Chapter 16 Smith

Chapter 16–1
Chapter 16 Aldehydes and Ketones

Solutions to In-Chapter Problems
16.1 An aldehyde has at least one H atom bonded to the carbonyl group.
A ketone has two alkyl groups bonded to the carbonyl group.
O O
C C
a. CH3CH2 H aldehyde c. (CH3)3C CH3 ketone
O O
C C
b. CH3CH2 CH3 ketone d. (CH3CH2)2CH H aldehyde
16.2 Draw the constitutional isomers of molecular formula C4H8O and then label each compound using
the definitions from Answer 16.1.
O O O
C C C
CH3CH2 CH3 ketone CH3CH2CH2 H aldehyde (CH3)2CH H aldehyde
16.3 Trigonal planar carbons are carbons bonded to three other groups. Each trigonal planar carbon is
labeled with an arrow.
CH3 CH3 H CH3 H

C C C H
C C C
H H C H
CH3 CH3 C
C
H O
16.4 To name an aldehyde using the IUPAC system, use the steps in Example 16.1:
[1] Find the longest chain containing the CHO group, and change the -e ending of the parent
alkane to the suffix -al.
[2] Number the chain or ring to put the CHO group at C1, but omit this number from the name.
Apply all of the other usual rules of nomenclature.
a. (CH3)2CHCH2CH2CH2CHO
5-methyl
CH3 O CH3 O
CH3CHCH2CH2CH2CH CH3CHCH2CH2CH2CH Answer: 5-methylhexanal
hexane hexanal
(6 C's)
© 2013 by McGraw-Hill Education. This is proprietary material solely for authorized instructor use. Not authorized for sale or distribution in any
manner. This document may not be copied, scanned, duplicated, forwarded, distributed, or posted on a website, in whole or part.
Chapter 16–2
b. (CH3)3CC(CH3)2CH2CHO
3,3,4,4-tetramethyl
CH3 CH3 H O CH3 CH3 H O
CH3 C C C C H CH3 C C C C H Answer:
CH3 CH3 H 5 CH3 CH3 H 1 3,3,4,4-tetramethylpentanal
4 2
pentane pentanal
(5 C's)
CH2CH3 CHO
c. CH3CHCHCH2CH2CHCH3
CH3 re-draw 2,5,6-trimethyl
CH3 CH3 CH3 CH3
CH3CH2CHCHCH2CH2CHCH CH3CH2CHCHCH2CH2CHCH Answer:
CH3 O CH3 O 2,5,6-trimethyloctanal
6 5 2 1
octane octanal
(8 C's)
16.5 Work backwards from the name to draw each structure.
!a. 2-chloropropanal !c. 3,6-diethylnonanal 3,6-diethyl

Cl 2-chloro CH2CH3
3 C chain with CH3CHCHO 9 C chain with
a CHO at C1 a CHO at C1 CH3CH2CH2CHCH2CH2CHCH2CHO
CH2CH3
d. o-ethylbenzaldehyde
b. 3,4,5-triethylheptanal CH3CH2 CH2CH3
4 CHO
7 C chain with CH3CH2CHCHCHCH2CHO benzene ring
a CHO at C1 5 3 with a CHO
CH2CH3 CH2CH3 o-ethyl
16.6 To name an aldehyde using the IUPAC system, use the steps in Example 16.1.
8-methyl
1 nonane nonanal 8-methylnonanal

a. 8 2 (9 C's)
1
8 decane decanal 8-methyldecanal
2
b. (10 C's)
8-methyl
Chapter 16–3
16.7 To name a ketone using IUPAC rules, use the steps in Example 16.2:
[1] Find the longest chain containing the carbonyl group, and change the -e ending of the parent
alkane to the suffix -one.
[2] Number the carbon chain to give the carbonyl carbon the lower number. Apply all of the other
usual rules of nomenclature.
O O4
a. CH3CH2CCHCH2CH2CH3 CH3CH2CCHCH2CH2CH3 Answer: 4-methyl-3-heptanone
CH3 1 2 3 CH
3
heptane heptanone
(7 C's) 4-methyl
CH3 CH3 2-methyl
b. 2
O O Answer: 2-methylcyclopentanone
cyclopentane cyclopentanone 1
(5 C's)
CH3 O 2 CH3 O
c. CH3C CCH2CH2CH2CH3 CH3C CCH2CH2CH2CH3 Answer: 2,2-dimethyl-3-heptanone
CH3 1 CH3 3
heptane heptanone
2,2-dimethyl
(7 C's)
O acetophenone
a. butyl ethyl ketone CH3CH2CH2CH2CCH2CH3 c. p-ethylacetophenone
O
p-ethyl CH3CH2 C CH3
butyl ethyl
b. 2-methyl-3-pentanone d. 2-propylcyclobutanone
O O
5 C chain with 4 C ring with
C=O at C3 CH3CH2CCHCH3
C=O at C1
CH3 2-methyl CH2CH2CH3 2-propyl
16.9 Aldehydes and ketones have higher boiling points than hydrocarbons of comparable size.
Aldehydes and ketones have lower boiling points than alcohols of comparable size.
a. O or CH3 c. O or OH
ketone hydrocarbon ketone alcohol

higher boiling point higher boiling point
b. (CH3CH2)2CO or (CH3CH2)2C=CH2 d. CH3(CH2)6CH3 or CH3(CH2)5CHO
ketone hydrocarbon hydrocarbon aldehyde

