, 24II. 3. 2. Reductive synthesis of symmetrical azo compounds using stoichiometric amount of electrogenerated SmI2, 4I. 1. The use of SmI2 in organic chemistry
, SmI2-electrocatalyzed reduction of nitroarenes into unsymmetrical azobenzenes, The Sm II electrocatalytic synthesis of azo compounds from nitrobenes ....-31II. 4. 1. Probe of Sm 2+ electrocatalytic reductive process
, 39II. 6. 2. General procedure for the synthesis of symmetrical azo compounds-39II. 6. 3. General procedure for the synthesis of asymmetrical azo compounds-49Chapter III. The Sm 2+ electrocatalytic reduction of nitroarenes into amino aromatics
, 6. 3. General condition for the electrocatalytic reduction of nitro compounds with activate hydrogens
, Electrocatalytic reduction of sulfoxide into sulfides mediated by SmI2
, The scope for reduction of sulfoxide into sulfides
, 101IV. 6. 2. General condition for the electrocatalytic reduction in MeOH ......-101IV. 6. 3. General condition for the electrocatalytic reduction in THF
, J. Am. Chem. Soc, vol.133, pp.12875-12879, 2011.
, Science, vol.342, pp.1073-1076, 2013.
, , vol.5, pp.1526-1529, 2015.
, Nat. Chem, vol.5, pp.537-543, 2013.
, Phthalic Acid and Derivatives; Ullmann's Encyclopedia of Industrial Chemistry, vol.143, pp.1519-1533, 1979.
, colorless oil (208 mg, 96%). (eluent: ethyl acetate/pentane: 1:3)
, IR (film) ?max: 2923, 1682, vol.746, pp.695-696, 1036.
, 300 MHz, CDCl3) ? 7.77 (d, J = 6.9 Hz, 1H)
, C NMR (90 MHz, CDCl3) ? 167.6 (C=O), 141.0 (C), 133.0 (C), 132.0 (CH), vol.129
, O-CH2), 26.6 (N-CH3), vol.123
, 3 (CH2), 3.1 (CH2), vol.3
,
, chloropropoxy)-2-methylisoindolin-1-one (17x)
, Following the general procedure, the product was obtained as a colorless oil (218 mg, 91%). (eluent: ethyl acetate/pentane: 1:3)
, IR (film) ?max: 3054, pp.745-746, 1032.
, 360 MHz, CDCl3) ? 7.80 (d, J = 7.2 Hz, 1H)
, C NMR (90 MHz, CDCl3) ? 167.7 (C=O), 140.6 (C), 133.0 (C), vol.132
,
, bromopropoxy)-2-methylisoindolin-1-one (17y)
, Following the general procedure, the product was obtained as a colorless oil (248 mg, 88%). (eluent: ethyl acetate/pentane: 1:2)
, IR (film) ?max: 3081, vol.3055, pp.697-698, 1031.
, 360 MHz, CDCl3) ? 7.82 (dd, J = 7.2, 1.0 Hz, 1H), 7.60-7.51 (m, 3H), vol.5
, C NMR (90 MHz, CDCl3) ? 167.6 (C=O), 140.5 (C), vol.132
, Br-CH2), O-CH2), vol.123
, Found: 306.0098 and 308.0078. (2S)-methyl 2-methyl-3-((2-methyl-3-oxoisoindolin-1-yl)oxy)propanoate (17z) Following the general procedure, the product was obtained as a colorless oil (251 mg, 95%)
, IR (film) ?max: 2976, vol.749, pp.697-698, 1032.
, 360 MHz, CDCl3) ? 7.80-7.73 (m, 1H), 7.58-7.44 (m, 3H), vol.5
, C NMR (90 MHz, CDCl3) ? 174.8 (C=O), 174.7 (C=O), 167.6 (C=O), vol.167
, 3 (2xCH), 123.0 (CH), vol.131, pp.132-140
, N-CH3), vol.26, p.158
, Found: 286.1051. N-substituted phthalimide (1.0 mmol), methanol (320 mg, 10 mmol, 0.4 ml) and SmCl3 (5.0 mg, 0.02 mmol) were added in anhydrous THF (10 ml), p.272
,
, IR (film) ?max: 2977, vol.750, pp.697-698, 1076.
, 360 MHz, CDCl3) ? 7.79 (dd, J = 4.5, 3.7 Hz, 1H), vol.7
, C NMR (90 MHz, CDCl3) ? 167.6 (C=O), 140.4 (C), 133.3 (C), vol.131
, O-CH3), vol.123
,
, 90%). (eluent: ethyl acetate/pentane: 1:5)
, IR (film) ?max: 3056, vol.749, pp.696-697, 0937.
