1Answers for Student Exercise 4.1

Answers for Student Exercise 4.2 - 3 (a)

45 40 35 30 25 20 15 10 5 ppm

Atom Base α β γ δ ε Other Calc Shift Comments

C1 Methane 2 3 4 0 0 α-Br The base and shifts

-2.5 9.1 9.4 -2.5 20 33.5 are from Table 4.4

C2 Methane 1,3 4 β-Br Other is from table 4.6

-2.5 18.2 9.4 11 36.1

C3 Methane 4,2 1 γ-Br

-2.5 18.2 9.4 −3 22.1

C4 Methane 3 2 1

-2.5 9.1 9.4 -2.5 13.5

Br

a1

23

4

1-bromobutane

O O

h

OH

O

c

SS

j

N

O

k

OAc

o

2

2'

1

1'

1 12 2 1 2

33

2

1

12

1'2'

12

12

2Answers for Student Exercise 4.2 - 3 (b)

160 140 120 100 80 60 40 20 ppm

Atom Base α β γ δ ε Other Calc Shift Comments

C1 Methane 2,6,7 OCOR,3,5 4 3°(3(2°)) The base and shifts

-2.5 3*9.1 6+9.4+9.4 -2.5 3*(-3.7) are from Table 4.4

value -2.5 27.3 24.8 -2.5 -11.1 36 Other is from table 4.6

C2 ethylene 1,4' 6,7,5' 5,6' γ-OCOR, Zcis

10.6+-7.9 7.2+7.2+-1.8 (-1.5)+(-1.5) (-3)+(-1.1)

123.3 2.7 12.6 -3 -4.1 131.5

C3 ethylene 4,1' 5,6',7' 6,5' Zcis

10.6+-7.9 7.2+2(-1.8) (-1.5)+(-1.5) -1.1

123.3 2.7 3.6 -3 -1.1 125.5

C4 Methane 3,5 6,2 1,1 7

2(9.1) 2(9.4) 2(-2.5) 0.3

-2.5 18.2 18.8 -5 0.3 29.8

C5 Methane 4,6 1,3 7,2,2

2(9.1) 2(9.4) 3(-2.5)

-2.5 18.2 18.8 -7.5 27

C6 Methane 1,5 2,4,7 2(3),OCOCH3 2°(3°)

2(9.1) 3(9.4) 2(-2.5)+(-3) -2.5

-2.5 18.2 28.2 -8 -2.5 33.4

C7 Table 4.12 1,OCOCH3 6,2 3,5 4 2°(3°)

-2.5 61 15.2 -4 0.3 -2.5 67.5

C8 Table 4.12

170.5 170.5 Table 4.12

C9 Table 4.12

20.7 20.7 Table 4.12

O

1

23

4

5 6

7

CH3

O

8 9

(b) (cyclohex-2-enyl)methyl acetate

3Answers for Student Exercise 4.2 - 3 (c)

200 180 160 140 120 100 80 60 40 20 ppm

OH

O

1

23

4

56

7

8

(c) 3-hydroxy-2-methyl-1-phenylpropan-1-one

Atom Base δ ε Other Calc Shift Comments

Table 4.12 These compare nicely

C1 128.5 7.8 136.3

C2 128.5 -0.4 128.1

C3 128.5 -0.4 128.1

C4 128.5 2.8 131.3

C5 198

Base α β γ δ ε Other Calc Shift Table 4.4 +

C6 methane 7,8,5 OH,Ph 3°(2°,3°) Table 4.6

-2.5 2(9.1)+24 10+9 (-3.7)+(-9.5)

-2.5 42.2 19 -13.2 45.5

C7 methane OH, 6 8, 5 1 2°(3°)

-2.5 48+9.1 9.4+1 -2 -2.5

-2.5 57.1 10.4 -2 -2.5 60.5

C8 methane 6 7,5 OH,Ph 1°(3°)

-2.5 9.1 9.4+1 (-5)+(-2) -1.1

-2.5 9.1 10.4 -7 -1.1 8.9

from table 4.12

From Table 4.19 the C=O is approximately 197.6 ppm,

4Answers for Student Exercise 4.2-3 (d)

