CHAPTER 26

STRUCTURES OF ORGANIC COMPOUNDS

PRACTICE EXAMPLES
1A

(E) We have shown only the C atoms and the bonds between them. Remember that there
are four bonds to each C atom; the remaining bonds not shown are to H atoms. First we
realize there is only one isomer with all six C atoms in one line. Then we draw the isomers
with one 1-C branch. The isomers with two 1-C branches can have them both on the same
atom or on different atoms. This accounts for all five isomers.
C
C C C C C C
CH3CH2CH2CH2CH2CH3

C C C C C
(CH3)2CHCH2CH2CH3

C
C

C
(CH3)3CCH2CH3

(CH3)2CHCH(CH3)2

1B

C C C C C
CH3CH2CH(CH3)CH2CH3

(E) We have shown only the C atoms and the bonds between them. Remember that there
are four bonds to each C atom; the remaining bonds not shown are to H atoms.
C
C

C C

C C

CH3CH2CH2CH2CH2CH2CH3

C C C

C C

(CH3)2CHCH2CH2CH2CH3

C C C

C C

CH3CH2CH(CH3)CH2CH2CH3
C

C C C

C C

(CH3)2CHCH2CHC(CH3)2

C C

C C

C C

C C

(CH3)2CHCH(CH3)CH2CH3

C
C C

C C

(CH3)3CCH2CH2CH3

C C
C

C
CH3CH2C(CH3)2CH2CH3

C C C
C

(CH3)3CCH(CH3)2

1221

C C

CH(CH2CH3)3

Chapter 26: Structures of Organic Compounds

2A (M)

Numbering starts from the right and goes left so that the substituents appear with the
lowest numbers possible. This is 3,6,6-trimethyloctane.
2B. (M)

This is a symmetrical molecule. Therefore it does not matter whether numbering starts
from left or right. The compounds name is 3,6-dimethyloctane.
3A. (M)

3B. (M)
3-isopropyl-2-methylpentane
CH3
H3C

CH

CH3
CH

H3C

CH
CH3

1222

CH2

Chapter 26: Structures of Organic Compounds

4A. (M) The structural diagram for 2-methyl-pentane is given below:

When the molecule is viewed along C1-C2 bond there are several possible staggered
conformations:

There are no gauche interactions in this molecule. Therefore, conformations (a), (b) and (c)
all have the same energy.
4B. (D) When 1-chloropropane molecule is viewed along the C1-C2 bond, several eclipsed and
staggered conformations can be identified:

1223

Chapter 26: Structures of Organic Compounds

5A. (M) We are dealing with a trans isomer, and so both methyl groups are adjacent to
opposite face of the ring. The conformation of the lowest energy will be the one that has
the methyl groups in the equatorial positions.

5B. (M) For this molecule, it is more favorable to place tert-butyl group in the equatorial
position.

6A. (M)
Cl

(a)

Cl
Cl

C
F3C

All three carbon atoms in this molecule are attached to at

least two groups of the same type; thus, the molecule is
achiral

H
H

H
(b)

C
CCl3

F2HC

This molecule contains a carbon atom that is bonded to

four different groups; consequently, the molecule is
chiral.

F
H

(c)

C
Cl

F
CH2CCl2F

This molecule contains a carbon atom that is attached to

four different groups; consequently, the molecule is
chiral.

1224

Chapter 26: Structures of Organic Compounds

6B.
(M)
(a)

C
H
CH2OH

ClH2C

None of the three carbon atoms in this alcohol are bonded

to four different groups; consequently the molecule is
achiral

OH
(b)

C
CH3

ClH2C

This molecule contains a carbon atom that is bonded to

four different groups; consequently, the molecule is
chiral.

(c)
C
CH2CH3

HO

Cl

This molecule contains a carbon atom that is bonded to

four different groups; consequently, the molecule is
chiral. The molecule is also unstable and eliminates HCl
to form propanal CH3CH2CHO.

7A. (M) Chiral carbon atoms (*) are indicated below:

7B. (M) The molecular structure of 1,1,3-trimethylcyclohexane is shown below and chiral
carbon atoms indicated by *:

8A. (D)
(a)
1 OH
3
H3C

(b)
2 Cl

(R)
2
CH2CH3

(c)
1 OH

(R)
C
1 Br

1225

3
CH2CH3

3
H3C

(R)
2
COOH

Chapter 26: Structures of Organic Compounds

8B.

3 CH3

(D)(a)

1
HO
(b)

(M)(a)

2
CH2CH3

(S)

2
3
CH2Cl H3CH2C

(S)

This is the (E) stereoisomer

H
H3CH2C

This is the (Z) stereoisomer

C
H

(Z) stereoisomer
H3CH2C
CH3
C

(E) stereoisomer
H
H3CH2C
C

C
H

C
H

H3C

C
CH2CH3

H3CH2C

(Z) stereoisomer
CH3
H3CH2C
C

CH3

(E) stereoisomer
H
Cl

H3CH2C

(Z) stereoisomer
CH2CH3
Cl
C

(c)

(b)

2
CH2Cl

Thus, the structures are

enantiomers.

This is the (Z) stereoisomer

ClH2CH2C
F

H3CH2C

(b)

(R)

CH2CH3

(M)(a)

2
CH2CH3

Thus, the structures are

enantiomers.

9B.

(R)

1 Br

(c)

3
H3C

3 H3CH2C
1
Br

9A.

