Robert M. Silverstein, Francis X. Webster, David Kiemle-Solutions Manual for Spectrometric Identification of Organic Compounds-Wiley (2005)

Answers for Student Exercises 1.1 to 1.5

1

a 3-ethyloctane C10H22

CnHmXxNyOz Index = (n) - (m/2) - (x/2) + (y/2) + 1 =

IHD 0

Atom Type Hydrogen Carbon Nitrogen Oxygen Sulfur Bromine

# of Atoms Mass 1.00783 22 10 12.00000 14.0031 0 15.9949 0 31.9721 0 78.9183 0 Exact Mass

Total Mass 22.17226 120.00000 0.00000 0.00000 0.00000 0.00000 142.17226

- (C2H5 ) Rule 3

- (C5H11 ) Rule 3 H

- (CH2=CH2) Rule 9

b

3-butylcyclohex-1-ene C10H18 CnHmXxNyOz Index = (n) - (m/2) - (x/2) + (y/2) + 1 =

IHD 2


or

- (C4H9 ) Rule 5 and 6

- (CH2=CH2) Rule 6

- (C3H7 ) Rule 3


Total Mass 18.14094 120.00000 0.00000 0.00000 0.00000 0.00000 138.14094


2 Atom Type Hydrogen Carbon Nitrogen Oxygen Sulfur Bromine

O c

2-methyl-1-phenylhexan-1-one C13H18O


IHD 5


O

O

Total Mass 18.14094 156.00000 0.00000 15.99490 0.00000 0.00000 190.13584

O

- (C6H13 ) Rule 8 O

O

- (C6H5 ) Rule 8

O

H

O

- (C4H8)

OH H

Rule 9 O - (CO) Rule 8+9 Atom Type Hydrogen Carbon Nitrogen Oxygen Sulfur Bromine

d (E)-undec-3-ene C11H22


IHD 1

or

- (CH3) Rule 5 - (C6H13) Rule 5 H

- (C7H14) Rule 9


Total Mass 22.17226 132.00000 0.00000 0.00000 0.00000 0.00000 154.17226

Answers for Student Exercises 1.1 to 1.5 e

1-(hexan-2-yl)benzene C12H18


IHD 4



Total Mass 18.14094 144.00000 0.00000 0.00000 0.00000 0.00000 162.14094

- (CH3 ) Rule 7

- (C4H9 ) Rule 7 - (C4H8 )

H

H

Rule 9 H f

OH heptan-2-ol C7H16O


OH

OH

H OH

H OH

IHD 0



Total Mass 16.12528 84.00000 0.00000 15.99490 0.00000 0.00000 116.12018

- (C5H11 ) Rule 8

OH

- (CH3 ) Rule 8

OH

- (H ) Rule 8 - (H2O) Rule 9

OH


g

COOH 3,5,7-trimethyloctanoic acid C11H22O2

CnHmXxNyOz

IHD 1

Index = (n) - (m/2) - (x/2) + (y/2) + 1 =



Total Mass 22.17226 132.00000 0.00000 31.98980 0.00000 0.00000 186.16206

O C O

- (OH ) OH

Rule 8

O C

O OH

H

O

O

- (C10H21 )

C

Rule 8

O

- (C9H18) Rule 9

HO h

OH hexan-1-ol C6H14O


IHD 0


O C

OH H

OH

OH

HO

HO


Total Mass 14.10962 72.00000 0.00000 15.99490 0.00000 0.00000 102.10452

H H

O

- (CH2=CH2 ) - (H2O) Rule 9

OH

- (C5H11 ) Rule 8

H 2C

OH

- (H ) OH

Rule 8

OH


i

OH 2-methylheptan-2-ol C8H18O CnHmXxNyOz

IHD 0

Index = (n) - (m/2) - (x/2) + (y/2) + 1 =



Total Mass 18.14094 96.00000 0.00000 15.99490 0.00000 0.00000 130.13584

- (C5H11 )

OH

OH

Rule 8 - (CH3 )

OH

OH

Rule 8

H H

O

- (H2O)

- (CH2=C(CH3)2)

Rule 8

Rule 8

j

S butyl(propyl)sulfane C7H16S


S

IHD 0



- (C3H7 ) Rule 8

- (CH2=CH2)

S

Rule 9

H

S

Total Mass 16.12528 84.00000 0.00000 0.00000 31.97210 0.00000 132.09738

- (C2H5 ) Rule 8

S

SH

S

Answers for Student Exercises 1.1 to 1.5 k

OH (2-hexylphenyl)methanol C13H20O CnHmXxNyOz

IHD 4

Index = (n) - (m/2) - (x/2) + (y/2) + 1 =

OH



OH

or

- (C5H11 )

OH

OH

Rule 7

CH2 CH2

- (OH )

OH

Total Mass 20.15660 156.00000 0.00000 15.99490 0.00000 0.00000 192.15150

Rule 7 OH

- (H2O)

H

Rule 9

O l

NO2 (4-nitrophenyl)(phenyl)methanone C13H9NO3

CnHmXxNyOz

IHD 10

Index = (n) - (m/2) - (x/2) + (y/2) + 1 =



Total Mass 9.07047 156.00000 14.00310 47.98470 0.00000 0.00000 227.05827

O

O - (C6H4NO2 ) NO2 O

Rule 7&8 - (CO) Rule 8&9 O

O - (C6H5 ) NO2

Rule 7&8

NO2


m

O

3-(ethoxymethyl)heptane C10H22O

CnHmXxNyOz

IHD 0

Index = (n) - (m/2) - (x/2) + (y/2) + 1 =



- (CH3 )

O

O CH2

Rule 8

- (C7H15 )

O

Total Mass 22.17226 120.00000 0.00000 15.99490 0.00000 0.00000 158.16716

O

Rule 8

- (C4H9)

O

O

Rule 3

O n

H Br 2-bromodecanal C10H19BrO

CnHmXxNyOz

IHD 1

Index = (n) - (m/2) - (x/2) + (y/2) + 1 =

O



Total Mass 19.14877 120.00000 0.00000 15.99490 0.00000 78.91830 234.06197

O

- (H ) H

Br

Rule 8

Br

O - (CO ) Rule 9

Br

Br H

H O H Br

- (C8H16) Rule 9

O H

H Br

Answers for Student Exercises 1.1 to 1.5 o

O O cyclohexyl acetate C8H14O2 CnHmXxNyOz

Index = (n) - (m/2) - (x/2) + (y/2) + 1 =

O

O

IHD 2


- (C6H11O )


Total Mass 14.10962 96.00000 0.00000 31.98980 0.00000 0.00000 142.09942

O

Rule 8

O

O

- (CH3 )

O

O

Rule 8

O H

O

- (CH2=C=O) Rule 9

O

H

Answers for Student Exercises 1.6 to 1.11 A

O

9

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

71

114

99 / C6H11O

15 / CH3

86 / C5H10

28 / C2H4

71 / C4H7O

43 / C3H7

58 / C3H5O

56 / C4H8

43 / C3H7

71 / C4H7O

4-Heptanone C7H14O Exact Mass: 114.1045 IHD = 1, match with (k)

B

OH

4-Bromotoluene C7H7Br Exact Mass: 169.9731 IHD = 4, match with (v)

D

Fragement Ion

Fragment Loss

59

116 by CI

115 / C7H15O

1/H

98 / C7H14

18 / H2O

87 / C5H11O

29 / C2H5

69 / C5H9

18 / H2O, 29 / C2H5

59 / C3H7O

57 / C4H9

45 / C2H5O

71 / C5H11

43 / C3H7

73 / C4H9O

41 / C4H5

18 / H2O, 57 / C4H9

R

Rearrangment R R

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

91

170

91 / C7H7

79 / Br

Rearrangment Tropylium Ion

75 / C6H3

80 / HBr, 16 / CH4

R

65 / C5H5

79 / Br, 26 / C2H2

R

50 / C4H2

120 / C7H5Br

39 / C3H2

131 / C4H5Br

Br

2-Bromopentane C5H11Br Exact Mass: 150.0044 IHD = 0, match with (r)

R

Molecular Ion

C7H16O Exact Mass: 116.1201 IHD = 0, match with (m)

Br

R

Base Peak

3-Heptanol

C

Rearrangment

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

71

150

121 / C3H6Br

29 / C2H5

107 / C2H4Br

43 / C3H7

71 / C5H11

79 / Br

55 / C4H7

80 / HBr, 16 / CH4

43 / C3H7

C2H4Br

Rearrangment

R

Answers for Student Exercises 1.6 to 1.11 O

E

10

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

43

100

85 / C5H9O

15 / CH3

71 / C4H7O

29 / C2H5

58 / C4H10

42 / C2H2O

57 / C3H5O

43 / C3H7

43 / C3H7

57 / C3H5O

2-Hexanone C6H12O Exact Mass: 100.0888 IHD = 1, match with (h)

O

F

OH Propionic Acid

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

74

74

73 / C3H5O2

1/H

57 / C3H5O

17 / OH

56 / C3H4O

18 / H2O

45 / CHO2

29 / C2H5

C3H6O2 Exact Mass: 74.0368 IHD = 1, match with(c)

G

H2N

OH

prop-2-yn-1-ol C3H4O Exact Mass: 56.0264 IHD = 2, match with (a)

R

Rearrangment

R

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

Rearrangment

73

73

56 / C4H8

17 / NH3

R

55 / C4H7

18 / NH4

R

44 / C2H6N

29 / C2H5

43 / C3H7

30 / CH4N

butan-1-amine C4H11N Exact Mass: 73.0896 IHD = 0, match with (b)

H

Rearrangment

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

55

56 by CI

55 / C3H3O

1/H

39 / C3H3

17 / OH

38 / C3H2

18 / H2O

Rearrangment


I

O N

+

O-

11

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

43

89 by CI

90 / C3H8NO2

Addition of H

72 / C3H6NO

17 / OH

43 / C3H7

46 / NO2

42 / C3H6

47 / HNO2

R

Rearrangment

1-Nitropropane C3H7NO2 Exact Mass: 89.0477 IHD = 1, match with (d)

J

OH O

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

94

138

107 / C7H7O

31 / CH3O

94 / C6H5O

44 / C2H4O

77 / C6H5

61 / C2H5O2

66 / C5H6

72 C3H5O2

51 / C4H3

87 / C4H7O2

39 / C3H2

99 / C5H8O2

2-Phenoxylethanol C8H10O2 Exact Mass: 138.0681 IHD = 4, match with (q)

K O Phenetole

O O Methyl Butyrate

C5H10O2 Exact Mass: 102.0681 IHD = 1, match with (i)

R

R R

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

Rearrangment

94

122

94 / C6H5O

28 / C2H4

R

77 / C6H5

45 / C2H5O

66 / C5H6

56 / C3H4O

51 / C4H3

71 / C4H7O

39 / C3H2

83 / C5H8O

C8H10O Exact Mass: 122.0732 IHD = 4, match with (o)

L

Rearrangment

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

43

102

87 / C4H7O2

15 / CH3

74 / C3H5O2

28 / C2H4

71 / C4H7O

31 / CH3O

59 / C2H3O2

43 / C3H7

43 / C3H7

59 / C2H3O2

Rearrangment R

Answers for Student Exercises 1.6 to 1.11 O

M HN

12

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

Rearrangment

113

113

85 / C5H11N

28 / CO

R

84 / C5H10N

29 / CHO

56 / C4H8

57 / C2H3NO

55 / C4H7

58 / C2H4NO

42 / C3H6

71 / C3H5NO

R

Rearrangment

Caprolactam C6H11NO Exact Mass: 113.0841 IHD = 2, match with (j)

N

N N 2-methylpyrazine

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

94

94

67 / C4H5N

27 / CHN

53 / C3H3N

41 / C2H3N

42 / C2H4N

52 / C3H2N

41 / C2H3N

53 / C3H3N

40 / C2H2N

54 / C3H4N

C5H6N2 Exact Mass: 94.0531 IHD =4, match with (e)

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

152

152

135 / C8H7O2

17 / OH

122 / C7H6O2

30 / CH2O

R

107 / C7H7O

45 / CHO2

R

Methyl salicylate

105 / C7H5O

17 / OH, 30 / CH2O

R

C8H8O3 Exact Mass: 152.0473 IHD = 5, match with (s)

92 / C6H4O

R

77 / C6H5

60 / C2H4O2 17 / OH, 58 / C2H2O2

63 / C5H3

89 / C3H5O3

39 / C3H2

113 / C5H6O3

Fragement Ion 141 / C6H4ClNO

Fragment Loss

127 / C6H4O

30 / NO

111 / C6H4Cl

46 / NO2

99 / C5H4Cl

58 / CNO2

75 / C6H3

46 / NO2, 36 / HCl

50 / C4H2

107 / C2H2ClNO2

O

HO O O

P O N+ -

Cl

O

1-Chloro-4-Nitrobenzene C6H4ClNO2 Exact Mass: 156.9931 IHD = 5, match with (t)

Base Peak

Molecular Ion

75 or 157

157

Rearrangment

Rearrangment

16 / O R

R

Answers for Student Exercises 1.6 to 1.11 Q

O

HO

Br

13

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

60

208 by CI

191 / C7H12OBr

17 / OH

149 / C5H10Br

59 / C2H3O2

129 / C7H13O2

79 /Br

111 / C7H11O

79 /Br, 18 / H2O

R

83 / C6H11

125 / CH2BrO2

R

60 / C2H4O2

147 / C5H9Br

R

Rearrangment

7-Bromo Heptanoic Acid C7H13BrO2 Exact Mass: 208.0099 IHD = 1, match with (w)

R HO 5-Hexyn-1-ol C6H10O Exact Mass: 98.0732 IHD = 2, mathc with (g)

O

S

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

70

98

97 / C6H9O

1/H

83 / C5H7O

15 / CH3

79 / C6H7

19 / H3O

70 / C4H6O

28 / C2H4

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

43

126

111 / C7H11O

15 / CH3

108 / C8H12

18 / H2O

R

93 / C7H9

33 / CH5O

R

83 / C6H11

43 / C2H3O

69 / C5H9

57 / C3H5O

58 / C3H6O

68 / C5H8

55 / C4H7

71 C4H7O

43 / C2H3O

83 / C6H11

6-Methyl-5-hepten-2-one C8H14O Exact Mass: 126.1045 IHD = 2, match with (p)

T O HO Hexanoic acid C6H12O2 Exact Mass: 116.0837 IHD = 1, match with (l)

Rearrangment

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

60

116 by CI

87 / C4H7O2

29 / C2H5

73 / C3H5O2

43 / C3H7

60 / C2H4O2

56 / C4H8

45 / CHO2

71 / C5H11

Rearrangment

R

Rearrangment

R

Answers for Student Exercises 1.6 to 1.11 U HO

Cl

14

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

Rearrangment

162

162

126 / C6H3OCl

36 / HCl

R

98 / C5H3Cl

64 / CHOCl

R

63 / C5H3

99 / CHOCl2

Cl 2,6-Dichlorophenol C6H4Cl2O Exact Mass: 161.9639 IHD = 4, match with (u)

V HO

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

122

122

121/C8H9O

1/H

107/C7H7O

15 / CH3

91 / C7H7

31 / CH3O

77 / C6H5

45 / C2H5O

65 / C5H5

57 / C3H5O

2,6-Dimethylphenol C8H10O Exact Mass: 122.0732 IHD = 4, match with (n)

W

O

2-Cyclohexen-1-one C6H8O Exact Mass: 96.0575 IHD = 3, match with (f)

Rearrangment

Base Peak

Molecular Ion

Fragement Ion

Fragment Loss

Rearrangment

68

96

68 / C4H4O

28 / C2H4

R

55 / C3H3O

41 / C3H5

53 / C4H5

43 / C2H3O

42 / C2H2O

54 / C4H6

R

Answers for Student Exercise 2.1 – 2.9

1

2.1. Since the indicated carbon of phenylacetonitrile is sp3 hybridized, it is reasonable for this compound to show C−H stretching at less than 3000 cm-1 (2960-2940 cm-1). Where as benzonitrile has only aromatic C−H stretching which is typically between 3100 - 3000 cm-1 (page 87).

CH2

N

C

C N

phenylacetonitrile

benzonitrile

2.2. O N

H 2N b. isobutylamine

a. benzonitrile

HO

O

S O

O

c. diphenyl sulfone

d. dioxane

O g. biphenyl

f. formic acid

N+

O

O-

e. 1-nitropropane

HO

H 2N

O

O

h. benzoic acid

i. benzamide

2.3.

1,3-Cyclohexadiene

Diphenylacetylene

Spectrum B

Spectrum A

1-Octene Spectrum D

2-Pentene Spectrum C

2.4. O O

O

NH2 O

H 2N

HO

O O-

C11H23

Na+

Butyl acetate

Butyramide

Isobutylamine

Lauric acid

Sodium propionate

Spectrum E

Spectrum H

Spectrum I

Spectrum F

Spectrum G

2.5. HO

O O Allyl phenyl ether Spectrum L

HO H

Benzaldehyde

Spectrum M

O

o-Cresol Spectrum K

m-Toluic acid Spectrum J


2

2.6. HO

N H 2N

N H 2N

NH2 Cl

N

Aniline

Azobenzene

Spectrum Q

Spectrum O

Benzophenone oxime Spectrum P

2.7.

Methyl isothiocyanate CH3−N=C=S

2.8.

This diketone exists primarily (~ 90%) in enol form (in CCl4) O

O

O

H

Benzylamine Spectrum N

Dimethylamine hydrochloride Spectrum R

O

enol

Enols such as this display broad, shallow O−H stretching bands (here from 3400-2500 cm-1). The strong band at ~1600 cm-1 is the enolic coupled C=C−OH band. (See pages 80, 94, and 98)


3

2.9. O

OH

4-Heptanone

3-Heptanol

4-Bromotoluene

A

B

C

Br

Br

2-Bromopentane

D

O

O

OH

H 2N

OH 2-Hexanone

Propionic Acid

Butylamine

Propargyl alcohol

E

F

G

H

OH

O N+

O-

O

1-Nitropropane

O

O

O 2-Phenoxylethanol

Phenetole

J

K

I

MethylHButyrate

L

HO

O

O

N

HN N

O N+

O

-

Cl

O

Caprolactam

2-methylpyrazine

Methyl salicylate

1-Chloro-4-Nitrobenzene

M

N

O

P

O

O

HO

Br

HO

7-Bromo Heptanoic Acid

5-Hexyn-1-ol

6-Methyl-5-hepten-2-one

R

S

Q

HO

Cl

O

HO

O Cl

HO Hexanoic acid

T

2,6-Dichlorophenol

U

2,6-Dimethylphenol

2-Cyclohexen-1-one

V

W

Answers for Student Exercise 3.1 to 3.3

1 4

3

2

1

Br

(a) 1-bromobutane

3.1(a) 1,2,3,4 are a spin system. Pople notation is A3M2S2X2. 1,2, and 3 are enantiotopic. 3.2 (a) Spin 1 2 3 4

Appr. δ δ 3.40 δ 1.85 δ 1.20 δ 0.85

Table Appendix A, Chart A.1 Appendix A, Chart A.2 Appendix A, Chart A.1 Appendix A, Chart A.1

Coupled with 2 1,3 3, 4 3

Multiplet (n+1) Triplet Quintet Sextet Triplet

Integration 2 2 2 3

3.3 (a)

1

2

3

4


2 5

6

4

1 3

2

7

O O 8

9

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

3.1 (b) 1,2,3,4,5,6,7 are one spin system, and 9 is the second. 4,4’ ; 5,5’ ; 6,6’and 7,7’ are diastereotopic. 3.2 (b) Spin Table or Calculation Coupled with Multiplet (n+1) Integration Appr. δ 1 Appendix A, Chart A.2 6,2,7 Sextet* 1 δ 2.80 2 Appendix D, Chart D2 3,1 Triplet* 1 δ 5.59 3 Appendix D, Chart D2 Quartet* 1 δ 5.59 Appendix D, Chart D2 Quartet** 2 δ 1.96 4 Appendix D, Chart D2 4,6 Quartet** 2 δ 1.65 5 Appendix A, Chart A.2 1,5 Triplet** 2 δ 1.80 6 Appendix A, Chart A.2 1 Doublet** 2 δ 4.05 7 Appendix A, Chart A.1 none Singlet 3 δ 2.10 9 * Coupling constants may not be the same, but make the assumption that they are. **These are diastereotopic, and are coupled to diastereotopic protons, they would not be first order. We will assume they are first order for the drawn spectrum.

3.3 (b)

2

2 and 3

7

1

9

4

6

5


3 2 3

O 1

7 6

4 5

9 8

OH

10

(c) 1-(cyclohexa-1,5-dienyl)-3hydroxy-2-methylpropan-1-one

3.1 (c) 2,3,4,5,6 are a spin system, and 8,9,10 another spin system. 3,3’ ; 4,4’ ; 9,9’ are diastereotopic. 3.2 (c) Spin Table or Calculation Coupled with Multiplet (n+1) Integration Appr. δ 2 Appendix D, Chart D.1 3 Triplet 1 δ 6.68 3 Appendix A, Chart A1 2,4 Quartet*** 2 δ 2.05 4 Appendix A, Chart A1 3,5 Quartet*** 2 δ 2.05 Appendix D, Chart D1 4,6 Quartet* 1 5 δ 5.68 Appendix D, Chart D1 5 Doublet 1 δ 6.22 6 Appendix A, Chart A.1 9,10 Sextet 1 δ 2.65 8 Appendix A, Chart A.1 8 Doublet** 2 δ 3.20 9 Appendix A, Chart A.2 8 Doublet 3 δ 1.05 10 1 δ 0.5-4.0 Appendix E ΟΗ * Coupling constants may not be the same, but make the assumption that they are. ** These are diastereotopic, and are coupled to diastereotopic protons; they would not be first order. We will assume they are first order for the drawn spectrum.