Chapter 16–4
16.10 Acetone will be soluble in water and organic solvents since it is a low molecular weight ketone
(less than six carbons). Progesterone will be soluble only in organic solvents since it has many
carbons and only two polar functional groups.
ketone
O
CH3
CH3 C
O
C CH3
CH3 CH3
small ketone large molecule with two ketones
acetone progesterone
O
ketone
16.11 Hexane is soluble in acetone because both compounds are organic and “like dissolves like.” Water
is soluble in acetone because acetone has a short hydrocarbon chain and is capable of hydrogen
bonding with water.
16.12 Compare the functional groups in each sunscreen. Dioxybenzone will most likely be washed off in
water because it contains two hydroxyl groups and is the most water soluble.
O OH O O OH O OH
C C C C
CH2
OCH3 CH3O C(CH3)3 OCH3
oxybenzone avobenzone dioxybenzone

one hydroxyl group two ketones two hydroxyl groups
one ketone one ether one ketone
one ether one ether
most water soluble
16.13 Draw the product of each reaction using the guidelines in Example 16.3. Compounds that contain
a C–H and C–O bond on the same carbon are oxidized with K2Cr2O7.
• Aldehydes (RCHO) are oxidized to RCO2H.
• Ketones (R2CO) are not oxidized with K2Cr2O7.
O
K2Cr2O7
a. CH3CH2CHO C
CH3CH2 OH
K2Cr2O7
b. (CH3CH2)2C=O No reaction
CH3 CH3 CH3 CH3 O

K2Cr2O7
c. CH3C=CHCH2CH2CHCH2CHO CH3C CHCH2CH2CHCH2C OH
Chapter 16–5
16.14 Draw the product of each reaction using Example 16.4 as a guide. Only aldehydes (RCHO) react
with Tollens reagent, and they are oxidized to RCO2H. Ketones and alcohols are inert to
oxidation.
O O
Ag2O Ag2O
a. CH3(CH2)6CHO CH3(CH2)6C OH c. CHO C
NH4OH NH4OH OH
Ag2O Ag2O
b. O No reaction d. OH No reaction
NH4OH NH4OH
16.15 Draw the products of reduction using the steps in Example 16.5.
• Locate the C=O and mentally break one bond in the double bond.
• Mentally break the H–H bond of the reagent.
• Add one H atom to each atom of the C=O, forming new C–H and O–H single bonds.
O OH O
H2 H2 OH
C CH3CH2CH2CH2 C
a. CH3CH2CH2 H c. CH3CHCH2CH3
Pd CH3 CH2CH3 Pd
O OH
H2 H2
b. d. CHO CH2OH
Pd Pd
CH3 CH3
16.16 Work backwards to determine what carbonyl compound is needed to prepare alcohol A.
O H2 OH
(CH3)2CHCH2 CCH3 Pd (CH3)2CHCH2 CHCH3
16.17 Recall that stereoisomers differ only in the three-dimensional arrangement of atoms in space, but
all connectivity is identical. Constitutional isomers have the same molecular formula, but atoms
are connected differently.
a. All-trans-retinal and 11-cis-retinal are stereoisomers, and differ only in the arrangement of
groups around one double bond.
b. All-trans-retinal and vitamin A are not isomers. They have different molecular formulas.
c. Vitamin A and 11-cis-retinol are stereoisomers, and differ only in the arrangement of groups
around one double bond.
Chapter 16–6
16.18 To form a hemiacetal and acetal from a carbonyl compound, use the steps in Example 16.6.
• Locate the C=O in the starting material.
• Break one C–O bond and add one equivalent of ROH across the double bond, placing the OR
group on the carbonyl carbon. This forms the hemiacetal.
• Replace the OH group of the hemiacetal by OR to form the acetal.
CH3OH
O OCH3 OCH3
H2SO4 H2SO4
a. C + CH3OH CH3COH CH3COCH3
CH3 H
H H
hemiacetal acetal
OCH3 CH3OH OCH3

H2SO4
H2SO4
b. (CH3CH2)2C=O + CH3OH (CH3CH2)2COH (CH3CH2)2COCH3
hemiacetal acetal
O OCH2CH3
CH3CH2OH OCH2CH3
C H2SO4 CHOH
H H2SO4 CHOCH2CH3
c. + CH3CH2OH
hemiacetal acetal
16.19 Recall the definitions from Example 16.7 to identify the functional groups:
• An ether has the general structure ROR.
• A hemiacetal has one C bonded to OH and OR.
• An acetal has one C bonded to two OR groups.
OCH3 OCH3 OH O
a. b. OCH3 c. CH3CH3CH2CH2 C OCH3 d. CH3
H O CH3
ether acetal hemiacetal acetal
16.20 Label the acetal or hemiacetal in each compound using the definitions in Example 16.7.
acetal
hemiacetal CH2OH
HOCH2
HOCH2 O O
O
a. HO OH b.
HO OH
HO NH2 OH
16.21 Draw the products of each reaction using the steps in Example 16.6.
O
H2SO4 O
a. OH + CH3CH2OH
OCH2CH3
Replace OH by OCH2CH3
Chapter 16–7
O O
H2SO4
b. OH + OH O
Replace OH by O
16.22 To draw the products of hydrolysis, use the steps in Example 16.8.
• Locate the two C–OR bonds on the same carbon.
• Replace the two C–O single bonds with a carbonyl group (C=O).
• Each OR group then becomes a molecule of alcohol (ROH) product.
H2O O
OCH3 H2SO4 H2O
C OCH3 O
CH3 CH2CH2CH3 H2SO4
a. CH3 C OCH3 C
c. C H
+ H
CH2CH2CH3
OCH3
2 CH3OH +
2 CH3OH
CH3CH2O OCH2CH3 H2O O
H2SO4
b. + 2 CH3CH2OH
Solutions to End-of-Chapter Problems
16.23 Draw a structure to fit each description.
CH2CH3 O O
a. CH3CH2CH2CHCH2CHO b. CH3CH2CCHCH3 c. O d. C
CH3 H
aldehyde ketone ketone aldehyde
C8H16O C6H12O C5H8O C6H10O
16.24 Draw the structure of a constitutional isomer to fit each description.
O
a. CH3CH2CH2CH2CH2CH2CHO b. CH3CH2CCH2CH2CH2CH3 c. CH3CH2CH2CH2CH CHCH2OH
16.25 Compare C=O and C=C bonds.

