1、show their degree of variability. Occasionally, in order to distinguish between peaks whose assignment was ambiguous,afurther1-2 Lofaspecificsubstratewere added and the spectra run again. Table 1. 1 H NMR Data proton mult CDCl3 (CD3)2CO (CD3)2SO C6D6 CD3CN CD3OD D2O solventresidualpeak 7.26 2.05 2.5
2、0 7.16 1.94 3.31 4.79 H2O s 1.56 2.84 a 3.33 a 0.40 2.13 4.87 aceticacid CH3 s 2.10 1.96 1.91 1.55 1.96 1.99 2.08 acetone CH3 s 2.17 2.09 2.09 1.55 2.08 2.15 2.22 acetonitrile CH3 s 2.10 2.05 2.07 1.55 1.96 2.03 2.06 benzene CH s 7.36 7.36 7.37 7.15 7.37 7.33 tert-butylalcohol CH 3 s 1.28 1.18 1.11
3、1.05 1.16 1.40 1.24 OH c s 4.19 1.55 2.18 tert-butylmethylether CCH3 s 1.19 1.13 1.11 1.07 1.14 1.15 1.21 OCH3 s 3.22 3.13 3.08 3.04 3.13 3.20 3.22 BHT b ArH s 6.98 6.96 6.87 7.05 6.97 6.92 OH c s 5.01 6.65 4.79 5.20 ArCH3 s 2.27 2.22 2.18 2.24 2.22 2.21 ArC(CH3)3 s 1.43 1.41 1.36 1.38 1.39 1.40 chl
4、oroform CH s 7.26 8.02 8.32 6.15 7.58 7.90 cyclohexane CH 2 s 1.43 1.43 1.40 1.40 1.44 1.45 1,2-dichloroethane CH2 s 3.73 3.87 3.90 2.90 3.81 3.78 dichloromethane CH2 s 5.30 5.63 5.76 4.27 5.44 5.49 diethylether CH3 t,7 1.21 1.11 1.09 1.11 1.12 1.18 1.17 CH2 q,7 3.48 3.41 3.38 3.26 3.42 3.49 3.56 di
5、glyme CH2 m 3.65 3.56 3.51 3.46 3.53 3.61 3.67 CH2 m 3.57 3.47 3.38 3.34 3.45 3.58 3.61 OCH3 s 3.39 3.28 3.24 3.11 3.29 3.35 3.37 1,2-dimethoxyethane CH3 s 3.40 3.28 3.24 3.12 3.28 3.35 3.37 CH2 s 3.55 3.46 3.43 3.33 3.45 3.52 3.60 dimethylacetamide CH3CO s 2.09 1.97 1.96 1.60 1.97 2.07 2.08 NCH3 s
6、3.02 3.00 2.94 2.57 2.96 3.31 3.06 NCH3 s 2.94 2.83 2.78 2.05 2.83 2.92 2.90 dimethylformamide CH s 8.02 7.96 7.95 7.63 7.92 7.97 7.92 CH3 s 2.96 2.94 2.89 2.36 2.89 2.99 3.01 CH3 s 2.88 2.78 2.73 1.86 2.77 2.86 2.85 dimethylsulfoxide CH3 s 2.62 2.52 2.54 1.68 2.50 2.65 2.71 dioxane CH2 s 3.71 3.59
7、3.57 3.35 3.60 3.66 3.75 ethanol CH3 t,7 1.25 1.12 1.06 0.96 1.12 1.19 1.17 CH2 q,7 d 3.72 3.57 3.44 3.34 3.54 3.60 3.65 OH s c,d 1.32 3.39 4.63 2.47 ethylacetate CH3CO s 2.05 1.97 1.99 1.65 1.97 2.01 2.07 CH2CH3 q,7 4.12 4.05 4.03 3.89 4.06 4.09 4.14 CH2CH3 t,7 1.26 1.20 1.17 0.92 1.20 1.24 1.24 et
8、hylmethylketone CH3CO s 2.14 2.07 2.07 1.58 2.06 2.12 2.19 CH2CH3 q,7 2.46 2.45 2.43 1.81 2.43 2.50 3.18 CH2CH3 t,7 1.06 0.96 0.91 0.85 0.96 1.01 1.26 ethyleneglycol CH s e 3.76 3.28 3.34 3.41 3.51 3.59 3.65 “grease” f CH3 m 0.86 0.87 0.92 0.86 0.88 CH2 brs 1.26 1.29 1.36 1.27 1.29 n-hexane CH3 t 0.