1 OH

(E) stereoisomer
H
H3CH2C
C

C
H3C

1226

C
CH3

Chapter 26: Structures of Organic Compounds

10A. (M) We need to establish the degree of unsaturation in the molecule and then construct
one example of each type of molecule that can be formed. The maximum number of
hydrogen atoms is 5x2+2=12. The molecular formula has only 11 hydrogen atoms, so we
know the degree of unsaturation is one. Several possibilities are possible:

10B. (D) We need to establish the degree of unsaturation in the molecule and then construct one
example of each type of molecule that can be formed. The maximum number of hydrogen
atoms is 5x2+2=12. The molecular formula has only 10 hydrogen atoms, so we know the
degree of unsaturation is one. Several possibilities are possible and some of them are
shown below:

1227

Chapter 26: Structures of Organic Compounds

INTEGRATIVE EXAMPLE
11A. (M) Compound A has a formula C3H8O and it is coordinatively saturated. It reacts with
sodium metal to produce gas and also is further oxidized by the treatment with chromic
acid. Compound A must therefore be a primary alcohol, CH3-CH2-CH2-OH. On treatment
with chromic acid, CH3-CH2-CH2-OH is completely oxidized to carboxylic acid, CH3CH2-CH2-COOH (compound B). CH3-CH2-CH2-COOH further reacts with base Na2CO3
to yield CH3-CH2-CH2-COO-Na+. It also reacts with ethanol to produce ester CH3-CH2CH2-COO-CH3-CH2 (compound C).
11B. (M) Compounds (a) and (b) are both ethers. Ethers are relatively unreactive and the ether
linkage is stable in the presence of most oxidizing and reducing agents, as well as dilute
acids and alkalis. Compound (c) is unsaturated secondary alcohol. It will decolorize a
Br2/CCl4 solution. Compound (d), on the other hand is an aldehyde. On treatment with
chromic acid it will be oxidized to carboxylic acid. The same reaction would not happen
with compound (c). Although the principal oxidation product of the unsaturated secondary
alcohols with chromic acid will be a ketone, the reaction of chromic acid with the aldehyde
will appear identical to that of the secondary alcohol (i.e., the chromic acid will change
from a red solution to a green solution). A subsequent NaHCO3 treatment would be needed
to test for the presence of carboxylic acid (evolution of CO2).

EXERCISES
______________________________________________________________________________

Organic Structures
1.

(E) In the following structural formulas, the hydrogen atoms are omitted for simplicity.
Remember that there are four bonds to each carbon atom. The missing bonds are C H
bonds.
(a)

CH 3CH 2 CHBrCHBrCH 3

(b)
C

Br Br
C

C
C

(c)

C
C
C

1228

C
C

C
C

Chapter 26: Structures of Organic Compounds

2.

(E) In the structural formulas drawn below, we omit the hydrogen atoms. Remember that
there are four bonds to each C atom. The bonds that are not shown are C H bonds.
(a)

3-isopropyloctane
C

(c)

2-chloro-3-methylpentane
Cl C

C C C

(b)
C

2-pentene

(d)

CC=CCC

3.

H3C

dipropyl ether
CCCOCCC

CH3

(E) (a)

C C

(b)
NO2

(c)
Cl

OH

COOH
Cl

CH3

NH2

4.

(E) In the following structural formulas, the hydrogen atoms are omitted for simplicity.
Remember that there are four bonds to each carbon atom. The missing bonds are CH
bonds.
(a) (CH3)3CCH2CH(CH3)CH2CH2CH3
(b) (CH3)2CHCH2C(CH3)2CH2Br
C
C

C
C

C
C

C
C

(c)

Br

Cl3CCH2CH(CH3)CH2Cl
Cl
Cl

CH2Cl
C

Cl

5.

(M) (a)

H Cl H
H C

H H

(b)

C C H

H O C

(M) (a)

H H O
H C C

H C

H H

H H H

6.

C O H

(c)

(b)

H
H C C N

C O H

H H

1229

C O

H H

(c)

H H H
H C C N H
H H

Chapter 26: Structures of Organic Compounds

7.

(M) (a)
Each carbon atom is sp 3 hybridized. All of the C H bonds in the structure
(drawn on the next page) are sigma bonds, between the 1s orbital of H and the sp 3
orbital of C. The CC bond is between sp 3 orbitals on each C atom.
(b)

Both carbon atoms are sp 2 hybridized. All of the C H bonds in the structure (see
next page) are sigma bonds between the 1s orbital of H and the sp 2 orbital of C. The
CCl bond is between the sp 2 orbital on C and the 3p orbital on Cl. The C = C
double bond is composed of a sigma bond between the sp 2 orbitals on each C atom
and a pi bond between the 2 pz orbitals on the two C atoms.

(c)

The left-most C atom (in the structure drawn on the next page) is sp 3 hybridized,
and the CH bonds to that C atom are between the sp 3 orbitals on C and the 1s
orbital on H. The other two C atoms are sp hybridized. The right-hand C H bond
is between the sp orbital on C and the 1s orbital on H. The C C triple bond is
composed of one sigma bond formed by overlap of sp orbitals, one from each C
atom, and two pi bonds, each formed by the overlap of two 2p orbitals, one from
each C atom (that is a 2 p y 2 p y overlap and a 2 pz 2 pz overlap).
(a)

8.

H H

C H

H H

(b)
H C

(c)

H H

Cl
H

C H

(M) (a)
The left- and right-most C atoms in the structure (drawn below) are sp 3
hybridized. All C H bonds are sigma bonds formed by the overlap of an sp 3 orbital
on C with a 1s orbital on H. The central C atom is sp 2 hybridized; both C C bonds
are sigma bonds, formed by the overlap between the sp 3 orbital on the terminal C atom
and an sp 2 orbital on the central C atom. The C = O double bond is composed of a
bond between the sp 2 orbital on the central C atom and a 2 p y orbital on the O atom,

and a bond between the 2 pz orbital on the central C atom and the 2 pz orbital on the
O atom.
(b)

The left C atom in the structure (drawn below) is sp 3 hybridized. All C H bonds are
sigma bonds formed by the overlap of an sp 3 orbital on C with a 1s orbital on H. The
central C atom is sp 2 hybridized; the C C bond is a sigma bond, formed by the
overlap between the sp 3 orbital on the terminal C atom and an sp 2 orbital on the central
C atom. The C = O double bond is composed of a bond between the sp 2 orbital on
the central C atom and an sp2 orbital on the O atom, and a bond between the 2 pz
orbital on the central C atom and the 2 pz orbital on the O atom. The right O atom is sp 3

1230

Chapter 26: Structures of Organic Compounds

hybridized; the C O sigma bond forms by the overlap of C sp 2 with O(sp3) and the

O H bond forms by overlap of the O sp 3 with the H(1s).