3.3 (c)

2

6

5

9

8

3,4

OH 10


5

4

4

3 2 1 (d) pent-1-yne

H

3.1 (d) 5,4,3 are a spin system and 1 is second. 5,4,3 is Pople notation is A3M2X2; may have long rang coupling. 3+4 are enantiotopic. 3.2 (d) Appr. δ δ 0.85 δ 1.50 δ 2.20 δ 1.80

Spin 5 4 3 1

Table or Calculation Appendix A, Chart A.2 Appendix A, Chart A2 Appendix A, Chart A1 Appendix D, Chart D3

Coupled with Multiplet (n+1) 4 Triplet 3,5 Sextet 4 Triplet none Singlet

3.3 (d)

3

1

4

5

Integration 3 2 2 1


5 O 1

5 6 4 (e) hex-3-en-2-one 2

3

3.1 (e) 3,4,5,6 are a spin system, and 1 is another spin system. Pople notation is A3G2MX. 5 is enantiotopic. 3.2 (e) Appr. δ δ 1.86 δ 6.09 δ 6.82 δ 2.05 δ 1.00

Spin 1 3 4 5 6

Table or Calculation Appendix D, Chart D.2 Appendix D, Chart D.1 Appendix D, Chart D.1 Appendix A, Chart A1 Appendix A, Chart A2

Coupled with Multiplet (n+1) None Singlet 4 Doublet 3, 5 Quartet* 4, 6 Quintet* 5 Triplet

Integration 3 1 1 2 3

* Coupling constants may not be the same, but make the assumption that they are. 3.3 (e)

4

3

5

1

6


6

1

O 2

4 3

5

(f) 1-methoxybut-1-ene

3.1 (f) 3,4,5,6 are a spin system, and 1 is another spin system. Pople notation is A3G2MX. 4 is enantiotopic. 3.2 (f) Appr. δ δ 3.20 δ 6.14 δ 4.63 δ 2.05 δ 1.00

Spin 1 2 3 4 5

Table or Calculation Appendix A, Chart A.1 Appendix D, Chart D.1 Appendix D, Chart D.1 Appendix A, Chart A1 Appendix A, Chart A2

Coupled with Multiplet (n+1) None Singlet 3 Doublet 2, 4 Quartet* 3, 5 Quintet* 4 Triplet


* Coupling constants may not be the same, but make the assumption that they are. 3.3 (f)

2

3

1

4

5


7

1

O N 2 O 3 H

4

5

(g) propyl methylcarbamate

3.1 (g) 3,4,5 are a spin system, and 1 is another spin system. Pople notation is A3M2X2. 3 and 4 are enantiotopic. 3.2 (g) Spin Table or Calculation Appr. δ 1 Appendix A, Chart A.1 δ 2.95 3 Appendix D, Chart D.1 δ 4.10 4 Appendix A, Chart A.2 δ 1.60 5 Appendix A, Chart A1 δ 0.85 NH δ 4.5-7.5 Appendix E *See Section 3.6.2 for coupling between 1 and N-H.

Coupled with Multiplet (n+1) None Singlet 3 Triplet 2, 4 Sextet 3, 5 Triplet * Singlet


3.3 (g)

NH

3

1

4

5


8

1

2 O 3 O (h) diethoxymethane

3.1 (h) 1 and 2 are a spin system, and 3 is another spin system. Pople notation is A3X2. 2 are enantiotopic. 3.2 (h) Spin 1 2 3

Appr. δ δ 1.20 δ 3.40 δ 4.95

Table or Calculation Appendix A, Chart A.2 Appendix A, Chart A.1 Appendix B, Table B.1

Coupled with Multiplet (n+1) 2 Triplet 1 Quartet none Singlet

Integration 3 2 2

3.3 (h)

3

2

1


9

1

HO

6 2

3

4

5

(i) 2-methylpentan-2-ol

3.1 (i) 3,4 and 5 is a spin system. 1 and 6 are enantiotopic to each other and 3 and 4 are also enantiotopic. Pople notation is A3M2X2. 3.2 (i) Spin 1 and 6 3 4 5 ΟΗ

Appr. δ δ 1.20 δ 1.50 δ 1.20 δ 0.85 δ 0.5-4.0

Table or Calculation Appendix A, Chart A2 Appendix A, Chart A2 Appendix A, Chart A1 Appendix A, Chart A2 Appendix E

Coupled with Multiplet (n+1) none Singlet 4 Triplet 3,5 Sextet 4 Triplet none Singlet

3.3 (i)

1 and 6 Large singlet of 6 H

OH

3

1,6,4



10

1

S 2

3

S

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

3.1 (j) Not First order (no Pople). See Section 3.11.2. Protons 2 and 3 are enantiotopic. Protons on 1,2,3 are Chemical Shift Equivalent. 3.2 (j) Spin Table or Calculation Coupled with Multiplet (n+1) Appr. δ 1 Appendix A, Chart A1 none Singlet δ 2.10 2 Appendix A, Chart A1 3 Triplet* δ 2.60 Appendix A, Chart A2 2,3 Quintet* 3 δ 1.60 * Would not be first order. We will assume they are first order for the drawn spectrum.

Integration 6 or 3 4 or 2 4 or 2

3.3 (j)

Actual spectrum would look like this!

2

PPM

1

0


11

3' 4

2'

O 1

5

6

N

2

7 3 (k) N,N,4-trimethylbenzamide 8

3.1 (k) 2,2’; 3,3’ are CSE but not ME. 6 and7 are diastereotopic. Pople notation for ring is AA’ XX’ 3.2 (k) Spin Table or Calculation Coupled with Multiplet (n+1) Appr. δ 2, 2’ Appendix D, Chart D1 none Doublet** δ 7.80 3, 3’ Appendix D, Chart D1 3 Doublet** δ 7.25 6,7 Appendix A, Chart A1 none Singlet* δ 2.95 8 Appendix A, Chart A1 none Singlet δ 2.25 * There will be two singlets because of the restricted rotation of the NR2 ** These can not be first order. Not magnetically equivalent. 3.3 (k)

2,2’

3,3’

6,7

8

Integration 2 2 6* 3


12

6 5

O 1 7

8

2

4

OH 3 (l) 1-(2-hydroxyphenyl)ethanone

3.1 (i) N.A. 3.2 (i) Spin Table or Calculation Appr. δ 3 Appendix D, Chart D.1 δ 6.85 4 Appendix D, Chart D.1 δ 7.05 5 Appendix D, Chart D.1 δ 7.25 6 Appendix D, Chart D.1 δ 7.70 8 Appendix A, Chart A1 δ 2.40 OH δ 5.5-12.5 Appendix E * Will have long range coupling.

Coupled with Multiplet (n+1) 4 Doublet* 3,5 Triplet* 4,6 Triplet* 5 Doublet* none Singlet none Singlet

3.3 (i)

OH

6

5

4

3

8

Integration 1 1 1 1 3 1


13

Cl 1

2 H

O (m) 2-chloroacetaldehyde

3.1(m) 1 and 2 is a spin system. Pople notation is A2X. 2 protons are enantiotopic. 3.2 (m) Spin 1

Appr. δ δ 4.95

Table Coupled with Multiplet (n+1) Appendix A, Chart A.1 2 Triplet Plus Appendix B, Table B.1* 2 Appendix D, Chart D.6 1 Doublet δ 9.80 extrapolation Calc is based on Chart A1 3.45 for ClCH2 plus Table B.1 value of 1.50 for HC=O

3.3 (m)

2

1

Integration 1 2


14

2H

3

1

H

H

F (n) fluoroethene

3.1(n) Charts are not available in text for this problem. Pople notation is AGMX, where X is F. 3.2 (n)

3.3 (n)

7

6

5

4 PPM

3

2

Protocol of the H-1 NMR Prediction: Node

Shift

H

4.85

H

6.79

H

4.23

Base + Inc. 5.25 -0.40 5.25 1.54 5.25 -1.02

Comment (ppm rel. to TMS) 1-ethylene 1 -F cis 1-ethylene 1 -F gem 1-ethylene 1 -F trans

1

0


15

3' 4

2'

O

1

O

5

2

6

3 (o) cyclohexyl acetate

3.1 (o) 1,2,2’,3,3’, and 4 is a spin system, and 6 is another spin system. 2,2,;2’,2’;3,3;3’,3’;4,4 protons are diastereotopic. 2 and 2’ are CSE, also 3 and 3’ are CSE. 3.2 (o) Spin Table or Calculation Coupled with Multiplet (n+1) Integration Appr. δ 1 Appendix A, Chart A.1 2,2’ Quintet 1 δ 4.95 2,2’ Appendix A, Chart A.2 1,(3or3’) Quartet* 4 δ 1.60 3,3’ Appendix C, Table C.1 (2 or 2’),4 Quintet* 4 δ 1.44 4 Appendix C, Table C.1 3,3’ Quintet* 2 δ 1.44 6 Appendix A, Chart A.1 none Singlet 3 δ 2.00 * These are diastereotopic, and are coupled to diastereotopic protons; they would not be first order. We will assume they are first order for the drawn spectrum. 3.3 (o)

4

1

6

2,2’

3,3’, and 4

Answers for Student Exercise 3.4

16

Problem Problem 3.4 4.3 A A C7H14O

1

O 1

2

3

3

4 4-Heptanone

2

ppm

2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 Problem 3.4 4.3 B B C7H16O Problem

OH 1

OH

2

3 4 5 6

1

7

2

3-Heptanol

3

4

5

6

3.5

3.0

Problem 4.3 C C H Br Problem 3.4 C 7 7 5

2.5 2 1

2.0

1.5

7

ppm

1.0

3 4

5

Br

4-Bromotoluene

3

2

7.5

7.0

6.5

6.0

Problem 3.4 4.3 D D C5H11Br Problem

5.5

5.0

4.5

4.0

3.5

3.0

2.5

1

Br

ppm

5

3 5 4 2 2-Bromopentane

1

2 3

4.0

3.5

3.0

2.5

2.0

4

1.5

1.0

ppm

Answers for Student Exercise 3.4 1 Problem Problem 3.4 4.3 E E C6H12O

17 O 3 5 2 4 2-Hexanone

1

3

6

6

4

5

2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8

ppm

O

Problem 3.4 4.3 FF C3H6O2 Problem x4

HO 1

2

3

3

Propionic Acid

OH

2

12.0

ppm

11.5

3.5

3.0

2.5

2.0

ppm

1.5

Problem 3.4 4.3 G G C4H11N Problem

H2N 1

2

3

4

4

Butylamine

1

NH2 2

3

2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 Problem 33.4 4.3 HH C3H4O Problem 1

OH

3 Propargyl alcohol

3

4.4

2

OH

1

4.2

4.0

3.8

3.6

3.4

ppm

3.2

3.0

2.8

2.6

2.4

2.2

2.0

ppm

Answers for Student Exercise 3.4 Problem 3.4 I Problem 4.3 I C3H7NO2 O N+ 1 2 O

18

3

3

1-Nitropropane

1

4.5

4.0

2

3.5

3.0

3

Problem 3.4 J Problem 4.3 J C8H10O24 3

2 1

6

5

2.5

OH

2.0

1.5

5

2

1.0

ppm

6

4

O 2-Phenoxylethanol 2200

2150

Hz

2100

1250

1200

1150

Hz

OH

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

ppm

Problem Problem 3.4 4.3 K K C8H10O 6

3

7.5

2

7.0

3

2 5

4

O

1

6

5

4

Phenetole

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

1.5 ppm

2.0

Problem Problem 3.4 4.3 L L C5H10O2 O O 1 2 3 5

5

4

2

4

3

Methyl Butyrate

3.5

3.0

2.5

2.0

1.5

1.0

ppm


2

19

4

Problem Problem 3.4 4.3 M M C6H11NO

5 3

6

O HN 1 2

NH

6

5 4

3

Caprolactam

7.0

6.5

6.0

5.5

5.0

4.5

Problem 3.4 4.3 N N aCpyrazine 5H6N2 A pyrazine Problem 3

4.0

3

3.0

2.5

1.5 ppm

2.0

N

2

7

3.5

4 5

7

N

6 1 2-methylpyrazine

6

5 2520

8.5

8.0

7.5

2510

7.0

6.5

2500

6.0

5.5

HO

Problem Problem 3.4 4.3 O O C8H8O3 3

1 proton (x32)

5 O

OH 13

O

12

7.5

Hz

2490

7

5.0 1

4.5

3.5

ppm

3.0

4

6

2

4.0

5

8

6

3 4 8 Methyl salicylate

ppm

7.0

6.5

Problem Problem 3.4 4.3 PP C6H4ClNO2 3

2300

2250

2200

6.0

5.5

5.0

3

O -

O

4.5

Hz

4.0

ppm

7.3

ppm

2

2 1

N+ 4

2150

Cl


8.2

8.1

8.0

7.9

7.8

7.7

7.6

7.5

7.4

Answers for Student Exercise 3.4 Problem 3.4 Q Problem 4.3 Q C7H13BrO2 Acid OH 1 proton (x32)

20 O 2

HO 1

7

3

4

5

6

7 Br


2 12

6

5 4

ppm

11

4.5

4.0

3.5

3.0

2.5

2.0

2

HO 1

4

3

5

6

5-Hexyn-1-ol

1

4

OH

3.4

3.2

3.0

ppm

1.5

6

Problem 4.3 3.4 R R C6H10O Unsaturated alcohol

3.6

3

2.8

2.6

Problem ketone ketone Problem 3.4 4.3 SS Unsaturated C8H14O Unsaturated

2.4

2 3

2.2

2.0

1.8

1

8

O

ppm

1.6

5 3 2 4 6 7 6-Methyl-5-hepten-2-one

1

78 3

5

1520

5.0

4.5

4.0

Problem Problem 3.4 4.3 T T C6H12O2

1510

1500

4

Hz

3.5

3.0

2.5

1.5 ppm

2.0

O

2

HO 1

OH

2

3

4

5

Hexanoic acid

6

4

5

6

3 13

12

2.8

ppm

2.6

2.4

2.2

2.0

1.8

1.6

1.4

1.2

1.0

ppm


21

Problem 4.3 3.4 U U C6H4OCl2

3

OH HO

4

Cl

1

2 3

Cl

4 2,6-Dichlorophenol

ppm

7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8 6.7 6.6 6.5 6.4 6.3 6.2 6.1 6.0 5.9 5.8 5.7

HO

3

Problem 4.3 Problem 3.4 V V C8H10O

5 1

2

4

3

5

4 2,6-Dimethylphenol

2120

2100

2080

2060

Hz

4.5

4.0

3.5

OH

7.0

6.5

6.0

5.5

5.0

3.0

ppm

2.5

Problem 4.3 3.4 W W Unsaturated ketone ketone C6H8O Unsaturated 6

4

5

O 1 6

3

2

5

4

2 3

2-Cyclohexen-1-one

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0 ppm

22 Answers for Student Exercise 3.5

3.5A. (1.58(300) – 0.90(300))/7 = about 29; (2.36(300) – 1.58(300))/7 = about 33 3.5E. (2.38(300) – 1.52(300))/7 = about 37; (1.52(300) – 1.38(300))/7 = about 6 (1.38(300) – 0.87(300))/7 = about 22 3.5F. (2.38(300) – 1.13(300))/7 = about 54 3.5G. (2.61(300) – 1.35(300))/7 = about 54; (1.35(300) – 1.29(300))/7 = about 2 to 3 (1.29(300) – 0.84(300))/7 = about 19 3.5H. Long range coupling; can’t measure coupling constant 3.5I.

(4.33(300) – 2.01(300))/7 = about 99; (2.01(300) – 0.99(300))/7 = about 44

3.5K. (4.08(300) – 1.44(300))/7 = about 113 3.5L. (2.26(300) – 1.62(300))/7 = about 27; (1.62(300) – 0.92(300))/7 = about 30 3.5Q. (3.39(300) – 1.86(300))/7 = about 66; (2.36(300) – 1.65(300))/7 = about 30 (1.86(300) – 1.47(300))/7 = about 17; (1.65(300) – 1.37(300))/7 = about 12 3.5U. (7.25(300) – 6.81(300))/9 = about 15

Answers for Student Exercises 3.6

23 O 1

3

2

4 4-Heptanone

A Pople Notation -- A3M2X2; 2 and 3 (and 5 and 6) are enantiotopic. 3 and 5, 2 and 6 are CSE. 1

OH

2

3 4 5 6

7

3-Heptanol

B One spin system. 2,2’; 4,4’; 5,5’, and 6,6’ are diastereotopic. 3

2 5

1

4

Br

4-Bromotoluene

C Two spin systems. Pople Notation -- AA’XX’. 2 and 2’ are CSE but not magnetically equivalent as are 3 and 3’.

Br 3 5 4 2 2-Bromopentane

1

D One spin system. 3 and 3’; 4 and 4’ are diastereotopic.

O 1

3 5 2 4 2-Hexanone

E

Two spin systems. 3, 4, and 5 are enantiotopic. O HO 1

2

3

Propionic Acid

F

A3X2. Protons on two are enantiotopic.

6


24 2

H2N 1

4

3

Butylamine

G Pople Notation – A3G2M2X2One spin system. 1, 2, and 3 are enantiotopic. 1

OH

2

3 Propargyl alcohol

H One spin system with long range coupling. Protons on 2 enantiotopic.

O -

O

N+ 1

3

2

1-Nitropropane

I

Pople Notation -- A3M2X2. 1 and 2 are enantiotopic. 3 4 3'

2 1

5

6

OH

O

2' 2-Phenoxylethanol

J Two spins systems; Pople Notation -- AA’MM’X and A2X2. 2 and 2’are CSE but not magnetically equivalent as are 3 and 3’. 5 and 6 are enantiotopic. 6

2 5

O

3

1

4

2' 3' Phenetole

K Two spins systems; Pople Notation -- AA’MM’X and A3X2. 2 and 2’are CSE but not magnetically equivalent as are 3 and 3’. 5 and 6 are enantiotopic. O O 1 2 3 5

4

Methyl Butyrate

L Two spin systems; Pople Notation --A3M2X2. 2 and 3 are enantiotopic.


25 O HN 1 2 6

3

5 4

Caprolactam

M One spin system. 2,2’; 3,3’; 4,4’; 5,5’ and 6,6’ are diastereotopic. 4

3

N

2

7

5

N


N Pople Notation –AB for 5 and 6. Three spins systems. HO O O

1

6

2

7

5


O

Two spin systems. Pople Notation – AGMX. 3

O -

2 1

N+ 4

Cl

O 3' 2' 1-Chloro-4-Nitrobenzene P One spin system. 2 and 2’ are CSE but not magnetically equivalent as are 3 and 3’.

O HO 1

2

3

4

5

6


Q One spin system. 2, 3, 4, 5, 6, and 7 are enantiotopic.

7 Br


26 6 2

HO 1

3

4

5

5-Hexyn-1-ol

R One spin system with long range coupling. 1, 2, 3, and 4 are enantiotopic. 8

O


1

S At 2 spins systems (7 and 8 probably have long range coupling). 3 and 4 are enantiotopic.

O 2

HO 1

3

4

5

6

Hexanoic acid

T

One spin system. 2, 3, 4, and 5 are enantiotopic. HO

1

Cl 2 3

Cl

3' 4 2,6-Dichlorophenol

U One spin system. 3 and 3’ are CSE but not magnetically equivalent.

HO

5 1

2

6

3

3' 4 2,6-Dimethylphenol

V One spin system. 3 and 3’ are CSE but not magnetically equivalent. 5 and 6 are CSE. O 1 6 5

4

2 3

2-Cyclohexen-1-one

W

One spin system. 4, 5, and 6 are enantiotopic.


