Chapter 5 NMR Spectroscopy

Table 5.3 Typical ihl Chemical Shift Ranges in Organic Compounds

Group"
Tetramethylsilane (CH3)4Si
Methyl groups attached to Sp3 hybridised carbon atoms
Methylene groups attached to Sp3 hybridised carbon atoms
Methine groups attached to Sp3 hybridised carbon atoms
Acetylenic protons
Olefinic protons
Aromatic and heterocyclic protons
Aldehydic protons
6
lH
(ppm from TMS)
o
0.8 - 1.2
1.0 - 1.5
1.2 - 1.8
2-3.5
5-8
6-9
9 - 10
-OR protons in alcohols, phenols or carboxylic acids; -SR protons in thio1s; -NH
protons in amines or amides do not have reliable chemical shift ranges (see page 49).
Table 5.4 'a Chemical Shifts (6) for Protons in Common Alkyl Derivatives
44
CH3-X CH3CH2-X (CH3)2CH-X
X
- CH3 -CH3 - CH2-
---:- C
H3 'CH-
-:
-H
0.23 0.86 0.86 0.91 1.33
-CH=CH2
1.71 1.00 2.00 1.00 1.73
-Ph
2.35 1.21 2.63 1.25 2.89
-CI
3.06 1.33 3.47 1.55 4.14
-Br
2.69 1.66 3.37 1.73 4.21
-I
2.16 1.88 3.16 1.89 4.24
-OH
3.39 1.18 3.59 1.16 3.94
-OCH3
3.24 1.15 3.37 1.08 3.55
-O-Ph
3.73 1.38 3.98 1.31 4.51
-OCO-CH3
3.67 1.21 4.05 1.22 4.94
-OCO-Ph
3.89 1.38 4.37 1.36 5.30
-CO- CH3
2.09 1.05 2.47 1.08 2.54
-CO-Ph
2.55 1.18 2.92 1.22 3.58
-CO-OCH3
2.01 1.12 2.28 1.15 2.48
-NH2
2.47 1.10 2.74 1.03 3.07
-NH-COCH3
2.71 1.12 3.21 1.13 4.01
-C=N
1.98 1.31 2.35 1.35 2.67
- N02
4.29 1.58 4.37 1.53 4.44
Table 5.5
Chapter 5 NMR Spectroscopy
Approximate IH Chemical Shifts (0) for Olefinic Protons
C=C-H
OC=C-H =5.25 + CJgem + CJcis + CJtrans
Xtrans", / X
gem
C=C
/ "
Xcis H
X
CJgem CJcis CJtrans
,
.'
-H
0.0 0.0 0.0
-alkyl
0.45 -0.22 -0.28
-aryl
1.38 0.36 -0.07
- C H = C ~
1.00 -0.09 -0.23
-CH=CH-conjugated
1.24 0.02 -0.05
-C=C-H
0.47 0.38 0.12
-CO-R
1.10 1.12 0.87
-CO-OH
0.80 0.98 0.32
-CO-OR
0.78 1.01 0.46
-C=:N
0.27 0.75 0.55
-CI
1.08 0.18 0.13
-Br
1.07 0.45 0.55
-OR
1.22 -1.07 -1.21
-NRz
0.80 -1.26 -1.21
Table 5.6 gives characteristic IH chemical shifts for the aromatic protons in benzene
derivatives. To a first approximation, the shifts induced by substituents are additive.
So, for example, an aromatic proton which has a -N0
2
group in the para position and
a -Br group in the ortho position will appear at approximately 7.82 ppm
[(7.26 + 0.38(p-N0
2
) + 0.18(o-Br)].
Tables 5.7 gives characteristic chemical shifts for IH nuclei in some polynuclear
aromatic compounds and heteroaromatic compounds.
45
Chapter 5 NMR Spectroscopy
Table 5.6
IH Chemical Shifts (0) for Aromatic Protons in Benzene
Derivatives Ph-X in ppm Relative to Benzene at 0 7.26 ppm
(positive sign denotes a downfield shift)
X ortho meta para
-H
0.0 0.0 0.0
-CH3
-0.20 -0.12 -0.22
-C(CH
3
h
-0.03 -0.08 0.20
-CH=CH2
0.06 -0.03 -0.10
-C=C-H
0.16 -0.04 -0.02
-CO-OR
0.71 0.11. 0.21
-CO-R
0.62 0.14 0.21
-OCO-R
-0.25 0.03 -0.13
- OCH3
-0.48 -0.09 -0.44
-OH
-0.56 -0.12 -0.45
-CI
0.03 -0.02 -0.09
-Br
0.18 -0.08 -0.04
-C:::N
0.36 0.18 0.28
- N0 2
0.95 0.26 0.38
-NR2
-0.66 -0.18 -0.67
-NH2
-0.75 -0.25 -0.65
Table 5.7 IH Chemical Shifts (0) in some Polynuclear Aromatic Compounds
and Heteroaromatic Compounds
7.71
7.81
7.46
8.31 7.91
CCO
"-':::: "-':::: "-':::: 7.39
~ ~ ~
Jh.8.12
l r U - ~ II _ ~ 7.82
8.93 7.88
46
6.30
o 7.40
a
7.04
o 7.19
S
7.46
o
N
7.06
8.50
Table 5.8
Chapter 5 NMR Spectroscopy
Typical ifl - IH Coupling Constants
Group
CH
3CHzCHzCH3
CH
3CHzCHzCH3
CH
3CHzCHzCH3
HzC=C=C=CH
z
HzC=CH-CH=CH
z
J(Hz)
ZJ
HH:::::
-16
3J
HH
= 7.2
4J
HH
= 0.3
5J
HH
= 7
5J
HH
= 1.3
4J
HH
= 1.5
Signal Multiplicity - the n+l rule. Spin-spin coupling gives rise to multiplet
splittings in IH NMR spectra. The NMR signal of a nucleus coupled to n equivalent
hydrogens will be split into a multiplet with (n+l) lines. For simple multiplets, the
spacing between the lines (in Hz) is the coupling constant. The relative intensity of
the lines in multiplet will be given by the binomial coefficients of order In'
(Table 5.9).
Table 5.9 Relative Line Intensities for Simple Multiplets
multiplicity relative line multiplet
n n+l intensities name
0 1 1 singlet
1 2 1 : 1 doublet
2 3 1 : 2 : 1 triplet
3 4 1 : 3 : 3 : 1 quartet
4 5 1:4:6:4:1 quintet
5 6 1 : 5 : 10: 10: 5 : 1 sextet
6 7 1 : 6 : 15 : 20 : 15 : 6 : 1 septet
7 8 1 : 7 : 21 : 35 : 35 : 21 : 7 : 1 octet
8 9 1 : 8 : 28 : 56 : 70 : 56 : 28 : 8 : 1 nonet
51
APPENDIX B 191
EFF'ECT ON CHEMICAL SHIFTS BY TO OR THREE DIRECTLY
APPENDIX B ATACHED FUNCTIONAL GROUPS
Y-CH -Z and Y-CH-Z
2

