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CHAPTER 26

STRUCTURES OF ORGANIC COMPOUNDS


PRACTICE EXAMPLES

1A 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 C C C C C C C C C C C
CH3CH2CH2CH2CH2CH3 (CH3)2CHCH2CH2CH3 CH3CH2CH(CH3)CH2CH3

C C C
C C C C C C C C
C
(CH3)2CHCH(CH3)2 (CH3)3CCH2CH3

1B 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 C C C C C C C C C C C C C C C
CH3CH2CH2CH2CH2CH2CH3 (CH3)2CHCH2CH2CH2CH3 CH3CH2CH(CH3)CH2CH2CH3

C
C C C C C C C C C
C C C C C C C C C C C
(CH3)2CHCH2CHC(CH3)2 (CH3)2CHCH(CH3)CH2CH3 (CH3)3CCH2CH2CH3

C C C
C C C C C C C C C C C
C C C C C C C

CH3CH2C(CH3)2CH2CH3 (CH3)3CCH(CH3)2 CH(CH2CH3)3

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Chapter 26: Structures of Organic Compounds

2A

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.

This is a symmetrical molecule. Therefore it does not matter whether numbering starts
from left or right. The compound’s name is 3,6-dimethyloctane.

3A.

3B.
3-isopropyl-2-methylpentane

CH3

H3C CH CH3

CH CH2

H3C CH

CH3

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Chapter 26: Structures of Organic Compounds

4A. 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. When 1-chloropropane molecule is viewed along the C1-C2 bond, several eclipsed and
staggered conformations can be identified:

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Chapter 26: Structures of Organic Compounds

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

6A.
Cl
Cl
(a) Cl All three carbon atoms in this molecule are attached to at
C
least two groups of the same type; thus, the molecule is
achiral
C
F3C H
H
H
(b) This molecule contains a carbon atom that is bonded to
C four different groups; consequently, the molecule is
F2HC CCl3 chiral.
F
H
(c) This molecule contains a carbon atom that is attached to
C four different groups; consequently, the molecule is
Cl F chiral.
CH2CCl2F

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Chapter 26: Structures of Organic Compounds

6B. H
(a) None of the three carbon atoms in this alcohol are bonded
C to four different groups; consequently the molecule is
ClH2C H achiral
CH2OH

OH
(b) This molecule contains a carbon atom that is bonded to
C four different groups; consequently, the molecule is
ClH2C CH3 chiral.
H
H
(c) This molecule contains a carbon atom that is bonded to
C four different groups; consequently, the molecule is
HO CH2CH3 chiral. The molecule is also unstable and eliminates HCl
Cl to form propanal CH3CH2CHO.

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

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

8A.
(a) (b) (c)
1 OH 2 Cl 1 OH
(R) (R) (R)
3 C 2 C 3 3 C 2
H3C CH2CH3 1 Br CH2CH3 H3C COOH

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Chapter 26: Structures of Organic Compounds

3 CH3
8B. (a) 1 OH
(R) Thus, the structures are
1 C 2 enantiomers.
3 C 2
HO CH2CH3
(S) H3C CH2CH3

(b) 3 H3CH2C 1 Br
(R) Thus, the structures are
1 C 2 C 2 enantiomers.
3
Br CH2Cl H3CH2C CH2Cl
(S)

9A. (a) This is the (E) stereoisomer (b) This is the (Z) stereoisomer
H3CH2C H

C C

H CH2CH3

(c) This is the (Z) stereoisomer


ClH2CH2C F

C C

H3CH2C H

9B. (a) (Z) stereoisomer (E) stereoisomer


H3CH2C CH3 H3CH2C H

C C C C

H H H CH3

(b) (Z) stereoisomer (E) stereoisomer


Cl CH2CH3 Cl H

C C C C

H3CH2C H H3CH2C CH2CH3

(c) (Z) stereoisomer (E) stereoisomer


H3CH2C CH3 H3CH2C H

C C C C

H3C H H3C CH3

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Chapter 26: Structures of Organic Compounds

10A. 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. 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:

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Chapter 26: Structures of Organic Compounds

INTEGRATIVE EXAMPLE

11A. 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, CH3-
CH2-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-CH2-
CH2-COO-CH3-CH2 (compound C).

11B. 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. 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 C
Br Br
C C C C C C C
C C C C C
C C
(c)
C
C
C C C C C C C

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Chapter 26: Structures of Organic Compounds

3. (a) CH3 (b) (c)


NO2 OH Cl COOH

H3C CH3 Cl
NH2

5. (a) H Cl H (b) H H (c) H


H C C C H H O C C O H H C C O
H H H H H H H

7. (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 C–C 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
C–Cl 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 C–H 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) (b) (c)
H H H H H C C Cl H
H C C C C H H H H C C C H
H H H H H

Isomers
9. 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

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Chapter 26: Structures of Organic Compounds

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.

11. 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 C C C C
C C C C C
C C C C C C C C C C C C C C C
C

C
C C C C
C C C C C C C C C C C C C C
C C

31.
13. (a) F (b) There are no (c) CH3
chiral carbon
2C 2C
atoms in
H compound (b) H
Carbon 2 is chiral Carbon 2 is chiral

33. (a)
15. Cl (b) NH2 (c) There are no
chiral carbon
2C 2C atoms in
CO2H CO2H compound (c)
H H
Carbon 2 is chiral Carbon 2 is chiral

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Chapter 26: Structures of Organic Compounds

Functional Groups
17. (a) Br
alkyl halide (bromide)
CH3CHCH2CH3
2-Bromobutane

(b)
aldehyde

(c)
ketone

(d)
HO OH
2, 3 or 4-hydroxyphenol phenol, hydroxyl group, phenyl group
(only 4-hydroxyphenol shown)

19. (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
O O
(c) 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.

