核磁共振常用数据表

Solvent Acetic Acid-d4 Acetone-d6 Acetonitrile-d3 Benzene-d6 Chloroform-d Cyclohexane-d12 D2O Dichloromethane-d2 p-Dioxane-d8 DMF-d7 DMSO-d6 Methanol-d4 Pyridine-d5 THF-d8 Toluene-d8
I = 1/2 [2] *1H 3H *13C
15Na
*19F 29Sia *31P Free electrona I = 0 [0] 12C 16O 28Si 30Si 32S 34S I = 1 [3] 2H 14N I = 3/2 [4] 11B 23Na 33S 35Cl 37Cl 79Br 81Br I = 5/2 [6] 17Oa 127I I = 3 [7] 10B
-CH-N- ó -CH2-N HC C OCH3-N CH3-SCH3-Ph CH3-C-X CH3-COCH3-C=C-
Methylenes (-CH 2-)
Ph-CH2-CO-CH2R-CH2-R
O -CH2-C=CH2C M-CH3
Cyclopropyl Metals (M-CH 3) ppm Relative to TMS (0 ppm) 12 11 10 9 8 7 6 5 4 3 2 1
ns=not soluble From: J. Org. Chem. 1997, 62, 7512-7515
1
H NMR Chemical Shifts in Organic Compounds
ppm 12 Phenol -OH Alcohols-OH T hiols-SH Amines-N H 2 Amides RCONHR Car boxylic acids-OH Aldehydes Heteroar omatics HO2CHCO11 10 9 8 7 6 R OH HS R R NH2 RCONH2 5 4 3 2 1 0 -1
0
-1
13
C NMR Chemical Shifts in Organic Compounds
ppm 230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
sp2
sp sp3
4o
3o
2o
Impurity Acetic Acid Acetone Acetonitrile Benzene t-Butanol Chloroform Cyclohexane Dichloromethane Diethyl Ether DMF DMSO p-Dioxane Ethanol Ethyl Acetate Methanol Petroleum Ether i-Propanol n-Propanol Pyridine THF Toluene Triethylamine
Relative magnetic moment () 1.0 1.07 0.25 -0.10 0.94 -0.20 0.41 -657.4 – – – – – – 0.31 0.14 0.96 0.79 0.23 0.23 0.25 0.75 0.81 -0.68 1.00 0.64
Relative quadrupole moment (Q) – – – – – – – – – – – – – – 0.17 1.0 2.2 9.3 -4.0 5.0 -4.0 20.7 17.6 -1.6 37.5 4.6
1H (ppm) (mult.) 11.65 (1) 2.04 (5) 2.05 (5) 1.94 (5) 7.16 (1) 7.27 (1) 1.38 (1) 4.80 5.32 (3) 3.53 (m) 8.03 (1) 2.92 (5) 2.75 (5) 2.50 (5) 4.87 (1) 3.31 (5) 8.74 (1) 7.58 (1) 7.22 (1) 3.58 (1) 1.73 (1) 7.09 (m) 7.00 (1) 6.98 (m) 2.09 (5) 11.50 (1) 13C (ppm) (mult.) 179.0 (1) 20.0 (7) 206.7 (13) 29.9 (7) 118.7 (1) 1.4 (7) 128.4 (3) 77.2 (3) 26.4 (5) 54.0 (5) 66.7 (5) 163.2 (3) 34.9 (7) 29.8 (7) 39.5 (7) 49.2 (7) 150.4 (3) 135.9 (3) 123.9 (5) 67.6 (5) 25.4 (1) 137.9 (1) 129.2 (3) 128.3 (3) 125.5 (3) 20.4 (7) 164.2 (4) 116.6 (4) Liquid Range (°C) 17 – 118 -94 – 57 -45 – 82 5 – 80 -64 – 62 6 – 81 4 – 101 -95 – 40 12 – 101 -61 – 153 18 – 189 -98 – 65 -42 – 116 -109 – 66 -95 – 111 Dielectric Constant 6.1 20.7 37.5 2.3 4.8 2.0 78.5 8.9 2.2 36.7 46.7 32.7 12.4 7.6 2.4 HOD (ppm) in 1H NMR 11.6 2.0 2.1 0.4 1.5 – 4.8 1.5 2.4 3.5 3.3 5.0 5.0 2.5 0.4
Nucleus
Natural abundance (%) 99.98 – 1.1 0.4 100.0 4.7 100.0 – 98.9 99.9 92.3 3.1 94.8 4.4 0.02 99.6 80.4 100.0 0.8 75.5 24.5 50.5 49.5 0.04 100.0 19.7
[ ] Number of energy levels. a Negative magnetic moment. * Most useful. 1 Data from Bruker Almanac adjusted for natural abundance
Some useful NMR solvents
OH
H H N H H
HRC=CR2 H2C=CR2 -HC-O- ó -HC-X
Z
Z=O, N, S
N
Aromatics Alkenes
H Z
Z=O, N, S Z
Alcohols, Halogens Amines R-NH 2 Alkynes Methyl gr oups (R-Me)
R
-CH2-OóCH2-X
Resonance frequency at 2.35 T (100 MHz) 100.0 106.7 25.3 10.1 94.1 19.9 40.5 65,820.0 – – – – – – 15.4 7.2 32.1 26.5 7.7 9.8 8.2 25.1 27.0 13.5 20.0 10.7
Tables For Organic Structure Analysis
Magnetic properties of commonly studied species.