(c)

The two end C's are sp 2 hybridized; all C H bonds form by the overlap of C(sp2)
with H(1s). The central C is sp hybridized. Both C = C bonds consist of a bond
formed by Ccentral(sp) with Cend(sp2) overlap and a bond formed by Ccentral 2 p
with Cend(2p) overlap. Note: The 2p orbitals that make up each pi bond are mutually
perpendicular relative the left or right side of the molecule.

(a)

(b)

(c)

H O H
H

C
H

C H

H O
H

O H

C
H

C H
H

Isomers
9.

10.

(E) Structural (skeletal) isomers differ from each other in the length of their carbon atom
chains and in the length of the side chains. The carbon skeleton differs between these
isomers. Positional isomers differ in the location or position where functional groups are
located attached to the carbon skeleton. Geometric isomers differ in whether two
substituents are on the same side of the molecule or on opposite sides of the molecule from
each other; usually they are on opposite sides or the same side of a double bond.
(a)

The structures are identical.

(b)

The two compounds are constitutional isomers.

(c)

The two compounds have no relationship. They have different molecular formulas.

(d)

The two compounds are constitutional isomers.

(e)

The two compounds are stereoisomers.

(M) (a)

The two compounds are identical.

(b)

The two compounds are tautomers.

(c)

The two compounds are enatiomers.

(d)

The two compounds are constitutional isomers.

(e)

The two compounds are constitutional isomers. They differ in the mode of
attachment of bromine atoms. In the first one, bromine atoms are attached to the
same carbon, whereas in the second one they are attached to two adjacent carbon
atoms.

1231

Chapter 26: Structures of Organic Compounds

11.

(D) We show only the carbon atom skeleton in each case. Remember that there are four
bonds to carbon. The bonds that are not indicated in these structures are C H bonds.
C

C
C

C
C

C
C

C
C

C
C

C
C

C
C
C
C

12.

C
C

(D) In each case, we draw only the carbon skeleton. It is understood that there are four
bonds to each carbon atom. The bonds that are not shown are C H bonds.
C
C
(a)
C

C C C
n-hexane

C C C C C
2-methylpentane

C C
C

C C C C
3-methylpentane

C C

C
2,3-dimethylbutane

2,2-dimethylbutane

(b)
C

C C

C C

1-butene

C C

1 -b u t y n e

31.
(a)
13. (M)

F
2C

H
Carbon 2 is chiral

2 - butyne

(b)

C
C

C C

C
cyclobutane methylcyclopropane 2-methyl-1-propene

2-butene

(c)
C

cyclobutene

There are no
chiral carbon
atoms in
compound (b)

1232

1,3-butadien e

(c)

1 ,2 -b u tadiene

CH3
2C

H
Carbon 2 is chiral

Chapter 26: Structures of Organic Compounds

32. (M)
(a)
14.

There are no
chiral carbon
atoms in
compound (a)

33.
(a)
15. (M)

(b)

H
Carbon 2 is chiral

(b)

2C

H
Carbon 2 is chiral
CH3

OH

There are no
chiral carbon
atoms in
compound (c)

(c)

There are no
chiral carbon
atoms in
compound (c)

C
CH3

Cl
H
chiral carbon

chiral carbon

Functional Groups
17.

(E) (a)

Br

CH3CHCH2CH3
2-Bromobutane

alkyl halide (bromide)

(b)

aldehyde

(c)

ketone

1233

There are no
chiral carbon
atoms in
compound (c)

(c)

CO2H
H
Carbon 2 is chiral
(b)

NH2
2C

CO2H

OH

(c)

2C

Cl

34. (M)
(a)
16.

Cl

Chapter 26: Structures of Organic Compounds

(d)

HO

OH

2, 3 or 4-hydroxyphenol
(only 4-hydroxyphenol shown)
18.

(E) (a)

C H3C H2C OH
propanoic acid

carboxylic acid

(b)

(CH 3 ) 2 CHCH 2OCH 3

isobutylmethyl ether

ether

(c)

CH3CH(NH2)CH2CH3
2-aminobutane

amine

(d)

19.

phenol, hydroxyl group, phenyl group

ester
CH3COCH3
methyl acetate
(M) (a)
A carbonyl group is >C=O , whereas a carboxyl group is C(O)-OH
The essential difference between them is the hydroxyl group, OH.
(b)

An aldehyde has a carbonyl group with a hydrogen and a carbon group attached.
O
R C H
In a ketone, the carbonyl group is attached to two carbons.
O
R

C R

(c)

20.

Acetic acid isH3C C OH , while an acetyl group is H3C C

The essential difference is the presence of the OH group in acetic acid.