A

X

JAX

JXA

1

AX

27

1

1

A

1 JXA

JAX 1

A2X

1 1

A2

X

1 2

1

X

1 X

JXA 1 JAX 1

A3X

1

3

A2X2

3

1

1 2

1

1 1

JXA

JAX 1

1 2

1 1

A3

1

JXA JAX 1 A3X2

1

1

2

1

1

A3

1 2

1

1

3

X2

1 2

1

1

A2

1 3

1

X2


28

With the AMX systems A and X do not change; they are represented as follows: JAM JMX 1

1

1

1

JAM

AMX 1

1 A

2

1

1

M

X

JMX

JAM 1 2

1 1

A2MX

A2

1

3

1

JAM

1

A3MX

1

1

3 4

JMX

A3

2

1

1 3

6

X

1 3

1

M

1 4

1 JMX

M

X

29

Answers for Student Exercise 3.8 Continued JAM

A2MX2 1

3

1

4

M

X2

1 2

1 1

A2

1 3

6

JMX

1 4

1

JAM M

1

A2MX3

1 A2

2

1 1 1 1

3 4

1 JMX

3 6

10

5

4 10

1 5

1

JAM

A3MX3

1

1 1 1 1

6

1

3 4

15

1 3

6 10

5

A3

2

1

1 4

10 20

X3

1

1 5

15

JMX 1

6

1

M

X3

30

Answers for Student Exercise 3.9 With the AMX systems A and X do not change; they are represented as follows: JAM JMX 1

1

1

1

The following are for M: JAM

AMX 1 1

1 1

1

1

JMX

A2MX JAM 1

1 2

1 1

1

2

A3MX

1 2

1 JMX

1

JAM 1

1 2

1 1 1

1

3 1

3

1

3 3

3

3

1

1

JMX

31 Answers for Student Exercise 3.9 Continued JAM

A2MX2 1

1

1

2

1 1

1 2

1 2

2 4

3

A2MX3

JMX

1 1 3

1

2

JAM 1

1 2

1 1

1 1 1

2

2

2 3

4 7

5

3

1 1 3

1

2 5

7

JMX

1

1

3

JAM

A3MX3

1

1 2

1 1 1 1 1

3 1

2 3

1

3 4

6

3 3

6 10

3 6

12

3 6

12

1

4 10

1

1 2 6

JMX 1

3

1

32 Answers for Student Exercise 3.10A

Spin System ab2c3 Coupling a-b 6 Hz b-c 12Hz a-c 3 Hz

1

1

(c)

1

1 Jcb

2

1 1

2

1

1 2

1 1 (b)

1

1

3 1

1 Jca

1

2

3

3

3

3

1 1

1 2

3

2 3

5

1

2 4

7

Jab

1

2

1 (a)

3

1

1

1

1

1 3

7

1 2

5

1 3

Jac 1

Jbc 1

Jba

33

Answers for Student Exercise 3.10B

Spin System ab2c3 Coupling a-b 6 Hz b-c 4Hz a-c 9 Hz

1 (c)

1 Jca

1

1

1

1

2

1

1

1

1 1

1 1

(b)

1 Jcb

2 1

1

1

Jba 1

2 1 1 2

Jbc 1

3 1 3 3 1 3

1

1

1

1

2

1

(a)

1 1 1

2

3 1

3

3

1

6

3 3

3

3

3

6

1 3

1

1

3

Jac 1 Jab

2

1

34

Answers for Student Exercise 3.10C

Spin System a2b2c2 Coupling a-b 6 Hz b-c 4Hz a-c 9 Hz

1 Jca

1

(c)

1

1 1

1 2

1 1 1

2

4

1

1 2

2 1

1 Jbc

2 2 1 4 1 2 2

1 2

1

2

1 Jba

2

1

1

1

1

1

1

1

(a)

1 Jcb

1

2

2

2

(b)

1

2

1

1 Jac

2 1

2

2

1

4

2

1

1

2

1 2

Jab 1


1

O

2 1

1

OH

2 O

1

O 2

1

S 2

3

3

1 2 S

2' 1'

O

2

1

1

N 1'

j

h

c

2'

2

OAc 2

1 o

k

Answers for Student Exercise 4.2 - 3 (a)

a 3

4

1 Br

2

1-bromobutane Atom C1

Base

α

β

γ

δ

Other

0

α-Br

Methane

2

3

4

-2.5

9.1

9.4

-2.5

C2

Methane

1,3

4

-2.5

18.2

9.4

11

C3

Methane

4,2

1

γ-Br

-2.5

18.2

9.4

C4

Methane

3

2

1

-2.5

9.1

9.4

-2.5

45

40

35

0

ε

Calc Shift

20

are from Table 4.4

33.5

Other is from table 4.6

β-Br 36.1

−3

30

Comments The base and shifts

22.1 13.5

25

20

15

10

5

ppm

Answers for Student Exercise 4.2 - 3 (b)

5

2

6 1

4

7 3

2

O O

8

9

CH3

(b) (cyclohex-2-enyl)methyl acetate α

β

Methane

2,6,7

OCOR,3,5

4

3°(3(2°))

-2.5

3*9.1

6+9.4+9.4

-2.5

3*(-3.7)

value

-2.5

27.3

24.8

-2.5

-11.1

C2

ethylene

1,4'

6,7,5'

5,6'

γ-OCOR, Zcis (-3)+(-1.1)

Atom

Base

C1

C3

C4

C5

δ

ε

Other

10.6+-7.9

7.2+7.2+-1.8

(-1.5)+(-1.5)

123.3

2.7

12.6

-3

-4.1

ethylene

4,1'

5,6',7'

6,5'

Zcis -1.1

10.6+-7.9

7.2+2(-1.8)

(-1.5)+(-1.5)

123.3

2.7

3.6

-3

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

Methane

4,6

1,3

7,2,2

2(9.1)

2(9.4)

3(-2.5)

18.2

18.8

-7.5

-2.5 C6

γ

Methane -2.5

2,4,7

2(3),OCOCH3

3(9.4)

2(-2.5)+(-3)

-2.5

18.2

28.2

-8

-2.5

6,2

3,5

4

2°(3°)

15.2

-4

0.3

-2.5

C8

Table 4.12

C9

Table 4.12

61

20.7

140

120

Other is from table 4.6

are from Table 4.4

131.5

125.5

2°(3°)

170.5

160

36

27

1,5

Table 4.12 1,OCOCH3


29.8

2(9.1) C7

-2.5

-1.1

Calc Shift

100

80

60

33.4 67.5 170.5

Table 4.12

20.7

Table 4.12

40

20

ppm

3

Answers for Student Exercise 4.2 - 3 (c)

O 1 4

5

6

2

7 OH 8

3

(c) 3-hydroxy-2-methyl1-phenylpropan-1-one

Atom

δ

from table 4.12

Base

ε

Other

Calc Shift

Table 4.12 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

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

C5 C6

C7

C8

α

β

methane

7,8,5

OH,Ph

3°(2°,3°)

-2.5

2(9.1)+24

10+9

(-3.7)+(-9.5)

-2.5

42.2

19

-13.2

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

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

180

160

140

δ

120

ε

198

Base

200

γ

100

Comments These compare nicely

Other

80

Calc Shift

Table 4.4 + Table 4.6

45.5

60.5

8.9

60

40

20

ppm

Answers for Student Exercise 4.2-3 (d)

4

5

4

3 2

1

H

(d) pent-1-yne

α

β

γ

δ

ε

Atom

Base

Other

C1

Table 4.11


67.0-68.1

are from Table 4.11

67.6 C2

Calc Shift

Increments from table 4.6

67.6

Table 4.11 84.7-84.5 84.6

C3

C4

C5

84.6 4,c≡

5,c≡

9.1+4.5

9.4+5.5

-2.5

13.6

13.9

Methane

5,3

c≡

2(9.1)

5.5

-2.5

18.2

5.5

Methane

4

3

γ-c≡

-2.5

9.1

9.4

-3.5

-2.5

9.1

9.4

-3.5

Methane

85

80

75

70

65

Base shifts Table 4.4 25

21.2

60

55

50

45

40

35

12.5

30

25

20

15

10

ppm

Answers for Student Exercise 4.2-3 (e)

5

O 1

α

β

5 6 4 (e) hex-3-en-2-one 2

γ

3

δ

ε

Atom

Base

C1

methane

2

3

4

5

6


-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

Table 4.10

1,3

3

4

6

C2

Other

Calc Shift

28.8

Table 4.10

196.9 C3

C4

C5

C6

approximate

196.9

ethylene

2,5'

6'

123.3

24+(-7.9)

-1.8

123.3

16.1

-1.8

ethylene

5,2'

6

123.3

10.6+1

7.2

137.6

123.3

11.6

7.2

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

142.1

2

1

0.3

0.1

methane

5

4

3

-2.5

9.1

9.4

-2.5

-2.5

9.1

9.4

-2.5

140

120

180

Increments from Table 4.6

160

100

23.4

13.9

80

60

40

20

ppm

6

Answers for Student Exercise 4.2-3 (f)

1

O 2

4 3

5

(f) (1-methoxybut-1-ene

Atom C1

C2

C3

C4

C5

α

Base

β

γ

δ

ε

Other

Comments

Calc Shift

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


Table 4.10 153.2

4'

5'

153.2

-7.9

-1.8

Table 4.10

4

5

84.2

10.6

7.2

Table 4.10 143.5

84.2

10.6

7.2

methane

5,3

2

γ-OR

102

-2.5

9.1+9.1

9.4

-2

-2.5

18.2

9.4

-2

23.1

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

140

130

120

110

100

90

80

70

13.6

60

50

40

30

20

ppm

Answers for Student Exercise 4.2-3 (g)

7

O

1

4

N 2 O 3 H

5

(g) propyl methylcarbamate Comments

Atom

Base

α

β

γ

δ

ε

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

Other

Calc Shift

28.4


C2 Table 4.20

Table 4.20

157.8 C3

C4

C5

157.8

methane

3,OCOR

5

NHR

-2.5

9.1+51

9.4

-4

-2.5

60.1

9.4

-4

methane

5,3

OCOR

-2.5

9.1+9.1

5

-2.5

18.2

5

methane

4

3

OCOR

-2.5

9.1

9.4

-3

-2.5

9.1

9.4

-3

150

140

130

120

63

20.7

110

100

13

90

80

70

60

50

40

30

20

ppm

Answers for Student Exercise 4.2-3 (h)

1

8

2 O 3 O (h) diethoxymethane

Atom

Base

α

β

C1

methane

2

OCOR


-2.5

9.1

5

are from Table 4.4

-2.5

9.1

5

methane

1,OCOR

3

-2.5

9.1+45

9.4

-2.5

54.1

9.4

methane

2(OR)

2(2)

2(1)

-2.5

51(2)

9.4(2)

2(-2.5)

-2.5

102

18.8

-5

110

100

C2

C3

90

γ

δ

ε

Other

Calc Shift

11.6

Increments from table 4.6 See Table 4.15 for comparison

61

80

113.3

70

60

50

40

30

20

10

ppm

9

Answers for Student Exercise 4.2-3 (i)

6

1

HO

2

3

5

4

(i) 2-methylpentan-2-ol Atom

Base

α

β

γ

δ

C1

methane

2

6,3,OH

4

5

1°(4°)

-2.5

9.1

2(9.4)+10

-2.5

0.3

C2

C3

C4

C5

C6

ε

0.3

Other

Calc Shift


-3.4

are from Table 4.4 29.8


-2.5

9.1

28.8

-2.5

methane

1,6,3,OH

4

5

-3.4 4°(2(1°)+2°)

-2.5

3(9.1)+48

9.4

-2.5

(2)(-1.5)+-8.4

-2.5

75.3

9.4

-2.5

-11.4

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

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

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

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

100

90

80

70

comparison 68.3

46.7

15.1

methane

110

See Table 4.14 for

60

14.1

50

29.8

40

30

20

10

ppm

10

Answers for Student Exercise 4.2-3 (j)

1

S 2

S

3

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

Atom

Base

α

C1

methane

SR


-2.5

20

are from Table 4.4

-2.5

20

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

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

35

30

C2

C3

45

40

β

γ

δ

ε

Other

Calc Shift

17.5


33.5

29.6

25

20

15

10

5

ppm

11

Answers for Student Exercise 4.2-3 (k)

O 1 4

5

6

N

2

8

7

3 (k) N,N,4-trimethylbenzamide Atom

Base

δ

from table 4.12

Table 4.12 C=ONH2

ε

Other

Calc Shift

CH3

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

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

C5 C6

C7

Base

α

β

γ

methane

NR2

C=O

Ph

-2.5

42

1

-2

-2.5

42

1

-2

methane

NR2

C=O

Ph

-2.5

42

1

-2

-2.5

42

1

-2

δ

ε

171 Other

Calc Shift

Table 4.4 + Table 4.6

38.5

38.5

C8 Table 4.12

160

Comments Table 4.12

Table 4.12

21.3

140

120

100

80

60

40

20

ppm

12

Answers for Student Exercise 4.2-3 (l)

6 5

O 1

8

7 2

4

OH 3 (l) 1-(2-hydroxyphenyl)ethanone

Atom

Base

δ

from table 4.12

Table 4.12 C=OCH3

ε

Other

Calc Shift

OH

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

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

197.6

C8

From Table 4.19 the CH3 is approximately 26.3 ppm,

26.3

180

160

140

120

100

80

60

Comments Table 4.12

Table 4.19

40

20

ppm

13

Answers for Student Exercise 4.2-3 (l)

Cl

1

2 H

O (m) 2-chloroacetaldehyde

Atom

Base

α

β

γ

δ

ε

C1

methane

Cl, CHO


-2.5

31+31

are from Table 4.4

-2.5

62

Other

Calc Shift

59.5

C2 Table 4.19

Increments from table 4.6 See Table 4.18 for

Cl

Comparison

199.7 199.7

200

199.7

180

160

140

120

100

80

60

40

20

ppm

14

Answers for Student Exercise 4.2-3 (n)

2

H

H

1

H

F (n) fluoroethene

Atom

Base

α

C1

Ethylene

F

Comments The base

123.2

68

are from Table 4.9

123.2

68

C2

β

γ

δ

ε

Other

Calc Shift

191.2


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.

19F couplings not shown

200

180

160

140

120

100

80

60

40

20

ppm

15

Answers for Student Exercise 4.2-3 (n)

O

1 2

4

O

5 6

3 (o) cyclohexyl acetate Atom

Base

α

C1

Table 4.7

OCOR


26.9

51

are from Table 4.7

26.9

51

C2

C3

C4

C5

β

γ

δ

ε

Other

Calc Shift


77.9

Table 4.7

OCOR

26.9

6

26.9

6

32.9

Table 4.7

OCOR

26.9

-3

26.9

-3

23.9

Table 4.7

OCOR

26.9

0

26.9

0

26.9

Table 4.20 Approx 168

C6

methane

COO

1

2,2

3,3

Table 4.20 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

160

168

140

120

100

80


20.8

60

40

20

ppm

Answers for Student Exercise 4.4 A-C

16

O

Problem Problem 5.7A 4.4 A

1

3

2

4 4-Heptanone

3

2

1

4 200

180

160 1

Problem 5.7B 4.4 B Problem

140 OH

2

120

100

80

60

40

20

ppm

7

3 4 5 6 3-Heptanol

2

3

85

80

75

70

65 5

Problem Problem 5.7C 4.4 C

60

2

55

50

3

1

4

45

40

4

35

30

5

6

25

1

20

15

7

10

ppm

Br

4-Bromotoluene

2

3 5

1 140

131 ppm

4 130

120

110

100

90

80

70

60

50

40

30

20

10 ppm

Answers for Student Exercise 4.4 D-F

17

Br

Problem Problem 5.7D 4.4 D

3 5 4 2 2-Bromopentane

1

2

95

90

85

80

75

70

Problem 5.7E 4.4 E Problem

65 60 O 1

55

3

50

3 5 2 4 2-Hexanone

45

1

40

35

30

4

25

20

5

15

ppm

10

6

3

4 5

6

2

200

180

160

Problem Problem 5.7F 4.4 F

140 O

HO 1

120 2

100

80

60

40

ppm

20

3

Propionic Acid

3

2 1

180

160

140

120

100

80

60

40

20

ppm

Answers for Student Exercise 4.4 G-I Problem Problem 5.7G 4.4 G

2

H2N 1

18

4

3

Butylamine

1

95

90

85

80

75

70

65 1

Problem 5.7H 4.4 H Problem

60

55

2

OH

50

3

85

35

30

25

4

20

15

10

ppm

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.

2

90

40

3

3 Propargyl alcohol

1

95

45

2

80

75

70

Problem Problem 5.7I 4.4 I

65 -

O

60 O

55

N+ 1

2

50

45

40

35

30

25

20

15

10

ppm

10

ppm

3

1-Nitropropane

1

3

2

77.5 95

90

85

80

75

70

65

ppm

77.0 60

55

50

45

40

35

30

25

20

15

3

Answers for Student Exercise 4.4 J-L Problem Problem 5.7J 4.4 J

4

2 1

6

5

OH

19

O 2-Phenoxylethanol

3

2 4

5

6

1 170

160

150

140

130

120

110

100

6

90

Problem 5.7K 4.4 K Problem

1

O

60 ppm

70

3

2 5

80 4

Phenetole

3

2 4

6

5

1 160 150 140 130 120 110 100

90

80

70

60 O

O 1 2 3 5

Problem Problem 5.7L 4.4 L

50

40

30

20

ppm

4

Methyl Butyrate

3 4

2

5 1 170 160 150 140 130 120 110 100

90

80

70

60

50

40

30

20

ppm

O

Answers for Student Exercise 4.4 M-O Problem Problem 5.7M 4.4 M

20

HN 1 2 6

5 4

3

Caprolactam

6

2 53

4

1 180

160

140

120

100

80

60

ppm

N

2

7

20

4

3

Problem 5.7N 4.4 N Problem

40 5

N


365 7 2 150

140

130

120

110

100

90

80

70

60

HO

Problem Problem 5.7O 4.4 O

O O

7

50 1

40

30

20

ppm

6

2

5


7

170

1

160

5

34

130

120

6

8

2

150

140

110

100

90

80

70

60 ppm

21

Answers for Student Exercise 4.4 P-R Problem 5.7P 4.4 P Problem 3

O -

O

2 1

N+ 4

Cl


2

4

3

ppm

148 146 144

1

155 150 145 140 135 130 125 120 115 110 105 100

95

90

85

80

ppm

20

ppm

O

Problem Problem 5.7Q 4.4 Q

2

HO 1

4

3

6

5

7 Br


276453 1

180

160

140

120

Problem 5.7R 4.4 R Problem

100

HO 1

2

80 3

4

5-Hexyn-1-ol

40

5

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.

1

6

60

6

2

3

4

25

20

5

85

80

75

70

65

60

55

50

45

40

35

30

15

10

ppm

Answers for Student Exercise 4.4 S-U Problem Problem 5.7S 4.4 S

22

8

O


1

7 4 5

3

8

1

6 2 200

180

160

140

120

100

80

60

40

20

ppm

O

Problem 5.7T 4.4 T Problem

2

HO 1

4

3

5

6

Hexanoic acid

2 4 35

6

1 180

160

140

120

100

HO

Problem Problem 5.7U 4.4 U

80 1

Cl

60

40

20

ppm

80

ppm

2 3

Cl

4 2,6-Dichlorophenol

3

4

4 2

1

121.2

155 150 145 140 135 130 125 120 115 110 105 100

ppm 95

90

85

Answers for Student Exercise 4.4 V-W

23

Problem Problem 5.7V 4.4 V HO

5 1

2 3

4 2,6-Dimethylphenol

3 5 1 150

2 140

130

4

120

110

100

90

80

70

60

50

40

ppm

30

20

6

45

O

Problem Problem 5.7W 4.4 W

1 6 5

4

2 3

2-Cyclohexen-1-one

3

2

1 200

180

160

140

120

100

80

60

40

20

ppm

Answers for Student Exercise 4.5 4.5

2nI +1 rule ID =1

1

24

Example

1

CDCl3

1

1

1

1

2

3

2

1

3

6

7

6

3

CD2Cl2 1

CD3Cl

Answers for Student Exercise 4.6 A-C

25

Problem 5.6A 4.6A Problem C5H10Br2

Br

2 Br 1 3 1,5-dibromopentane

1 2 3

75

70

65

60

55

50

45

40

35

30

Problem 5.6B 4.6B Problem C8H8O2

25

20

HO

15

10

5 ppm

O 7 1

2

6

8

3

5

4 2-methylbenzoic acid

4

6

3

5 8

7

2

1

132

170 160 150 140 130 120 110 100

Problem 5.6C 4.6C Problem C12H27N

1

2

3

4

130 90

128

80

70

60

50

4

2

40

30

20

ppm

H

5

6 N dihexylamine

6

75

70

ppm

65

60

55

50

5 3

45

40

35

30

25

1

20

15

10

5 ppm

Answers for Student Exercise 4.6 D-F Problem 5.6D 4.6D Problem C16H22O4

26 O

2

1

3

4 O 5

6

7

8

O O dibutyl phthalate

3 2

4

5

7

8

1

170 160 150 140 130 120 110 100

90

80

70

60

50

40

30

20

ppm

7

Problem 5.6E 4.6E Problem C7H12O

1

2

4

3

6

5

O 5-methylhex-5-en-2-one

6

3 41 7

2 200

180

160

140

Problem 5.6F 4.6F Problem C8H14O

120

100

80

2

4 6 5 3 oct-3-yn-1-ol

7

4

80

20

ppm

8

6

1

85

40

OH 1

3

60

75

27 82

70

65

60

55

80

50

78

45

40

5

8

ppm

35

30

25

20

15

10

ppm

27

2 3 3

2

O 1

1

4 O 5 4 O 5

6 6

O ortho-diethyl phthalate 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.

DEPT 90

DEPT 135

Carbon - 13 4

180

160

1,3,2

140

6

5

120

100

PPM

80

60

40

20

0

28

O 7

O

4

6 O 51 2

1 5 O 6

7

2 3

meta-diethyl phthalate

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..

DEPT 90

DEPT 135

Carbon - 13 21

5

7

6

4 3

180

160

140

120

100

PPM

80

60

40

20

0

29

5

4

O O

2

2 3

3 1

1 2

2

O

4

5

O

para-diethyl phthalate

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.