W
The chemical shift of a methylene group attached to two
functional groups can be calculated by means of the
substituent constants (0 values) in Tablc B. 1. Shoolery's rule*
states that the sum of the constants for the attached functional
groups is added to [ 0.23, the chemical shift for CH4:
The chemical shift for the methylene protons, of
C6H,CHzBr, for example, is calculated from the 0 values in
Table 8.1.
0.23
(Ph
= 1.85
(Sr = 2.33
( 4.41 Found, ( 4.43
Shoolery's original constants have been revised and
extended in Table 8.1. Te observed and calculated chemical
shifts for 62% of the samples tested were within 0.2 ppm,
92% within 0.3 ppm. 96% within 0.4 ppm, and 99%
within 0.5 ppm.t Table B. l contains substituent constants
(Friedrich and Runkle, 1984) for the more common functional
* Shoolery, J.N. (1959). Varian Technicallnforratiol Bulletin, Vol 2,
No.3. Palo Alto, CA: Varian Associates.
t Data from Friedrich, E.c., and Runkle, K.G. (1984). 1. Cher. Educ.
61,830;(1986)63,127.
TABLE B.1 Substituent Constants for Alkyl Methylene
(and Methyl) Protons.
Substituent Substituent
Constants Constants
YorZ
(0
YorZ
(0)
-H 0.34 -OC(=O)R 3.01
-CH
3
0.68 -OC(=O)Ph 3.27
-C-C 1.32 -C(=O)R 1.50
-C=C 1.44 -C(=O)Ph 1.90
Ph 1.83 -C(=O)OR 1.46
-CFz 1.12 -C(=O)NRz(Hz) 1.47
-CF3 1.14 -C=N 1.59
-F 3.30 -NRz(Hz) 1.57
-Cl 2.53 -NHPh 2.04
-Br 2.33 -NHC(=O)R 2.27
-I 2.19 -N] 1.97
-OH 2.56 -NOz 3.36
-OR 2.36 -SR(H) 1.64
-OPh 2.94 -OS02R 3.13
groups. Note that chemical shifts of methyl protons can be
calculated by using the constant for H (0.34). For example
H-CH z-Br is equivalent to CH3Br.
Tables B.2a, B.2b, and B.2c: Chemical
Shift Correlations for Methine Protons
Table B. 2a gives the substituent constants* to be used with
the formulation
8 CHXYZ 2.50 + (x + (y
+
(z
which is satisfactory if at leas t two of the substituents are
electron-withdrawing groups. In other words, only a single
substituent may be an alkyl group (R). Within these limits,
the standard error of estimate is 0.20 ppm. For example, the
chemical shift of the methine proton in
OEt