85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 ppm

H

(d) pent-1-yne

13 24

5

Atom Base α β γ δ ε Other Calc Shift Comments

C1 Table 4.11 The base and shifts

67.0-68.1 are from Table 4.11

67.6 67.6 Increments from table 4.6

C2 Table 4.11

84.7-84.5

84.6 84.6

C3 Methane 4,c≡ 5,c≡9.1+4.5 9.4+5.5 Base shifts Table 4.4

-2.5 13.6 13.9 25

C4 Methane 5,3 c≡2(9.1) 5.5

-2.5 18.2 5.5 21.2

C5 Methane 4 3 γ-c≡-2.5 9.1 9.4 -3.5

-2.5 9.1 9.4 -3.5 12.5

5Answers for Student Exercise 4.2-3 (e)

180 160 140 120 100 80 60 40 20 ppm

Atom Base α β γ δ ε Other Calc Shift Comments

C1 methane 2 3 4 5 6 The base and shifts

-2.5 24 9.4 -2.5 0.3 0.1 are from Table 4.4

-2.5 24 9.4 -2.5 0.3 0.1 28.8 Increments from Table 4.6

C2 Table 4.10 1,3 3 4 6 Table 4.10

196.9 196.9 approximate

C3 ethylene 2,5' 6'

123.3 24+(-7.9) -1.8

123.3 16.1 -1.8 137.6

C4 ethylene 5,2' 6

123.3 10.6+1 7.2

123.3 11.6 7.2 142.1

C5 methane 6,4 3 2 1

-2.5 2(9.1) 9.4 -2 0.3

-2.5 18.2 9.4 -2 0.3 23.4

C6 methane 5 4 3 2 1

-2.5 9.1 9.4 -2.5

-2.5 9.1 9.4 -2.5 0.3 0.1 13.9

O

(e) hex-3-en-2-one

1 34

52 6

6Answers for Student Exercise 4.2-3 (f)

140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

O

(f) (1-methoxybut-1-ene

1 23

45

Atom Base α β γ δ ε Other Calc Shift Comments

C1 methane O-R 2 3 4 5 The base and shifts

-2.5 51 9.4 -2.5 0.3 0.1 are from Table 4.4

-2.5 51 9.4 -2.5 0.3 0.1 55.8 Increments from table 4.6

C2 Table 4.10

153.2 4' 5' Table 4.10

153.2 -7.9 -1.8 143.5

C3 Table 4.10 4 5

84.2 10.6 7.2

84.2 10.6 7.2 102

C4 methane 5,3 2 γ-OR

-2.5 9.1+9.1 9.4 -2

-2.5 18.2 9.4 -2 23.1

C5 methane 4 3 2 1

-2.5 9.1 9.4 -2.5 0.1

-2.5 9.1 9.4 -2.5 0.1 13.6

7Answers for Student Exercise 4.2-3 (g)

150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

Atom Base α β γ δ ε Other Calc Shift Comments

C1 methane NH COO 3 4 5 The base and shifts

-2.5 31 2 -2.5 0.3 0.1 are from Table 4.4

-2.5 31 2 -2.5 0.3 0.1 28.4 Increments from table 4.6

C2 Table 4.20 Table 4.20

157.8 157.8

C3 methane 3,OCOR 5 NHR

-2.5 9.1+51 9.4 -4

-2.5 60.1 9.4 -4 63

C4 methane 5,3 OCOR

-2.5 9.1+9.1 5

-2.5 18.2 5 20.7

C5 methane 4 3 OCOR

-2.5 9.1 9.4 -3

-2.5 9.1 9.4 -3 13

NH

O

O

(g) propyl methylcarbamate

1

2 34

5

8Answers for Student Exercise 4.2-3 (h)

110 100 90 80 70 60 50 40 30 20 10 ppm

Atom Base α β γ δ ε Other Calc Shift Comments

C1 methane 2 OCOR The base and shifts

-2.5 9.1 5 are from Table 4.4

-2.5 9.1 5 11.6 Increments from table 4.6

C2 methane 1,OCOR 3 See Table 4.15 for

-2.5 9.1+45 9.4 comparison

-2.5 54.1 9.4 61

C3 methane 2(OR) 2(2) 2(1)

-2.5 51(2) 9.4(2) 2(-2.5)

-2.5 102 18.8 -5 113.3

O O

(h) diethoxymethane

12 3

9Answers for Student Exercise 4.2-3 (i)