a. Both are trigonal planar.
b. A C=O is polar and a C=C is not polar.
c. Both functional groups undergo addition reactions.
16.26 Compare RCHO and RCOR.
a. An aldehyde has at least one hydrogen bonded to the carbonyl group and a ketone has two
alkyl groups bonded to the carbonyl group.
b. Both are trigonal planar.
c. Both are polar.
Chapter 16–8
16.27 An aldehyde cannot have the molecular formula C5H12O. C5H12 has too many H’s. Since an
aldehyde has a double bond, the number of C’s and H’s resembles an alkene, not an alkane. An
aldehyde with 5 C’s would have the molecular formula C5H10O.
16.28 A ketone cannot have the molecular formula C4H10O. C4H10 has too many H’s. Since a ketone has
a double bond, the number of C’s and H’s resembles an alkene, not an alkane. A ketone with 4
C’s would have the molecular formula C4H8O.
16.29 To name the aldehyde and ketone, use the IUPAC rules in Examples 16.1 and 16.2.
2-methyl
a. 1 b.
2
1
3
3-ethyl
pentane pentanal
(5 C's)
cyclohexane cyclohexanone
2-methylpentanal (6 C ring)
3-ethylcyclohexanone
16.30 To name the aldehyde and ketone, use the IUPAC rules in Examples 16.1 and 16.2.
m-fluoro H H
O
F
a. O b. Cl
H H Br
H 2-chloro-2-fluoro
benzene benzaldehyde cyclopentane cylcopentanone

m-fluorobenzaldehyde 2-chloro-2-fluorocyclopentanone
Apply all other usual rules of nomenclature.
a. CH3CH2CH2CHCH2CHO CH3CH2CH2CHCH2CHO Answer: 3-methylhexanal
CH3 CH3
3-methyl
hexane hexanal
(6 C's)
CH3 CH3 3 1
b. CH3CH2CHCH2CHCH2CHO CH3CH2CHCH2CHCH2CHO Answer: 3,5-dimethylheptanal
CH3 5 CH3
3,5-dimethyl
heptane heptanal
(7 C's)
Chapter 16–9
O C H O C H
H C H H C H
c. CH3CH2CH2 C CH2CH2CH3 CH3CH2CH2 C CH2CH2CH3 Answer: 3-propylhexanal
H H 3
hexane hexanal 3-propyl
(6 C's)
CH2CH3 CH3 CH2CH3 CH3 2,2-dimethyl

d. CH3CH2CCH2CH2CH2 C CHO CH3CH2CCH2CH2CH2 C CHO Answer:
CH2CH3 CH3 CH2CH3 CH3 1 6,6-diethyl-2,2-dimethyloctanal
6 2
octane octanal
(8 C's)
e. Cl CHO Cl CHO Answer: p-chlorobenzaldehyde
benzaldehyde p-chloro
Apply all other usual rules of nomenclature.
CH3
a. (CH3)3CCH2CHO CH3CCH2CHO Answer: 3,3-dimethylbutanal
butane butanal CH3 2 methyls on C3
(4 C's)
CH2CH3
b. (CH3CH2)2CHCH2CH2CHO CH3CH2CHCH2CH2CHO Answer: 4-ethylhexanal
hexane hexanal 4-ethyl
(6 C's)
CH3 CH3
c. CH3CH2CH2CH2CHCHCH3 CH3CH2CH2CH2CHCHCH3 Answer: 3,4-dimethyloctanal
CH2CHO CH2CHO
octane octanal 3,4-dimethyl
(8 C's)
d. (CH3CH2CH2CH2)2CHCH2CHO CH3CH2CH2CH2CHCH2CHO Answer: 3-butylheptanal

CH2CH2CH2CH3
heptane heptanal 3-butyl
(7 C's)
Chapter 16–10
CH3CH2 CH3CH2 m-ethyl

f. Answer: m-ethylbenzaldehyde
CHO CHO
benzaldehyde benzaldehyde
16.33 Work backwards to draw the structure.
a. 3,3-dichloropentanal Cl 3,3-dichloro c. o-bromobenzaldehyde

CHO
CH3CH2CCH2CHO
5 C chain Cl
benzene ring with CHO Br o-bromo
d. 4-hydroxyheptanal OH 4-hydroxy
b. 3,4-dimethylhexanal CH3 3,4-dimethyl
CH3CH2CH2CHCH2CH2CHO
CH3CH2CHCHCH2CHO
6 C chain CH3 7 C chain
16.34 Work backwards to draw the structure.
a. 2-bromooctanal 2-bromo Br c. 3,4-dimethoxybenzaldehyde 4