(M) (a)

aromatic nitro compound, C 6 H 5 NO 2 , nitrobenzene

(b)

aliphatic amine, C 2 H 5 NH 2 , ethylamine

(c)

chlorophenol, p - ClC6 H 4 OH , para-chlorophenol (drawn below)

(d)

aliphatic diol, HOCH 2 CH 2 OH , 1,2-ethanediol

(e)

unsaturated aliphatic alcohol, CH 2 =CHCH 2 CH 2 OH , 3-butene-1-ol

(f)

alicyclic ketone, C6 H10 O , cyclohexanone (drawn below)

1234

Chapter 26: Structures of Organic Compounds

(g)

halogenated alkane, CH 3CHICH 2 CH 3 , 2-iodobutane

(h)

aromatic dicarboxylic acid, o-C6H4(COOH)2, phthalic acid (drawn below)

(c)

(f)

(h)

COOH

Cl
O

COOH

OH
O

37.
(a)
21. (M)

(b)
C

OH
H3C

HO

(d)

O
H3C

HO
ether group
H3C O

CH3

aldehyde group
disubstituted
aromatic ring
OH

(b)

ketone
group

hydroxyl group
OH

amide group
O

(d)
H2C

CH CH2 N CH3
amine group
trisubstituted aromatic ring

1235

hydroxyl group

H3C CH2 C NH CH3

CH2 CH2 C CH3

ketone
group
hydroxyl
group

CHO

carboxylic acid
group

H3C C

(c)

CH2

CH2 CH2 CO2H

ketone
group
22.
38.(M(a)

ester group

carboxylic disubstituted hydroxyl

acid group aromatic ring group
(c)

C OH
O
carboxylic
HO
C C OH acid
groups
O
hydroxyl
group H2C C OH

Chapter 26: Structures of Organic Compounds

24.
40. (M)

O
O

25. (M)
O

O H

O H

26. (M)
O

O H

27. (M)
O

O
O

O
H

O
O

28. (M)
O

O
O

O
H

O
H

29. (M)
OH

HO
HO

O
O

O
OH

OH
O
OH

1236

OH
OH

OH

OH

OH

Chapter 26: Structures of Organic Compounds

30. (D)

There are numerous isomers; here are a few of them

OH

OH

HO

O
H

O
HO

OH H

OH
O

O
OH

OH

OH

HO

OH

H
OH

OH

OH

HO

OH

O
OH

OH

OH

Nomenclature and Formulas

31.

(E) (a) The longest chain is eight carbons long, the two substituent groups are methyl
groups, and they are attached to the number 3 and number 5 carbon atom. This is
3,5-dimethyloctane.
(b)

The longest carbon chain is three carbons long, the two substituent groups are methyl
groups, and they are both attached to the number 2 carbon atom. This is 2,2dimethylpropane.

(c)

32.

33.

The longest carbon chain is 7 carbon atoms long, there are two chloro groups
attached to carbon atom 3, and an ethyl group attached to carbon 5. This is 3,3dichloro-5-ethylheptane.
(E) (a) There are 2 chloro groups at the 1 and 3 positions on a benzene ring. This is 1,3dichlorobenzene or, more appropriately, meta-dichlorobenzene.

(b)

There is a methyl group at position 1 on a benzene ring, and a nitro group at position
3. This is 3-nitrotoluene or meta-nitrotoluene.

(c)

There is a COOH group at position 1 on the benzene ring, and a NH 2 group at

position 4, or para to the COOH group. This is 4-aminobenzoic acid or paminobenzoic acid.

(M) (a)
The longest carbon chain has four carbon atoms and there are 2 methyl groups
attached to carbon 2. This is 2,2-dimethylbutane.
(b) The longest chain is three carbons long, there is a double bond between carbons 1
and 2, and a methyl group attached to carbon 2. This is 2-methylpropene.
(c)

Two methyl groups are attached to a three-carbon ring. This is 1,2dimethylcyclopropane.

1237

Chapter 26: Structures of Organic Compounds

34.

(d)

The longest chain is 5 carbons long, there is a triple bond between carbons 2 and 3
and a methyl group attached to carbon 4. This is 4-methyl-2-pentyne.

(e)
(f)

The longest chain is 6 carbons long. This compound is 3,4-dimethylhexane

The longest carbon chain containing the double bond is 5 carbons long. The double
bond is between carbons 1 and 2. There is a propyl group on carbon 2, and carbons 3
and 4 each have one methyl group. This is 3,4-dimethyl-2-propyl-1-pentene.

(M) Again we do not show the hydrogen atoms in the structures below. But we realize that
there are four bonds to each C atom and the missing bonds are C H bonds.
(a) methylbutane
(b)
cyclohexene
C
C

(c)

2-methyl-3-hexyne

(d)

2-butanol

(f)

Propanal

C
C
(e)

ethyl isopropyl ether

C
C

35.

36.

O
O

C H

(M) (a)
The name pentene is insufficient. 1-pentene is CH 2 =CHCH 2 CH 2 CH 3 and 2pentene is CH 3CH=CHCH 2 CH 3 .
(b)

The name butanone is sufficient. There is only one four-carbon ketone.

(c)

The name butyl alcohol is insufficient. There are numerous butanols. 1-butanol is
HOCH 2 CH 2 CH 2 CH 3 , 2-butanol isCH3CH(OH)CH2CH3, isobutyl alcohol is
HOCH2CH(CH3)2, and t-butyl alcohol is (CH3)3COH.

(d)

The name methylaniline is insufficient. It specifies CH 3 C6 H 4 NH 2 , with no

relative locations for the NH 2 and CH 3 substituents.

(e)

The name methylcyclopentane is sufficiently precise. It does not matter where on a

five-carbon ring with only C C single bonds a methyl group is placed.

(f)

Dibromobenzene is insufficient. It specifies Br C6 H 4 Br, with no indication of

the relative locations of the two bromo groups on the ring.

(M) (a)
3-pentene specifies CH 3CH 2CH=CHCH 3 . The proper name for this compound
is 2-pentene. The number for the functional group should be as small as possible.
(b)

Pentadiene is insufficient. Possible pentadienes are 1,2 pentadiene,

CH 2 =C=CHCH 2 CH 3 , 1,3-pentadiene, CH 2 =CHCH=CHCH 3 , and 2,3
pentadiene, CH 3CH=C=CHCH 3 .