Approximate sensitivity at constant Bo for natural abundance1 1.0 0.0 1.8 x 10-4 3.8 x 10-6 0.83 3.6 x 10-3 0.07 – – – – – – – 1.5 x 10-6 1.0 x 10-3 0.13 0.09 1.7 x 10-5 3.6 x 10-3 6.7 x 10-4 0.04 0.05 1.1 x 10-5 0.09 3.7 x 10-3
1o
C=O Ketone C=O Aldehyde C=O Acid C=O Ester, Amide C=S Thioketone C=N- Azomethine C=N- Heteroaromatic C=C Alkene C=C Aromatic C=C Heteroaromatic Alkyne C C C N Nitrile C Quat. C-OC-NC-S C-X Halogen CH-C (C T ertiary) CH-OCH-NCH-SCH-X Halogen CH2-C (C Secondary) CH2-OCH2-NCH2-SCH2-X Halogen CH3-C (C Primary) CH3-OCH3-NCH3-SCH3-X Halogen ppm 230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40
TFA-d
-15 – 72
39.5
11.5
1
H NMR shifts of common impurities in various solvents ( ppm (mult))
Chloroform-d 2.13 (s) 2.17 (s) 1.98 (s) 7.37 (s) 1.28 (s) 7.27 (s) 1.43 (s) 5.30 (s) 3.48 (q) 1.20 (t) 8.01 (s) 2.95 (s) 2.88 (s) 2.62 (s) 3.70 (s) 3.72 (q) 1.24 (t) 4.12 (q) 2.04 (s) 1.25 (t) 3.48 (s) 1.28 (bs) 0.90 (t) 4.03 (m) 1.22 (d) 3.60 (t) 1.60 (m) 0.93 (t) 8.60 (m) 7.69 (m) 7.28 (m) 3.74 (m) 1.85 (m) 7.19 (m) 2.34 (s) 2.56 (q) 1.03 (t) DMSO-d6 1.95 (s) 2.12 (s) 2.09 (s) 7.40 (s) 1.14 (s) 8.35 (s) 1.42 (s) 5.79 (s) 3.42 (q) 1.13 (t) 7.98 (s) 2.92 (s) 2.76 (s) 2.52 (s) 3.61 (s) 3.49 (q) 1.09 (t) 4.08 (q) 2.02 (s) 1.21 (t) 3.20 (s) 1.28 (bs) 0.89 (t) 1.06 (d) 1.45 (m) 0.87 (t) 8.61 (m) 7.83 (m) 7.21 (m) 3.63 (m) 1.78 (m) 7.22 (m) 2.32 (s) 2.47 (q) 0.99 (t) Pyridine-d5 2.13 (s) 2.00 (s) 1.85 (s) 7.33 (s) 1.37 (s) 8.41 (s) 1.38 (s) 5.62 (s) 3.38 (q) 1.12 (t) 2.72 (s) 2.66 (s) 2.49 (s) 3.61 (s) 3.86 (q) 1.29 (t) 4.06 (q) 1.94 (s) 1.10 (t) 3.57 (s) 1.20 (bs) 0.86 (t) 4.16 (m) 1.29 (d) 3.75 (t) 1.70 (m) 0.97 (t) 8.71 (m) 7.58 (m) 7.21 (m) 3.67 (m) 1.64 (m) 7.22 (m) 2.22 (s) 2.43 (q) 0.96 (t) Benzene-d6 1.63 (s) 1.62 (s) 0.67 (s) 7.30 (s) 1.06 (s) 6.41 (s) 1.40 (s) 4.46 (s) 3.27 (q) 1.10 (t) 2.40 (s) 1.98 (s) 1.91 (s) 3.38 (s) 3.39 (q) 0. 97 (t) 3.91 (q) 1.68 (s) 0.94 (t) 3.09 (s) 1.22 (s) 0.89 (t) 3.76 (m) 1.01 (d) 3.76 (t) 1.40 (m) 0.80 (t) 8.50 (m) 7.05 (m) 6.70 (m) 3.01 (m) 0.87 (m) 7.10 (m) 2.13 (s) 2.40 (q) 0.95 (t) D2O 2.16 (s) 2.22 (s) 2.05 (s) 7.44 (s) 1.23 (s) ns ns ns 3.56 (q) 1.17 (t) 7.91 (s) 3.00 (s) 2.86 (s) 2.70 (s) 3.75 (s) 3.64 (q) 1.16 (t) 4.14 (q) 2.08 (s) 1.23 (t) 3.35 (s) ns 1.18 (d) 3.61 (t) 1.57 (m) 0.89 (t) 8.50 (m) 7.90 (m) 7.47 (m) 3.75 (m) 1.88 (m) ns 2.59 (q) 1.02 (t)