110 100 90 80 70 60 50 40 30 20 10 ppm

Atom Base α β γ δ ε Other Calc Shift Comments

C1 methane 2 6,3,OH 4 5 1°(4°) The base and shifts

-2.5 9.1 2(9.4)+10 -2.5 0.3 -3.4 are from Table 4.4

-2.5 9.1 28.8 -2.5 0.3 -3.4 29.8 Increments from table 4.6

C2 methane 1,6,3,OH 4 5 4°(2(1°)+2°) See Table 4.14 for

-2.5 3(9.1)+48 9.4 -2.5 (2)(-1.5)+-8.4 comparison

-2.5 75.3 9.4 -2.5 -11.4 68.3

C3 methane 2,4 1,6,OH,5 2°(4°)

-2.5 9.1(2) 3(9.4)+10 -7.2

-2.5 18.2 38.2 -7.2 46.7

C4 methane 3,5 2 1,6,OH

-2.5 2(9.1) 9.4 2(-2.5)+(-5)

-2.5 18.2 9.4 -10 15.1

C5 methane 4 3 2 1,6

-2.5 9.1 9.4 -2.5 (2).3

-2.5 9.1 9.4 -2.5 0.6 14.1

C6 methane 2 6,3,OH 4 5 1°(4°)

-2.5 9.1 2(9.4)+10 -2.5 0.3 -3.4

-2.5 9.1 28.8 -2.5 0.3 -3.4 29.8

HO

(i) 2-methylpentan-2-ol

1

23

45

6

10Answers for Student Exercise 4.2-3 (j)

45 40 35 30 25 20 15 10 5 ppm

SS

(j) 1,4-bis(methylthio)butane

1 23

Atom Base α β γ δ ε Other Calc Shift Comments

C1 methane SR The base and shifts

-2.5 20 are from Table 4.4

-2.5 20 17.5 Increments from table 4.6

C2 methane SR,3 3 2 SR See Table 4.18 for

-2.5 20+9.1 9.4 -2.5 0 Comparison

-2.5 29.1 9.4 -2.5 33.5

C3 methane 2,2 3,SR 2 SR

-2.5 2(9.1) 9.4+7 -2.5 0

-2.5 18.2 16.4 -2.5 29.6

11Answers for Student Exercise 4.2-3 (k)

160 140 120 100 80 60 40 20 ppm

N

O

(k) N,N,4-trimethylbenzamide

1

2

3

4

5

6

78

Atom Base δ ε Other Calc Shift Comments

Table 4.12 C=ONH2 CH3 Table 4.12

C1 128.5 5 -2.9 130.6

C2 128.5 -1.2 -0.1 127.2

C3 128.5 0 0.7 129.2

C4 128.5 3.4 9.3 141.2

C5 171

Base α β γ δ ε Other Calc Shift Table 4.4 +

C6 methane NR2 C=O Ph Table 4.6

-2.5 42 1 -2

-2.5 42 1 -2 38.5

C7 methane NR2 C=O Ph

-2.5 42 1 -2

-2.5 42 1 -2 38.5 Table 4.12

C8 Table 4.12 21.3

From Table 4.20 the C=O is approximately 171 ppm,

from table 4.12

12Answers for Student Exercise 4.2-3 (l)

180 160 140 120 100 80 60 40 20 ppm

O

OH(l) 1-(2-hydroxyphenyl)ethanone

1

2

34

5

6

78

Atom Base δ ε Other Calc Shift Comments

Table 4.12 C=OCH3 OH Table 4.12

C1 128.5 7.8 -12.7 123.6

C2 128.5 -0.4 26.6 154.7

C3 128.5 -0.4 -12.7 115.4

C4 128.5 2.8 1.6 132.9

C5 128.5 -0.4 -7.3 120.8

C6 128.5 -0.4 1.6 129.7

C7 197.6 Table 4.19

C8 26.3From Table 4.19 the CH3 is approximately 26.3 ppm,

from table 4.12

From Table 4.19 the C=O is approximately 197.6 ppm,

13Answers for Student Exercise 4.2-3 (l)

200 180 160 140 120 100 80 60 40 20 ppm

Atom Base α β γ δ ε Other Calc Shift Comments

C1 methane Cl, CHO The base and shifts

-2.5 31+31 are from Table 4.4

-2.5 62 59.5 Increments from table 4.6

C2 Table 4.19 Cl See Table 4.18 for

199.7 Comparison

199.7 199.7

ClH

O(m) 2-chloroacetaldehyde

12

14Answers for Student Exercise 4.2-3 (n)

200 180 160 140 120 100 80 60 40 20 ppm

Atom Base α β γ δ ε Other Calc Shift Comments

C1 Ethylene F The base

123.2 68 are from Table 4.9

123.2 68 191.2 Increments from table 4.6

C2 Ethylene F See Table 4.9 for

123.2 9 Comparison

123.2 9 132.2

Note -- These are not close to observed values, but are the only answer from given tables.

