkane with the formula C6H14 can be prepared by reduction (with Zn and HCl) of only two
alkyl chlorides (C6H13Cl) and by the hydrogenation of only two alkenes (C6H12). Write the structure of
this alkane, give its IUPAC name. And show the reactions.

2,3-dimethylbutane

Zn
HCl

CH2Cl

1-chloro-2,3-dimethylbutane 2,3-dimethylbutane

Zn
Cl HCl

2-chloro-2,3-dimethylbutane 2,3-dimethylbutane

H2

2,3-dimethyl-2-butene 2,3-dimethylbutane
H2

2,3-dimethyl-1-butene 2,3-dimethylbutane

4.26 Four different cycloalkenes will all yield methylcyclopentane when subjected to catalytic
hydrogenation. What are their structures? Show the reactions.

Answer:

CH3 CH3 CH3 CH2

Reactions:

Pt
CH3 CH3
H2

3-Methylcyclopentene 1-Methylcyclopentane

Pt
CH3 H2 CH3

4-methylcyclopentene 1-Methylcyclopentane
Pt
CH3 H2 CH3

1-Methylcyclopentene 1-Methylcyclopentane

Pt
CH2 H2 CH3

1-Methylenecyclopentene
1-Methylcyclopentane

4.27 The heats of combustion of three pentane (C5H12) isomers are CH3(CH2)3CH3, 3536 KJ mol-1;
CH3CH(CH3)CH2CH3, 3529 KJmol-1; and (CH3)3CCH3, 3515KJmol-1. Which isomers is most stable?
Construct a diagram such as that in Fig.4.9 showing the relative potential energies of the three
compounds.
Answer: (CH3)3CCH3 (neopentane) is the most stable one of the three.
CH3CH2CH2CH2CH3 +8O2
CH3

7KJmol-1
CH3CHCH2CH3 +8O2 CH3

CH3CCH3 +8O2
14KJmol-1
CH3
Δ H。

Δ H。= -3536KJmol-1

Δ H。 = -3529KJmol-1

Δ H。 = -3515KJmol-1

5CO2 +6H2O

4.28 Tell what is meant by homologous series and illustrate your answer by writing structures for a
homologous series of alkyl halides.
Answer: A series of compounds that each member differs from the next member by a constant units
(the taxis are based on the number of one atom that they all have, for example C atom). And their
molecule structures must be the same, all of them are linear or branched.
These alkyl halides are all homologs:

X
X X

4.29 Write the structures of two chair conformations of 1-tert-butyl-1-methylcyclohexane. Which


conformation is more stable? Explain your answer.

Answer:
CH3
H3C CH3 CH3
C CH3
CH3

CH3
CH3

The tert-butyl is much bigger than methyl. It provides larger 1,3-Diaxial interactions between the
two hydrogen atoms located 3,5-carbon atoms. Compared with the methyl in the equatorial
conformation of methylcyclohexane, less crowding occurs in the other conformation. The tert-butyl
group of axial methylcyclohexane does have a larger gauche interaction be it is anti more to C3 and C5.
The second conformation is more stable.

4.30 Ignoring compounds with double bonds, write the structural formulas and give names for all of the
isomers with the formula C5H10.

Answer:

CH3
CH3

CH3

methylcyclobutane 1,1-dimethylcyclopropane
cyclopentane

H H H CH3

CH3 H H

H CH3 H H

CH3 CH3
ethylcyclopropane
trans-1,2-Dimethyl-cyclopropane trans-1,2-Dimethyl-cyclopropane

4.31 Write structure for the following bicyclic alkanes.


(a) Bicyclo [1.1.0]butane

Solution:
(b) Bicyclo[2.1.0]pentane

Solution:
(c) 2-chloro-bicyclo[3.2.0]heptane
Cl

Solution:
(d) 7-methylbicyclo[2.2.1]heptane

Solution:

4.32 Use the S-A+1=N method (study tip, Section 4.15) to determine the number of rings in
cubane.
Answer: Because the cubane has twenty single bonds, so S=20.And there are sixteen atoms in the
ring system, so A=16.
N=S-A+1=20-16+1=5

4.33 Rank the following compounds (a) in order of increasing heat of combustion and (b) in order
of increasing stability.

Answer:
(a) the order of increasing heat combustion

(b) the order of increasing stability

4.34 Sketch curves similar to the one given in Fig.4.8 showing the energy changes that arise from
rotation about the C2-C3 bond of (a) 2,3-dimethybutane and (b) 2,2,3,3-tetramethybutane. You need
not concern yourself with actual numerical values of the energy changes, but you should label all
maxima and minima with the appropriate conformations.