9、88 0.88 0.86 0.89 0.89 0.90 CH2 m 1.26 1.28 1.25 1.24 1.28 1.29 HMPA g CH3 d,9.5 2.65 2.59 2.53 2.40 2.57 2.64 2.61 methanol CH3 s h 3.49 3.31 3.16 3.07 3.28 3.34 3.34 OH s c,h 1.09 3.12 4.01 2.16 nitromethane CH3 s 4.33 4.43 4.42 2.94 4.31 4.34 4.40 n-pentane CH3 t,7 0.88 0.88 0.86 0.87 0.89 0.90 C
10、H2 m 1.27 1.27 1.27 1.23 1.29 1.29 2-propanol CH3 d,6 1.22 1.10 1.04 0.95 1.09 1.50 1.17 CH sep,6 4.04 3.90 3.78 3.67 3.87 3.92 4.02 pyridine CH(2) m 8.62 8.58 8.58 8.53 8.57 8.53 8.52 CH(3) m 7.29 7.35 7.39 6.66 7.33 7.44 7.45 CH(4) m 7.68 7.76 7.79 6.98 7.73 7.85 7.87 siliconegrease i CH3 s 0.07 0
11、.13 0.29 0.08 0.10 tetrahydrofuran CH2 m 1.85 1.79 1.76 1.40 1.80 1.87 1.88 CH2O m 3.76 3.63 3.60 3.57 3.64 3.71 3.74 toluene CH3 s 2.36 2.32 2.30 2.11 2.33 2.32 CH(o/p) m 7.17 7.1-7.2 7.18 7.02 7.1-7.3 7.16 CH(m) m 7.25 7.1-7.2 7.25 7.13 7.1-7.3 7.16 triethylamine CH 3 t,7 1.03 0.96 0.93 0.96 0.96
12、1.05 0.99 CH2 q,7 2.53 2.45 2.43 2.40 2.45 2.58 2.57 a In these solventstheintermolecularrateofexchangeisslowenoughthatapeakduetoHDOisusuallyalsoobserved;itappearsat 2.81 and 3.30 ppm in acetone and DMSO, respectively. In the former solvent, it is often seen as a 1:1:1 triplet, with 2 JH,D ) 1 Hz. b
13、 2,6-Dimethyl-4-tert-butylphenol. c The signals from exchangeable protons were not always identified. d In some cases (see note a), the couplinginteractionbetweentheCH2andtheOHprotonsmaybeobserved(J )5Hz). e InCD3CN,theOHprotonwasseenasamultiplet at 2.69, and extra coupling was also apparent on the
14、methylene peak. f Long-chain, linear aliphatic hydrocarbons. Their solubility in DMSOwastoolowtogivevisiblepeaks. g Hexamethylphosphoramide. h Insomecases(seenotesa,d),thecouplinginteractionbetween the CH3 and the OH protons may be observed (J ) 5.5 Hz). i Poly(dimethylsiloxane). Its solubility in D
15、MSO was too low to give visible peaks. Notes J. Org. Chem., Vol. 62, No. 21, 1997 7513Table 2. 13 C NMR Data a CDCl3 (CD3)2CO (CD3)2SO C6D6 CD3CN CD3OD D2O solventsignals 77.16 (0.06 29.84 (0.01 39.52 (0.06 128.06 (0.02 1.32 (0.02 49.00(0.01 206.26 (0.13 118.26 (0.02 aceticacid CO 175.99 172.31 171.
16、93 175.82 173.21 175.11 177.21 CH3 20.81 20.51 20.95 20.37 20.73 20.56 21.03 acetone CO 207.07 205.87 206.31 204.43 207.43 209.67 215.94 CH 3 30.92 30.60 30.56 30.14 30.91 30.67 30.89 acetonitrile CN 116.43 117.60 117.91 116.02 118.26 118.06 119.68 CH 3 1.89 1.12 1.03 0.20 1.79 0.85 1.47 benzene CH
17、128.37 129.15 128.30 128.62 129.32 129.34 tert-butylalcohol C 69.15 68.13 66.88 68.19 68.74 69.40 70.36 CH 3 31.25 30.72 30.38 30.47 30.68 30.91 30.29 tert-butylmethylether OCH3 49.45 49.35 48.70 49.19 49.52 49.66 49.37 C 72.87 72.81 72.04 72.40 73.17 74.32 75.62 CCH 3 26.99 27.24 26.79 27.09 27.28
18、27.22 26.60 BHT C(1) 151.55 152.51 151.47 152.05 152.42 152.85 C(2) 135.87 138.19 139.12 136.08 138.13 139.09 CH(3) 125.55 129.05 127.97 128.52 129.61 129.49 C(4) 128.27 126.03 124.85 125.83 126.38 126.11 CH 3Ar 21.20 21.31 20.97 21.40 21.23 21.38 CH3C 30.33 31.61 31.25 31.34 31.50 31.15 C 34.25 35.