, 81 (s, 1H), 3.73 (dt, 360 MHz, CDCl3) ? 7.82-7.68 (m, 1H), 7.58-7.38 (m, 3H), vol.5
, C NMR (90 MHz, CDCl3) ? 167.5 (C=O), 140.3 (C), 133.2 (C), 131.8 (CH), vol.129
, 3 (2xCH), vol.123
,
, colorless oil (245 mg, 97%). (eluent: ethyl acetate/pentane: 1:5)
, , p.160, 1102.
, 360 MHz, CDCl3) ? 7.89 (dd, J = 6.5, 1.1 Hz, 1H), 7.64-7.46 (m, 3H)
, C NMR (90 MHz, CDCl3) ? 167.5 (C=O), 140.4 (C), 136.8 (C), 133.0 (C), vol.132
,
, colorless oil (203 mg, 85%). (eluent: ethyl acetate/pentane: 1:5)
, , vol.3059, pp.732-733, 1152.
, 300 MHz, CDCl3) ? 7.95 (d, J = 7.4 Hz, 1H), 7.88-7.76 (m, 2H)
, 75 MHz, CDCl3) ? 166.7 (C=O), 139.7 (C), 137.3(C), vol.132, p.132
, 1 (2xCH), vol.130, pp.49-50
,
, colorless oil (298 mg, 94%). (eluent: ethyl acetate/pentane: 1:5)
, , p.161, 1058.
, 360 MHz, CDCl3) ? 7.94 (dd, J = 7.3, 1.2 Hz, 1H), 7.83-7.78 (m, 2H), 7.73-7.68 (m, 1H), 7.65-7.60 (m, 2H)
, MHz, CDCl3) ? 166.6 (C=O), 139.5 (C), 136.6 (C), 133.0 (CH), vol.132
, 132.1 (2xCH), 130.5 (CH), 124.0 (CH), 123.5 (CH), 122.7 (2xCH), vol.118
,
, colorless oil (249 mg, 88%). (eluent: ethyl acetate/pentane: 1:4)
, IR (film) ?max: 2929, 1051.
, 360 MHz, CDCl3) ? 7.89-7.77 (m, 1H), 7.65-7.47 (m, 3H), 5.90 (s, 1H)
, MHz, CDCl3) ? 167.9 (C=O), 140.4 (C), 132.8 (C), vol.132
, O-CH3), 38.5 (N-CH2), vol.86
,
, Following the general procedure, the product was obtained as a colorless oil (191 mg, 88%). (eluent: ethyl acetate/pentane: 1:2)
, IR (film) ?max: 3078, vol.747, p.162, 0918.
, 360 MHz, CDCl3) ? 7, vol.87
, Hz, 3H), 5.95 (s, 1H), 5.94-5.81 (m, 1H), vol.5
, C NMR (90 MHz, CDCl3) ? 167.7 (C=O), 140.3 (C), 135.2 (=CH), 133.1 (C)
, 1 (=CH2), OCH3), vol.129
,
, Following the general procedure, the product was obtained as a colorless oil (193 mg, 90%). (eluent: ethyl acetate/pentane: 1:3)
, IR (film) ?max: 3083, vol.802, pp.697-698, 0962.
, 360 MHz, CDCl3) ? 7.88-7.74 (m, 1H)
, C NMR (90 MHz, CDCl3) ? 167.7 (C=O), 140.4 (C), 132.8 (C), vol.132
, 123.5 (CH), 123.5 (CH), vol.86
,
, Following the general procedure, the product was obtained as a colorless oil (200 mg, 93%). (eluent: ethyl acetate/pentane: 1:5)
, IR (film) ?max: 3024, vol.945, pp.747-748, 1072.
, 400 MHz, CDCl3) ? 7.88-7.82 (m, 1H), 7.65-7.51 (m, 3H), vol.6
,
, MHz, CDCl3) ? 166.9 (C=O), 140.5 (C), 132.8 (C), vol.132
,
, Following the general procedure, the product was obtained as a colorless oil (177 mg, 88%). (eluent: ethyl acetate/pentane: 1:4)
, IR (film) ?max: 2929, vol.797, pp.752-753, 0934.