Answer:

2,3-dimethybutane
H H
H3C H H3C H

CH3
CH3 H
H3C CH3
H3C CH3 H3C CH3
H3C
H H3C

H H H H
H3C CH3 H CH3 H3C H H3C CH3

H3C CH3 H3C CH3 H3C CH3 H3C CH3


H CH3 CH3 H

(b) 2,2,3,3-tetramethybutane
H3C CH3 H3C CH3 H3 C CH3

CH3 CH3 CH3


H3C CH3 H3C CH3 H3C CH3
H3C H3 C H3C

CH3 CH3 CH3


CH3
H3C CH3 H3C CH3 H3C CH3 H3C CH3

H3C CH3 H3C CH3 H3C CH3 H3C CH3


CH3 CH3 CH3 CH3

4.35 Without referring to tables, decide which member of each of the following pairs would have

the higher boiling point. Explain your answer .


(a) Pentane or 2-methylbutane

pentane 2-methylbutane
Because 2-methylbutane contains more branch chain than pentane so pentane has the higher boiling
point.
(b). Heptane or pentane

pentane heptane
Because heptane and pentane both have no branch chains and heptane has more carbon atoms, so
heptane has the higher boiling point.
(c). propane or 2-chloropropane

Cl
propane 2-chloropropane
At normal room temperature 2-chloropropane is liquid and propane is gaseous state so 2-chloropropane
has the higher boiling point.
(d). Butane or 1-propanol

OH
butane 1-propanol
At normal room temperature 1-propanol is liquid and butane is gaseous state so 2-chloropropane has
the higher boiling point.
(e). Butane or propan-2-one
O

butane acetone

At normal room temperature acetone is liquid and butane is gaseous state so acetone has the higher
boiling point.

4.36 One compound whose molecular formula is C4H6 is a bicyclic compound. Another compound
with the same formula has an infrared absorption at roughly 2250 cm-1 (the bicyclic compound
does not). Draw stuctures for each of these two compounds and explain how the IR absorption
allows them to be differentiated.

Answer:

and H
The IR stretch at ~2250 cm-1 for the terminal alkyne sp C-H bond distinguishes these two compounds.

4.37 Which compound would you expect to be the more stable: cis-1,2-dimethylcyclopronpane
or trans-1,2-dimethylcyclopropane ? Explain your answer.
Answer:
Trans-1,2-dimethylcyclopropane is the more stable .
The two methyl groups of trans-1,2-dimethylcyclopropane are farther away from each other than
those of cis-1,2-dimethylcyclopropane, therefore the two methyl groups of trans-1,2-dimethylcyclo-
propane has less repulsive interaction than those of cis-1,2-dimethylcyclopropane, so
trans-1,2-dimethylcyclopropane has lower potential energy and is the more stable .

4.38 Which member of each of the following pairs would you expect to have the larger heat of
combustion? (a) cis- or trans-1,2-dimethyclohexane, (b) cis- or trans-1,3-dimethylcyclohexane,
(c) cis- or trans-1,4-dimethylcyclohexane. Explain your answers.

Answer:
Those members have larger heat of combustion are:
(a) cis-1,2-dimethyclohexane
(b) trans-1,3-dimethylcyclohexane
(c) cis-1,4-dimethylcyclohexane

Explanation:
Table: Conformations of Dimethylcyclohexanes
Compound Cis Isomer Trans Isomer
1,2-Dimethyl- a,e or e,a e,e or a,a
1,3-Dimethyl- e,e or a,a a,e or e,a
1,4-Dimethyl- a,e or e,a e,e or a,a
Cyclohexanes with more methyl groups are equatorial have less ring strain and more stable. And also
have less heat of combustion. From the table above, we can see that cis-1,2-dimethyclohexane,
trans-1,3-dimethylcyclohexane and cis-1,4-dimethylcyclohexane have conformations of a,e or e,a
while trans-1,2-dimethyclohexane, cis-1,3-dimethylcyclohexane and trans-1,4-dimethylcyclohexane
have conformations of e,e or a,a (usually e,e take up more than 99%). So cis-1,2-dimethyclohexane,
trans-1,3-dimethylcyclohexane and cis-1,4-dimethylcyclohexane have more heat of combustion .

4.39 Write the two chair conformations of each of the following and in each part designate which
conformation would be the more stable. (a) cis-1-tert-butyl-3-methylcyclohexane, (b)
trans-1-tert-butyl-3-methylcyclohexane, (c) trans-1-tert-butyl-4-methylcyclohexane, (d)
cis-1-tert-butyl-4-methylcyclohexane

(a) cis-1-tert-butyl-3-methylcyclohexane
H
H
H
H
H3C

CH3 C(CH3)3 C(CH3)3 More stable

(b) trans-1-tert-butyl-3-methylcyclohexane
CH3
H
H3 C
H
H

H C(CH3) 3 C(CH3)3 More stable

(c) trans-1-tert-butyl-4-methylcyclohexane
C(CH3)3 H

H C(CH3)3
H
H3C

CH3 H More stable

(d) cis-1-tert-butyl-4-methylcyclohexane
C(CH3)3 CH3

H3C C(CH3)3
H
H

H H More stable

4.40 trans-1,3-Dibromocyclobutane has a measurable dipole moment. Explain how this proves that the
cyclobutane ring is not planar.

Answer:
If the cyclobutane ring were plNAR, THE c-Br bond moments would exactly cancel in the trns isomer.
The fact that trans-1,3-dibromocyclobutane has a dipole moment shows the ring is not planar.