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Chapter 26: Structures of Organic Compounds

37.
21. (a) O (b) O
C OH C CH2
HO H3C O CH3
ester group
carboxylic disubstituted hydroxyl
acid group aromatic ring group

(c) (d) CHO aldehyde group


O
H3C C CH2 CH2 CO2H disubstituted
aromatic ring
ketone carboxylic acid
group group OH hydroxyl group

25.

O O O H O H
H H

O O
O O

27.
O
O O O

O H
O H O H O H
O O
O O O
O O
O O O

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Chapter 26: Structures of Organic Compounds

29.
OH HO OH OH

O HO O O
O O
O
O OH O
O
OH H OH
H H
OH
O
OH
O
OH

Nomenclature and Formulas


31. (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 2,2-
dimethylpropane.
(c) 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 3,3-
dichloro-5-ethylheptane.

33. (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 1,2-
dimethylcyclopropane.
(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) The longest chain is 6 carbons long. This compound is 3,4-dimethylhexane
(f) 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.

35. (a) The name pentene is insufficient. 1-pentene is CH 2 =CHCH 2 CH 2 CH 3 and 2-pentene
is CH 3CH=CHCH 2 CH 3 .
(b) The name butanone is sufficient. There is only one four-carbon ketone.

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Chapter 26: Structures of Organic Compounds

(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— C 6 H 4 — Br, with no indication of
the relative locations of the two bromo groups on the ring.

37. (a) 2,4,6-trinitrotoluene: (b) methylsalicylate:


NO2 O
COCH3
O2N CH3

OH
NO2

(c) 2-hydroxy-1,2,3-propanetricarboxylic acid: HOOCCH 2 C  OH  COOH  CH 2 COOH

39. (a) HN(CH2CH3)2 (b) H2N NO2

N,N-diethylamine p-nitroaniline

(c) NH CH2 CH3


(d) CH3CH2N(CH3)CH2CH3
N-cyclopentyl-N-ethylamine N,N-diethyl-N-methylamine

Alkanes and Cycloalkanes

41.

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Chapter 26: Structures of Organic Compounds

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

45. The most stable conformation is:

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

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Chapter 26: Structures of Organic Compounds

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

Alkenes
49. 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 .

51. 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.

53.

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Chapter 26: Structures of Organic Compounds

Aromatic Compounds
55. (a) phenylacetylene (b) meta-dichlorobenzene (c) 1,3,5-trihydroxybenzene
Cl OH
C CH

Cl HO OH

Organic Stereochemistry
57. The four structural isomers are 1,2-dichloropropane, 1,3-dichloropropane, 2,2-
dichloropropane and 1,1-dichloropropane.

59.

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Chapter 26: Structures of Organic Compounds

61.

63.

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Chapter 26: Structures of Organic Compounds

65.

Integrative and Advanced Exercises


 Fe3  3 e  }
79. (a) Oxdn : {Fe  2

Redn : C 6 H 5 NO 2  7 H   6 e  
 C 6 H 5 NH 3  2 H 2 O

C 6 H 5 NO 2  7 H   2 Fe 
 C 6 H 5 NH 3  2 H 2 O  2 Fe 3

 C 6 H 5 COOH  4 H   4 e  }  3
(b) Oxdn : {C 6 H 5 CH 2 OH  H 2 O 
2
Redn : {Cr2 O 7  14 H   6 e  
 2 Cr 3  7 H 2 O} 2
2
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: {CH 3 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  } 2

 3 CH 3 CHOHCH 2 OH  2 MnO 2  2 OH 
3 CH 3 CH  CH 2  2 MnO 4  4 H 2 O 

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Chapter 26: Structures of Organic Compounds

81. 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:
1atm
(735  9) mmHg   0.0402 L
PV 760 mmHg
amount N 2    1.57  10 3 mol N 2
RT 0.08206 L atm mol 1 K 1  298 K

28.01 g N 2
1.57  10 3 mol N 2 
1 mol N 2
% N  100 %  24.1% N
0.1825 g sample
Now we determine the amounts of C, H, N, and O in the first sample.
1 mol CO 2 1 mol C
amount C  0.2895 g CO 2    0.006578 mol C
44.010 g CO 2 1 mol CO 2
12.011 g C
mass C  0.006578 mol C   0.07901 g C
1 mol C
1 mol H 2 O 2 mol H
amount H  0.1192 g H 2 O    0.01323 mol H
18.015 g H 2 O 1 mol H 2 O
1.0079 g H
mass H  0.01323 mol 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
From this information we determine the empirical formula of the compound.
0.006578 mol C  0.00328 
 2.01 mol C 0.01323 mol H  0.00328 
 4.03 mol H
0.00328 mol N  0.00328 
 1.00 mol N 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 3.66C - 5.50C
solution: m    0.359 m
Kf  5.12 C/m
0.359 mol solute
amount solute  0.02600 kg benzene   0.00933 mol solute
1 kg benzene
1.082 g
M   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

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Chapter 26: Structures of Organic Compounds

84. (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.

89. (a) ester, amine(tertiary), arene


(b) C1= sp2, C2 = sp3, C3 = sp3, C4 = sp3, N = sp3
(c) Carbons 2 and 4 are chiral.

SELF-ASSESSMENT EXERCISES

101. 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. The molecular formula of cyclobutane is C4H8. The correct answer is (b).

103. 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:

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Chapter 26: Structures of Organic Compounds

108. The correct answer is (c).

Ethyl methyl ketone

109. C4H10 has only two constitutional isomers, whereas C4H8 has three (2-butene, 1-butene and
cyclobutane).

110. (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.

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