, 360 MHz, CDCl3) ? 7.84 (d, J = 7.2 Hz, 1H), vol.7
,
, C NMR (90 MHz, CDCl3) ? 166. 9 (C=O), 140.5 (C), 132.4 (CH), vol.130
,
, methoxy-3-oxoisoindolin-2-yl)propanenitrile (19k)
, Following the general procedure, the product was obtained as a colorless oil (197 mg, 91%). (eluent: ethyl acetate/pentane: 1:2)
, IR (film) ?max: 2934, vol.749, pp.697-698, 1076.
, 07 (s, 1H), 3.98 (ddd, 360 MHz, CDCl3) ? 7.92-7.82 (m, 1H), 7.71-7.52 (m, 3H), vol.6
, C NMR (90 MHz, CDCl3) ? 168.0 (C=O), 140.3 (C), 132.7 (CH), vol.132, pp.130-133
, O-CH3), vol.123
, Found: 239.0790. methyl 2-(1-methoxy-3-oxoisoindolin-2-yl)acetate (19l) Following the general procedure, the product was obtained as a yellow oil
, IR (film) ?max: 2954, vol.946, pp.750-751, 1078.
, 360 MHz, CDCl3) ? 7.85 (dd, J = 7.3, 1.0 Hz, 1H), vol.7
, 8 (C=O), 140.6 (C), C NMR (90 MHz, CDCl3) ? 169.3 (C=O), vol.167
,
, Following the general procedure, the product was obtained as a colorless oil (246 mg, 83%). (eluent: ethyl acetate/pentane: 1:1)
, IR (film) ?max: 2920, vol.946, pp.750-751, 1194.
, 250 MHz, CDCl3) ? 8.89 (s, 1H), 7.94-7.76 (m, 1H), vol.7
, C NMR (90 MHz, CDCl3) ? 168.7 (C=O), 166.5 (C), 141.0 (C), vol.137, pp.132-139
, O-CH3), vol.50
,
, 93%). (eluent: ethyl acetate/pentane: 1:5)
, IR (film) ?max: 2935, vol.881, pp.744-745, 0923.
, 360 MHz, CDCl3) ? 7.87-7.76 (m, 1H)
, C NMR (90 MHz, CDCl3) ? 167.7 (C=O), 140.8 (C), 133.1 (C), vol.131
, 3 (2xCH), SiO-CH2), vol.123, pp.41-48
, HRMS (ESI) [M+Na + ] calculated for C20H33NNaO3Si + : 386.2122. Found: 386.2124. 3-methoxy-2-(2-(methoxymethoxy)ethyl)isoindolin-1-one
, Following the general procedure, the product was obtained as a colorless oil (228 mg, 91%). (eluent: ethyl acetate/pentane: 1:1)
, IR (film) ?max: 2935, vol.917, pp.749-750, 1071.
, 360 MHz, CDCl3) ? 7.80 (dd, J = 7.3, 0.9 Hz, 1H), vol.7
, C NMR (90 MHz, CDCl3) ? 167.7 (C=O), 140.6 (C), vol.132
, 3 (OCH2O), vol.96
,
, 92%). (eluent: ethyl acetate/methanol: 5:1)
, IR (film) ?max: 3419, vol.748, pp.697-698, 1076.
, 360 MHz, CDCl3) ? 7.88-7.78 (m, 1H)
, C NMR (90 MHz, CDCl3) ? 169.0 (C=O), 140.4 (C), 132.6 (C), vol.132
,
, Condition 2: nBu4NPF6 (156 mg, 0.4 mmol, 0.04 mol/L in THF) as the electrolyte, 2(3-hydroxypropyl)isoindoline-1,3-dione (205 mg, 1.0 mmol), methanol (320 mg, p.10
, 4 ml) and SmCl3 (5.0 mg, 0.02 mmol) were added in anhydrous THF (10 ml), oil (183 mg, 97%
, Following the condition 2, the product was obtained as a colorless oil (176 mg, 93%). (eluent: ethyl acetate/pentane: 1:1)
, IR (film) ?max: 2957, 1057.
, 360 MHz, CDCl3) ? 7.84 (dd, J = 7.0, 1.1 Hz, 1H)
, C NMR (90 MHz, CDCl3) ? 165.9 (C=O), 141.2 (C), 132.8 (C), vol.131
,
, mg). (eluent: ethyl acetate/petane: 1:4)
, methoxy-2-methyl-5-phenylisoindolin-1-one (21a)
, 360 MHz, CDCl3) ? 7.87 (d, J = 8.2 Hz, 1H), 7.75-7.71 (m, 1H)
, methoxy-2-methyl-6-phenylisoindolin-1-one (21a')
, 360 MHz, CDCl3) ? 8.04 (d, J = 1.5 Hz, 1H), 7.80 (dd, J = 7.8, 1.6 Hz 1H)
, Found: 276.0997. Following the general procedure, the mixture of 5.6b and 5.6b' was obtained in 95% yield (269 mg)
, methoxyphenyl)-2-methylisoindolin-1-one (21b)
, IR (film) ?max: 3039, vol.825, p.779, 0960.