DEPT 90

DEPT 135

Carbon - 13

2

3

180

160

140

5

4

1

120

100

PPM

80

60

40

20

0

Answers for Student Exercises 5.1 3.5

ppm

3.0

2.5

1 2.0

1.5

1.0

0.5

4

0.5 1.0

COSY

ppm

(a)

0.5 1.0

3

1.5

1.5 2

F1 2.0

2.0

2.5

2.5

3.0

3.0

4

3

2

Group # 1 2 3 4

δH 3.40 1.85 1.20 0.85

3.5

F2 HMQC

ppm 5

5

10

10

15

15

20

20

F1 25

25

30

30

35

35

40

40

45

45

3.0

2.8

2.6

2.4

2.2

2.0

F2

1.8

1.6

1.4

1.2

1.0

ppm

Br

(a) 1-bromobutane

1 3.5

1

δC 33.5 36.1 22.1 13.5


2

1

ppm

3

2

HMBC

4

(a)

5 10

4

15

3

4

2

1 Br

(a) 1-bromobutane

20

3

F1 25 30

1 2

35

Group # 1 2 3 4

δH 3.40 1.85 1.20 0.85

δC 33.5 36.1 22.1 13.5

40 45 50 3.0

2.8

2.6

2.4

2.2 2

Hz

1

2.0

1.8

1.6

F2

1.4

1.2

ppm

1.0

3

INADEQUATE 4

Center Frequency

-3000

-3000

-2000

-2000

-1000

-1000

F1 0

0

1000

1000

2000

2000

3000

3000

45

40

35

30

F2

25

20

15

10

5

ppm

Answers for Student Exercises 5.1 ppm 6.0

5.5

5.0

4.5

4.0

3 3.5

3.0

2.5

2.0

1.5 5

1.5 9

2.0

4

6

COSY

ppm 5

1.5 2.0

6

4

1 3

2

(b) 7

O O 8

9


2.5

2.5

1

3.0

3.0

F1 3.5

3.5 7

4.0

4.0

4.5

4.5

5.0

5.0 2

5.5

3

Group # 1 2 3 4 5 6 7 8 9

δH 2.80 5.59 5.59 1.96 1.65 1.80 4.05 NA 2.10

5.5

F2 HMQC

ppm 20

9

1

4

20

5 6

40

40

60

60 7 7

F1 80

80

100

100

120

120

2 3 6.0

5.5

5.0

4.5

4.0

3.5

F2

3.0

2.5

2.0

1.5

ppm

δC 36.0 131.5 125.5 29.8 27.0 33.4 67.5 170.5 20.7

Answers for Student Exercises 5.1 3 2

4 7

ppm

HMBC

9 46 5

1

5

56 9 41

40

6

4

1 3

2

(b) 7

O O 8

9


7

60

Group # 1 2 3 4 5 6 7 8 9

80

F1

100

32

120 140

δH 2.80 5.59 5.59 1.96 1.65 1.80 4.05 NA 2.10

δC 36.0 131.5 125.5 29.8 27.0 33.4 67.5 170.5 20.7

160 8

180 6.0 Hz

5.5

5.0

4.5

4.0

3.0

2.5

2.0

1.5 ppm

F2 Center

Frequency

2 3

8

3.5

INADEQUATE 16 4 5 9

7

-10000

-10000

-5000

-5000

F1 0

0

5000

5000

10000

10000

180

160

140

120

100

F2

80

60

40

20

ppm

Answers for Student Exercises 5.1 ppm 7

6

5

1

3

2

4

O

2

1

7 6

4

5 3

1

9 8

ppm

COSY

(c)

10 1

OH

10

5

2

34 OH

Group # 1 2 3 4 5 6 7 8 9 10 OH

2

8 9

3

3

F1 4

4

5

5

δH NA 6.68 2.05 2.05 5.68 6.22 NA 2.65 3.20 1.05 0.5-4

5 6

6

6

2

F2 HMQC ppm

10

20

20 4

40

3 40

8 9

60

60

F1 80

80

100

100

120

5

6

140

120 140

2

7

6

5

4

3

F2

2

1

ppm

δC 143.2 150.0 28.3 30.7 122.1 131.1 206.7 45.5 60.5 8.9 NA

Answers for Student Exercises 5.1 2 6

6

5

4 3

8

9

HMBC

10

(c)

10

ppm 20

2

34 8

40

F1

Group # 10 3 4 8 9 5 6 1 2 7 OH

100 56 1 2

140 160 180 200

7

9 8

OH

10

5

80

120

1 6

4

9

60

3

O

δH 1.05 2.05 2.05 2.65 3.20 5.68 6.22 NA 6.68 NA 0.5-4

δC 8.9 28.3 30.7 45.5 60.5 122.1 131.1 143.2 150.0 206.7 NA

7 7

6

5

7

4 2 1

Hz

3

2

1

F2 Center 6

5 Frequency

ppm INADEQUATE 9

43

8

10

-10000

-10000

-5000

-5000

F1 0

0

5000

5000

10000

10000

15000

15000 200

180

160

140

120

F2

100

80

60

40

20

Hz

Answers for Student Exercises 5.1 ppm

2.5

2.0

7 1.5

1.0

0.5

COSY

ppm

(d) 0.5

0.5

5

4

3 2

1

5 1.0

1.0 4

1.5

F1

1.5

Group # 1 2 3 4 5

δH 1.80 NA 2.20 1.50 0.85

1 2.0

2.0

3

2.5

2.5

F2 HMQC ppm 5

10 20

F1

10

4

3

20

30

30

40

40

50

50

60

60

1

70

70

80

80

2.5

2.0

1.5

F2

1.0

0.5

ppm

δC 67.6 84.6 25.0 21.2 12.5

H

Answers for Student Exercises 5.1 1

3

ppm

8 4

HMBC

5

(d)

10

5

20

4

5

3 2

1

δH 1.80 NA 2.20 1.50 0.85

δC 67.6 84.6 25.0 21.2 12.5

H

4 3

30

Group # 1 2 3 4 5

F1 40 50 60 1

70 80

2 90 2.5 1

2.0 2

1.5

1.0

F2 Center

Frequency

0.5

ppm INADEQUATE 3 4

5

Hz

-4000

-4000

-2000

-2000

F1 0

0

2000

2000

4000

4000

6000

6000 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10

F2

5

Hz


9

ppm 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 6

1 5

2

(e)

O

1

1

1

2

3

2

3

3

F1 4

4

5

5 3

6

COSY

ppm

Group # 1 2 3 4 5 6

4

δH 1.86 NA 6.09 6.82 2.05 1.00

6

4

F2 HMQC ppm

6 5

20

F1

1

20

40

40

60

60

80

80

100

100

120

120

140

4

3 140

7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0

F2

ppm

5

δC 28.8 196.9 137.6 142.1 23.4 13.9

6


4

10 5 1

3

HMBC

6 6 5 1

20 40 60

(e)

O 1

2

3

Group # 1 2 3 4 5 6

F1 80 100 120

4 δH 1.86 NA 6.09 6.82 2.05 1.00

5

6

δC 28.8 196.9 137.6 142.1 23.4 13.9

3 4

140 160 180

2

200 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 4 3

2

ppm

INADEQUATE

F2 Center

Frequency

15

Hz

6

-10000

-10000

-5000

-5000

F1 0

0

5000

5000

10000

10000

15000 200

180

160

140

120

F2

100

80

60

40

20

15000 Hz


11

ppm 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 5

1 4

2

1 1

2

1

3

ppm

O 2

Group # 1 2 3 4 5

3

F1 4

COSY

(f) 4

3 δH 3.20 6.14 4.63 2.05 1.00

4 3

5

5 2

6

6

F2 HMQC ppm

5 4

20 40

20 40

1

F1

60

60

80

80 3

100

100

120 140

120 2

140

7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0

F2

ppm

δC 55.8 143.5 102.0 23.1 13.6

5


12 3

ppm

HMBC

5

4

1

(f) 5

20

1

O 2

4

4

5

3

40 Group # 1 2 3 4 5

1

F1 60 80 100

δH 3.20 6.14 4.63 2.05 1.00

δC 55.8 143.5 102.0 23.1 13.6

3

120 140

2 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5

ppm INADEQUATE

F2 Center 2

Hz

Frequency

3

4

1

5

-5000

-5000

F1 0

0

5000

5000

10000

10000

150 140 130 120 110 100

90

80

F2

70

60

50

40

30

20

10

Hz


13

ppm 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 5

1

ppm 1 1

2

3

F1 3

4

4

5

6

5 NH

6

F2 HMQC ppm

5

20

1

4

40 60

F1

20 40 60

3

80

80

100

100

120

120

140

140 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0

F2

(g) 4

δH δC Group # 1 2.95 28.4 2 NA 157.8 3 4.10 63.0 4 1.60 20.7 5 0.85 13.0 NH 4.5-7.5 NA

1 3

O N 2 O 3 H

4 2

COSY

ppm

5


14 3

1

4

ppm

HMBC

5 5

20

4

1

F1

1

4

5

δH δC Group # 1 2.95 28.4 2 NA 157.8 3 4.10 63.0 4 1.60 20.7 5 0.85 13.0 NH 4.5-7.5 NA

80 100

(g)

N 2 O 3 H

40 60

O

3

120 140

2 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5

ppm

F2 Center

Frequency 3

2

INADEQUATE 1

4 5

Hz -10000

-10000

-5000

-5000

F1 0

0

5000

5000

10000

10000 140

120

100

F2

80

60

40

20

Hz


5.5

5.0

4.5

4.0

15 3.5

3.0

2.5

2.0

1.5

1.0

ppm

1

1.0

1.0

1

1.5

1.5

2.0

2.0

2.5

2.5

F1 3.0

3.0

3.5

COSY

2 O 3 O

(h) Group # 1 2 3

δH 1.20 3.40 4.95

3.5

2

4.0

4.0

4.5

4.5

3

5.0

5.0

5.5

5.5

F2 HMQC

ppm

F1

1

20

20

40

40 2

60

60

80

80

100

100 3

120

120 6.0

5.5

5.0

4.5

4.0

3.5

F2

3.0

2.5

2.0

1.5

1.0

ppm

δC 11.6 61.0 113.3


16 2

HMBC

1

ppm 1

1

20

(h)

40

F1

2 O 3 O

60

Group # 1 2 3

2

δH 1.20 3.40 4.95

δC 11.6 61.0 113.3

80

100 3 120 6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

ppm

1.5

INADEQUATE

F2 Center

Frequency 2

3 Hz

1

-8000

-8000

-6000

-6000

-4000

-4000

-2000

-2000

F1 0

0

2000

2000

4000

4000

6000

6000

8000

8000 120

110

100

90

80

70

F2

60

50

40

30

20

10

Hz


1.8

1.6

17

1.4

1.2

1.0

0.8

0.6

0.6

0.6 5

0.8

0.8

1.0

1.0

F1 1.2

4

6

1.4

1.2

1

1.4

3

1.6

COSY

ppm

(i)

6

1

HO

2

3

δH Group # 1 1.20 2 NA 3 1.50 4 1.20 5 0.85 6 1.20 OH 0.5-4.0

1.6 OH

1.8

1.8

F2 HMQC

ppm 10

10

5

4

20

20 6 1

30

F1 40

30 40

3

50

50

60

60

70

70

80

80 ppm

2.0

1.8

1.6

1.4

1.2

F2

1.0

0.8

0.6

5

4 δC 29.8 68.3 46.7 15.1 14.1 29.8 NA


18 6 4 1

3

HMBC

5

ppm 10

4

5

20

F1

6

1

HO 16

30 40

3 50

(i)

2

3

5

4

δH Group # 1 1.20 2 NA 3 1.50 4 1.20 5 0.85 6 1.20 OH 0.5-4.0

δC 29.8 68.3 46.7 15.1 14.1 29.8 NA

60 2

70

2.0

1.8

1.6

1.4

1.2

1.0

ppm

0.8

F2 Center

3 Frequency

2 Hz

INADEQUATE 45

1,6

-4000

-4000

-2000

-2000

F1 0

0

2000

2000

4000

4000

6000 75

70

65

60

55

50

45

F2

40

35

30

25

20

15

10

5

6000 Hz


2.8

2.6

2.4

19

2.2

2.0

1.8

1.6

1.4

1.2

ppm

COSY

(j) 1.2

1.2 1

1.4

1.4 3

1.6

F1

1.6

1.8

1.8

2.0

Group # 1 2 3

S

3 δH 2.10 2.60 1.60

2.0

1

2.2

2.2

2.4

2.4 2

2.6

S 2

2.6

2.8

2.8

F2 HMQC ppm 15

15 1

20

20

F1 25

25 3

30

30 2

35

35

40

40 ppm

3.0

2.8

2.6

2.4

2.2

2.0

F2

1.8

1.6

1.4

1.2

δC 17.5 33.5 29.6


20 1

2

HMBC

3

ppm

(j) 1

S 2

15 1 20

F1

Group # 1 2 3

S

3 δH 2.10 2.60 1.60

δC 17.5 33.5 29.6

25 3

30

2 35

40 3.0

2.8

2.6

2.4

2.2

2

3

2.0

1.8

1.6

ppm

1.4

F2 Center

Frequency

INADEQUATE

1

Hz -1500

-1500

-1000

-1000

-500

-500

F1 0

0

500

500

3 to 3'

1000

1000

1500

1500

2000

2000 40

38

36

34

32

30

28

26

F2

24

22

20

18

16

14

12

Hz


21

ppm 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5

COSY

ppm

(k)

8

1

6,7 3

3

4 8

4

4

5

5

6

6

5 2

δH NA 7.80 7.25 NA NA 2.95 2.95 2.25

7

3 2

F2 HMQC ppm

8

40

40

6,7

60

60

80

80

100

100

120

120

F1

2 3.0

3 2.8

2.6

2.4

2.2

2.0

F2

1.8

1.6

1.4

1.2

ppm

6

N 7

3 Group # 1 2 3 4 5 6 7 8

F1

7

O

δC 130.6 127.2 129.2 141.2 171.0 38.5 38.5 21.3


22 7 6

3

HMBC

8

ppm

(k)

8

1

67

40

4 8

60

F1 80

23 1 4

140

6

5

N

2

7

3 Group # 1 2 3 4 5 6 7 8

100 120

O

δH NA 7.80 7.25 NA NA 2.95 2.95 2.25

δC 130.6 127.2 129.2 141.2 171.0 38.5 38.5 21.3

160 5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 5

4

Hz

ppm

F2 Center

Frequency

13 2

INADEQUATE 7 6

8

-10000

-10000

-5000

-5000

F1 0

0

5000

5000

10000

10000

160

140

120

100

F2

80

60

40

20

Hz


23

ppm 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5

COSY

ppm

O

(l)

6

3

5

3

2 3

4

5

5

6

6

7

5

4

3 7

6

F2 HMQC ppm 8 40

40

60

60

80

80

100

100

F1

3

5

120

6

3.0

120 4

2.8

2.6

2.4

2.2

2.0

F2

1.8

1.6

1.4

1.2

OH

δH Group # 1 NA 2 NA 3 6.85 4 7.05 5 7.25 6 7.70 7 NA 8 2.40 OH 5.5-12.5

F1

ppm

8

7

4 4

1

δC 123.6 154.7 115.4 132.9 120.8 129.7 197.6 26.3 NA


24

54 3

HMBC

8

ppm

8

40

(l) 6 5

60

3

3 51 64

140

2

160

8

2

80

120

1 7

4

F1 100

O

OH

δH Group # 1 NA 2 NA 3 6.85 4 7.05 5 7.25 6 7.70 7 NA 8 2.40 OH 5.5-12.5

δC 123.6 154.7 115.4 132.9 120.8 129.7 197.6 26.3 NA

180 7 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0

ppm

INADEQUATE

F2

7

Center 4 6 1 5 3 Frequency

2

8

Hz -10000

-10000

-5000

-5000

F1 0

0

5000

5000

10000

10000

180

160

140

120

F2

100

80

60

40

Hz


10

9

25 8

7

6

5

ppm

COSY

(m) 1

5

5

Cl

1

2 H

O 6

6

F1 7

7

8

8

9

Group # 1 2

δH 4.95 9.80

9 2

10

10

F2 HMQC

ppm 1

60

60

80

80

100

100

F1 120

120

140

140

160

160

180

180 2

200 11

200 10

9

8

7

F2

6

5

ppm

δC 59.5 199.7


26 HMBC

1

2 ppm 60

1

(m)

Cl

1

80

2 H

O

100

Group # 1 2

F1

120

δH 4.95 9.80

δC 59.5 199.7

140 160 180 2

200 11

10

9

8

7

6

5

F2 Center

Frequency

2

ppm

INADEQUATE

1

Hz -10000

-10000

-5000

-5000

F1 0

0

5000

5000

10000

10000

200

180

160

140

F2

120

100

80

60

Hz


7.5

7.0

6.5

27 6.0

5.5

5.0

4.5

ppm

(n)

1trans

4.5

COSY

1cis

4.5

H

1cis

5.0

5.0

5.5

5.5

6.0

6.0

6.5

6.5

F1

H

H 1trans Group # 1cis 1trans 2

2

F δH 4.85 4.23 6.79

2

7.0

7.0

7.5

7.5

F2 HMQC

ppm 1

130

130

140

140

150

150

F1 160

160

170

170

180

180 2

190

190

200 8.0

7.5

7.0

6.5

6.0

F2

5.5

5.0

4.5

200 ppm

δC 132.2 132.2 191.2


28 1cis

2

HMBC

1trans

ppm

(n)

130

H

1

140

H 1trans

150

F1

Group # 1cis 1trans 2

160 170

1cis

H

2

F δH 4.85 4.23 6.79

δC 132.2 132.2 191.2

180 190

2 7.0

6.5

6.0 2

5.5

5.0

4.5

F2 Center

Frequency

ppm

INADEQUATE

1

Hz -4000

-4000

-2000

-2000

F1 0

0

2000

2000

4000

4000

6000

6000 Hz

190

180

170

F2

160

150

140

130


5.5

5.0

4.5

4.0

29 3.5

3.0

2.5

2.0

1.5 33' 4

1.5

F1

1.5

22' 6

2.0

3'

2'

2.5

3.0

3.0

3.5

3.5

4.0

4.0

4.5

4.5 1

2

Group # 1 2,2' 3,3' 4 5 6

δH 4.95 1.60 1.44 1.44 NA 2.00

5.5

F2 HMQC

ppm

33' 4

6 22'

40 60

40 60

1

F1

80

80

100

100

120

120

140

140

160

160

6.0

5.5

5.0

4.5

4.0

3.5

F2

3.0

2.5

2.0

1.5

ppm

O

5 6

3

5.0

5.5

(o)

O

1

2.0 4

2.5

5.0

COSY

ppm

δC 77.9 32.9 23.9 26.9 168.0 20.8


30 6

1

ppm

33' 22' 4

HMBC 6 3 3' 4 2

40

2'

(o)

O

5

2

4 60

O

1

6

3 1

F1 80

Group # 1 2,2' 3,3' 4 5 6

100 120

δH 4.95 1.60 1.44 1.44 NA 2.00

δC 77.9 32.9 23.9 26.9 168.0 20.8

140 160

5 6.0

5.5

5.0

4.5

4.0

3.5

3.0

F2

Center Frequency 1

5

2.5

2.0

ppm INADEQUATE 2 43 6

Hz -10000

-10000

-5000

-5000

F1 0

0

5000

5000

10000

10000

160

140

120

100

F2

80

60

40

20

Hz


31

CH2 H

g= geminal v= vicinal lr= long range

5 4

HO

7

7 8 CH2

3

H3C

8

6

2

1 CH3

CH3 1

CH2=

4

5 5'

OH 2

3 3'

ppm 0.5

v 1.0

v

v

1.5

g v

v

2.0

lr

2.5

v

g

3.0

F1

3.5

v

4.0

v

4.5 5.0

g

v

lr

5.5 6.0 6.5

v

7.0 7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

F2

3.0

2.5

2.0

1.5

1.0

0.5

ppm


32

CH2 H

5

6

4

HO

8 CH2

3

H3C

7

2

CH3 1

Carbon 13 Signals 1

2

3

1

Bonded

α

β

2

α

Bonded

α

β

S

3

β

α

Bonded

α

β

I

4

β

α

Bonded

α

β

g

5

β

α

Bonded

α

β

n

6

l

7

β

α

Bonded

α

a

8

β

α

Bonded

l

CH3

s

CH2=

1

H

β

α

4

5

6

7

8

CH3

CH2=

β α β

β

β β Bonded

β

α

β

Bonded


33

H NMR 600 MHz

4

5’ 3

5

1300

6

2

Hz 1250

Hz

4’

Hz

1150

3’ 6

1000 Hz

1050

2.3 13

2.2

2.1

860 840 820 Hz

2.0

1.9

1.8

1.7

620 600 580 Hz

1.6

1.5

1.4

1.3

1.2

ppm

1.1

1.0

5

3 4

C/DEPT 600 MHz

O 6

1 2 5 3 4

6

2

2-methylcyclopentanone

1

220

200

180

160

140

120

100

80

60

40

20

ppm


COSY 600 MHz

1.0

1.0

6

1.2

1.2

1.4

1.4

ppm 2.4

F1

34

2.2

2.0

1.8

1.6

1.4

1.2

1.0

1.6

O

3’

6

1 2 5 3 4

1.6

4’ 1.8

1.8

2.0

2.0

2.2

2.2

4

5 3 2 5’

ppm

F2

4

4’

5’ 2

3 5

HMQC 600 MHz

6

3’

2-methylcyclopentanone

6 15

15

20

20

25

25

F1 30

30

35

35

40

40

45

45

2.4

2.2

2.0

1.8

1.6

F2

1.4

1.2

1.0

ppm

4

3

5

2


35

H NMR 600 MHz 7

9

4750 Hz

4800

8

4400 Hz

4450

2

3

1700 Hz 1550

9

4300 Hz

4350

4

1750

6

1500 Hz

2

1200 Hz

1250

4 3

7 8 6 O 9

10

8 7

5

6

8.0 13

7.5

7.0

6.5

6.0

5.5

1

2 3

4

5.0

4.5

4.0

3.5

3.0

2.0 ppm

2.5

C/DEPT 600 MHz

8 6 97

5

1

200

180

160

140

2

4

3

10

120

100

80

60

40

ppm


8

7

6

36 5

4

3

2

2

COSY 600 MHz

2

3

3

8.0

4

7.5

7.0 ppm

5

O

4

7.0

10

1

2

8

7

5

7 6

5

3 4

6

9

8.0

9 8

6

7.5

6

4

2

3 ppm

F1

ppm

7

7

8

8

F2

HMQC 600 MHz

ppm

3

4

40

60

40

ppm 125

7 9 6

130

F1

80

60

80

8

135 8.2 8.0 7.8 7.6 7.4 7.2

ppm

100

100

120

120

140

140 9

8

7

6

5

F2

4

3

2

ppm

2


H NMR 600 MHz

Hz

5470 4

5200

Hz

5190

2590

8

8

Hz

2580

790

7

3

1

5

3

4

2

5

6

Hz

780

O

4

4900 Hz

4910

7

4360 Hz

4370

3

5

1

5480

37

O

CH2

7

8 CH3

1

N

ethyl nicotinate

9.0

8.5

8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

ppm

13 13C/DEPT

MHz C/DEPT600 NMR 150.9 MHz

5

1

7

4

3

8 2

6

160

150

140

130

120

110

100

90

80

70

60

50

40

30

ppm


ppm

9

7

6

5

4

3

2

ppm

2

3 4

2

5

6

O

CH2

7

8 CH3

3

1

N

4

4

ethyl nicotinate

F1 5

5

6

6

7

7

8

8

9

9

ppm

F1

1

COSY 600 MHz 8

O

2 3

8

38

5 3

F2

4

7

4 3 5 1

8

7

HMQC 600 MHz

20

20

40

40

60

60

80

80

100

100

120

120

8

7

2

140

140

4 3 1

160

160 9

8

7

6

5

F2

4

3

2

ppm

6

5


39 INADEQUATE 600 MHz INADEQUATE 150.9 MHz

Hz -25000

7

O

3

-20000 -15000

4

2

5

1

N

-10000

6

O

-25000

8

-20000

8

CH2

7

CH3

-15000 -10000

ethyl nicotinate

-5000

F1

-5000

0

0

5000

5000

10000

10000

15000

15000

20000

20000

25000

25000 160

140

120

5 Hz

6

100

1

80

60

F2

40

3

ppm

20

2

4

12000

12000

13000

13000

F1

14000

14000

15000

15000

16000

16000

17000

17000

165

160

155

150

145

F2

140

135

130

125

ppm


INADEQUATE 150.9 MHz

13

40

Hz -10000

-10000 15 H3C

-5000

H3C 14

CH3 12

4

1

11

5 9

10

-5000

O 6

8

H

F1

3

2

H

7

CH2 13

0

0

8-7 8-9

5000

5000 8-13

10000

10000 160 150 140 130 120 110 100 5

90

1 9

4

80

70

60 50 14 11 67 2

10 3

40

30 15

ppm

20 12

Hz -9000

-9000

11-15 11-14

3-2

-8000

C6-C7

-8000

10-11

4-12

F1-7000

-7000

1-2 1-11 5-6

-6000

9-10

-6000

4-3

-5000

-5000

1-9

-4000

-4000 5-4

65

60

55

50

45

F2

40

35

30

25

20

15

ppm


41

The following correlations can be found in the INADEQUATE spectrum of caryophyllene oxide Carbon 1 correlates with carbons 2, 9, and 11 Carbon 2 correlates with carbons 1 and 3 Carbon 3 correlates with carbons 2 and 4 Carbon 4 correlates with carbons 3, 4, and 12 Carbon 5 correlates with carbons 4, and 6 Carbon 6 correlates with carbons 5, and 7 Carbon 7 correlates with carbons 6, and 8 Carbon 8 correlates with carbons 7, 9, and 13 Carbon 9 correlates with carbons 1, 8, and 10 Carbon 10 correlates with carbons 9 and 11 Carbon 11 correlates with carbons 1, 10, 14, and 15 Carbon 12 correlates with carbons 4 Carbon 13 correlates with carbons 8 Carbon 14 correlates with carbons 11 Carbon 15 correlates with carbons 11