1238

Chapter 26: Structures of Organic Compounds

37.

(c)

1-propanone is incorrect. There cannot be a ketone on the first carbon of a chain. The
compound specified is either propionaldehyde, CH 3CH 2 CHO , or propanone (2propanone).

(d)

Bromopropane is insufficient. It could be either 1-bromopropane, BrCH 2 CH 2 CH 3 ,

or 2-bromopropane, CH 3CHBrCH 3 .

(e)

Although 2,6-dichlorobenzene conveys enough information, the proper name for the
compound is meta-dichlorobenzene, or 1,3-dichlorobenzene. Substituent numbers
should be as small as possible.

(f)

2-methyl-3-pentyne is (CH3)2CHCCCH3. The proper name for this compound is 4methyl-2-pentyne. The number of the triple bond should be as small as possible.

(M) (a)

2,4,6-trinitrotoluene:

(b)

methylsalicylate:
O

NO2
O2N

COCH3

CH3

OH

NO2

(c)

2-hydroxy-1,2,3-propanetricarboxylic acid: HOOCCH 2 C OH COOH CH 2 COOH

38.

(M)

39.

(M) (a)

HN(CH2CH3)2

(b)

N,N-diethylamine

(d)

N-cyclopentyl-N-ethylamine
40.

(M) (a)

NO2

p-nitroaniline

NH CH2 CH3

(c)

H2N

CH3CH2N(CH3)CH2CH3

N,N-diethyl-N-methylamine

ethylamine:

(b)

H3C-CH2-NH2

H2N

1239

3-chloroaniline:
Cl

Chapter 26: Structures of Organic Compounds

(c)

Dicyclopropylamine

(d)

2-chloroethylamine

ClCH2CH2NH2

Alkanes and Cycloalkanes

41.

(M)

42.

(M)

43.

(M) Conformation (d) is lowest in energy. Conformation (a) is highest in energy.

1240

Chapter 26: Structures of Organic Compounds

44.

(M) Conformations (b) and (d) are lowest in energy.

45.

(E) The most stable conformation is:

46.

(E) The most stable conformation is:

47.

(M) (a) The more stable conformation involves placing OH group in the equatorial
position:

1241

Chapter 26: Structures of Organic Compounds

(b) The more stable configuration involves placing OH group in the axial position:

48.

(M) (a) The more stable conformation involves placing the isopropyl group in the
equatorial position:

(b) The more stable conformation involves placing tert-butyl group in the equatorial
position:

Alkenes
49.

(E) In the case of ethene there are only two carbon atoms between which there can be a
double bond. Thus, specifying the compound as 1-ethene is unnecessary. In the case of
propene, there can be a double bond only between the central carbon atom and a terminal
carbon atom. Thus here also, specifying the compound as 1-propene is unnecessary. The
case of butene is different, however, since 1-butene, CH 2 CHCH 2 CH 3 , is distinct from
2-butene, CH 3CH = CHCH 3 .

1242

Chapter 26: Structures of Organic Compounds

50.

(E) In an alkene there is a C = C double bond. On the other hand, in an cyclic alkane there
are no double bonds, but rather a chain of carbon atoms joined at the ends into a ring.

51.

(M) The E,Z system is used to name highly substituted alkenes. The stereochemistry
about the double bond is assigned Z is the two groups of higher priority at each end of the
double bond are on the same side of the molecule. If the two groups of higher priority are
on the opposite sides of the double bond, the configuration is denoted by an E.

52

(M)

53.

(M)

54.

(M)

1243

Chapter 26: Structures of Organic Compounds

Aromatic Compounds
55.

(E) (a)

phenylacetylene (b)
C

meta-dichlorobenzene
Cl

(c) 1,3,5-trihydroxybenzene
OH

CH

Cl

56.

(E) (a)

p-phenylphenol (b)

3-hydroxy-4-isopropyltoluene

HO

(c)

OH

meta-dinitrobenzene
NO2

OH

NO2

Organic Stereochemistry
57.

(E) The four structural isomers are 1,2-dichloropropane, 1,3-dichloropropane, 2,2dichloropropane and 1,1-dichloropropane.

58.

(M) (a) The molecules are not constitutional isomers. The first compound is alkane and the
second one is alkene.
(b) The two compounds are constitutional isomers, they have the same chemical formula but
different structure.
(c) The two compounds are not constitutional isomers. They have different chemical
formulas.
(d) The same compound.
(e) The same compound.
(f) The two compounds are constitutional isomers. In the first one, the NO2 group is ortho to
OH group. In the second one, the NO2 group is para to OH group.

1244

Chapter 26: Structures of Organic Compounds

59.

(M)

60.

(M)

1245

Chapter 26: Structures of Organic Compounds

61.

(M)

62.

(M)

1246

Chapter 26: Structures of Organic Compounds

63.

(M)

64.

(M)

1247

Chapter 26: Structures of Organic Compounds

65.

(M)

66.

(M)
(a)

(b)

(d)

(c)

(e)

1248

Chapter 26: Structures of Organic Compounds

Structures and Properties of Organic Compounds

67.

(E) (a) C4H11N has zero elements of unsaturation. (b) C4H6O has two elements of
unsaturation. (c) C9H15ClO has two elements of unsaturation.

68.

(E) (a) C5H9NO has two elements of unsaturation. (b)

unsaturation. (c) C5H9ClO has one element of unsaturation.

69.

(M) There are two elements of unsaturation in the molecule (one bond and one ring
structure). The molecular formula is C8H15NO.

70.