HH

H

F(n) fluoroethene

1

2

19F couplings not shown

15Answers for Student Exercise 4.2-3 (n)

160 140 120 100 80 60 40 20 ppm

O

(o) cyclohexyl acetate

O1

2

34

5

6

Atom Base α β γ δ ε Other Calc Shift Comments

C1 Table 4.7 OCOR The base and shifts

26.9 51 are from Table 4.7

26.9 51 77.9 Increments from table 4.6

C2 Table 4.7 OCOR

26.9 6

26.9 6 32.9

C3 Table 4.7 OCOR

26.9 -3

26.9 -3 23.9

C4 Table 4.7 OCOR

26.9 0

26.9 0 26.9

C5 Table 4.20

Approx

168 168 Table 4.20

C6 methane COO 1 2,2 3,3 The base and shifts

-2.5 25 -2.5 2(.3) 2(.1) are from Table 4.4

-2.5 25 -2.5 0.6 0.2 20.8 Increments from table 4.6

16

200 180 160 140 120 100 80 60 40 20 ppm

140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 ppm

131 ppm

Problem 5.7A

Problem 5.7B

Problem 5.7C

Problem 4.4 A

Problem 4.4 C

Problem 4.4 B

O

4-Heptanone

1 23

4

OH

3-Heptanol

1 23 4 5 6

7

Br

4-Bromotoluene

1

2 3

45

1

2

4

3

1 7 6 2 4

5

3

1

2

4

5

3

Answers for Student Exercise 4.4 A-C

17

95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 ppm

180 160 140 120 100 80 60 40 20 ppm

200 180 160 140 120 100 80 60 40 20 ppm

Problem 5.7D

Problem 5.7E

Problem 5.7F

Problem 4.4 E

Problem 4.4 D

Problem 4.4 F

Br

2-Bromopentane

1 23

45

1 23

45 6

O

2-Hexanone

12

3

O

HOPropionic Acid

1 2 4 5 3

6

2

4 5 3

1

2 3

Answers for Student Exercise 4.4 D-F

18

95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 ppm

95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 ppm

95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 ppm

Problem 5.7G

Problem 5.7H

Problem 5.7I

77.077.5 ppm

Problem 4.4 I

Problem 4.4 H

Problem 4.4 G 12

34

H2N

Butylamine

1 23

OH

Propargyl alcohol

N+

O

-O1-Nitropropane

1 2 3

1

2 3

1

2

3

1 2 4 3

Note that it is often the case that the DEPT spectra are incorrect for alkynes. Intensities of the ≡CH are quite different than the ≡C−, which is apparent here.

Answers for Student Exercise 4.4 G-I

19

60708090100110120130140150160170 ppm

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

Problem 5.7J

Problem 5.7K

Problem 5.7L

Problem 4.4 L

Problem 4.4 K

Problem 4.4 J

46

O

OH

2-Phenoxylethanol

1

23

5

45

6

O

Phenetole

12 3

5

OO

Methyl Butyrate

1 2 34

1

2 4 5

3

1

6

2

4 5

3

1

5

2

4 6

3

Answers for Student Exercise 4.4 J-L

20

180 160 140 120 100 80 60 40 20 ppm

60708090100110120130140150160170 ppm

150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

Problem 5.7M

Problem 5.7N

Problem 5.7O

Problem 4.4 O

Problem 4.4 N

Problem 4.4 M 5

6

O

HN

Caprolactam

1 23

4

6

7

N

N

2-methylpyrazine1

2

3 4

5

6

7

HOO

O

Methyl salicylate

1

2

3 4

5

8

1 7

4

2

6 5 3 8

7

6

2

5 3

1

6 2 4 5 3

Answers for Student Exercise 4.4 M-O

21

80859095100105110115120125130135140145150155 ppm

85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 ppm

180 160 140 120 100 80 60 40 20 ppm

Problem 5.7P

Problem 5.7Q

Problem 5.7R

144146148 ppm

Problem 4.4 R

Problem 4.4 Q

Problem 4.4 P

N+O

-OCl

1-Chloro-4-Nitrobenzene

1

23

4

7

O

HO Br7-Bromo Heptanoic Acid

12 3 4

5 6

HO5-Hexyn-1-ol

52

341

6

1 6

2 4

5

3

1

7 6 2 4 5 3

1

2

4

3

Note that it is often the case that the DEPT spectra are incorrect for alkynes. Intensities of the ≡CH are quite different than the ≡C−, which is apparent here.