CH -CH-OEt
3
is calculated from Table 8.2a as follows:
8 2.50 + 1.14 + 1.14 + 0.00 4.78
Te found value is 4.72.
Tables B.2b and B.2c are used jointly for methine pro
tons that are substituted by at least two alkyl groups
"Bell, H.M., Bowles, D.B. and Senese, F (1981). Org. Magn. Resol.,
16,285. With permission.
TABLE B.28 Substituent Constants for Methine Protons.
Group
(0)
-F 1.59
-Cl 1.56
-Br 1 .53
-N02 1.84
-NH2 0.64
-NH +
3
1.34
-NHCOR 1.80
-OH,-OR 1.14
-OAr 1.79
-OCOR 2.07
-Ar 0.99
-C=C 0.46
-C
-
C 0.79
-C=N 0.66
-COR,-COOR,-COOH 0.47
-CONHz 0.60
-COAr 1.22
-SH, -SR 0.61
-S02R 0.94
-R 0
192 CHAPTER 3 PROTON NMR SPECTROMETRV
TABLE B.2b Observed Methine Proton Chemical Shifts
of Isopropyl Derivatives.
(CH3hCHZ (CH3hCHZ
o (ppm) o (ppm)
Z obs Z obs
H 1.33 HO 3.94
H3C 1.56 RO 3.55
R 1.50 C6HsO 4.51
XCH2 1.85 R(H)C(=O)O 4.94
R(
H
)C(=O) 2.54 C6HSC(=O)O 5.22
C6HSC(=O) 3.58 F3CC(=O)O 5.20
R(H)OC(=O) 2.52 ArS020 4.70
R2(H2)NC(=O) 2.44
C
o
H
s
2.89 R(H)S 3.16
R2(H2)C=CR(H) 2.62 RSS 2.63
R(H)C C 2.59
N=C 2.67 F 4.50
CI 4.14
R2(H2)N 3.07 Br 4.21
R(H)C(=O)NH 4.01 1 4.24
02N 4.67
(or other groups of low polarity). Friedrich and Runkle pro
posed the relationship
0CHXYZ

O(CH,)zCHZ

xy
in which the X and Y substituents are alkyl groups or other
groups of low polarity. Te Z susbstituent covers a range of
polarities . .xy is a correction factor. The relationship states
that the chemical shift of a methine proton with at least two
low-polarity groups is equivalent to the chemical shift of an
isopropyl methine proton plus correction factor.
The substituent constants for a Z substituent on an
isopropyl methine proton are given in Table B.2b. Te y
correction factors are given in Table B.2e.
The following example illustrates the joint use of Tables
B.2b and B.2e, with CH3, CH=CH2, and CoHs as sub
stituents. The most polar substituent is always designated Z.
TABLE B.2e Correction Factors for Methine
Substituents of Low Polarity.
Cyclic
Open-Chain Methine
Methine Proton Proton
Systems
a
xy Systems
a
xy
z
I