15 H3C H3C 14

3

2

H

CH3 12

4

1

11

5 9

10

6 8

H CH2 13

O

7


42

H NMR 600 MHz 2

1

1’ 6

3500

Hz

3450

3050

5

8

OH

3000

Hz

1400

9

Hz

1350

10

9

10

4

1200

Hz

1150

950

8

Hz 9 750

900

Hz

700

OH

1

2

6

1’

4 5

3

2

5

4

1

6

OH

7 8 10 3,7-dimethylocta-1,6-dien-3-ol

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

ppm

1.5

13 13 C/DEPT

NMR 150.9 MHz C/DEPT 600 MHz

1 6

2

140

130

5

8

7

150

9

4

3

120

110

100

90

80

10

70

60

50

40

30

20 ppm

Answers for Student Exercises 5.8 ppm 6.0 5.5 5.0 4.5 4.0 3.5

43 3.0

2.5

2.0

1.5

ppm

COSY 600 MHz 9

1.5

1.5

2.0

2.0 9

2.5 3.0

F1

3

4 5

3.5 4.0

2.5

OH

6

2

8

10

5 OH

3.0

1

3.5 4.0


4.5

4

4.5

5.0

5.0

5.5

5.5

1’ 6 1 2

2

ppm

F2

1,6,1’

8 10 4 5

HMQC 600 MHz

9

20

20

40

40

60

60

10

5

4

3

F1

80

80

100

100

1 120

120

6 7

140

140

6.0

5.5

5.0

4.5

4.0

3.5

F2

3.0

2.5

2.0

1.5

ppm

8 9

2

HMBC 600 MHz


8

161

2

OH

ppm 20 4 5

44

9

4 10

9

40

5

10

5 8 9

OH

3

2

4

1

6

60

F1

3


80

100

1 120

6 7

140

2

160 6.0

5.5

5.0

4.5

4.0 F2 3.5

3.0

2.5

2.0

ppm

1.5 ppm

20

20

40

40

60

60

F1

ppm

ppm

120

120

140

140 6.0

5.9

5.8

ppm

5.2

5.0

F2

ppm

2.0

1.5

ppm

ppm


6

45 1

INADEQUATE 150.9 INADEQUATE 600MHz MHz

3

4

7

9 85 10

Hz 9 4

-15000

-10000

5

OH

3 6

2

-15000

1


-10000

-5000

-5000

F1 0

0

5000

5000

10000

10000

15000

15000

140

120

100

80

F2

60

40

20

ppm


ppm

5.2 5.0 4.8 4.6 4.4 4.2 4.0

F1

3.6

α2 α4

β5 β3 β4

3.8

α3 α6 α5

β6’

TOCSY 600 MHz

3.8 3.6 3.4

β2

3.4

4.0

46

3.4 G2

3.6

G3 G5 G6

3.8

G4

β6

4.0

4.2

4.2

4.4

4.4

4.6

4.6

4.8

4.8

5.0

5.0

5.2

5.2 5.2 5.0 4.8 4.6 4.4 4.2 4.0

3.8 3.6 3.4

G1 β1

HDO α1

ppm

F1 Correlations from the three anomeric protons are drawn. These correlations show the ring protons for the three monosaccharide residues of lactose. Correlations among the ring protons are difficult to decipher due to overlap. Results from the 1D HOHAHA in Figure 5.26 agree with these findings.


47

H NMR 600 6MHz CH2OH O H HO CH2OH 5 H 4 O H H 1 HO HO H HHO 3 H 2 H HO H

H

HO

6 CH52 H HO 4 H HO HO 3 H HO

α-Galactose Ring A

C3

1

CH2

O H O H

H

O H

H1

H

O

3.9

O

3

HO

4

3.7

CH2OH

β-Fructose Ring C

C1

B2 B4

3.6

ppm

3.5

C3

A1

6

H

A6 C1 A2 B3 C6 C6’ B6’

3.8

CH2OH

H

HO

HO

5H

HO

HO

HDO B1

H

O

H

O

α-Glucose Ring B

4.0

CH2OH

2 CH2HOH

H2 HO

C4 B5 B6 A4 A5 C5 A3

4.1

O

C4

5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6

ppm

13 13C/DEPT

150.9 MHz C/DEPT NMR 600 MHz

74.0

B5

B3

C3

73.5

73.0

100

72.0

71.5

95

71.0

C5

B1

A1

C2

72.5

A5 B2

90

85

A3 B4 A4

70.5

70.0

69.5

C3 C4

80

75

A2

69.0

C6 C1A6

B6

70

ppm

65

ppm


48

Mixing time 300 ms 5.40 ppm irradiated

1-d TOCSY 600 MHz

B6

B6’

Mixing time 80 ms B5

B4

Mixing time 40 ms B3 B2

Mixing time 20 ms

4.05

4.00

3.95

3.90

3.85

3.80

3.75

3.70

3.65

3.60

Mixing time 300 ms 4.97 ppm irradiated

A5

3.55

3.50

ppm

1-d TOCSY 600 MHz

A6

Mixing time 80 ms A4 A3

Mixing time 40 ms

Mixing time 20 ms

A2

1

4.05

4.00

3.95

3.90

3.85

3.80

3.75

3.70

3.65

3.60

H NMR 600 MHz

3.55

3.50

ppm


49

Mixing time 80 ms

1-d TOCSY 600 MHz C6 C6’

Mixing time 40 ms C5

Mixing time 20 ms C4

1

4.05

4.00

3.95

3.90

3.85

6 CH2OH HO

4

H HO

H H

5

O

1

3

HO

2

O H

3.70

4

1

CH2 H HO

HO

H

α-Galactose Ring A

3.75

3.65

3.60

3.55

3.50

6

H

H

3.80

H NMR 600 MHz

5

O

H

3

2 HO

α-Glucose Ring B

2

1

H

CH2OH H

O

HO

3 HO

H

O

4 H

β-Fructose Ring C

5 CH2OH

6

ppm


F1

5.4 5.2 5.0 4.8 4.6

50 4.4 4.2 4.0 3.8 3.6

COSY 600 MHz

ppm

3.6

3.6

3.8

3.8

4.0

4.0

4.2

4.2

4.4

4.4

4.6

4.6

4.8

4.8

5.0

5.0

5.2

5.2

5.4

5.4

C3

HDO A1

B1

COSY 600 MHz

ppm

B4 B2

3.5 3.6

C1

B6’ 3.7

F1

C6’B3 C6 A2 C5 A3 A5 A4 B6 B5 C4

3.8 3.9 4.0 4.1

C3

4.2 4.2

4.1

4.0

3.9

3.8

F2

3.7

3.6

3.5

ppm

A6

Answers for Student Exercises 5.10 ppm 5.4 5.2 5.0 4.8 4.6 4.4 4.2 4.0 3.8 3.6

F1

ppm

3.6

3.6

3.8

3.8

4.0

4.0

4.2

4.2

4.4

4.4

4.6

4.6

4.8

4.8

5.0

5.0

5.2

5.2

5.4

5.4

51

TOCSY 600 MHz

C3

HDO A1

B1

TOCSY 600 MHz

ppm

B4 B2

3.5 3.6

C1

B6’ 3.7

F1

C6’B3 C6 A2 C5 A3 A5 A4 B6 B5 C4

3.8 3.9 4.0 4.1

C3

4.2 4.2

4.1

4.0

3.9

3.8

F2

3.7

3.6

3.5

ppm

A6

Answers for Student Exercises 5.10 B1 A1 C1 B5A4 A6 C3 C4 B6 C6 C6’ A5 A3C5 A2 B3 B6’ ppm 5.5

ppm

4.1

4.0

3.9

3.8

3.7

3.6

52

HMQC 600 MHz B2 B4 3.5

ppm

60

A6 C1 C6

F1 65

B6

ppm

A2 A4 B4 A3

69 70

B2 A5 B5

71 72

B3

73

C4

74

F1

75 76

C3

77 78 79 80 81

C5

ppm

B1

95

F1

A1

100

C2

105 5.5

ppm

4.1

4.0

F2

3.9

3.8

3.7

3.6

3.5

ppm

Answers for Student Exercises 5.10 B1

HMQC-TOCSY 600 MHz C1 B5A4 A6 C4 B6 C6 C6’ A5 A3C5 A2 B3 B6’ B2 B4

A1 C3

ppm 5.5

ppm

53

4.1

4.0

3.9

3.8

3.7

3.6

3.5

ppm

60

A6 C1 C6

F1 65

B6

ppm

A2 A4 B4 A3

69 70

B2A5 B5

71 72

B3

73

C4

74

F1

75 76

C3 77 78 79 80 81

C5

ppm

B1

95

F1

A1

100

C2

105 5.5

ppm

4.1

4.0

F2

3.9

3.8

3.7

3.6

3.5

ppm

Answers for Student Exercises 5.10 B1 A1 C1 B5A4 A6 C3 C4 B6 C6 C6’ A5 A3C5 A2 B3 B6’ ppm 5.5

ppm

4.1

4.0

3.9

3.8

3.7

3.6

54

HMBC 600 MHz B2 B4 3.5

ppm

60

A6 C1 C6

F1 65

B6

ppm

A2 A4 B4 A3

69 70

B2A5 B5

71 72

B3

73

C4

74

F1

75 76

C3

77 78 79 80 81

C5

ppm

B1

95

F1

A1

100

C2

105 5.5

ppm

4.1

4.0

F2

3.9

3.8

3.7

3.6

3.5

ppm


55

H NMR 600 MHz 22

6

23

Hz

3200 7’,8,24,25 3100 2’ 11

15

1000

2200

4

Hz

1’

14

HO HO

3

10

4

600 Hz

6

CH3

CH3 18 20 CHCH 3 3

13

15

7

1

Hz

1100

29 27 26

18

500

Hz

29

16

1000 Hz

28 23

24

H

27 25 26

16

HH

7

4.5

600

22

17

14

8

5

5.0

12

9

21 9

700

19 11 CH 33 H 1 CH

1300

19

21

2

20

Hz

2100 17 15’

28 16’ 12’

28

900

12

3

4.0

3.5

3.0

2.5

2.0

1.5

1.0

ppm

13 13

C/DEPT600 NMR 150.9 MHz C/DEPT MHz

21

8 25

22

23

6

130

120

7 32.0

27

29

11

2 ppm

3

ppm

21.5

5

140

110

100

90

80

70

18

13 20 12 1417 9 24 4 15 1 16 28 10 19 26

60

50

40

30

20 ppm


56

ppm 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0

COSY 600 MHz

ppm

18

1

1

2

2

19

4 29

21

311

19

2

HO

1 CH3

3

10

4

6

CH3 20

13

9 8

5

CH3

7

28

22

12 18

17

14 15

4

23

3

27

24

25 26

4

16

2

3

2’

4

20

24

4 7

7’

5

23 22 6

5

COSY 600 MHz

ppm 0.6 0.8 9 14

1.0 29 to 28’

1.2 29 to 28

1.4

F1

1.6

27 26 to 25 15 7’

1.8

16

17

2

15’

15 to 14

1’ 8

2.0

7’,11

2.2

7 2lr

7’

17

1’ 15’ 28’ 17 12’ 16

2.2

2.0

1.8

1.6

1.4

21 7 12 20

21

4

F2

1.27 1.0

0.8 7’ 0.6

21

28 2 11 7’ 8 24 25 15 16

2.4 2.4

18 26 27

ppm

17

29

19


22

3

23

4 ppm 5.5

ppm

3.6

ppm

57

8 29 25 21 HMQC 600 MHz 7’11 1927 26 242 12’ 28’15’ 14 2 18 12 1 16 15 28 16’ 17 1 9 20 7

2.2

2.0

1.8

1.6

1.4

1.2

1.0

0.8

0.6

ppm

18

29

15

26 19 27 2111 15 28

20 25

16 2

30 35

725 8

10

F1

1 12 20 13 4

40 45 50

9 24

55

17 14

60 65

29

21 19

70 3

HO

11

1 CH3

2

10

4

CH3 20

23

17

14

8

5

ppm

12 18 13

9

28

22

CH3

15

24

27

3

25 26

16

6

7

6

23

130

22

140

5 5.5

ppm

3.6

ppm

2.2

2.0

F2

1.8

1.6

1.4

1.2

1.0

0.8

0.6

ppm


6

3

23

4 ppm 5.5

ppm

3.6

ppm

2.2

2.0

1.8

1.6

1.4

1.2

12-18

15 23-26 6-19 22,23-21

0.8

0.6

ppm

18

14-18

29

28’-29

13C Satellite peaks

24 25-26

26 19

27-26

1

1’9

2711 21 15 28

28’ 12-11

22,23-28

25

1.0

17-18 24-29 28-29

20

24+25-27

9-11 14-15

16-15 24 25-28

26-27

29-28 17 15 14-16

30

6-7 22,23-25

3-2

4-2

7-8

1-2 15-8

12’-8 6-10 3-1

F1

4-10

1,2-10

8,7’,-10

2-1

22,23-20

40

2’-1 11-12

3-4 12-13

6-4

45 50

22,23-24

55

22,23-17

2-4

7-14

1 CH3

HO

3

10

4

8

5 6

6-3 4-3

CH3

CH3 20

27,29,26-24

15

17 14

18-17 18-14

29

28

22 23

27

24

17

14

9 24

21

16’ 12 15-14

12 18 13

9

28’-24 16’ 12

21

11

18-13

12’ 1-9 19-9

15 8-14 19

1 12 20 13 4

9-1 21-20 18-12

17-12 16-20 17-20

25-24 28-24

2

10

9-10

19

16-17

60

70

1’19

7’,8,11

25 26

16

7

1,2 -3

725 8

27 26-25

16-13 15,11-13 12’,15’,17-13 14-13

12-9, and 7-9

65

16 2

24,28-25 28’-25 15’-8 14,9-(7,8)

.

35

58

8 25 21 HMBC 600 MHz 7’11 19272926 242 12’ 28’15’ 14 2 18 12 1 16 15 28 16’ 17 1’ 9 20 7

3 2’-3

1’-3

ppm

6 4-6

22-23

130

7-6 1-6(4b) 20-23 20-22

140

6-5

24,25 28-23 24-22

23

28’-23 27 26-23(4b) 17-22 21-22

22

3-5 4-5

5.5

7’-6

ppm

3.6

ppm

2.2

7-5

2.0

F2

1-5

1.8

7’-5

1.6

5

19-5

1.4

1.2

1.0

0.8

0.6

ppm


59

1

H NMR 600 MHz 0o C in 5%/95% D2O/H2O

KNH

T2

SNH

S3

T3 K2 S2

5400

5300

5200

Hz

5100

2700

2600

T4

K6

K3 K3’

2500

Hz

2400

T4

Impurity

K4

K5

K6 1800 Hz

1100

800 Hz

900

KNH

SNH

1

1

9.0

1000

2

8.5

8.0

# of protons

7.5

7.0

6.5

6.0

5.5

1

5.0

2 3

4.5

4.0

11 2 2 3

2 3.5

3.0

2.5

2.0

TNH SNH

Threonine (Thr) (T) Serine (Ser) (S) Lysine (Lys) (K) 13 O O O 2 H 2 H 2

C/DEPT 600 MHz

H2N

CH C

3

HO CH

1

N

CH C

3 CH2

OH

4 CH3

1

N

CH C

3 CH2

1

ppm

OH

KNH

4 CH2 5

CH2

6 CH 2

K1

S1 NH2 T1

T3

T2 K2 S3

175

170

ppm

S2

K6

K3 K5

70 65 60 55 50 45 40 35 30 25

K4 T4

ppm


F1

8

7

6

60 5

4

3

2

1

ppm

1

1

2

2

3

3

4

4

5

5

6

6

7

7

8

8

COSY 600 MHz K5 K4

T4

K3K3’ K6 S3 K2 T3T2 S2

TNH KNH SNH

COSY 600 MHz

ppm

F1

1.0

1.0

1.5

1.5

2.0

2.0

2.5

2.5

3.0

3.0

3.5

3.5

4.0

4.0

4.5

4.5 ppm

4.5

4.0

3.5

3.0

2.5

F2

2.0

1.5

1.0

T4 K4 K5 K3K3’

K6

S3 T2 T3K2 S2


F1

8

7

6

61 5

4

3

2

1

ppm

1

1

2

2

3

3

4

4

5

5

6

TNH

TOCSY 600 MHz K5 K4

T4

K3K3’ K6 S3 K2 T3T2 S2

6

7

7

8

8

KNH2 KNH SNH

TOCSY 600 MHz

ppm

F1

1.0

1.0

1.5

1.5

2.0

2.0

2.5

2.5

3.0

3.0

3.5

3.5

4.0

4.0

K4 K5 K3K3’

K6

S3 T2 T3K2 S2

4.5 4.5

4.0

3.5

3.0

2.5

F2

2.0

1.5

1.0

4.5 ppm

T4


62

COSY 600 MHz SNH

KNH

Threonine (Thr) (T) Serine (Ser) (S)

1.5

H2N

2

3

1

CH C 3 CH2

1

KNH

ROESY 600 MHz SNH

KNH2

KNH

KNH2 T4 K4 K5 K3

Lysine (Lys) (K)

O

2

H N

CH C

3 CH2

OH

4 CH3

2.0

O

2

H N

CH C

HO CH

F1

O

SNH

KNH2

ppm 1.0

TOCSY 600 MHz

1

OH

4 CH2 5

CH2

6 CH 2

2.5

K6

NH2

3.0 S3 T2 K2 T3

3.5 4.0

S2

4.5 9.0

8.5

8.0

ppm

7.5

8.5

F2

8.0

7.5

ppm

F2

8.5

8.0

7.5

7.0 ppm

F2 HMQC 600 MHz

T3 T2S3 K2

S2

ppm

Threonine (Thr) (T) Serine (Ser) (S)

20

H2N

30

2

O

CH C 3

HO CH 4 CH3

F1

K6

1

H N

2

O

CH C 3 CH2

OH

1

K5 K4 K3

T4

T4

Lysine (Lys) (K)

H N

O

2

CH C

3 CH2

1

K4 K5

OH

K3

4 CH2 5

K6

CH2

40

6 CH 2

NH2

50

K2 S2T2 S3

60

T3

4.5

4.0

3.5

3.0

F2

2.5

2.0

1.5

1.0

ppm

Answers for Student Exercises 5.11 ppm 9.0 8.5 8.0

ppm

63 4.0

3.5

3.0

2.5

2.0

1.5

1.0

HMBC 600 MHz ppm

T3 T2

20

K2

F1

K3 K5

K6

K3

T4 K4 K5

K4

K2

KNH-K3

30

K6

K5

K4

K3 K5

K4

K6

40

50 KNH-K2

K2 S2 T2 S3

K3 K3’ K4 S3 T3

60

T4

S2 T2

T4

T3

F2 SNH

KNH

KNH2 S2

ppm

168 170

S2-T1

SNH-T1

T2 K2 S3 T3

T3-T1

T4

K5 K4 K3

K6

T2-T1

T1 KNH-S1

S2-S1 K2-S1

T2,S3-S1 Threonine (Thr) (T) Serine (Ser) (S)

F1 172

H2N

O

2

CH C 3

HO CH

174

1

4 CH3

H N

2

O

CH C 3 CH2

OH

1

S1

Lysine (Lys) (K)

O

2

H N

CH C

3 CH2

1

OH

4 CH2 5

CH2

6 CH 2

176

NH2

178

KNH-K1

K2-K1

K3-K1

K1

180 9.0 8.5 8.0

ppm

4.0

3.5

F2

3.0

2.5

2.0

1.5

1.0

ppm

Answers for Student Exercise6.1 1

1 NOTE: The formula should be C5H10N2

H NMR 300 MHz

4

3

2

ppm

2.75 2.70 2.65 2.60 2.55 2.50 2.45 2.40 2.35 2.30 2.25 2.20 2.15 2.10 13

C/DEPT NMR 75.5 MHz

4

4 1

N

2

3

N

3

4

2

C5H10N2 Mol. Wt.: 98 3-(dimethylamino)propanenitrile

1

130 15

120

110

100

90

80

70

60

50

40

30

20

ppm

20

ppm

N NMR 30.4 MHz N

N

240

220

200

180

160

140

120

100

80

60

40

Answers for Student Exercise 6.2 1

2

H NMR 300 MHz 1 1

1

3

2 Si Cl 1 3 C6H15ClSi Mol. Wt.: 151

3

tert-butylchlorodimethylsilane

1.3 13

1.2

1.1

1.0

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.1 ppm

0.2

C/DEPT NMR 75.5 MHz

1 3

2

35 29

30

25

20

15

10

5

0

ppm

-5

Si NMR 59.6 MHz

55

50

45

40

35

30

25

20

15

10

5

ppm

Answers for Student Exercise 6.3 1

3 2

5

H NMR 300 MHz

3 4

H3C 1 P

2 34

5

Br C19H18BrP Mol. Wt.: 357

2340

8.5 13

8.0

7.5

7.0

6.5

2320

Hz

2300

6.0

5.5

5.0

4.5

4.0

3.0 ppm

3.5

C/DEPT NMR 75.5 MHz 4

3

a

b

10200

Hz

10000 Hz

1

5

2 3

2 c

d

4

9800

e

Hz 9000

8900 Hz

800

5

Hz

750

1 ab c 130 31

d 120

e 110

100

90

80

70

60

50

40

30

20

10 ppm

4

2 ppm

P NMR 121.5 MHz, 1H Decoupled

28

26

24

22

20

18

16

14

12

10

8

6

Answers for Student Exercise 6.4 % of Base Peak

MASS

4

105 175

100

244 77

50

127

50

205

100

m/z

IR

F3C

1

50

OH CF3

5'

2 3 4 5

6'

6 7

717

F NMR 282.4 MHz See Table 6.2

7

5,5’

972

1000 19

6,6’

1165 1219 1273

H NMR

1504

3070

4000 1

200

C9H6F6O Mol. Wt.: 244 1,1,1,3,3,3-hexafluoro2-phenylpropan-2-ol 3000 2000 Wavenumber (cm-1)

3548 3602

%Transmittance

100

150

OH 7.8

7.5 13

7.0

6.5

7.7

6.0

7.6

5.5

7.5 ppm

5.0

4.5

4.0

ppm

6,6’

5,5’

128

126

4

130

ppm

-74.7

Septet caused by 6 F two bond coupling (JCCF) to carbon 2

C/DEPT

7

-74.6

C1 and C3, with coupling to 3F, J value of 288 Hz

124

122

120

118 ppm

78

77

76

ppm

Answers for Student Exercise 7.7A

1

% of Base Peak

MASS

100

103

100

72

43

50

CI Reagent gas methane

x 30

57

50

85

40

50

60

70 m/z

IR

85

80

90

143

131

100

100

m/z

833

3000

H NMR 600 MHz

972 1049

2870 2954

4000 1

1149

1388 1458

50 3417

%Transmittance

100

2000 Wavenumber (cm-1)

1000

6 OH

2680 2660 2640 2620 2600 2580

2

4

4.5

5

4.0

2140 2120 2100 2080 2060 2040 Hz

Hz

2 is closer to CH2OH in space, therefore is more deshielded than 4. NOE experiments would confirm this.