H3CO CHO
CH3CH2CH2CH2CH2CH2CHCHO
3
8 C chain benzene ring with CHO H3CO 3,4-dimethoxy
d. 3,4-dihydroxynonanal OH OH
b. 2-propylheptanal 2-propyl CH2CH2CH3
CH3CH2CH2CH2CH2CH CHCH2CHO
CH3CH2CH2CH2CH2CHCHO
7 C chain 9 C chain 3,4-hydroxy
O O
C 4 C 1
a. CH3CHCH2 CH3 CH3CHCH2 2 CH3 Answer: 4-methyl-2-pentanone
CH3 CH3
pentane pentanone
(5 C's) 4-methyl
O O
CH3 CH3 CH3 CH3
b. 6 1
2 Answer: 2,6-dimethylcyclohexanone
cyclohexane cyclohexanone 2,6-dimethyl

(6 C's)
Chapter 16–11
O O
C C
c. CH3 CH3
Answer: o-butylacetophenone
CH2CH2CH2CH3 CH2CH2CH2CH3
benzene ring with CH3C=O
acetophenone o-butyl
O O
d. C 1 2
C 4
CH3CH CHCH2CH3 CH3CH 3 CHCH2CH3 Answer: 2,4-dimethyl-3-hexanone
CH3 CH3 CH3 CH3
hexane hexanone
2,4-dimethyl
(6 C's)
3-chloro
Cl Cl 3 2
e. 1
O O Answer: 3-chlorocyclopentanone
cyclopentane cyclopentanone
(5 C's)
3
3-ethyl
a. CH3CH2CH2CH2CHCH2CH3 CH3CH2CH2CH2CHCH2CH3 Answer: 3-ethyl-2-heptanone
C C
O CH3 O 2 CH3
heptane heptanone
(7 C's)
O O 1
3,3-dichloro
b. Answer: 3,3-dichlorocyclobutanone
Cl 3
Cl
Cl Cl
cyclobutane cyclobutanone
(4 C's)
O O
c. C C 9 Answer: 9-methyl-3-decanone
CH3CH2 (CH2)5CH(CH3)2 CH3CH2 3 (CH2)5CHCH3
CH3
9-methyl
decane decanone
(10 C's)
Chapter 16–12
O O
C 4C
3 5
d. CH3CH2CH CHCH2CH3 CH3CH2CH CHCH2CH3 Answer:
CH3 CH3 CH3 CH3 3,5-dimethyl-4-heptanone
heptane heptanone
(7 C's) 3,5-dimethyl
CH2CH3 CH2CH3 2-ethyl

2
e. Answer: 2-ethyl-4-methylcyclopentanone
O 4 O
CH3 CH3 4-methyl
cyclopentane cyclopentanone
(5 C's)
a. 3,3-dimethyl-2-hexanone c. m-ethylacetophenone O
3 CH3 O C
CH3CH2CH2C C 2 CH3
6 C chain benzene ring with a
CH3 CH3 CH3C=O
1
3,3-dimethyl m-ethyl CH2CH3
b. methyl propyl ketone O d. 2,4,5-triethylcyclohexanone O

C 2 CH2CH3
CH3 CH2CH2CH3 6 C ring 1
two alkyl groups with a 5
C=O in the middle 4
propyl CH3CH2
methyl 2,4,5-triethyl CH2CH3
a. dibutyl ketone O c. p-bromoacetophenone O

C C
CH3CH2CH2CH2 CH2CH2CH2CH3 CH3
benzene ring with a
two butyl groups CH3C=O
with a C=O in the middle butyl Br
p-bromo
O
b. 1-chloro-3-pentanone O d. 3-hydroxycyclopentanone
1 C 1
ClCH2CH2 3 CH2CH3 5 C ring 3
5 C chain
hydroxy OH
chloro
Chapter 16–13
16.39 Draw the four aldehydes and then name them using the steps in Example 16.1.
2,2-dimethyl 3,3-dimethyl 2,3-dimethyl 2-ethyl

2
2 CH3 3 CH3 CH3
1 1 CH2CH3
CH3CH2CCHO CH3CCH2CHO CH3CHCHCHO CH3CH2CHCHO
3
CH3 1 CH3 CH3 2 1
4 C chain 4 C chain 4 C chain 4 C chain

2,2-dimethylbutanal 3,3-dimethylbutanal 2,3-dimethylbutanal 2-ethylbutanal
16.40 Draw the three ketones and then name them using the steps in Example 16.1.
O O O
C C 3 C
CH3CH2CH2 2 CH3 CH3CH2 3 CH2CH3 CH3 CH 2 CH3
5 C chain 5 C chain 3-methyl CH3 4 C chain

2-pentanone 3-pentanone 3-methyl-2-butanone
16.41 Draw the structure and correct each name.
O O O O
a. CH3CH2CH2CH2CH b. CH3CH2CH2CCH2CH3 c. CH3CH2CH2CHCCH3 d. CH3CH2CH2CH2CH2CH2CHCH
CH3 CH3
1-pentanone 4-hexanone 2-methyl-1-octanal
A ketone cannot be at C1. Re-number to use a 3-propyl-2-butanone An aldehyde is always at C1.
It must be an aldehyde. lower number. Find the longest chain. Omit the "1."
pentanal 3-hexanone 3-methyl-2-hexanone 2-methyloctanal
16.42 Draw the structure and correct each name.
O
O O
CH3 O
a. CH3CH2CH2CH2CH2CCH2CH3 b. CH3CH2CH2CH2CH2CH2CH c. d.
6-octanone 1-heptanone
Re-number to use a A ketone cannot be at C1. CH2CH2CH3
lower number. It must be an aldehyde.
3-octanone heptanal 3-propyl-1-cyclopentanone 5-methylcyclohexanone
The ketone is always at Re-number to use a
C1 on a ring. lower number.
3-propylcyclopentanone 3-methylcyclohexanone
16.43 Draw benzaldehyde and then the hydrogen bond.
H
hydrogen bond O
H
O
C
H
Chapter 16–14
16.44 Draw the structures and then determine if hydrogen bonding is possible.
a. Hydrogen bonding is not possible between two molecules of acetaldehyde.