CH)-CJ-CH3 0.00 -1.0

Z
Z
I
I
l
CH)-CJ: -R -0.20 +0.40
Z

I
R-CH-R -0.40 +0.20
Z
,
I
CH}-C! -CH2X +0.20 monosub. -0.20
axial H -0.45
Z
I
CH3-C!:-CH=CH2 +0.40 equat. H +0.25
Z

I
CH3-CH-C6Hs + 1.15 0.00
Z

I
R-CH-Cr
H
s +0.90 0.00
C6H
S
I
From Table B.2b, (

2.89 for CH3-CH-CH].

From Table B.2e,.y = 0.00 for CH} . .y 0.40 for
CH=CHz
C6H-
I )
Terefore, 0 CH}-Ct-CH=CH2

2.89 + 0.00 +
0.40 3.29 (Found: ( 3.44).
TABLE C.1
TABLE C.2
Chemicals Shifts in Alicyclic Rings.
`

0
0.22
1.96
1.51
1.44
1.54

`
1.65

1.96 3.03
o
2 06

.
38

1.8
2.02
1.8
Chemical Shifs in Heterocyclic Rings.
2.54

1.62
\
N
H 0
.
03
2.27
\
S

2.72 4.73
H 2.38

2.23 3.54

3.17 3.43

1.85
3.75
o
1.59
2.75
N
H 2.01
_1.93
2.82
S
R O

3.9-4.1
H o
5.90

o

4.75-4.90

3 01

2.08 38
2.31

o
o

1
.51
3.52

1.50

1.50
2.74
N
H 1.84

.3
S
3.00
O
2

4.70
1.68
3.80
1.62
1.62

4.06
2.27

1.78

3
0
1.94
1.52 1.52

f
e
B
,
1.90
3.70
S
O
2

)
S
5
o
APPENDIX c 193
194 CHAPTER 3 PROTON NMR SPECTROMETRY
(See Table D.1)
5.25 + Zgem + Zcs + Ztrans
For example, the chemi cal shifts of the alkene
protons in
are calculated:
Ha
C
6HSgem
o R
trans
H
b
OR/em
C6HStran.,
TABLE D.1 Substituent Constants (
Z
) for Chemical Shifts of Substituted Ethylenes.
Z Z
Substituent R gem cis trans Substituent R gem cis
-H 0 0 0
H
-Alkyl 0. 44 -0.26 -0.29 / 1.03 0.97
-Alkyl-ringa 0.71 -0.33 -0. 30
-C=O
-CH20, -CH21 0.67 -0.02 -0.07
N
-CH2S 0.53 -0o15 -0.15
/
1.37 0.93
-C=O
-CH2CI, -CH2Br 0.72 0.12 0.07
-CH2N 0.66 -0.05 -0.23
/
CI
1.10 1.41
-C=C 0.50 0.35 0.10 -C=O
-C
-
N 0.23 0.78 0.58 -OR, R: aliph 1.18 -1.06
-C=C 0.98 -0.04 -0.21 -OR, R: conj
b
1.14 -0.65
-C=Ccon? 1.26 0.08 -0.01 -OCOR 2.09 -0.40
-C=O 1.10 1.13 0.81 -Aromatic 1.35 0.37
-C=Oconl 1.06 1.01 0.95 -Cl 1.00 0.19
-COOH 1.00 1.35 0.74 -Br 1.04 0.40
R
-COOHconjb 0.69 0.97 0.39
/
0.69 -1.19
-N R:aliph
"
R
R
-COOR 0.84 1.15 0.56
/
2.30 -0.73
-N R:conjb
"
R
-COORconjb 0.68 1.02 0.33 -SR 1.00 -0.24
-S02 1. 58 1.15
Ie
Alkyl ring indicates that the double bond is part of the ring R II.
"- e
1.35
~
1 o 28
0.07
1.18
-0.10
1.08
trans
1.21
0.35
0.99
-1.28
-1o05
-0.67
-0.10
0.03
0.55
-1.31
-0.81
-0.04
0. 95
b The Z factor for the conjugated substituent is used when either the substituent or the double bond is further conjugated
with other groups.
Source: Pascual C, Meier, 1, and Simon, W. (1966) Helv. Chim. Acta, 49, 164.
5.25
0.07
85.32
5.25
1.08
86.33
TABLE 0.2 Cemical Shifts of Miscellaneous Alkenes
R = C(=O)OCH3
----------------