(M) There are five elements of unsaturation in the molecule (two bonds, one ring structure
and additional triple bond for CN which counts as two). The molecular formula is C6H4BrN.

71.

(M) Compound 1 contains carbon-carbon double bond and ether linkage. It will decolorize
bromine water according to the following chemical reaction:

C5H8O3 has two elements of

Compound 2 is a primary alcohol. Primary alcohols readily react with sodium metal to
liberate hydrogen gas according to the following chemical reaction:

Compound 3 is a carboxylic acid. It reacts with Na2CO3(aq) to generate CO2(g):

72.

(M) Compound 1 absorbs hydrogen in the presence of a metal catalyst:

Compound 2 forms an ether when heated strongly with concentrated sulfuric acid:

Compound 3 neutralizes dilute NaOH and forms an ester with ethanol:

1249

Chapter 26: Structures of Organic Compounds

73.

(M) Cyclic ethers do not contain OH groups. Possible structures for the compound with
molecular formula C4H6O (two elements of unsaturation) are:

74.

(M) Possible structures for cyclic alcohols having the formula C4H6O are:

Integrative and Advanced Exercises

75. (E).

(a)

1,5-cyclooctadiene

(b) 3,7,11-trimethyl-2,6,10,dodecatriene-1-ol
HOCH 2 CH C (CH 3 )CH 2 CH 2 CH C(CH 3 )CH 2 CH 2 CH C(CH 3 ) 2

(c) 2,6-dimethyl-5-heptene-1-al
OHCCH(CH 3 )CH 2 CH 2 CH C(CH 3 ) 2

1250

Chapter 26: Structures of Organic Compounds

76. (M) We have show only the carbon atom skeleton in each case. Remember that there are
four bonds to carbon. The bonds that are not indicated in these structures are CH bonds.
Boiling points are given in parentheses after the name of each compound.
(0.5C) Hexane

C4H10

Butane
C C

C C

C6H14

C C C

2-methylpropane
C C

C C

(58.0C)

C
C C

2-methylbutane

C C C C

(27.9C) 2,3-dimethylbutane

C
C C

C C

2,2-dimethylpropane

(58.0C)

C
C C

(9.5C) 2,2-dimethylbutane

C
C

C C C

(36.1) 2-methylpentane

C5H12

C C C

C C

(63.3C)

Pentane
C C

C C C

(11.7C) 3-methylpentane

C
C

(68.7C)

(49.7C)

C C

C C

C C

As we proceed down each list of isomeric alkanes, the structures become more compact, and
the boiling points decrease.

77. (D) In the structures below we have omitted the hydrogen atoms. Remember that there are
four bonds to each C atom. The bonds that are missing are C H bonds.
Cl

Cl
C

C C
C

Cl C C C
C Cl

Cl

C
C

C
C

C C
Cl

C
C

Cl

C
C

Cl

Cl
Cl
Cl C
C

C
C

C
C

Cl C

Cl
C

Cl

C
C

Cl C

C
C

C
C

Cl C
C

Cl

C C

78. (M) In one regard, benzene and 1,3,5-cyclohexatriene are the same substance; whenever
there are alternating single and double bonds around a six-membered ring of carbon atoms,
an aromatic ring forms. In another sense, these two compounds are different, thus, the

1251

Chapter 26: Structures of Organic Compounds

name 1,3,5-cyclohexatriene implies that the three alternating double bonds in a sixmembered carbon ring do not interact with each other, but they clearly do and the
compound should be called benzene.

79. (D) (a) Oxdn : {Fe

Fe3 3 e }

C 6 H 5 NH 3 2 H 2 O
Redn : C 6 H 5 NO 2 7 H 6 e

C 6 H 5 NO 2 7 H 2 Fe
C 6 H 5 NH 3 2 H 2 O 2 Fe 3

(b) Oxdn : {C 6 H 5 CH 2 OH H 2 O
C 6 H 5 COOH 4 H 4 e } 3

Redn : {Cr2 O 7

14 H 6 e
2 Cr 3 7 H 2 O}

3 C 6 H 5 CH 2 OH 2 Cr2 O 7

16 H
3 C 6 H 5 COOH 4 Cr 3 11 H 2 O

(c) Oxdn: {CH3 CH == CH 2 2 OH

CH 3 CHOHCH 2 OH 2 e } 3

Redn : {MnO 4 2 H 2 O 3 e
MnO 2 4 OH }

3 CH 3 CH CH 2 2 MnO 4 4 H 2 O
3 CH 3 CHOHCH 2 OH 2 MnO 2 2 OH
80. (D)We first write the equation for the reaction that occurs. Note that each mole of

benzaldehyde yields one mole of benzoic acid. We are given the mass of each reagent; we
need to determine which reagent is limiting.
3 C6 H 5 CHO 2 KMnO 4 KOH
3 C6 H5 COO K 2 MnO2 2 H 2 O
3 C 6 H 5 COO K 3 H
3 C 6 H 5 COOH 3 K
massC H COOH = 10.6 g C6 H 5CHO
6

1 mol C6 H 5CHO 1 mol C6 H 5COOH 122.1 g C6 H 5COOH

106.1 g C6 H 5CHO 1 mol C6 H 5CHO

1 mol C6 H 5COOH

= 12.2 g C6 H 5COOH
mass C H COOH = 5.9 g KMnO4
6

1 mol KMnO4
3 mol C6 H 5COOH 122.1 g C6 H 5COOH

158.0 g KMnO 4
2 mol KMnO 4
1 mol C6 H 5COOH

= 6.8 g C6 H 5COOH
6.1 g C6 H 5COOH produced
100% = 90.% yield
% yield =
6.8 g C6 H 5COOH calculated