b. Hydrogen bonding is possible between ethanal and water.
H
hydrogen bond O
H
O
C
CH3 H
c. Hydrogen bonding is possible between ethanal and methanol.
CH3
hydrogen bond O
H
O
C
CH3 H
a. (CH3)3CCH2CH2CH3 or (CH3)3CCH2CHO b. COCH3 or CH2CH2OH
hydrocarbon aldehyde ketone alcohol

a. CH3(CH2)6CHO or CH3(CH2)7OH b. CH3(CH2)6CHO or CH3(CH2)2CHO
aldehyde aldehyde aldehyde

alcohol higher molar mass
16.47 Aldehydes and ketones have higher melting points than hydrocarbons of comparable size.
Aldehydes and ketones have lower melting points than alcohols of comparable size.
CH3 O OH
Increasing melting point
16.48 Menthol is a solid at room temperature but menthone is a liquid because menthol has a hydroxy
group attached to the cyclohexane ring, whereas menthone has a ketone. Alcohols will have
higher melting points than ketones for compounds of comparable size.
Chapter 16–15
16.49 Low molecular weight aldehydes and ketones (less than six carbons) are water soluble.
O
CHO
C
a. b. CH3 CH2CH3 c. CH3CH2CH2CH3
7 C aldehyde 4 C ketone hydrocarbon

insoluble soluble insoluble
16.50 Low molecular weight aldehydes and ketones (less than six carbons) are water soluble.
O
a. b. CH3CH2CH2CHO c. CH3CH2CH2OH
CH3 4 C aldehyde alcohol
7 C ketone soluble soluble
insoluble
16.51 2,3-Butanedione has two carbonyl groups capable of hydrogen bonding whereas acetone has one
carbonyl group. This makes 2,3-butanedione more water soluble than acetone. 2,3-Butanedione
would also be soluble in an organic solvent like diethyl ether by the “like dissolves like” rule.
16.52 Acetone has a much higher boiling point than formaldehyde because acetone contains three
carbons (CH3COCH3), whereas formaldehyde contains only one carbon (HCHO). Boiling points
increase with the number of carbons in a molecule.
16.53 Draw the product of each reaction using the steps in Example 16.3. Compounds that contain a
C–H and C–O bond on the same carbon are oxidized with K2Cr2O7.
• 1° Alcohols (RCH2OH) are oxidized to RCO2H (Section 14.5B).
K2Cr2O7 K2Cr2O7
CH3(CH2)4COOH CH2CHO CH2COOH
a. CH3(CH2)4CHO b.
K2Cr2O7 K2Cr2O7
c. CH2CH3 No reaction d. CH3(CH2)4CH2OH CH3(CH2)4COOH
16.54 Draw the product of each reaction using the steps in Example 16.3. Compounds that contain a
C–H and C–O bond on the same carbon are oxidized with K2Cr2O7.
• 1° Alcohols (RCH2OH) are oxidized to RCO2H (Section 14.5B).
Cl Cl OH O
K2Cr2O7 K2Cr2O7
a. c. CH3CHCH2CH2CH3 CH3CCH2CH2CH3
CHO COOH
O
K2Cr2O7 C K2Cr2O7
b. CH3(CH2)8CHO CH3 No reaction
CH3(CH2)8COOH d.
Chapter 16–16
16.55 Draw the product of each reaction using Example 16.4 as a guide. Only aldehydes (RCHO)
react with Tollens reagent, and they are oxidized to RCO2H. Ketones and alcohols are inert to
oxidation.
O
Ag2O Ag2O
a. CH3(CH2)4CHO CH3(CH2)4COOH No reaction
NH4OH
c. CH2CH3
NH4OH
Ag2O Ag2O
b. CH2CHO CH2COOH d. CH3(CH2)4CH2OH No reaction
NH4OH NH4OH
16.56 Draw the product of each reaction using Example 16.4 as a guide. Only aldehydes (RCHO)
react with Tollens reagent, and they are oxidized to RCO2H. Ketones and alcohols are inert to
oxidation with Tollens reagent.
Cl Cl OH
Ag2O Ag2O
a. c. CH3CHCH2CH2CH3 No reaction
NH4OH NH4OH
CHO COOH
O
Ag2O C Ag2O
b. CH3(CH2)8CHO CH3 No reaction
CH3(CH2)8COOH d.
NH4OH NH4OH
16.57 Answer each question about erythrulose.
O
ketone Tollens reagent
c. HO No reaction
a, b.
1° OH
1° OH
erythrulose O O O
K2Cr2O7
d. HO HO
2° OH OH
OH O O
16.58
2° ROH
H OH H OH H OH
a, b, c. 1° ROH HO C H d. HO C H Ag2O HO C OH
C C C C C C
aldehyde NH4OH
H H H H H H
O O O
chirality center
Chapter 16–17
16.59 Work backwards to determine what aldehyde can be used to prepare each carboxylic acid.
CH3 CH3
a. CH3CH2CHCH2CO2H CH3CH2CHCH2CHO c. CH3CH2CHCH2CH3 CH3CH2CHCH2CH3
CO2H CHO
b. CH3 CO2H CH3 CHO
16.60 Work backwards to determine what aldehyde can be used to prepare each carboxylic acid.
Cl Cl
a. CH2CH2CO2H CH2CH2CHO c. CH3(CH2)8CHCO2H CH3(CH2)8CHCHO
Br Br
b. CO2H CHO
H2 O OH
H2
a. CH3CH2 CHO CH3CH2 CH2OH b.
Pd Pd
CH3 CH3
O
H2 HO
C H2
a. CH3CH2 CH2CH(CH3)2 CH3CH2CHCH2CH(CH3)2 b. CH3(CH2)6CHO CH3(CH2)6CH2OH
Pd
Pd
16.63
CH3 CH3 CH3
H2
a, b: CH3CH2 CH (CH2)4CHO c. CH3CH2 CH (CH2)4CHO CH3CH2 CH (CH2)4CH2OH
Pd
chirality center
16.64
O O OH
H2
a. b, c.
Pd
chirality center
Chapter 16–18
16.65 Work backwards to determine what carbonyl compound is needed to make each alcohol.
OH O
O
C
a. CH3CH2CH2CH2CH2OH CH3CH2CH2CH2 H b.
CH3 CH3
16.66 Work backwards to determine what carbonyl compound is needed to make each alcohol.
OH O O
a. CH3CH2CHCH2CH2CH3 CH3CH2CCH2CH2CH3 b. (CH3)2CHCH2CH2OH (CH3)2CHCH2CH
16.67 1-Methylcyclohexanol is a 3o alcohol and cannot be produced from the reduction of a carbonyl
compound because only 1° or 2° alcohols can be formed in these reactions.
16.68 (CH3)3COH cannot be prepared by the reduction of a carbonyl compound because it is a tertiary
alcohol. A carbonyl group attached to the tertiary carbon would give the carbon five bonds.
16.69 Recall the definitions from Example 16.7 to draw a compound of molecular formula C5H12O2 that
fits each description:
• An ether has the general structure ROR.
• A hemiacetal has one C bonded to OH and OR.
• An acetal has one C bonded to two OR groups.
H H H
a. CH3CH2 O C O CH2CH3 c. CH3CH2 O C C O CH3
H H H
acetal two ethers
H
H H OH alcohol
b. CH3 C O CH2CH2CH3 d. CH3 C O C C CH3
OH
H H H
hemiacetal
ether
16.70 Locate the two acetals in amygdalin.
HOCH2 acetal CN
O O CH
HO O O
CH2 OH
HO OH
HO OH
16.71 Label the functional groups using the definitions from Example 16.7.
hemiacetal ether ether