2.12 "
.

. .

. . . . . .
1.84 5.62
' 1
.

. .

0
6
.
42 1.65

2.02

7
9
7.36



6
.
7

.82

.
0

4
.
20
0
3
.97 0 6.37
7.53 7.72

0
.

7.32
R C(=O)CH3
2.06
.
. .
1.86
5
.
9
7
R = OC(=O)CH3

H3C .
1.65 6.67
2.57

0.92
5.95 2.28
2.20 7.71
_

6.40
.
3

2.13

4.63
3
34 ,."

0
5.1 J

6.15 7.63

piperitone linalool a-terpinene

TABLE 0.3 Chemical Shifts of
A
lkyne Protons
HC=CR
HC=C-C=CR
HC-C-Ph
1.73-1.88
1.95
2.71-3.37
HC=C-COH
HC=CH
HC=C-CH=CR2
TABLE 0.4 Chemical Shifts of Protons on Fused
A
romatic Rings
7.81

7.46


,

8.69
7
.
81
2.23
1.80
2.60-3.10

APPENDIX D 195
196 CHAPTER 3 PROTON NMR SPECTROMETRY
CHE' MICAL SHIFTS OF PROTONS ON MONOSUBSTITUTED
BENZENE RINGS
Benene a
CH, (omp)
CH,CH2 (omp)
(CH3hCH (omp)
(CH,),C o,m,p
C=CH2 (omp)
CaH 0, (mp)
Penyl 0, m, p
CF, (omp)
CH2Cl (omp)
CHCl2 (omp)
CC1, 0, (mp)
:
CH20H (omp)
CH20R (omp)
CH2O(=O)H, (omp)
CH2NH2 (omp)
F m,p.o
Cl (omp)
Br 0, (pm)
Io,p,m :
OH m,p,o
OR m,(op)
OC( -O)CHa m,p,o
OTsb (mp), 0
CH(-O)o,p,
.

C(=O)H, 0, (mp)

C(=O)H 0, p, m

C(=O)R 0, p, m
:
C(-O)l 0, p, m
.
.
DN (omp)
N2 m,p,o
N(CH,h m(op)
NHC(=O)R o,m,p
.
.
Nj 0 (mp)


N020,p,
.
. .
SR(omp)
N-C-O (op)
:
:
.
.
:

:
:
;

G
:

.
:
:
:
B
B
:
:

M B
B

:
:

M
M

M
& B
M

:
M

:


:
:
:

: :
.
. .
.
.
The benzene ring proton is at 07.27, from which the shift increments are calculated as shown at the end of Section 3.4.
b OTS p-toluenesulfonyloxy group.
APPENDIX E 197
TABLE 0.5 Chemical Shifts of Protons on Heteroaromatic Rings
-
0
3.88

..
H

.,

0
.

7.30
S

7.10

-0
..
,
.
3
.
88

6.1 .0
S
H
0 0
......
...
.

7
.3 0.57 .
.

H \
H -H.O
-
-11.0
\\ NH

7.54

.
,
.
_

_
.

6
.7
/
_ N
. ,. 27
.

.
.