OH

3.5

3.0

2.5

2.0

ppm

1.5

13 13

C/DEPT MHz C/DEPT NMR NMR 150.9 600 MHz 3-methyl-3-oxetanemethanol 5 CH2OH 2 1O

24

CH3

3 4

6

C5H10O2 Mol. Wt.: 102

5

6 3

80

75

70

65

60

55

50

45

40

35

30

25

20 ppm

Answers for Student Exercise 7.7B ppm

1.5

4.5

4.0

3.5

3.0

2 2.5

2.0

1.5

ppm

6

3-methyl-3-oxetanemethanol 5 CH2OH 2

2.0

1O

1.5

CH3

3 4

2.0

6

C5H10O2 Mol. Wt.: 102

2.5

COSY 600 MHz

2.5

F1 3.0

3.0

3.5

3.5

4.0

4.0

4.5

OH 5

2 4

4.5

2

4

5

ppm

OH

F2

HMQC 600 MHz

6

20

20

30

30

40

40

F1 50

50

60

60

70

70

80

80 4.5

4.0

3.5

3.0

F2

2.5

2.0

1.5

ppm

6

3

5

2 4

Answers for Student Exercise 7.8A

3

MASS % of Base Peak

221

100 50

97 55

203

177

50

IR

137

81

100

150

m/z

236

200

100 %Transmittance

1003

1

910

1381 1458

2924

4000

3000

H NMR 600 MHz

9

11’

11


12

2300

Hz

1200

8’

800

Hz

1150

750

1000

16

5’

Hz

1050

Hz

700

Hz

900

600

850

15

7

3’

31

5 9’ 4’

4

8 2350

1000

Hz

550

Hz

13 14

Hz

500

16

(-)-ambroxide 11 13

CH3 12

4 5

3 6

2

1 10 9

7

14

H3C 15CH3

O CH3

16

8

C16H28O Mol. Wt.: 236

4.0

3.5

3.0

2.5

2.0

1.5

1.0

ppm

Answers for Student Exercise 7.8B

4

13 13 C/DEPT

NMR 600 150.9 MHz C/DEPT NMR MHz

3 11

9

7 1

15

5

13

10

80

2

75

70

65

60

11’ 11

55

50

45

8

40

6

35

30

25

51 4’3

4

9’

ppm

8’

5’

20

15 ppm

HMQC 600 MHz

16

12 9

14,16 12 8 4

1513 14

3’

7

13 4 8 16 14 12

20

30

6 15 2

F1 40

39 5

(-)-ambroxide 11 13

CH3 12

50 4 5

60

3 6

2

14

ppm

1.9

1.8

O CH3

9

16

1.7

1.6

7

H3C 15CH3

4.0

1 10

7 1 11

8

F2

1.5

1.4

1.3

1.2

1.1

1.0

0.9

0.8

ppm

Answers for Student Exercise 7.8C 11

5

11’

12 9

ppm

4.0

3.9

ppm

2.0

8 1.8

51 4’ 3 8’ 9’

4 1.6

1.4

HMBC 600 MHZ HMQC 600 MHz 16 1513 14 5’ 3’ 7 1.2

1.0

0.8

ppm

13

15

4 20

8 14,16 12

ppm

6

34

15

(-)-ambroxide 11

F1

13

CH3 12

36 4 5

38

3 6

2

9

7

14

40

1 10

H3C 15CH3

2

O CH3

16

9 3

8

42

5 ppm

7

58 60

1

62 64

11

ppm

10

80 82 4.0

3.9

ppm

2.0

1.8

F2

1.6

1.4

1.2

1.0

0.8

ppm

Answers for Student Exercise 7.8D

6

INADEQUATE MHz INADEQUATE150.9 600 MHz

11 1

10

539

7

2

1416 12 8 4

15

6

13

Hz (-)-ambroxide 11 13

-7000

CH3 12

4 5

-6000 -5000

2-13 6-14 or 15

3 7

6

O 1 10 2 CH3 9

3-4 9-8

16

14

H3C 15CH3

-7000 -6000

5-4

8

-5000

6-15 or 14

-4000

-4000

5-6 7-8

-3000

3-2

-3000

1-12

-2000

-2000

11-12 7-6 7-2

-1000

-1000

1-2

F1

0

0

10-8

1000

1000

2000

2000 10-9

3000

3000

4000

4000

5000

5000 10-1

6000

6000

7000

7000

80

75

70

65

60

55

50

F2

45

40

35

30

25

20

15

ppm

CHAPTER 8 ASSIGNED PROBLEMS Problem 8.1

% of Base Peak

MASS 68

55

100 41

112 84

50

97

40

50

60

70

IR

m/z O

90

100

110

1 2 3 4

50

Cycloheptanone C7H12O Mol. Wt.: 112

11

856 941


1161

3000

1342 1454

4000

1701

2858 2927

%Transmittance

100

80

1000

4

NMR 300 MHz HHNMR 2 3

2.7

2.6

2.5

2.4

2.3

2.2

2.1

2.0

1.9

1.8

1.7

1.5 ppm

1.6

1313

C/DEPT NMR 75.5 MHz C/DEPT

2

4

3

1

200

180

160

140

120

100

80

60

40

ppm


MASS % of Base Peak

124

100 94

50

53

50

60

95

81

66

70

80

m/z

IR

100

110

120

OH

100

3

50

4

2

5

1

687 768 837 945 1041 1149

11

1284

3000

m-Methoxyphenol C 7H 8 O 2 Mol. Wt.: 124

1493 1601

2839 2947 3005

4000

7

OCH3

6

3398

%Transmittance

90


1000

H NMR NMR 300 MHz H 6

5

7

2 4

2150

2140

Hz

1960

1950

Hz

1920 Hz

1930

OH

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

ppm

13 13

C/DEPT NMR 75.5 MHz C/DEPT

4 1

5

3 2

7

3 1 190 180 170 160 150 140 130 120 110 100

90

80

70

60

50

40

ppm


MASS % of Base Peak

55 M-1 83

100 39 41

M

50

53

40

45

65

50

55

IR

m/z

60

84

66

65

70

75

80

85

50 741


1014

11

1138 1227 1319

3000

1454

4000

2229 2291

2877 2939 2978

3332

%Transmittance

100

1000

H H NMR NMR 300 MHz

5 1

4 1280

4.0

1260 Hz

3.5

OH

660 Hz

680

3.0

2.5

2.0

ppm

1.5

13 13C/DEPT

C/DEPT NMR 75.5 MHz

3

HO

4

H 2C

C

C

1

2

3

CH2 5 CH3

2-Pentyn-ol C5 H 8 O Mol. Wt.: 84

CDCl3

5 4

1 78.0 77.5 77.0 76.5

2

95

90

85

80

75

70

65

ppm

60

55

50

45

40

35

30

25

20

ppm


MASS % of Base Peak

75


100 49 61

50

77 99 97

m/z

IR

146 148 146

100

113

100

112 M 114

50

x 30

111

110 75 77

50

150

148 150 152

115

100

150

m/z

Cl Cl 1 CH 3 Cl CH2 2 CH2

90 80

1,2,3-Trichloropropane C3H5Cl3 Mol. Wt.: 146

70

H NMR NMR 300 MHz

663 717

1 1H


910

3000

1219 1288

4000

1435

2962 3016

%Transmittance

100

1000

1+3

2

4.35

4.30

4.25

4.20

4.15

4.10

4.05

4.00

3.95

3.90

3.85

ppm

3.80

13 13C/DEPT

C/DEPT NMR 75.5 MHz

1+3 2

75

70

65

60

55

50

45

ppm


% of Base Peak

MASS

m/z 126 (M) 127 (M+1) 128 (M+2)