1252

Chapter 26: Structures of Organic Compounds

81.(D)
We suspect the compound contains C, H, N, and O. The %N by mass in the
compound can be found using the ideal gas law:

amount N 2

PV

RT

1atm
0.0402 L
760 mmHg
1.57 10 3 mol N 2
0.08206 L atm mol 1 K 1 298 K

(735 9) mmHg

28.01 g N 2
1 mol N 2
100 % 24.1% N
0.1825 g sample

1.57 10 3 mol N 2
% N

Now we determine the amounts of C, H, N, and O in the first sample.

amount C 0.2895 g CO 2
mass C 0.006578 mol C

1 mol CO 2
1 mol C

0.006578 mol C
44.010 g CO 2 1 mol CO 2

12.011 g C
0.07901 g C
1 mol C

amount H 0.1192 g H 2 O

1 mol H 2 O
2 mol H

0.01323 mol H
18.015 g H 2 O 1 mol H 2 O

1.0079 g H
0.01334 g H
1 mol H
24.1 g N
1 mol N
amount N 0.1908 g
0.0460 g N
0.00328 mol N
100.0 g sample
14.007 g N
1 mol O
amount O (0.1908 g 0.0460 g N 0.07901 g C 0.01334 g H)
0.00328 mol O
15.999 g O
mass H 0.01323 mol H

From this information we determine the empirical formula of the compound.

0.006578 mol C 0.00328
2.01 mol C
0.00328 mol N

0.00328
1.00 mol N

0.01323 mol H

0.00328
4.03 mol H

0.00328 mol O

0.00328
1.00 mol O

The compound has an empirical formula of C2H4NO, which has a molar mass of 58.1 g/mol.
We use the freezing point depression data to determine the number of moles of compound
dissolved,
and
then
its
molar
mass.
First,
the
molality
of
the
T f 3.66C - 5.50C
solution: m

0.359 m
Kf
5.12 C/m
amount solute 0.02600 kg benzene
M

0.359 mol solute

0.00933 mol solute
1 kg benzene

1.082 g
116 g/mol This molar mass is twice the empirical molar mass.
0.00933 mol

Thus, the molecular formula is twice the empirical formula. Namely, the molecular formula
= C4H8N2O2

1253

Chapter 26: Structures of Organic Compounds

82. (M)

1254

Chapter 26: Structures of Organic Compounds

83. (M) There are four different monochloro derivatives of 2-methylbutane:

84. (D) (1)

The molar masses of the five compounds are the same to one significant figure:

1-butanol

diethyl ether

methyl propyl ether

butyraldehyde

propionic acid

74.12 g/mol

74.12 g/mol

74.12 g/mol

72.11 g/mol

74.08 g/mol

Since the freezing point depression is known to only one significant figure, the molar
mass of the unknown can only be determined to one significant figure. Thus, the cited
freezing point depression data are insufficiently precise to differentiate between the
compounds.
(2) Propionic acid would produce an aqueous solution that would turn blue litmus red. The
unknown compound cannot be propionic acid.
(3) Both alcohols and aldehydes are oxidized to carboxylic acids by aqueous KMnO4. Ethers
are not oxidized by KMnO4. Thus, the unknown must be 1-butanol or butyraldehyde.

The identity of the unknown can be established by treatment with a carboxylic acid. If the
unknown is an alcohol, it will form a pleasant smelling ester upon heating with a carboxylic
acid such as acetic acid. If the compound is an aldehyde, it will not react with the
carboxylic acid under these conditions.

1255

Chapter 26: Structures of Organic Compounds

85. (M)

86. (M) (a) 2-chloro-4-methyloctane

(c) Ethyl methyl ether
(e) (Z)-1,3-dichloro-2-methyl-2-butene
87.

(D) 4-chloro-1-butene
Cl

(b) 2-amino-3-chloropentanoic acid

(d) 1-amino-3-chloro propane

3-chloro-1-butene

Cl

2-chloro-1-butene

*(R and S)
Cl

(Z)-1-chloro-1-butene

(E)-1-chloro-1-butene

1-chloro-2methyl-1-propene

Cl
Cl
3-chloro-2-methyl-1-propene

Cl

(E)-1-chloro-2-butene

Cl

(Z)-1-chloro-2-butene

Cl

Cl

(Z)-2-chloro-2-butene

(E)-2-chloro-2-butene

Cl
Cl

1256

(cis&trans)-1-chloro-2-methycyclopropane

Cl cis

CH3

H trans CH3

Cl

Chapter 26: Structures of Organic Compounds

1-chloro-1-methylcyclopropane chloromethylcyclopropane

chlorocyclobutane

Cl
Cl

Cl

88. (D) From the formula C5H12O we can see that this is a saturated alcohol. This question
involves chiral alcohols, hence the possibilities are:
2-pentanol
HO

OH

CrO3 /pyridine

(achiral)

3-methyl-2-butanol
HO

OH

CrO3 /pyridine

(achiral)

2-methy-1-butanol
H 3C H

H 3C H

H CH3
OH

OH

CrO3 /pyridine

H CH3 H

(chiral aldehydes)

Thus: Compound A must be either (S)-2-methy-1-butanol or (R)-2-methy-1-butanol

Hence: Compound B must be either (S)-2-methyl butanal or (R)-2-methyl butanal

89. (M) (a)

ester, amine(tertiary), arene

(b) C1= sp2, C2 = sp3, C3 = sp3, C4 = sp3, N = sp3

(c) Carbons 2 and 4 are chiral.

90. (M) (a)

alcohol, secondary amide, sulfone, arene, alkyl halide

(b) C1= sp3, C2 = sp2, C3 = sp3, C4 = sp3, C5 = sp2, N = sp3

(c) Carbons 3 and 4 are chiral.