Answers for Student Exercise 4.4 P-R

22

200 180 160 140 120 100 80 60 40 20 ppm

80859095100105110115120125130135140145150155 ppm

180 160 140 120 100 80 60 40 20 ppm

Problem 5.7S

Problem 5.7T

Problem 5.7U

121.2 ppm

Problem 4.4 T

Problem 4.4 S

Problem 4.4 U

7

8O

6-Methyl-5-hepten-2-one2

341 5

6

O

HOHexanoic acid

342

1 5 6

Cl

ClHO

2,6-Dichlorophenol

1

3

4

2

1

2

4 3

1

6 2 3 5 4

1

7

6

2

4

5 3 8

4

Answers for Student Exercise 4.4 S-U

23

150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

200 180 160 140 120 100 80 60 40 20 ppm

Problem 5.7V

Problem 5.7W

Problem 4.4 W

Problem 4.4 V 5

HO

2,6-Dimethylphenol

3

4

1 2

O

2-Cyclohexen-1-one

34

12

5

6

1

6

2

4 5

3

1 2 4

5

3

Answers for Student Exercise 4.4 V-W

24

1

1 1 1

1 2 3 2 1

1 3 6 7 6 3 1

Example

CDCl3

CD2Cl2

CD3Cl

2nI +1 ruleID =1

4.5

Answers for Student Exercise 4.5

25

75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 ppm

75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 ppm

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

Problem 5.6A

Problem 5.6B

Problem 5.6C

128130132 ppm

C5H10Br2

C8H8O2

C12H27N

Problem 4.6A

Problem 4.6B

Problem 4.6C

BrBr1,5-dibromopentane

12

3

HO O

2-methylbenzoic acid

1 2

3

45

6

78

HN1

23

45

6

dihexylamine

1 6 2 4 5 3

1 2

3

2 7

6

1

4 5 3

8

Answers for Student Exercise 4.6 A-C

26

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 ppm

85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 ppm

200 180 160 140 120 100 80 60 40 20 ppm

Problem 5.6D

Problem 5.6E

Problem 5.6F

788082 ppm

C16H22O4

C7H12O

C8H14O

Problem 4.6D

Problem 4.6E

Problem 4.6F

O

O

O

O1

2

3 4 56

78

dibutyl phthalate

O5-methylhex-5-en-2-one

1 23

45 6

7

OH

oct-3-yn-1-ol

12

3

45

67

8

1 7

6

2

4

5

3

8

1 7 6

2 4 3

1

7 2

4

5 3

8

Answers for Student Exercise 4.6 D-F

27

020406080100120140160180PPM

DEPT 135

DEPT 90

Carbon - 13

O

O

O

O1

2

3 4 56

ortho-diethyl phthalate

12

3 4 5 6

654 1,3,2

There is one mirror image. There are 6 nonequivalent carbons, and there are 4 distinct proton signals, 2,3,5,6 with a integration ratio of 2:2:4:6, or 1:1:2:3.

28

020406080100120140160180PPM

DEPT 135

DEPT 90

Carbon - 13

O

O

meta-diethyl phthalate

O

O

1

2

3

456

7

21 5 6

7

765

3

12

4

There is one mirror image. There are 7 nonequivalent carbons, and there are 5 distinct proton signals, 2,3,4,5,6 with a integration ratio of 2:1:1:4:6..

29

020406080100120140160180PPM

DEPT 135

DEPT 90

Carbon - 13

3 1

2

4 5

O

O

para-diethyl phthalate

O

O

3

4 5

1

2

45

12

2

3

2

There are two mirror images. There are 5 nonequivalent carbons, and there are 3 distinct proton signals, 2,4,5 with a integration ratio of 4:4:6, or 1:1:3.