100 50

%M 100.0 8.2 4.9

111

126

39 43

40

83

57

49

50

60

70

80 m/z

IR

90

100

110

120

130

50

11

590


725

856 933 1061

1273

3000

1415

4000

1662

3089

%Transmittance

100

1000

H H NMR NMR 300 MHz 3

1

2300

2280 Hz

4

7.5

7.0

6.5

6.0

5.5

6

2

5.0

2120 Hz

2140

5

4.5

13 13 C/DEPT

C/DEPT NMR 75.5 MHz

4.0 2

3.5

3.0

2.5

ppm

3

1

S

4

O 5 6 CH3

1

5

3

2

Ethanone, 1-(2-thienyl)2-Acetylthiophene C6H6OS Mol. Wt.: 126

6

4

190 180 170 160 150 140 130 120 110 100

90

80

70

60

50

40

ppm


% of Base Peak

MASS

x 10

105

100

186 184

50

77

51

50

IR

100

150

m/z

100

80 70

2

3

2260

2250

2240

2230

2220

13

7.0

6.5

6.0

1000

6

4

2210

5.5

5.0

C/DEPT NMR 75.5 MHz

1590

1580

1570

Hz

640

630

620

Hz

Hz

2200

5

7.5

594 694 764

H NMR 300 MHz


964

1

3000

1211

4000

1450 1496

2985 3032

%Transmittance

90

4.5

H3C 6

5

4.0

3.5

3.0

2.5

ppm

Br

1 2 3 4

(1-Bromoethyl)benzene C8H9Br Mol. Wt.: 184

4 3

2

6

5

1 140

130

120

110

100

90

80

70

60

50

40

30 ppm


MASS % of Base Peak

109 124

100

81 53

50

63

50

75

60

70

80

IR

90

m/z

100

110

120

50

513

733 825


1034

11

1234

3000

1512 1612 1701

4000

1859

2835 2951

3348

%Transmittance

100

1000

H H NMR NMR 300 MHz 2

5

3

OH

7.0

6.5

6.0

5.5

5.0

4.5

4.0

ppm

3.5

OH

13 13

C/DEPT C/DEPT NMR 75.5 MHz

4 3 2 1

OCH3 5

3 1

p-Methoxyphenol C 7H 8 O 2 Mol. Wt.: 124

2

5

4

150

140

130

120

110

100

90

80

70

60

50

ppm


MASS % of Base Peak

128

100 64

130

50

92 73

50

60

70

80

IR

90

m/z

100

110

120

130

50

2000 Wavenumber (cm-1) OH

1 1H

H NMR NMR 300 MHz 6

3

1

4 6

5

1000

Cl

2 3

5

679 748

3000

1030

4000

1200 1338 1454 1481 1585

3039 3074

3464 3521

%Transmittance

100

OH

4

o-Chlorophenol C6H5ClO Mol. Wt.: 128

7.4

7.2

7.0

6.8

6.6

6.4

6.2

6.0

5.8

5.6

5.4

ppm

13 13


5

4

3

1

155

6

2

150

145

140

135

130

125

120

115

ppm

CHAPTER 8 ASSIGNED PROBLEMS Problem 8.9 x 20

55 87

100

115 196 194

73 135

0

50

100

137

165

150

m/z

IR

163

1203

50

1365 1435

% of Base Peak

MASS

50

3000


1 1H

H NMR NMR 300 MHz

748

4000

1736

2954

%Transmittance

100

1000

O 6

6 Br

5

4

3

1

2

O

Methyl 5-bromo valerate C6H11BrO2 Mol. Wt.: 194

5

2 4

3.6

3.4

3.2

3.0

2.8

2.6

2.4

2.2

2.0

3

1.8

1.6

ppm

13 13


5 2

4

3

6 1

33.0

32.5

170 160 150 140 130 120 110 100

32.0

90

ppm

80

70

60

50

40

30

ppm


MASS % of Base Peak

54

100

67

84 93

50

111

50

60

70

80

IR

m/z

90

100

126

110

120

7

1 1H

H NMR NMR 300 MHz

6

2000 4 OH 5 1 Wavenumber (cm-1) 2

849

3000

1045

8

1331

4000

1466

2873 2931 2958

3344

%Transmittance

100

1000

3

8

3-Octyn-1-ol C8H14O Mol. Wt.: 126

1

2

6 7

5

OH

3.5

3.0

2.5

2.0

1.5

ppm

1.0

13 13C/DEPT

C/DEPT NMR 75.5 MHz

6

1

2 84

82

80

85

5

8

ppm

78

4

7

3 80

75

70

65

60

55

50

45

40

35

30

25

20

ppm

CHAPTER 8 ASSIGNED PROBLEMS

% of Base Peak

MASS

Problem 8.11 162

100

164

63 98

50

126

73

50

60

70

80

90

100 110 m/z

IR

120

128

130

140

150

160

50

1 1H

H NMR NMR 300 MHz


3

1000

OH

6

1

2

6

5

Cl

3

5

OH

4

7.4

7.2

7.0

555

3000

725 814

4000

1188 1277 1404 1477 1585

3097

3521

%Transmittance

100

6.8

6.6

Cl 2,4-Dichlorophenol C6H4Cl2O Mol. Wt.: 162 6.4 6.2 6.0

5.8

5.6

5.2 ppm

5.4

13 13C/DEPT

C/DEPT NMR 75.5 MHz

3

5

6

1

155

150

145

140

135

130

4

2

125

120

115

ppm

CHAPTER 8 ASSIGNED PROBLEMS Problem 8.12 % of Base Peak

MASS

123

100

95 75

50

50

63

70

80

90 m/z

100

110

120

1157 1265 1358

60

1597 1685

50

IR

138

130

140

50

1

3000


H NMR 300 MHz 2

3

567

4000

841 960

3005 3074

3356

%Transmittance

100

1000 19

F NMR 282.4 MHz

1

H Coupled

1

H Decoupled

6 2400

2390

2380

Hz

2140

Hz

2130

ppm

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 13

-104.5 ppm

-104.4 5

C/DEPT NMR 75.5 MHz

6

COCH3

1 2 3 4

2

5

4

F 4-Fluoroacetophenone C8H7FO Mol. Wt.: 138

3

130 128 126 124 122 120 118

6 ppm

1 190 180 170 160 150 140 130 120 110 100

90

80

70

60

50

40

ppm


MASS % of Base Peak

96

100 50

70

50

50

55

60

65

75 77

70 m/z

IR

75

80

85

90

95

F

100

2 3 4

95


756

3000

1234

4000

1504 1604 1697

Fluorobenzene C 6H 5 F Mol. Wt.: 96

3062

3749

%Transmittance

1

1000

11H

19

NMR 300 MHz H NMR

F NMR 282.4 MHz 1

H Coupled

2

3

4

7.4

7.3

7.2

7.1

ppm

-80.1

-80.3 ppm

-80.2

13 13


3

2 4

130

128

126

124

122

120

118

116 ppm

1 165

160

155

150

145

140

135

130

125

120

115 ppm


MASS % of Base Peak

82

100 50

138

54

95

67

50

60

70

80

90 m/z

IR

123

100

110

120

130

140

50

6

1750

1740 Hz

Hz

640

570

1000

89

7

4

525

H NMR NMR 300 MHz


903

1 1H

1246

3000

1381

4000

1670

2870 2958

%Transmittance

100

560 Hz

300

3.5

3.0

Hz

290

2

6.0

5.5

5.0

4.5

4.0

2.5

13 13


2.0

ppm

1.5

7

CH3 3 4 9

2 5

H 3C H3 C

1 6

O

89

8

Isophorone C9H14O Mol. Wt.: 138

2 1 200

6 4

7

3 180

160

5 140

120

100

80

60

40

ppm


MASS % of Base Peak

54

68

50

81 79

50

60

70

93

80

90

IR

95

m/z

107

100

109

149 147 119

110

121

120

130

140

150

100 %Transmittance

90 80

H H NMR NMR 300 MHz Br

4

756

2000 Wavenumber (cm-1) 2

11

4

1250

3000

1435

4000

2245

2970

70

3

1000

1

2

3

N 4-Bromobutanoyl nitrile C4H6BrN Mol. Wt.: 147

3.6

3.5

3.4

3.3

3.2

3.1

3.0

2.9

2.8

2.7

2.6

2.5

2.4

2.3

ppm

2.2

13 13


3

2

4 1 120

110

100

90

80

70

60

50

40

30

20

ppm


MASS % of Base Peak

106

100 137

50 77

50

60

70

80

IR

m/z

90

100

110

120

130

140

90 80

1 1H

H NMR NMR 300 MHz


1000

6

3 2

OH 5

7.5

825

3000

1049

1442 1512 1620

4000

2931

3194

3348

%Transmittance

100

7.0

6.5

4

3

6.0

5.5

5.0

5

ppm

2

4.5

4.0

3.5

3.0

2.5

2.0

1.5 ppm

OH

13 13


6

5 1

OH

2 3

2

3

4

NH2

4

1 140

130

6

5

p-Aminophenylethanol C8H11NO Mol. Wt.: 137

120

110

100

90

80

70

60

50

40

ppm


MASS % of Base Peak

119

100 50

91

64 76

50

60

70

80 m/z

IR

90

100

110

120

90 80 70

H NMR NMR 300 MHz 2

671 787

1 1H

1342

3000

1481 1589

4000

2245

3309

%Transmittance

100


1000

3

OH

7.6

7.5

7.4

7.3

7.2

7.1

7.0

6.9

6.8

6.7

6.6

6.5

6.4

6.3

ppm

6.2

13 13

C/DEPT C/DEPT NMR 75.5 MHz 2 5

N

C

1

3 4

OH

p-Cyanophenol C7H5NO Mol. Wt.: 119

2

3

4

165

160

5

155

150

145

140

135

130

125

120

1 115

110

ppm


MASS % of Base Peak

163

100 178

50 91

77

50

135

100

IR

150

m/z

%Transmittance

100

50


748

11

1149 1203

3000

1458

2870 2962

3572

4000

1000

H H NMR NMR 300 MHz

3

6

2100 Hz

2150

950 Hz

1000

4

450

OH

7.0

6.5

6.0

5.5

5.0

Hz

400

5

4.5

4.0

3.5

13 13C/DEPT

C/DEPT NMR 75.5 MHz

2.5

1.5 ppm

2.0

6

OH 1

3.0

2

5 6

3 4

2,6-Diisopropyl phenol C12H18O Mol. Wt.: 178

3

6 5

4 1 150

2 140

130

120

110

100

90

80

70

60

50

40

30

20 ppm


MASS % of Base Peak

106 78

100

121

51

50

50

60

70

80 m/z

IR

90

100

110

120

50

2

1000

4 7

5

2720

9.0

702

H NMR NMR 300 MHz

957

1 1H


1273

3000

1419

1689

4000

3047

3363

%Transmittance

100

2700 Hz

8.5

2580 Hz

2600

8.0

7.5

7.0

2440

6.5

6.0

2420 Hz

5.5

13 13C/DEPT

2180 Hz

2200

5.0

4.5

4.0

3.5

ppm

3.0

3

C/DEPT NMR 75.5 MHz

4

2

5

1

N

7 6

C

CH3

O

5 6

4

2

3

2-Acetylpyridine C7H7NO Mol. Wt.: 121

7

1

190 180 170 160 150 140 130 120 110 100

90

80

70

60

50

40

ppm


MASS % of Base Peak

108

123

100 53

50

40

80

50

60

70

80

IR

90

m/z

100

110

120

50


1000

7

5

4

7.0

2060 3

6.5

Hz

Hz 1820

2020

633 741

H NMR NMR 300 MHz

1095

1 1H

1404

3000

1651

4000

2947

3109

%Transmittance

100

Hz

2

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

ppm

13 13

C/DEPT C/DEPT NMR 75.5 MHz 3 4

1

N

4

2

H3C5

3

2 7 6

CH3

O

1-Methyl-2-acetylpyrrole C7H9NO Mol. Wt.: 123

1

5

7

6 180

160

140

120

100

80

60

40

ppm


% of Base Peak

MASS

100

159

100

85

57

50


x 20

43

103

158

50 50

100

m/z

IR

187

150

150

m/z

50


11

1034 1149

3000

1319

4000

1651 1720

2962

%Transmittance

100

1000

H H NMR NMR 300 MHz 7 1 3 5 6

3.5

3.0

2.5

2.0

1.5

ppm

1.0

13 13C/DEPT

C/DEPT NMR 75.5 MHz 7 1 2

3

4

O

6

5

7

O O Isobutylacetoacetate C8H14O3 Mol. Wt.: 158

2

200

5

3

6

7

1

4

180

160

140

120

100

80

60

40

ppm


MASS % of Base Peak

119

100 50

91

64 76

50

60

70

80

IR

90

m/z

100

110

120

100

80 70

11

H NMR 600 300 MHz 42 5

671 787

3000

1342

4000

1481 1589

2245

3309

%Transmittance

90

2000 Wavenumber (cm-1) OH

1000

3 4

6

2 1

5

7

C

6

OH

N

m-Cyanophenol C7H5NO Mol. Wt.: 119

7.4

7.3

7.2

7.1

7.0

6.9

6.8

6.7

6.6

6.5

6.4

6.3

ppm

6.2

13 13 C/DEPT

NMR 600 75.5MHz MHz C/DEPT NMR

5

6

4

2

3

1

7 155

150

145

140

135

130

125

120

115

ppm


MASS % of Base Peak

x 20 183

185

100 155

75

50

100

157

150 m/z

IR

224

200 198

264 262 260

226

200

250

50

H NMR NMR 300 MHz

6

3

2

617

1 1H

810


995 1068

3000

1223

1396 1485 1585 1685

4000

2962 3059 3089

3356

%Transmittance

100

1000

8

5

7

7.9

7.8

7.7

7.6

ppm

3.6

3.4

13 13C/DEPT

C/DEPT NMR 75.5 MHz

3.2

3.0 6

5

7

2.8

2.6

ppm

2.4

8

COCH2CH2CH2Cl 1 2 3 4

3

2

5 1

Br 4’Bromo-4-chlorobutyrophenone C10H10BrClO Mol. Wt.: 260

6

7

8

4

190 180 170 160 150 140 130 120 110 100

90

80

70

60

50

40

ppm

CHAPTER 8 ASSIGNED PROBLEMS Problem 8.24 % of Base Peak

MASS

100

100


55

50

147 69

74 83

50

128

175

50

100

150

150

m/z

187

200

m/z

IR

50

H NMR NMR 300 MHz

930

1 1H

1238 1277 1419 1466

3000

1709

4000

2669

2978 3039

%Transmittance

100


1000

4

2x OH

6

x64

3 2

12

11

ppm

2.6

2.4

2.2

2.0

1.8

1.6

1.2 ppm

1.4

13 13C/DEPT

C/DEPT NMR 75.5 MHz O HO 1

O

3

CH2 C 5 CH CH2 OH 2

CH3

4

6

15

2-Methyl glutaric Acid C6H10O4 Mol. Wt.: 146

180 170 160 150 140 130 120 110 100

90

80

70

60

50

2

4 3

40

30

6

ppm

CHAPTER 8 ASSIGNED PROBLEMS Problem 8.25 91 66

100

93

92


50

100

51

% of Base Peak

MASS

50

50

60

m/z

IR

70

80

80

90

90

m/z

90 80


H NMR 300 MHz

725 802

1065

1

3000

1342

4000

1720

2962 3055

%Transmittance

100

1000

3

2 1

2050

7.0 13

6.5

Hz

2040

6.0

5.5

1080 Hz

1090

5.0

4.5

Hz

615 610 605

4.0

3.5

3.0

2.5

2.0

ppm

C/DEPT NMR 75.5 MHz

3

2

1

1

Bicyclo[2,2,1] hepta-2-5-diene C7 H 8 Mol. Wt.: 92

140

130

120

110

100

3

2

90

80

70

60

50

ppm


% of Base Peak

MASS

M 156

100 M+2

63

158

50 98

50

60

70

80

121

90

100 110 m/z

IR

120

130

140

150

160

6

1041

H NMR 600 MHz

1234

1473

3000

802

933

50

4000 1

586

2900

%Transmittance

100


1000

3

7

4

6.85

6.80

6.75

6.70

6.65

ppm

6.00 5.95

ppm

1313

C/DEPT MHz C/DEPTNMR NMR600 150.9 MHz 3 4

2

O 7

5 1

Cl

6

O

5-chloro-1,3-benzodioxole C7H5ClO2 Mol. Wt.: 156

1 155

150

4

7

5

2 145

36

140

135

130

125

120

115

110

105 ppm

CHAPTER 8 ASSIGNED PROBLEMS Problem 8.27A

% of Base Peak

MASS 55

42

100 84

50

114

70

40

50

60

70

IR

m/z

80

90

100

110

50

O 2

1000

1 O

1

6

2 6

3 4

571

H H NMR NMR 300 MHz


856

11

1057 1165

3000

1442

4000

1728

2931

%Transmittance

100

4

3 5

5

ε-Caprolactone C6H10O2 Mol. Wt.: 114

4.0

3.5

3.0

2.5

2.0

ppm

1.5

13 13 C/DEPT

C/DEPT NMR 75.5 MHz

43

6

2

5

1

170

160

150

140

130

120

110

100

90

80

70

60

50

40

ppm

CHAPTER 8 ASSIGNED PROBLEMS Problem 8.27B

ppm 4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.5

ppm

1.5

COSY 300 MHz

4 1

O

2.0 2

2.5

2.0 O

1

F1

2.5

6

3 4

3

4

5

6

2

5

ε-Caprolactone C6H10O2 Mol. Wt.: 114

3.0

2

5 3

3.0

3.5

3.5

4.0

4.0 6

F2 ppm

6

2

5

HETCOR 75.5MHz MHz HETCO 300

4 3

1.5

1.5

2.0

2.0

2.5

2.5

3.0

3.0

3.5

3.5

4.0

4.0

4.5

4.5 ppm

F1

65

60

55

50

45

F2

40

35

30

25


MASS % of Base Peak

CI Reagent gas methane 55

x 10

69

100

82

137

120 118

90

50

5

139

92

50

100

m/z

IR

130

140

m/z

150

50

H NMR 600 MHz 1


648 725

1

3000

1057

4000

1458

2862 2939

3332

%Transmittance

100

1000

6 HO 1

3

2

4

5 6

Cl

2

5

1-Hexanol-6-chloro C6H13ClO Mol. Wt.: 136

4 3

OH

3.6

3.4

3.2

3.0

2.8

2.6

2.4

2.2

2.0

1.8

1.4 ppm

1.6

1313 C/DEPT

MHz C/DEPTNMR NMR600 150.9 MHz

1

5

6

60

55

50

45

40

35

2

4

30

3

25

ppm


3.5

ppm

3.0

2.5

1.5

ppm

1.5

1.5

2.0

2.0 HO 1

F1

2.0

2

3

4

5 6

Cl

1-Hexanol-6-chloro C6H13ClO Mol. Wt.: 136

2.5

2.5

3.0

3.0

3.5

3.5

1

6

OH

ppm

F2

5

HMQC 600 MHz

2 4 3

25 30

COSY 600 MHz

3

25 4

OH

30

35

35

40

5

F1

40

2

45

ppm

45

50

32

50

55

6

55 33

60

2.0 3.5

3.0

1.8 2.5

F2

1.6

1.4 2.0

ppm 1.5

60 1

ppm


MASS % of Base Peak

95

100 67

45

50

69

55

110

81

50

60

70

80

IR

128 113

90

m/z

100

110

120

130

%Transmittance

100

50


11

825

1041 1126

3000

1377 1450

2924 2966

3344

4000

1000

HNMR NMR 300 MHz H

1 7

Hz

1540

Hz

1140

5

480 Hz

500

4.5

3

Hz

440

2

5.0

4

4.0

3.5

3.0

8

2.5

OH

2.0

ppm

1.5

13 13 C/DEPT

C/DEPT NMR 75.5 MHz

7

OH 5

8

5

4

3

2

1

120

110

100

90

80

3

2

6-Methyl-5-hepten-2-ol C8H16O Mol. Wt.: 128

6

130

6

4

1

8 7

70

60

50

40

30

20 ppm


ppm 5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0 ppm

1.0

COSY 300 MHz

1.0 1

1.5

3

2.0

2.0

OH 4

2.5

2.5

F1 3.0

3.0

3.5

3.5

4.0

4.0

4.5

4.5

5.0

5.0

1.5

7 8

2

F2 2

5

3

ppm

84 1

HETCOR300 75.5 MHz HETCO MHz

7

1.0 7

OH

1.5 5

F1

6

4

3

2

2.0

8

2.5

6-Methyl-5-hepten-2-ol C8H16O Mol. Wt.: 128

1

3.0 3.5

OH

4.0 4.5 5.0 5.5 120

100

80

60

F2

40

20

5

ppm


MASS

CI Reagent gas methane 223 225

100 69

100

0

143

50

100

177

159

179 50 194

150

m/z

230

240 250 m/z

IR

263 265

50

251 253

% of Base Peak

88

260

%Transmittance

100

50

6

1000

8

2

5

3.5

1034

H NMR NMR 300 600 MHz MHz

4.0

1188


11 H

7

1458

3000

1736

2870 2939

4000

3.0

2.5

3

2.0

4

ppm

1.5

13 13 C/DEPT

NMR 75.5 600 MHz C/DEPT NMR MHz

Br

6

5

4

3

2

1

O

7

8

2,6,5 7

O

1

4 3 8

Ethyl 6-Bromohexanoate C8H15BrO2 Mol. Wt.: 222

170 160 150 140 130 120 110 100

90

80

70

60

50

40

30

ppm


ppm

4.0

3.5

3.0

2.5

2.0

1.5

1.0

1.0

F1

ppm

COSY 300 MHz

1.0

1.5

1.5

2.0

2.0

2.5

8 4 3 5 2

2.5 1 1

3.0

3.0 6

3.5

3.5

4.0

4.0

F2 2 6 5 4 3

7

8

7

HETCOR HETCO75.5 300MHz MHz

ppm 1.0 Br

6

5

4

3

2

1

O

7

1.0

8

8

O 1.5 Ethyl 6-Bromohexanoate C8H15BrO2 Mol. Wt.: 222 2.0

1.5

2.0

F1 2.5

2.5

3.0

3.0

4 3 5 2

6

3.5

3.5

4.0

4.0 60

55

50

45

40

35

F2

30

25

20

15

ppm

7


MASS % of Base Peak

134

100 41 94

50

65

40

50

77

60

119

91 105

70

80

IR

m/z

90

100

110

120

130

50


690 752

1

3000

1242

4000

1496 1601

2866 2916 3032 3066

%Transmittance

100

1000

H NMR 600 MHz 5

2

3 4

3680

Hz 3300

3660

Hz 3220

3280

Hz

3200

6

7.4

7.2

7.0

6.8

6.6

6.4

6.2

2760

2740

Hz

7

6.0

5.8

5.6

5.4

5.2

5.0

ppm

4.8

13 13

C/DEPT NMR NMR 150.9 600 MHz C/DEPT MHz 5

6

7

OCH2CH=CH2 1 2

3 4 6

1

160

150

140

130

3

2 4

7

120

5

Allylphenyl ether C9H10O Mol. Wt.: 134

110

100

90

80

70

ppm


ppm 7.5

7.0

6.5

6.0

5.5

5.0

4.5

ppm

4.5

4.5

5.0

5.0

5.5

5.5

6.0

6.0

6.5

6.5

7.0

7.0

COSY 600 MHz

F1

3

4

2

F2

6

ppm 5

6

7

OCH2CH=CH2

70

HMQC 600 MHz

5

7

5

70

1 2

80

80

3

90

90

4

Allylphenyl ether C9H10O Mol. Wt.: 134

100

100

F1 110

110

diastereotopic

2

120

120

130

130

7

3 6

140

140

150

150 1

7.5

7.0

6.5

6.0

F2

5.5

5.0

4.5

ppm

4


% of Base Peak

MASS x 20

95

100 50

110 109

67

55

70

80

90

IR

100 m/z

110

120

130

1365

60

1712

50

139 136

121

154

140

150

50

H NMR 600 MHz


829

1

3000

1057

4000

1227

2877 2951

3317

%Transmittance

100

1000

8 9 10

OH

2400

2

Hz

1350 Hz 1150

Hz 1050

Hz

950 Hz

4.0

3.5

3.0

Hz

750

In the above insets each tick mark is 10 Hz 3

6

2.5

550 Hz

5 4

2.0

500 Hz

5 6

3

ppm

1.5

13 13

C/DEPT NMR NMR 150.9 600 MHz C/DEPT MHz 10

9

H 3C

CH3 7

6

2

1 4

5

8

CH3

3 OH

4

Borneol C10H18O Mol. Wt.: 154

2

3

5

6

9 10

25

20

8

1 7

75

70

65

60

55

50

45

40

35

30

15 ppm


ppm

4.0

3.5

3.0

2.5

7 2.0

1.5

1.0

ppm

COSY 600 MHz 9.10,8

1.0

3

1.0

5

1.5

1.5

2.0

2.0

F1

10

2.5

6

3.0 5

3.5

8

CH3

3.0

2

1 4

4

2.5

CH3 7

5 6 3

9

H 3C

OH

6

3 OH

3.5

Borneol C10H18O Mol. Wt.: 154

4.0

4.0

F2

2

HMQC 600 MHz

ppm 8

ppm 20

10 9

20

6 5

15 30

30 20

40

F1

diastereotopic

25 0.90

0.85

3

40

ppm

50

50

60

60

70

70

4

7 1

2

4.0

3.5

3.0

2.5

F2

2.0

1.5

1.0

ppm


MASS % of Base Peak

85

100 50

57

70

50

60

70

IR

114

m/z

80

90

100

110

656

1180

1774

4000 1

972

50

1358 1466

2885 2970

%Transmittance

100

3000

H NMR 600 MHz

1000

6 2

3

6

4

1

2

O

O

5

4


3

3 5

5

γ-Caprolactone C6H10O2 Mol. Wt.: 114

4.0

3.5

3.0

2.5

2.0

1.5

1.0

ppm

13 13

C/DEPT NMR NMR 150.9 600 MHz C/DEPT MHz

2

5

3

4

1

180

6

29

160

140

120

100

80

28

60

ppm

40

20

ppm


ppm 4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

COSY 600 MHz

ppm

1.0

1.0

1.5

1.5

6

5 3

2.0

2.0 3

F1 2.5

2

2.5 2

3

6

4

3.0

1

3.0

O

O

5

γ-Caprolactone C6H10O2 Mol. Wt.: 114

3.5

3.5

4.0

4.0 4

F2

HMQC 600 MHz

ppm 10

10

20

20

30

30

6

diastereotopic

40

40

ppm

F1 50

3 5 2

28

60

50 60

30 2.5

2.0

1.5 ppm

70

70

80

80

4.5

4.0

3.5

3.0

2.5

F2

2.0

1.5

1.0

ppm

4


MASS % of Base Peak

41 69

100

81

55

95

50

123

109

60

70

80

90

IR

m/z

100

110

120

130

140

1057

50

156

1381 1450

40

138

150

160

50

4000 1

3000 HO

H NMR 600 MHz

2000 9 10 Wavenumber (cm-1) CH3 CH3

1

6

2

3 4

5

833

2924

3332

%Transmittance

100

1000

9

7

8 10

CH3 8

Citronellol C10H20O Mol. Wt.: 156

6

1

5.0

4.5

3

5 OH

4.0

3.5

3.0

2.5

2.0

2

4

1.5

ppm

1.0

13 13


9

6

24

1

3

8

10

7

130

5

26

120

110

25

100

ppm

90

80

70

60

50

40

30

20 ppm


ppm 5.5

F1

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

ppm

1.0

1.0

1.5

1.5

2.0

2.0

2.5

2.5

3.0

3.0

3.5

3.5

4.0

4.0

4.5

4.5

5.0

5.0

F2

COSY 600 MHz 10 4 2

3 8 9

OH 5

1

6

HMQC 600 MHz

ppm HO

20 CH3 2

10

9

10

1

6

3

8

20

CH3

40

95 3 4 2

60

1

7

CH3

40 4 5 Citronellol C10H20O Mol. 60 Wt.: 156

8

ppm

F1 80

80 20

100

100

30 40

120

120

5.5

5.0

4.5

4.0

3.5

3.0

F2

2.5

2.0

7

ppm

2.0 1.5 1.0 1.5

1.0

6

ppm


MASS % of Base Peak

95 81

100

41 108

69

55

50

152 137

50

60

70

80

90 100 m/z

IR

9

130

140

10CH3

2954

O

Camphor C10H16O Mol. Wt.: 152

1743

3000

1041

1

748

3

1450

6

50

1273

4 2

4000


1000

H NMR 600 MHz

2.3

8 9

4

3

2.4

150

8

5

%Transmittance

120

H3C 7 CH3

100

1

110

3 5

2.2

2.1

2.0

1.9

6 1.8

1.7

5

6 1.6

1.5

1.4

10

1.3

1.2

1.1

6

5

9

30

25

1.0

ppm

0.9

13 13


4 3 2

220

1

ppm

10

8

7

55

50

45

40

35

20

15

ppm


ppm

F1

2.4

2.2

2.0

1.8

1.6

1.4

1.2

1.0

0.8

0.6

ppm

0.6

0.6

0.8

0.8

1.0

1.0

1.2

1.2

1.4

1.4

1.6

1.6

COSY 600 MHz

10 9 8 5 6 6

1.8

1.8

2.0

2.0

2.2

2.2

2.4

2.4

5

3

4

F2

3

HMQC 600 MHz

ppm 10

10

10

20

20

8 9

9

30

8

30

H3C 7 CH3

F1

4

5

3 2

40

6

40

1 10CH3

4

O


50

5 6

3 7

50 1

2.4

2.2

2.0

1.8

1.6

F2

1.4

1.2

1.0

0.8

0.6

ppm

CHAPTER 8 ASSIGNED PROBLEMS Problem 8.35C

INADEQUATE INADAQUATE150.9 150.9MHz MHz 2

1

3

Hz 9

-20000

8

-20000

H3C 7 CH3

-15000

4

5

-15000

3 2

6

-10000

1

-10000

10CH3

-5000

O

-5000


F1 0

0

5000

5000

10000 220

200

180

160

140

120

100

F2

80

60

5

9 8

40

10000 ppm

20

Hz

1

7 43

6

10

-25000

-25000

-24000

-24000

-23000

-23000

-22000

-22000

F1 -21000

-21000

-20000

-20000

-19000

-19000

-18000

-18000

-17000

-17000 ppm

65

60

55

50

45

40

35

F2

30

25

20

15

10

5


% of Base Peak

MASS

x 30

43 70

100 55

50 40

50

130

115

60

70

80

IR

m/z

90

100

110

120

130

1041

2962 1242

1743

50 4000

1

1373 1466

2877

%Transmittance

100

3000


H NMR 600 MHz

2350 Hz

2300 Hz

1000 Hz

850

Hz

1000 7 is doublet

6 is triplet

Hz

700

Hz

550

In the above insets each tick mark is 10 Hz

3

4

3.5

3.0

2.5

2.0

5

5 ppm

1.5

13 13


O 3

H3C 2 O

4

5

1

6

CH3

3

7 CH3

2

5 4

2-Methylbuty acetate C7H14O2 Mol. Wt.: 130

170 160 150 140 130 120 110 100

90

80

70

60

50

40

7 6 1

30

20

ppm


ppm 4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

ppm

COSY 600 MHz 6

1.0

1.0

1.5

1.5

5 5

7

4

2.0

2.0

2.5

2.5

3.0

3.0

3.5

3.5

4.0

4.0

1

F1

3

F2

HMQC 600 MHz

ppm 10

10 ppm 10

6

20

20

6 7 1 5

15

30

30

7 0.95

40

0.90

4

ppm

0.85

40

F1 O

50

50

3 4

H3C 2 O

5

1

60

6

CH3

60

7 CH3

2-Methylbuty acetate C7H14O2 Mol. Wt.: 130

70

4.5

4.0

3.5

3.0

2.5

F2

2.0

1.5

70

1.0

ppm

3


MASS

m/z 151 (M-1) 152 (M) 153 (M+1) 154 (M+2)