91. (M) (a) alcohol, amine(secondary), arene

(b) C1= sp2, C2 = sp3, C3 = sp3, C4 = sp3, N = sp3
(c) Carbons 2 and 3 are chiral.
(d) C10H15NO has a molar mass of 165.24 g/mol.
Assume no volume change and
1 g water = 1 mL water, hence, 1g in 200 g of water represents 0.030 M.
Since the pH = 10.8, it is a base (symbolized as A-). Set up I.C.E. table.

1257

Chapter 26: Structures of Organic Compounds

Reaction
Initial
Change
Equilibrium

A-(aq)
0.030 M
-x
0.030-x

H2O(l)

HA(aq)
+
0M
+x
x

pH = 10.8 hence pOH = 3.2 and [OH ] = 0.00063 M = x

Kb = x2/(0.30-x) = (0.00063)2/(0.030-0.00063) = 1.35 10-5, pKb=4.87

92. (M)

93.

(M)

94.

(D)

1258

OH-(aq)
0M
+x
x

Chapter 26: Structures of Organic Compounds

95. (D) Cholesterol has eight chiral centers. The configuration of the carbon atom bonded to
the OH group is S and the configuration of the double bond is Z.

96.

(D)

1259

Chapter 26: Structures of Organic Compounds

FEATURE PROBLEM
97.

(D) (a) The corresponding values are tabulated below:

(b) The two compounds of interest are acetone and 1-propanol, both of which are colorless
liquids.

Absorption labeled A clearly corresponds to O-H stretch. Absorptions labeled B and C

correspond to C-H stretches. Lastly, absorption labeled D indicates the presence of a carbonyl
group C=O. Therefore, the spectrum with C and D labeled peaks corresponds to acetone.

(c) The characteristic IR absorption at 1645 cm-1 corresponds to C=C, which is further
confirmed by the fact that the compound decolorizes Br2. Strong absorption band from
2860-3600 cm-1 is indicative of an alcohol. Alcohols react with sodium metal to liberate
hydrogen gas. Based on the information provided, the isomer of acetone is most likely 2propene-1-ol.

SELF-ASSESSMENT EXERCISES
98.

(E) (a) In organic chemistry, tert group is a four carbon group with the general formula
C4H9 ,derived from the isomer of butane. Structure of tert butyl group is:

(b) -R group is commonly used in organic chemistry to indicate different substituents,

such as methyl, ethyl, isopropyl, etc.
1260

Chapter 26: Structures of Organic Compounds

(c) Compound shown is benzene with the molecular formula C6H6.

(d) Carbonyl group is a functional group composed of a carbon atom double-bonded to
an oxygen atom, C=O.
(e) Amines are organic compounds that contain basic nitrogen atom with a lone pair.
Primary amines arise when one of the three hydrogen atoms in ammonia is replaced by a
carbon group such as alkyl or aryl.
99.

(E) (a) Alkanes are saturated compounds with the general formula CnH2n+2. Alkenes, on
the other hand, are unsaturated compounds containing C=C double bonds. General
formula of alkenes is CnH2n.
(b) In organic chemistry, compounds composed of carbon and hydrogen are divided into
two classes: aromatic compounds, which contain benzene rings or similar rings of atoms,
and aliphatic compounds, which do not contain aromatic rings.
(c) Phenols are aromatic compounds that contain -OH group bonded to a benzene ring.
Alcohols are compounds that contain OH groups bonded to sp3 carbon atoms.
(d) Ether is a class of organic compounds that contain an oxygen atom connected to two
alkyl or aryl groups, of general formula ROR. Esters are chemical compounds derived
by reacting an oxoacid (one containing an oxo group, X=O) with a hydroxyl compound
such as an alcohol or phenol. Ester functionality is C(O)O-R.
(e) Amines are ammonia derivatives with one, two or three hydrogens replaced by an alkyl
or aryl groups.

100. (E) (a) Structural isomerism, or constitutional isomerism, is a form of isomerism in which
molecules with the same molecular formula have atoms bonded together in different
orders, as opposed to stereoisomerism. Three categories of constitutional isomers are
skeletal, positional, and functional isomers.
(b) Stereoisomers are isomeric molecules that have the same molecular formula and
sequence of bonded atoms (constitution), but which differ only in the three-dimensional
orientations of their atoms in space.
(c) When the substituent groups are oriented in the same direction, the diastereomer is
referred to as cis, whereas, when the substituents are oriented in opposing directions, the
diastereomer is referred to as trans.
(d) Ortho position refers to 1,2-disubstituted benzene.
101. (M) The main carbon-carbon chain in isoheptane contains six carbon atoms. Furthermore,
isoheptane contains isopropyl group, CH(CH3)2. The correct structure is structure (c).
102. (M) The molecular formula of cyclobutane is C4H8. The correct answer is (b).
103. (M) Hydrocarbons with four of more carbon atoms form isomers. The correct answer is
(e). The three isomers of the compound with molecular formula C5H12 are:

1261

Chapter 26: Structures of Organic Compounds

104. (M)

105. (M)

(a)
(b)
(c)
(d)

(2) and (3) are identical.

(1) and (2) are constitutional isomers.
(1) and (5) are diastereomers.
(3) and (4) are enatiomers.

1262

Chapter 26: Structures of Organic Compounds

106. (M)

(d) stereoisomers (E and Z)

107. (M)

1263

Chapter 26: Structures of Organic Compounds

108. (M) The correct answer is (c).

Ethyl methyl ketone

109. (M) C4H10 has only two constitutional isomers, whereas C4H8 has three (2-butene, 1butene and cyclobutane).
110. (M) (a) C6H12 is expected to have higher boiling point than C6H6. (b) C3H7OH is
expected to have higher solubility in water because of smaller hydrocarbon chain. (c)
Benzoic acid (C6H5COOH) has greater acidity than benzaldehyde.
111. (M)

1264