.
7.
3
7

6.7
6
-10.0
6.LO .
7.12 7.18
TABLE 0.6 Chemical Shifts of HC=O, HC=N, and HC(O)3 Protons.
RCH=O
PhCH=O
RCH=CHCH=O
9.70
9.98
9.78
HC(=O)OR
HC(=O)NR2
8.05
8.05
5.00
RCH=NOHcis
RCH=NOH trans

N0
2
R
y
'

H N0
2
7.25
6.65
6.05

8O
N EFFECTS
N E
S 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 0
Proton Class
OH Carboxylic acids
Sulfonic acids
Phenols
Phenols (intramolecular H bond)
in DMSO
Alcohols
Enols (cyclic a-diketones) ..
Enols (f-diketones)
Enols (f-ketoesters) l

inDMSO, . in acetone
Water I

H H
.
Oximes
NH2 and NHR Alkyl and cyclic amines
Aryl amines
Amides
Urethanes
Amines in trifluoroacetic acid
SH Aliphatic mercaptans H
Thiophenols t-
S 17 16 l5 14 13 12
11
10 9 8 7 6 5 4 3 2
1
0
Solvent CDCI). Chemical shifts within a range are a function of concentration.
b See Section 3.6.1.2.
198 CHAPTER 3 PROTON NMR SPECTROMETRY
APPFNDIX F PROT0N 8PIN.
Type
H
,
/
a
/
C
"
H"
CHa -CH" (free rotation)
I
CH -C-CH
a
I
h
ax-ax
ax-eq
eq-eq
Q
H
,
H
b
( cis or trans)
H
a
H"
Jab (Hz)
0-30
6-8
0-1
6-14
0-5
0-5
cis5-10
trans 5-10
Jab
Typical
12-15
7
0
8-10
2-3
2-3
Type
H
a
H"
'=C
/
/
"
CH
a
CH
h
`=;

/ "
CH
a
`C
/
/ "
H"
CHb
"
C
=
C
/
/ "
H
a
H
a
CH,)
'-
/
/
-C"
C=CH-CH C
L b
H H
""
/
"
C=C

CH,,-C-CH
b
c
H
,
cis 4-12
-CHa-C-C-CHb-
trans 2-10
H
/J
(cis or trans)

H
b
(cis or trans)
CH
a
-OHb (no exchange)

/
CH,,-
CHb

C=CHa-CHb
H
a
`;

/ "
H

C=C

H
b
H
"
cis 7-13
trans 4-9
4-10
1-3
5-8
12-18
0-3
5
2-3
6
17
0-2
H
a

Hi
HlI

H
b
0

H
I)
H
a
0
H
a

6 ,
N

0
] (ortho)
] (meta)
]
(para)
] (2-3)
] (3-4)
] (2-4)
] (3-5)
] (2-5
)
] (2-6)
] (2-3)
] (3-4)
] (2-4)
] (2-5)
Jab
(Hz)
Jab
Typical
6-12 10
0-3 1-
2
4-10 7
0-3 1.5
0-3 2
9-13 10
3 member 0.5-2.0
4 member 2.5-4.0
5 member 5.1-7.0
6 member 8.8-11.0
7 member 9-13
8 member 10-13
2-3
2-3
6
4
2.5
6-10
1-3
3
0-1 -0
5-6 5
7-9 8
1 -2 1. 5
1-2 1.5
0-1 1
0-1 -0
1.3-2.0 1 .8
3.1-3.8 3.6
0-1 -0
1-2 1.5
T
yp
e
[
s

H
4
s

N
6 .
N
J (2-3)
J(3-4)
J(2-4)
J (2-5)
J (1-3)
J (2-3)
J (3-4)
J(2-4)
J (2-5)
J (4-5)
J (2-S)
J (2-4)
J (4-6)
J (4-5)
J (2-4)
J (2-5)
Jab (Hz)
Jab
T
yp
ical
4.9-6.2 5.4
3.4-5.0 4.0
1.2-1.7 1.5
3.2-3.7 3.4
2-3
2-3
3-4
1-2
1.5-2.5
46
1-2
0-1
2-3
3-4
-0
1-2
T
yp
e
Proton -Carbon-13
(See Tables 5.17,5.18)
Proton -Fuorine
H
"" /
"
/
C
""
F
{)