% of Base Peak

111

100

%M 37.5 100.0 12.7 5.2

152

50 83

69

50

60

70

80

90

IR

m/z

100

110

120

130

140

150

1234

1419

1651

3000


H NMR 600 MHz

725

957

50

4000 1

1057

3008 3093

%Transmittance

100

1000

7 and 8 are diastereotopic 78

Hz

4680

3

1

2

7.5

7.0

4260 Hz 1520

Hz

4560

Hz 740

720 Hz

Hz

600

6

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

ppm

1.5

13 13

C/DEPT NMR NMR 150.9 600 MHz C/DEPT MHz O S

4

1 2

1 5

3

3

C 5

6

7 8

cyclopropyl(thiophen-2-yl)methanone C8H8OS Mol. Wt.: 152

2

7 8 6

4 180

160

140

120

100

80

60

40

20

ppm


ppm

8

7

6

5

4

3

2

1

ppm

1

1

2

2

COSY 600 MHz 87

6

F1

3

3

4

4

5

5

6

6

7

7

8

8

F2

2 1 3

HMQC 600 MHz

ppm

20

20

O S

40

C

4

5

1 2

60

3

6

7

40

8

60

cyclopropyl(thiophen-2-yl)methanone C8H8OS Mol. Wt.: 152

F1

78

6

80

80

100

100

120

120 2 3 1

8

7

6

5

4

F2

3

2

1

ppm

CHAPTER 8 ASSIGNED PROBLEMS

IR

164

121

70

80

90

100

m/z

110

120

130

149

136

103

91

77

50 60

140

150

160

3

6

3940

3920


7

Hz

3880

663 764

3000

1265 1412 1473 1550 1612

2962

50

H NMR 600 MHz

949

2870

3201

%Transmittance

100

4000 1

Problem 8.38A

100 65

% of Base Peak

MASS

1000

5

3860 Hz

9 10

8

Hz

3720

Hz

1280

320

Hz

300

OH

9 13

8

7

6

5

4

C/DEPT NMR 150.9 MHz

2

5

171.5

3

10

150

140

130

120

CH3

9

9

β-Thujaplicin C10H12O2 Mol. Wt.: 164

537

171.0 ppm

160

OH

4

H 3C 8

1

4

170

ppm

1

1

6

6

2

O 7

2

3

110

100

90

80

70

10

8

60

50

40

30

ppm


ppm

1 2

7

6

ppm 6.8

5

6.6

6.4

4

3

6.2

2

1

ppm

ppm

9 10

1

6.2

O

5

2

7

8

6.4

1 2

6

7

3

3

36

6.6

F1

COSY 600 MHz

3

5

4

4

4

H 3C 8 10

5

5

6

6

7

7

CH3 9

β-Thujaplicin C10H12O2 Mol. Wt.: 164

F2

HMQC 600 MHz

ppm 20

20 9 10 ppm

40

40 7 3 5

125

60

8

60

130

F1 80

80

135

6 140

100

6.8

6.6

6.4

100

ppm

6.2

120

120

140

140 7

6

5

4

F2

OH

3

2

1

ppm

7 3 5 6


INADEQUATE 600 MHz INADEQUATE 150.9 MHz 4

9 10

8

Hz -20000

-20000

-15000

-15000

-10000

-10000

-5000

-5000

F1

0

0

5000

5000

10000

10000

15000

15000

20000

20000 160 2 1

140

120 4

100

80

F2

60

6

5

40 3 7

20

ppm

Hz 0

0

5000

5000

F1 10000

10000

15000

15000

O 7

1 2

6

OH

20000

20000 5

175

170

165

160

155

3 4

H C 8 CH3 150 3 10 145 140 135 9

F2 β-Thujaplicin

C10H12O2 Mol. Wt.: 164

130

125

120

115

ppm


% of Base Peak

MASS

123

100

83 55

41

50

151 69

95

232 230

110

50

100

4000

3000

150

m/z

200

IR 1034

1219 1365 1442 1473

80 70

1751

1

90 2954

%Transmittance

100


1000

10

H NMR 600 MHz 8

2800

Hz

1350

1300

1250

1200

1150

1100

1050

4

3

4.5

4.0

3.5

3.0


H3 C

7

5

900

5

6

2.0

Hz

850

6

ppm

1.5

CH3 4

5 6

950

8

9 13

2.5

1000

9

1

2

3

Br

CH3 O 3-Bromocamphor C10H15BrO Mol. Wt.: 230 10

8

2

20.0

200

180

19.9

160

9

19.8

140

ppm

120

3

1

100

80

60

6

4

5

10

7

40

20

ppm

CHAPTER 8 ASSIGNED PROBLEMS Problem 8.39B ppm 5.0

F1

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

ppm

1.0

1.0

1.5

1.5

2.0

2.0

2.5

2.5

3.0

3.0

3.5

3.5

4.0

4.0

4.5

4.5

F2

COSY 600 MHz

9

10

8 6 6 5 5 4

3

HMQC 600 MHz

ppm 8

9

10

H3 C

7

4

5

20 6

1

3

2

CH3 O 3-Bromocamphor C10H15BrO Mol. Wt.: 230

F1

20

89 5

30

6

Br

10

30

10

10

CH3

40

40

7 50

4

50

3 1 60

60 5.0

4.5

4.0

3.5

3.0

F2

2.5

2.0

1.5

1.0

ppm


INADEQUATE 150.9 INADEQUATE 600MHz MHz 13

2 Hz

-20000

-20000

-15000

-15000

-10000

-10000

F1 -5000

-5000

0

0

5000

5000

200

1

180 3

160 4

140

120

7

100 6

F2

80

60

40

ppm

20 10

5

Hz

-25000

-25000

-24000

-24000

-23000

-23000

-22000

-22000 8

9

F1

H3 C

-21000

7

4

5

-20000 1

6

CH3

2

-21000 3

Br

CH3 O 3-Bromocamphor C10H15BrO Mol. Wt.: 230

-19000

10

-18000 -17000 60

55

50

45

40

35

F2

30

25

20

15

10

5

-20000 -19000 -18000 -17000 ppm


% of Base Peak

MASS

FM (found) = 154.1351 154

108

100

81 71

139

111

93

55

50

136

50

60

70

80

90

m/z

IR

100

110

120

130

140

150

841 1080 987

4000 1

1219

1373 1466

50 2970

%Transmittance

100

3000


H NMR 600 MHz

1000

8,9

10

4,6 3,7 3,7

4,6 2

2.1

2.0

1.9

1.8

1.7

1.6

1.5

1.4

1.3

1.2

1.0 ppm

1.1

13 13

C/DEPT MHz C/DEPT NMR NMR 150.9 600 MHz 6

10

CH3

7 4 3

5 2

1

O CH3 8

9 CH3

1

75

Cineole C10H18O Mol. Wt.: 154

5

70

4,6

65

60

55

50

8,9 10

2

45

40

35

3,77

30

25

ppm


ppm 2.2

2.0

1.8

1.6

1.4

1.2

1.0

ppm

1.0

1.0

1.2

1.2

1.4

1.4

1.6

1.6

1.8

1.8

2.0

2.0

COSY 600 MHz 10

8,9

2 3,7

4,6

F1

1

4

5

4,6

3,7

6

F2

HMQC 600 MHz

ppm

22

22 3,7 7 10

24 6 5

26 4

3

24

CH3 1 O 2

26 CH3

10

8

F1 28

9 CH3

28

Cineole C10H18O Mol. Wt.: 154

30

8,9

30 4,6

32

32 2

34

34 2.2

2.0

1.8

1.6

F2

1.4

1.2

1.0

ppm


MASS % of Base Peak

82


67

100

155 54

FM (found) = 155.0711 by CI

100

50 110

50

183

100

m/z

IR

50 160

195

170 180 m/z

190

903

1219

1790

4000 1

1450

50

1859

2862 2947

%Transmittance

100

3000

H NMR 600 MHz

3

2000 Wavenumber (cm-1) O

4

2

1000

4

2 1

O

3

O 1,2-cyclohexanedicarb oxylic acid anhydride C8H10O3 Mol. Wt.: 154

3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 1.4

ppm

13 13


2 3

4

1

170

160

150

140

130

120

110

100

90

80

70

60

50

40

30

ppm


ppm

3.4 3.2 3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2

1.5

ppm

COSY 600 MHz

4

1.5

3

2.0

2.0

2.5

2.5

3.0

3.0

F1

F2

2

HMQC 600 MHz

ppm 4 3

25

25

3

30

4

O 2

30

1

O

F1 35

O 1,2-cyclohexanedicarb oxylic acid anhydride C8H10O3 Mol. Wt.: 154

35

40

40

45

45 ppm

3.4 3.2 3.0 2.8 2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2

F2

2


MASS % of Base Peak

104

100 121

50

131

91

77

164

65

50

146

60

70

80

90

100 110 m/z

IR

130

140

150

160

5 6

100

1

8

OH

10

1720

9

50

OCH3

6 7

4400

4350

1000

10

5

Hz

2750

2700

Hz 2000

1950

Hz

1650

1

7.0

6.5

748


H NMR 600 MHz 8

972

3000

1-methoxy-2-indanol C10H12O2 Mol. Wt.: 164

1088

4000

1350 1466

2831 2939

3402

%Transmittance

3 2

4 7

1

120

6.0

5.5

5.0

1600 Hz

2

3

4.5

4.0

3.5

OH

3

3.0

ppm

13 13


9

4

6

8

7

5

2

1

3 10

140

130

120

110

100

90

80

70

60

50

40

ppm


ppm 7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

3.0

ppm

COSY 600 MHz 3

5

3.0

3.0

6 4

3.5

7

9

1

8

4.0

3

3 2

3.5 OH

F1

4.5

1-methoxy-2-indanol C10H12O2 Mol. Wt.: 164

5.0

10

4.0

10

OCH3

4.5

OH

2 1

5.0

5.5

5.5

6.0

6.0

6.5

6.5

7.0

7.0

F2

5 7 6 8

HMQC 600 MHz

ppm 3

40 ppm

40 58

126

60

7

10

60

128

6

130 7.4

80

7.3

7.2

ppm

2

80 1

F1 100

100

120

120

7.5

7.0

6.5

6.0

5.5

5.0

F2

4.5

4.0

3.5

3.0

ppm

CHAPTER 8 ASSIGNED PROBLEMS Problem 8.42C 8

7

6

5

10 1 2

ppm

7.5

7.4

HMBC 600 MHz

7.3

7.2

7.1 ppm

4.5

3

4.0

3.5

OH

3.0

40

3

ppm ppm 3

40 5

50

50

6 4 7

F160

9 8

1

3 2

10 OH

60

10

OCH3 1-methoxy-2-indanol C10H12O2 Mol. Wt.: 164

70

70

80

80

90

90

2

1

F1 ppm

ppm

125

125

130

130

135

135

140

140

145

145 ppm

7.5

7.4

7.3

7.2

7.1 ppm

F2

4.5

4.0

3.5

3.0

5

6

94

8 7


% of Base Peak

MASS

x 30

43

100

131

85

109

95

182

185 200

50 50

100

IR

150

m/z

200

100

HO

3000

H NMR 600 MHz 6

7


10

8

1000

11

Ethyl 3-hydroxy-3,6dimethylhept-6-enoate C11H20O3 Mol. Wt.: 200

8

9

1260

1240

Hz

780

740 Hz

760

4

2

7

OH

4.5

887

O4000

1034

10

1188

9

1373 1458

1

O

1 C

1728

5

70 2978

H3C 3 11 4

2

80

3518

%Transmittance

90

4.0

5

3.5

3.0

2.5

2.0

ppm

1.5

13 13

C/DEPT MHz C/DEPT NMR NMR 150.9 600 MHz

7

9

2

4

5

8

3 1

170

6

160

150

11

140

130

120

110

100

90

80

70

60

50

40

30

10

ppm


ppm 5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.5

F1

ppm

1.5

2.0

2.0

2.5

2.5

3.0

3.0 6

3.5

3.5

4.0

COSY 600 MHz 11 10 4

8

5 2

OH

4.0 9

4.5

4.5 7

F2

HMQC 600 MHz

ppm 10

20

20

8

11

40

40

60

60

H3C 3 11 4

F1 100

1 C

2 5

O

9

10

O

7

80

7

120

8


140

9

100

6

120

160

140

6

160 1

5.0

4.5

4.0

3.5

3.0

F2

2

3

HO

80

5 4

2.5

2.0

1.5

ppm


HMBC 600 MHz 8

9

7

OH

2

5

10

11

4

ppm 10

20

8 11

30

5 4

40

2

50 9

60 70

3

F180 F1 HO

90

H3C 3 11 4

100

1 C

2 5

O

9

10

O

7

6

110

7

8


120 130 140

6

150 160 170

1

5.0

4.5

4.0

3.5

F2

3.0

2.5

2.0

1.5

ppm


MASS % of Base Peak

121

100 136

50

93

65

178

149

50

100

IR

150

m/z

50

H NMR 600 MHz


841

1

3000

1173 1211 1281

4000

1597 1658

2962

3325

%Transmittance

100

1000

9

3 7

2

8

6 OH

8.0 7.8 7.6 7.4 7.2 7.0 6.8 ppm

3.0

2.5

2.0

ppm

1.5

13 13

C/DEPT MHz C/DEPT NMR NMR 150.9 600 MHz

6

O 5

8 7

9

1 2 3 4

2 5

200

4

180

160

3 1

140

120

OH 4'-Hydroxy valerphenone C11H14O2 Mol. Wt.: 178

100

80

60

6

40

8 7

9

ppm


ppm

8

7

6

5

4

3

2

1

1

ppm

COSY 600 MHz 9

1 6

O

2

5

8

8 7

7

2

9

1 2

3

6

3

3

F1

4

4

4


5

5

6

6 OH

7

7

8

8

F2

3 2

HMQC 600 MHz

ppm 9

20

20

8 7

40

40

60

60

F1 80

80

100

100

6

3

120

120 2

8

7

6

5

F2

4

3

2

1

ppm


HMBC 600 MHz

3

2

7

6

8

9

OH

ppm

8.0

7.5

7.0

ppm

3.0

2.5

2.0

1.5

1.0

15

ppm ppm

9

15 6

O 5

20

8 7

9

20

1

F1

2

8 3

25

25

4

30

7


30

35

35 6

ppm

ppm

120

120

130

130

3

1 2

140

140

150

150

160

160

170

170

180

180

190

190

200

200

210

210 ppm

8.0

7.5

7.0

ppm

F2

3.0

2.5

2.0

1.5

1.0

4

5


MASS % of Base Peak

68

100 108 53

50

79

0

50

153 151

125

93

100 m/z

IR

168

150

50

7 3

887 933

H NMR 600 MHz

1242

2000 Wavenumber (cm-1) 5,4 7 4

1412 1442

1

1705

3000

2669

2893 2962 3078

%Transmittance

100

1000

5 10

1 2900

Hz

2850

1600

1550

x64

Hz

1200

1150

1100

Hz

1050

9

OH

ppm

12

4.5

4.0

3.5

3.0

2.5

2.0

1.5

7

5 10 4 1

ppm

9 C/DEPT MHz C/DEPT NMR 150.9 600 MHz H2CNMR

13 13

H

3 1 7 8

HO

4

2 6

5

CH3

10

O 2-((1R,2S)-1-methyl-2-(prop-1-en-2yl)cyclobutyl)acetic acid C10H16O2 Mol. Wt.: 168 8

9

3

6

2

180 170 160 150 140 130 120 110 100

90

80

70

60

50

40

30

ppm


5.0

ppm

4.5

4.0

3.5

3.0

2.5

2.0

1.5

COSY 600 MHz

ppm

10

1.5

1.5

2.0

2.0

2.5

2.5

54 5,4 7

1

7 3

F1 3.0

3.0

3.5

3.5

4.0

4.0

4.5

4.5 9

5.0

5.0

F2

HMQC 600 MHz

ppm 20

9

H2C

3

40

20

H 4

2

1 7 8

HO 60

40

5

6

3

CH3

60

10

O 2-((1R,2S)-1-methyl-2-(prop-1-en-2yl)cyclobutyl)acetic acid ppm 80 C10H16O2 Mol. Wt.: 168

F1

100

20

120

30

140

80 1 10

100 120 140

40

160

160 50

180

180 3.0

5.0

4.5

4 1 10 5 7

4.0

3.5

2.5

3.0

F2

2.0

2.5

1.5

2.0

ppm

1.5

ppm

9


HMBC 600 MHz 9

1 3

5.0

ppm

4.8

ppm

7

2.6

7 2.4

2.2

5,4

2.0

4 1.8

10

5 1.6

1.4

1.2

ppm

4 20

1 25 9

H2C 30

10 H 3

4

5

2

1 7 8

HO 35

5

6

CH3

10

O F1 2-((1R,2 S)-1-methyl-2-(prop-1-en-2yl)cyclobutyl)acetic acid C10H16O2 40 Mol. Wt.: 168

7 6

45

50

3

9

ppm

2

150

8 5.0

4.8

ppm

2.6

2.4

F2

2.2

2.0

1.8

1.6

1.4

1.2

ppm

CHAPTER 8 ASSIGNED PROBLEMS % of Base Peak

100 50 53

IR

91

77

122

65

50

60

70

80

90

100

110 m/z

120

151 148

133

130

140

166

150

160

787

1365 1466

%Transmittance

100

50

2916

1049

3332

4000 1

Problem 8.46A

105

MASS

3000

H NMR 600 MHz


1000

10 4

2180

2160 Hz

1440

9

1420

1400

1380

5

9

1360

1340

1320

1300

1280

1

1260

1240

1220 Hz

8

7 3

11

5.0 13

4.5

4.0

4

OH

3.5

3.0

2.5

2.0

1.5

ppm

1.0

C/DEPT NMR 150.9 MHz 10 11

CH2CH2OH 2 1

3 8

6

9

7 4

5

3

130

120

1

Nopol C11H18O Mol. Wt.: 166

2

140

11

110

100

90

80

5 10

9

4 7

8

6

70

60

50

40

30

ppm


ppm 5.5

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

COSY 600 MHz

ppm

8

1.0

1.0

1.5

1.5

2.0

2.0

4 7 5 10

2.5

2.5

4 9

F1 3.0

3.0

3.5

3.5

4.0 2 4.5

4.0

5.0

5.0

5.5

5.5

1 OH

11

4.5

F2

3

HMQC 600 MHz

ppm 10 11

20

8 7

20

CH2CH2OH 2 1

40

3 8

6

9

40

7

6

4

1

5


60

F1

ppm 30

80

11

60

4 9

80

6 10 5

100

35

100 40

120

2.5

5.5 2 OH

5.0

4.5

4.0

3.5

2.4

3.0

F2

2.3

2.2

2.5

2.0

2.1

1.5

ppm

1.0

120 ppm

3

CHAPTER 8 ASSIGNED PROBLEMS Problem 8.46C INADEQUATE MHz INADEQUATE 150.9600 MHz

2

3

1

11

Hz -15000

-15000

-10000

-10000 10 11

-5000

-5000

CH2CH2OH 2

F1

1

0

6

9

5000

0

3 8

7 4

5000

5


10000

10000

15000

15000 140

1

130

120

5

110 10

100

6

90

F2

80

70

9 4

60 7

50

40

30

20

ppm

8

Hz -16000

-16000

-14000

-14000

-12000

-12000

-10000

-10000

-8000

-8000

-6000

-6000

F1 -4000

-4000

-2000

-2000

0

0

2000

2000

4000

4000 45

40

35

F2

30

25

20

ppm


% of Base Peak

MASS

105


100

277

100 77

50

136 154

50

FM (found) = 277.1083 by CI

100

150

IR

50 200

m/z

305

250

m/z

317

300

2877 2939

1

3000

H NMR 600 MHz 3

2

1281

1712 1751

4000


6

1000

9

12

10

4

4800

4700

4600

717

50

1072

3456

%Transmittance

100

7

10

OH

4500 Hz 3300

3200 O

3100

3000 Hz

1500

11

1400

Hz

1300

8 12

O 13 9

O 10

CO

12 8

6

O C O 5 1

7

O O

CH2OH

11

2200 Hz

2250

1750

1700 Hz

3.0

2.5

2 HOH 2C 4

3

5-(Benzoyloxy)hexahydro-4(hydroxymethyl) C15H16O5 Mol. Wt.: 276

8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

ppm


ppm 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5

ppm

COSY 600 MHZ 7

O O 13 9

3

10 6

O C O 5

41

3

12 8 7

11

CH2OH

4

11

2 4

3

5

5

F1 5-(Benzoyloxy)hexahydro-4(hydroxymethyl) C15H16O5 Mol. Wt.: 276

6

9 6

6 O C

7

O O

O

7 3

4

HOH2C

8

2

8

COSY 600 MHZ

ppm

7

2.5

2.5

3.0

3.0

3.5

3.5

10 12

10 12 8

11

F1 4.0

4.0

4.5

4.5

5.0

5.0

5.5

5.5 5.5

5.0

4.5

4.0

3.5

F2

3.0

2.5

ppm

9 6

CHAPTER 8 ASSIGNED PROBLEMS Problem 8.47C 13


2 3

1

13 180

170

160 3

2

9

129 ppm

130

5

4

150

140

77.5

130

4

6

11

8 1012

7

ppm

77.0

120

6

110

100

90

80

70

40 ppm

50

HMQC 600 MHz

11

9

60

7

ppm O

40

O 13 9 10

50

C O 5

60

1

O

12

O 7

13

O

7

OH HOH2C

CH2OH

11

11 13

2

70 4

C

8 6

O

12 8 10

O

3

6

F1805-(Benzoyloxy)hexahydro-4(hydroxymethyl) C15H16O5 Mol. Wt.: 276

12 8

90

ppm

100

35

12

10

9

10

12 10 8

110 40

120 3.0

2.9

2.8

2.7

2.6

2.5

2.4

3

ppm

130

2 4 8.0

7.5

7.0

6.5

6.0

5.5

5.0

F2

4.5

4.0

3.5

3.0

2.5

ppm

CHAPTER 8 ASSIGNED PROBLEMS Problem 8.47D

HMBC 600 MHz

2 4

ppm

8.2

8.0

7.8

3

7.6

40

6

7.4 ppm

11

9

5.0

4.5

4.0

12 8

3.5

3.0

10 7 OH

2.5

ppm

12 10 8

O O 13 9 10

50

6

O C

5 O

60

1

12 8 7

7

CH2OH

11

11

2 4

70

3

5-(Benzoyloxy)hexahydro-4(hydroxymethyl) C15H16O5 Mol. Wt.: 276

6

80

9

F1 ppm

3 2

1

130

4 140

150

160

5 170

13 180 8.2

8.0

7.8

7.6

7.4 ppm

5.0

F2

4.5

4.0

3.5

3.0

2.5

ppm

Robert M. Silverstein, Francis X. Webster, David Kiemle-Solutions Manual for Spectrometric Identification of Organic Compounds-Wiley (2005)

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