OCH3 OCH2CH3 OCH3 O
a.
CH3 C H b. CH3 C H c. HOCH2CHCH2CH3 d.
acetal OCH3 OH
alcohol
Chapter 16–19
16.72 Label the functional groups using the definitions from Example 16.7.
hemiacetal ether
OCH3 OH acetal
O
a. ether b. CH3 C OCH2CH2CH3 c. O O
d.
OCH3 CH3 OCH2CH2CH3
• Break one C–O bond and add one equivalent of CH3OH across the double bond, placing the
OCH3 group on the carbonyl carbon. This forms the hemiacetal.
• Replace the OH group of the hemiacetal by OCH3 to form the acetal.
2 CH3OH 2 CH3OH
CH3 O CH3O
CH3 H2SO4
H2SO4 OCH3 c. C CH3 C OCH3
a. O CH3 CH2CH2CH3
OCH3 CH2CH2CH3
CH3 CH3
2 CH3OH
2 CH3OH
H2SO4 OCH3
b. CH2 O CH2(OCH3)2 H2SO4
d. CH2CHO CH2CH
OCH3
• Break one C–O bond and add one equivalent of CH3CH2OH across the double bond, placing
the OCH2CH3 group on the carbonyl carbon. This forms the hemiacetal.
• Replace the OH group of the hemiacetal by OCH2CH3 to form the acetal.
O 2 CH3CH2OH CH3CH2O
C H2SO4 CH3CH2CH2 C OCH2CH3
a. CH3CH2CH2 CH2CH3
CH2CH3
O OCH2CH3
2 CH3CH2OH
b. H2SO4 OCH2CH3
CH3 CH3
2 CH3CH2OH OCH2CH3
H2SO4
c. (CH3)2CHCH2CH2CHO (CH3)2CHCH2CH2CH
OCH2CH3
OCH2CH3
2 CH3CH2OH
CH3CH2CH
H2SO4
d. CH3CH2CHO OCH2CH3
Chapter 16–20
16.75 Draw the products of each reaction.
a. b.
HO HO
O OH O
H2SO4 H2SO4
C CH3 C O CH3 C O
CH3 CH3
CH3 CH3
a. b.
O HO OH HO
C C O O
H H2SO4 H2SO4
H C O
H
16.77 Answer each question.
hemiacetal carbon CH3OH

O O H2SO4 O
a. OH c. OH OCH3
O O
b. OH HOCH2CH2CH2CH
CH3 hemiacetal carbon CH3CH2OH CH3