19、00 34.33 34.35 35.05 35.36 chloroform CH 77.36 79.19 79.16 77.79 79.17 79.44 cyclohexane CH 2 26.94 27.51 26.33 27.23 27.63 27.96 1,2-dichloroethane CH2 43.50 45.25 45.02 43.59 45.54 45.11 dichloromethane CH2 53.52 54.95 54.84 53.46 55.32 54.78 diethylether CH3 15.20 15.78 15.12 15.46 15.63 15.46 14
20、.77 CH2 65.91 66.12 62.05 65.94 66.32 66.88 66.42 diglyme CH3 59.01 58.77 57.98 58.66 58.90 59.06 58.67 CH2 70.51 71.03 69.54 70.87 70.99 71.33 70.05 CH2 71.90 72.63 71.25 72.35 72.63 72.92 71.63 1,2-dimethoxyethane CH3 59.08 58.45 58.01 58.68 58.89 59.06 58.67 CH2 71.84 72.47 17.07 72.21 72.47 72.7
21、2 71.49 dimethylacetamide CH3 21.53 21.51 21.29 21.16 21.76 21.32 21.09 CO 171.07 170.61 169.54 169.95 171.31 173.32 174.57 NCH3 35.28 34.89 37.38 34.67 35.17 35.50 35.03 NCH3 38.13 37.92 34.42 37.03 38.26 38.43 38.76 dimethylformamide CH 162.62 162.79 162.29 162.13 163.31 164.73 165.53 CH3 36.50 36
22、.15 35.73 35.25 36.57 36.89 37.54 CH3 31.45 31.03 30.73 30.72 31.32 31.61 32.03 dimethylsulfoxide CH3 40.76 41.23 40.45 40.03 41.31 40.45 39.39 dioxane CH2 67.14 67.60 66.36 67.16 67.72 68.11 67.19 ethanol CH3 18.41 18.89 18.51 18.72 18.80 18.40 17.47 CH2 58.28 57.72 56.07 57.86 57.96 58.26 58.05 et
23、hylacetate CH3CO 21.04 20.83 20.68 20.56 21.16 20.88 21.15 CO 171.36 170.96 170.31 170.44 171.68 172.89 175.26 CH 2 60.49 60.56 59.74 60.21 60.98 61.50 62.32 CH3 14.19 14.50 14.40 14.19 14.54 14.49 13.92 ethylmethylketone CH3CO 29.49 29.30 29.26 28.56 29.60 29.39 29.49 CO 209.56 208.30 208.72 206.55
24、 209.88 212.16 218.43 CH 2CH3 36.89 36.75 35.83 36.36 37.09 37.34 37.27 CH2CH3 7.86 8.03 7.61 7.91 8.14 8.09 7.87 ethyleneglycol CH2 63.79 64.26 62.76 64.34 64.22 64.30 63.17 “grease” CH2 29.76 30.73 29.20 30.21 30.86 31.29 n-hexane CH3 14.14 14.34 13.88 14.32 14.43 14.45 CH2(2) 22.70 23.28 22.05 23
25、.04 23.40 23.68 CH2(3) 31.64 32.30 30.95 31.96 32.36 32.73 HMPA b CH3 36.87 37.04 36.42 36.88 37.10 37.00 36.46 methanol CH3 50.41 49.77 48.59 49.97 49.90 49.86 49.50 c nitromethane CH3 62.50 63.21 63.28 61.16 63.66 63.08 63.22 n-pentane CH3 14.08 14.29 13.28 14.25 14.37 14.39 CH2(2) 22.38 22.98 21.
26、70 22.72 23.08 23.38 CH2(3) 34.16 34.83 33.48 34.45 34.89 35.30 2-propanol CH3 25.14 25.67 25.43 25.18 25.55 25.27 24.38 CH 64.50 63.85 64.92 64.23 64.30 64.71 64.88 pyridine CH(2) 149.90 150.67 149.58 150.27 150.76 150.07 149.18 CH(3) 123.75 124.57 123.84 123.58 127.76 125.53 125.12 CH(4) 135.96 13
27、6.56 136.05 135.28 136.89 138.35 138.27 siliconegrease CH 3 1.04 1.40 1.38 2.10 tetrahydrofuran CH2 25.62 26.15 25.14 25.72 26.27 26.48 25.67 CH2O 67.97 68.07 67.03 67.80 68.33 68.83 68.68 toluene CH3 21.46 21.46 20.99 21.10 21.50 21.50 C(i) 137.89 138.48 137.35 137.91 138.90 138.85 CH(o) 129.07 129
28、.76 128.88 129.33 129.94 129.91 CH(m) 128.26 129.03 128.18 128.56 129.23 129.20 CH(p) 125.33 126.12 125.29 125.68 126.28 126.29 triethylamine CH 3 11.61 12.49 11.74 12.35 12.38 11.09 9.07 CH2 46.25 47.07 45.74 46.77 47.10 46.96 47.19 a See footnotes for Table 1. b 2 JPC ) 3 Hz. c Reference material; see text. 7514 J. Org. Chem., Vol. 62, No. 21, 1997 Notes