CHu-CF
b
/

/
CH,,-C-CFh
I I
=C
/
/ "
H
a
F
h
H
a"
/
C=C
/ "
F
F
b
_

QRC-C-CHoFy
.,
{ -
Proton -Phosphorus
o

/PH
(CHJ)
J
P
(CH
3)JP=0
(CHJCH2)JP
(CH3CH2)JP=0
o

CH3P (OR)2
o

CRCP(OR)o

CH30P (OR)2
P[N(CHJ)2b
O=P[N(CH3hb
630-707
2.7
13.4
0.5 (HCCP) 13.7 (HCP)
11.9 (HCCP) 16.3 (HCP)
10-13
15-20
10.5-]2
8.8
9.5
Source: Complied by Varian Associates. Absolute values. Reproduced with permission.
APPENDIX F 199
Jab (Hz)
44-81
3-25
0-4
1-8
12-40
() 6-10
mS-6
p2
a
-
4.3
1-
48
Jab
T
yp
ical
200 CHAPTER 3 PROTON NMR SPECTROMETRY
CHEMICAL SHIFTS AND MULTIPLICITIES OF RESIDUAL
PROTON' S IN COMMERCIALL AI'LABLE DEUTERATED
APPENDIX G SOLVENTS (MERCK & CO., INC.)
Compounda Molecular Weight
Acetic acid-d4
64.078
Acetone-do
64.117
Acetonitrile-d]
44.071
Benzene-do
84.152
Chloroform-d
120.384
Cyclohexane-d
12
96.236
Deuterium oxide
20.028
1,2-Dichloroethane-d4
102.985
Diethyl-dl ether
84.185
Diglyme-d14
148.263
N, N-Direthylforraride-d7
80.138
Dimethyl-do sulphoxide
84.170
p-Dioxane-dH
96.156
Ethyl alcohol-do (anh)
52.106
Glyme-dl
100.184
Hexafuroacetone deuterate
198.067
HMPT-d
18
197.314
Methyl alcohol-d4
36.067
Methylene chloride-d2
86.945
Nitrobenzene-d,
128.143
0. (multiplet)
11.53 (1)
2.03 (5)
2.04 (5)
1.93 (5)
7.15 (br)
7.26(1)
1.38 (br)
4.63 (ref DSSY
4.67 (ref. TSP),
3.72 (br)
3.34 (m)
1.07 (m)
3.49 (br)
3.40 (br)
3.22 (5)
8.01 (br)
2.91 (5)
2.74 (5)
2.49 (5)
3.53 (m)
5.19 (1)
3.55 (br)
1.11 (m)
3.40(m)
3.22 (5)
5.26 (1)
2.53 (2 x 5)
4.78(1)
3.30 (5)
5.32 (3)
8.11 (br)
7.67 (br)
7.50 (br)
" Purity (Atom % D) up to 99.96 % (100 % ) for several solvents.
Compounda Molecular Weight
Ni tromethane-d]
64.059
Isopropyl alcohol-dB
68.146
Pyridine-ds
84.133
Tetrahydrofuran-dg
80.157
Toluene-ds
100.191
Trifuoroacetic acid-d
115.030
2,2,2-Trifuoroethyl alcohol-d]
103.059
(multiplet)
4.33 (5)
5.12 (1)
3.89 (br)
1.10 (br)
8.71 (br)
7.55 (br)
7.19 (br)
3.58 (br)
1.73 (br)
7.09 (m)
7.00 (br)
6.98 (m)
2.09 (5)
11.50 (1)
5.02 (1)
3.88 (4 X 3)
{'Te residual proton consists of one proton of each kind in an otherwise completely deuterated molecule. For example, deuterated acetic acid has two
different kinds of residual protons: CD2H-COOD and CD]-COOH. Te CD2H proton, coupled to two D nuclei is at D 2.03 with a multiplicity of 5
(i.e .. 2nl + 1 2 X 2 X 1 + 1 5). Te carboxylic proton is a singlet at D 11.53.
DSS is 3-trimethylsilyl)-I-propane sulfonic acid, sodi um salt. TSP is sodium-3-tr imethylpropionate-2,2,3,3-d4. Both are reference standards used
in aqueous solutions.