CH3 H2SO4
O O O
a. CH3 c. CH3
CH3
OH OH OCH2CH3
CH3 CH3 O
O
b. CH3 HOCH2CCH2CH2CH
OH CH3
16.79 Draw the product of cyclization.
O OH
C CH3
HOCH2CH2CH2CH H O
C CH3
Chapter 16–21
16.80 Draw the product of cyclization.
O OH
C
HOCHCH2CH2CH2 H O
CH3 D
CH3
H2O
OCH2CH2CH3 H2SO4
a. O + 2 HOCH2CH2CH3
OCH2CH2CH3
H2O
OCH3 O
H2SO4
b. H C CH2CH2CH3 H C CH2CH2CH3 + 2 HOCH3
OCH3
H2O
OCH2CH3 H2SO4 O
a. CH3CH2 C CH2CH3 CH3CH2 C CH2CH3 + 2 HOCH2CH3
OCH2CH3
H2O
OCH3 H2SO4
b. CH3O CH3O O + 2 CH3OH
OCH3
16.83 Answer each question about compound A.
p-methyl
OCH3
O * * O O 2 CH3OH
a, b. CH3 c. CH3 * * d. CH3 CH3 C CH3
* (acid)
CH3 CH3 CH3 OCH3
* *
p-methylacetophenone seven trigonal
planar C's
Chapter 16–22
16.84
H H H OCH3
C O * * C* O C O 2 CH3OH
H C OCH
3
a. C b. * * C c. C C
H H H (acid) H
H * * H H H
7 planar carbons
H
C O H2
d. C CH2CH2OH
H Pd
H
O O
H2 OCH3
a. C d. 2 CH3OH
CH2OH C C H
H Pd H2SO4
H OCH3
O O O 2 CH CH OH OCH2CH3
K2Cr2O7 3 2
b. C COH e. C C H
H2SO4
H H OCH2CH3
O O OCH2CH3 O
Ag2O H2O
c. C COH f. C H C + 2 CH3CH2OH
NH4OH H2SO4
H OCH2CH3 H
O
H2
a. CH3O C CH3O CH2OH
Pd
H
O O
K2Cr2O7
b. CH3O C CH3O COH
H
O O
Ag2O
c. CH3O C CH3O COH
H NH4OH
O OCH3
2 CH3OH
d. CH3O C CH3O C H
H2SO4
H OCH3
O 2 CH CH OH OCH2CH3
3 2
e. CH3O C CH3O C H
H2SO4
H OCH2CH3
OCH2CH3 O
H2O
f. CH3O C H CH3O C + 2 CH3CH2OH
H2SO4
OCH2CH3 H
Chapter 16–23
O OH OCH3
H2 O
a. C CH3 C (CH2)4CH3 d. 2 CH3OH
C CH3 C (CH2)4CH3
CH3 (CH2)4CH3 Pd CH3 (CH2)4CH3 H2SO4
H OCH3
O 2 CH3CH2OH OCH2CH3
K2Cr2O7 O
b. C No reaction e. CH3 C (CH2)4CH3
CH3 (CH2)4CH3 C H2SO4
CH3 (CH2)4CH3 OCH2CH3
O OCH2CH3 O
Ag2O H2O
c. C No reaction f. CH3 C (CH2)4CH3 C
CH3 (CH2)4CH3 H2SO4 CH3 (CH2)4CH3
NH4OH OCH2CH3
+ 2 CH3CH2OH
O OH
H2
a. C (CH3)2CH C (CH2)2CH(CH3)2
(CH3)2CH (CH2)2CH(CH3)2 Pd
H
O
C K2Cr2O7
b. (CH3)2CH (CH2)2CH(CH3)2 No reaction
O
C Ag2O
c. (CH3)2CH (CH2)2CH(CH3)2 No reaction
NH4OH
O
OCH3
C 2 CH3OH
d. (CH3)2CH (CH2)2CH(CH3)2 (CH3)2CH C (CH2)2CH(CH3)2
H2SO4 OCH3
O
2 CH3CH2OH OCH2CH3
C
e. (CH3)2CH (CH2)2CH(CH3)2 (CH3)2CH C (CH2)2CH(CH3)2
H2SO4
OCH2CH3
OCH2CH3 O
H2O
f. (CH3)2CH C (CH2)2CH(CH3)2 (CH3)2CH C (CH2)2CH(CH3)2 + 2 CH3CH2OH
H2SO4
OCH2CH3
16.89 Draw the three constitutional isomers that can be converted to 1-pentanol. The starting material
needs a C=O at C1 and a C=C.
CH2 CHCH2CH2CHO
or
H2
CH3CH CHCH2CHO CH3CH2CH2CH2CH2OH
or Pd
CH3CH2CH CHCHO
Chapter 16–24
16.90 Work backwards to determine the identity of A–C.
H2 H2SO4 H2
O OH
Pd Pd
A B C
CH3 O CH3 OH
a.
CH3 CH3
H2
Pd
HO HO
CH3 O CH3 O
b.
CH3 CH3
K2Cr2O7
HO O
CH3 O CH3 OCH3
OCH3
CH3 CH3
2 CH3OH
c.
H2SO4
HO HO
CH3 O CH3 OCH2CH3
OCH2CH3
d. CH3 2 CH3CH2OH CH3
H2SO4
HO HO
Chapter 16–25
O OH
a. HO CCH2NH(CH2)6O(CH2)4 excess H2 HO CCH2NH(CH2)6O(CH2)4
Pd H
O C X HO CH salmeterol
H H
chirality center
OH
b. HO CCH2NH(CH2)6O(CH2)4
H
HO CH salmeterol
H
H H
C C
c. CH2NH(CH2)6O(CH2)4 (CH2)4O(CH2)6NHCH2
OH HO
HO OH
enantiomers CH2OH
CH2OH
16.93 Draw the product of oxidation.
O
NAD+
CH CH CHO CH CH C OH
enzyme
ether
O O H2O O O
a. b. + OH
H2SO4 OH
O alkene O O O
benzene
16.95 Label each hemiacetal or alcohol.
HOCH2 O OH of a hemiacetal
OH
alcohol HO
16.96 Label the actetal carbons in paraldehyde.
CH3 O CH3
acetal O O acetal
acetal CH3
16.97 The main reaction that occurs in the rod cells in the retina is conversion of 11-cis-retinal to its
trans isomer. The cis double bond in 11-cis-retinal produces crowding, making the molecule
unstable. Light energy converts this to the more stable trans isomer, and with this conversion an
electrical impulse is generated in the optic nerve.
Chapter 16–26
16.98 All-trans-retinal is converted back to 11-cis-retinal by a series of reactions that involve biological
oxidation and reduction. NADH reduces the aldehyde in all-trans-retinal to all-trans-retinol. The
trans double bond is isomerized to a cis double bond. NAD+ oxidizes 11-cis-retinol to 11-cis-
retinal.
16.99 Identify the alcohol, acetal, hemiacetal, ether, and carboxylic acid functional groups.
alcohol HO
CH2CH3
carboxylic acid CH3
CH3
CH3 O O O
CH3 O
HO2CCHCH CH CH3
ether
CH3O CH3 hemiacetal
acetal O
ether alcohol HOCH2 OH CH3
16.100 Determine the structure of chloral hydrate.
Cl O Cl OH
H2O
Cl C C H Cl C C H
Cl Cl OH