Br H

H Br
H
H
H

4.41 Specify the missing compounds and/or reagents in each of the following syntheses
(more than one step may be necessary in some cases):
Answer:
Pt, Pd, or Ni solvent
(a) trans-5-Methyl-2-hexene 2-methylhexane
pressure

C Na

NaNH2
(b)
-NH3

CH2CH2CH2CH3

CH3CH2CH2CH2X

C: Na
(C) CH3CH2CH2Br

Pt, Pd, or Ni solvent

pressure

Zn, HBr
(d) 4-bromo-3,4-diethylheptane 3,4-diethylheptane

Pt, Pd, or Ni
(e) + H2
solvent pressure

Zn, HX
(f) (CH3)3CCH2X 2,2-dimethylpropane

4.42 When 1,2-dimethylcyclohexene (below) is allowed to react with hydrogen in the presence of a
platinum catalyst, the product of the reaction is a cycloalkane that has a melting point of -50°C and a
boiling point of 130°C (at 760 torr). (a) What is the structure of the product of this reaction? (b)
Consult an appropriate table and tell which stereoisomer it is. (c) What does this experiment suggest
about the mode of addition of hydrogen to the double bond?

CH3

CH 3

Answer:
(a)

CH3

CH 3

(b) From the table 4.8 we find that this is cis-1,2-dimethy;lcyclohexane.


(c) Since the catalytic hydrogenation produces the cis-isomer, both hydrogen atoms must
have added from the same side of the double bond.
H H
+ H2

CH3 CH3

4.43 When cyclohexene is dissolved in an appropriate solvent and allowed to react with chlorine, the
product of the reaction, C6H10Cl2, has a melting point of -7℃ and a boiling point (at 16 torr) of 74 ℃.
(a) Which stereoisomer is this? (b) What does this experiment suggest about the mode of addition of
chlorine to the double bond?

Answer:

(a)
H Cl Cl H
Cl2
+

Cl H H Cl
(b) Since the products are the trans isomer, we can conclude that the chlorine atoms have added
from opposite sides of the double bonds.

4.44 Consider the cis and trans isomers of 1, 3-di-tert-butylcyclohexane (build molecular models).
What unusual feature accounts for the fact that one of these isomers apparently exists in a twist boat
conformation rather than a chair conformation?

Answer:
The structure of cis-1, 3-di-tert-butylcyclohexane is:
And in the second conformation both tert-butyls are in the equatorial position, .so the molecular has
low energy and therefore it can exist stably.
The chair form structure of trans-1, 3-di-tert-butylcyclohexane is:

So the 2 tert-butyls can’t be in the equatorial position at the same time. The van der Waals forces
between the axial tert-butyl and hydrogen atoms on the same side are repulsive. So the energy of
the molecular is too high to make it exists stably. This makes the conformation convert into the
twist boat form the repulsion in which is much smaller:

So the twist boat form is more stable.


That is why one isomer of 1, 3-di-tert-butylcyclohexane exists in the twist boat conformation
rather than the chair conformation.

4.45 Using the rules found in this chapter, give systematic names for the following or indicate that
more rules need to be provided:
Answer:
(a)
H Cl
C

C Z-1-Bromo-2-chloro-1-fluoro-ethene
F Br

H Cl
C

C E-1-Bromo-2-chloro-1-flouro-ethene
Br F

(b)
Bicyclo[4,4,0]decane

(c)

Bicyclo[4,4,0]-2-decene

(d)

Bicyclo[4,4,0]-1-decene

4.46 This is the predominant conformation for D-glucose


H

HOH2C O
HO
H
H
HO OH
OH

H H

Why is it not surprising that D-glucose is the most commonly found sugar in nature?
(Hint: look up structures for sugars such as D-galactose and D-mannose, and compare these with
D-glucose.)

Answer:
Through comparing the structure of D-galactose and D-mannose with D-glucose, I notice that there are
more –OH group equatorial in D-glucose than the others (almost all of the –OH group is equatorial).It’s
stable.
However, the other two have axial –OH group and they have 1,3-Diaxial interactions between -OH and
–H group. Their energy are higher.
Then I can say that D-glucose is more stable then the others. So it is the most commonly found sugar in
nature.

4.47 Using Newman projections, depict the relative positions of the substituents on the bridgehead
atoms of cis- and trans-decalin. Which of these isomers would be expected to be more stable, and why?
Answer:
H H H
H H H
H H H
H H

H H
H H H H
H H H

trans cis

4.48 Starting with any two compounds containing no more than four carbon atoms, write
equations for a synthesis of dodecane, CH3 (CH2) 10CH3
Answers:
H2
C
H3C C + NaNH2 CH3CH2C C-Na + + NH3 ;
CH

2 CH3CH2C CNa + Br(CH2)4Br CH3CH2C C(CH2)4C CCH2CH3 + 2NaBr ;

CH3CH2C C(CH2)4C CCH2CH3 + 4H2 CH3(CH2)10CH3