Chapter 16 Smith

Uploaded by

Copyright:

Available Formats

Chapter 16 Smith

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Chapter 16 Smith

Uploaded by

Copyright:

Available Formats

What are the steps to name an aldehyde using IUPAC rules?

What are the steps to name an aldehyde using IUPAC rules?

What are the steps to name a ketone using IUPAC rules?

What are the steps to name a ketone using IUPAC rules?

Chapter 16–1

Chapter 16 Aldehydes and Ketones

CH3 CH3 H CH3 H

16.5 Work backwards from the name to draw each structure.

!a. 2-chloropropanal !c. 3,6-diethylnonanal 3,6-diethyl

1 nonane nonanal 8-methylnonanal

CH3 CH3 2-methyl

16.8 Work backwards from the name to draw each structure.

ketone hydrocarbon ketone alcohol

b. (CH3CH2)2CO or (CH3CH2)2C=CH2 d. CH3(CH2)6CH3 or CH3(CH2)5CHO

ketone hydrocarbon hydrocarbon aldehyde

OCH3 CH3O C(CH3)3 OCH3

oxybenzone avobenzone dioxybenzone

CH3 CH3 CH3 CH3 O

OCH3 CH3OH OCH3

Solutions to End-of-Chapter Problems

16.23 Draw a structure to fit each description.

16.24 Draw the structure of a constitutional isomer to fit each description.

16.25 Compare C=O and C=C bonds.

16.26 Compare RCHO and RCOR.

benzene benzaldehyde cyclopentane cylcopentanone

a. CH3CH2CH2CHCH2CHO CH3CH2CH2CHCH2CHO Answer: 3-methylhexanal

CH2CH3 CH3 CH2CH3 CH3 2,2-dimethyl

e. Cl CHO Cl CHO Answer: p-chlorobenzaldehyde

d. (CH3CH2CH2CH2)2CHCH2CHO CH3CH2CH2CH2CHCH2CHO Answer: 3-butylheptanal

CH3CH2 CH3CH2 m-ethyl

16.33 Work backwards to draw the structure.

a. 3,3-dichloropentanal Cl 3,3-dichloro c. o-bromobenzaldehyde

16.34 Work backwards to draw the structure.

a. 2-bromooctanal 2-bromo Br c. 3,4-dimethoxybenzaldehyde 4

cyclohexane cyclohexanone 2,6-dimethyl

CH2CH3 CH2CH3 2-ethyl

16.37 Work backwards from the name to draw each structure.

b. methyl propyl ketone O d. 2,4,5-triethylcyclohexanone O

16.38 Work backwards from the name to draw each structure.

a. dibutyl ketone O c. p-bromoacetophenone O

2,2-dimethyl 3,3-dimethyl 2,3-dimethyl 2-ethyl

4 C chain 4 C chain 4 C chain 4 C chain

5 C chain 5 C chain 3-methyl CH3 4 C chain

16.41 Draw the structure and correct each name.

16.42 Draw the structure and correct each name.

16.43 Draw benzaldehyde and then the hydrogen bond.

a. Hydrogen bonding is not possible between two molecules of acetaldehyde.

c. Hydrogen bonding is possible between ethanal and methanol.

a. (CH3)3CCH2CH2CH3 or (CH3)3CCH2CHO b. COCH3 or CH2CH2OH

hydrocarbon aldehyde ketone alcohol

a. CH3(CH2)6CHO or CH3(CH2)7OH b. CH3(CH2)6CHO or CH3(CH2)2CHO

aldehyde aldehyde aldehyde

Increasing melting point

7 C aldehyde 4 C ketone hydrocarbon

16.57 Answer each question about erythrulose.

b. CH3 CO2H CH3 CHO

16.70 Locate the two acetals in amygdalin.

hemiacetal ether ether

16.75 Draw the products of each reaction.

16.76 Draw the products of each reaction.