, 250 MHz, CDCl3) ? 7.85 (d, J = 8.3 Hz, 1H), 7.77-7.64 (m, 2H), 7.57 (d, J = 8.7 Hz, 2H)
, C NMR (90 MHz, CDCl3) ? 167.8 (C=O), vol.159, pp.141-142
, ArO-CH3), vol.128
, HRMS (ESI) [M+Na + ] calculated for C17H17NNaO3 + : 306.1101. Found: 306.1111. 3-methoxy-6-(4-methoxyphenyl)-2-methylisoindolin-1-one
, IR (film) ?max: 3039, vol.825, pp.700-701, 0959.
, 360 MHz, CDCl3) ? 8.02 (d, J = 1.5 Hz, 1H), 7.78 (dd, J = 7.8, 1.7 Hz, 1H)
, C NMR (90 MHz, CDCl3) ? 167.8 (C=O), 159.7 (C), vol.142, pp.133-142
, ArO-CH3), 49.2 (O-CH3), 26.5 (N-CH3), vol.55
, Found: 306.1111. Following the general procedure, the product was obtained as a white solid (161 mg, 99%), HRMS (ESI) [M+Na + ] calculated for C17H17NNaO3 + : 306.1101
, 360 MHz, CDCl3) ? 7.48
, C NMR (90 MHz, CDCl3) ? 167.7, 143.9
, HRMS (ESI) [M+Na + ] calculated for C9H9NNaO2 + : 186.0525. Found: 186.0531. solid (203 mg, 99%)
, 360 MHz, CDCl3) ? 7.58 (dt, J = 15.2, 7.4 Hz, 2H), 7.48 (d, J = 7.4 Hz, 1H), vol.7
,
, C NMR (90 MHz, CDCl3)
,
, 99%). (eluent: ethyl acetate/pentane: 1:2)
, 360 MHz, CDCl3) ? 7.49-7.37 (m, 3H), 7.35-7.25 (m, 1H), vol.5
, C NMR (90 MHz, CDCl3)
,
, mg, 91%). (eluent: ethyl acetate/pentane: 1:2)
, 360 MHz, CDCl3) ? 7.67-7.50 (m, 3H), 7.52-7.39 (m, 1H)
, C NMR (90 MHz, CDCl3)
,
, mg, 97%). (eluent: ethyl acetate/pentane: 1:1)
, 300 MHz, CDCl3) ? 7.78-7.54 (m, 5H), vol.7
, C NMR (90 MHz, CDCl3)
,
, mg, 97%). (eluent: ethyl acetate/pentane: 1:1)
, 360 MHz, MeOD) ? 7.83 (d, J = 7.5 Hz, 1H), 7.76-7.66 (m, 4H)
, C NMR (90 MHz, MeOD)
,
, Following the general procedure, the product was obtained as a white solid (181 mg, 89%). (eluent: ethyl acetate/pentane: 1:2)
, 360 MHz, CDCl3) ? 7.55 (dt, J = 14.5, 7.4 Hz, 2H), 7.47 (d, J = 7.2 Hz, 1H), 7.39 (t, J = 7.3 Hz, 1H), vol.5
,
, C NMR (90 MHz, CDCl3)
,
, Following the general procedure, the product was obtained as a white solid (187 mg, 93%). (eluent: ethyl acetate/pentane: 1:2)
, 360 MHz, CDCl3) ? 7.60-7.43 (m, 3H), 7.45-7.31 (m, 1H), vol.5
, C NMR (90 MHz, CDCl3)
,
, but-2-yn-1-yl)-3-hydroxyisoindolin-1-one (27i
, Following the general procedure, the product was obtained as a white solid (177 mg, 88%). (eluent: ethyl acetate/pentane: 2:1)
, 360 MHz, CDCl3) ? 7.67-7.51 (m, 3H), vol.7
, C NMR (90 MHz, CDCl3)
, Found: 224.0689. methyl 2-(1-hydroxy-3-oxoisoindolin-2-yl)acetate (27j) Following the general procedure, the product was obtained as a white solid
, 360 MHz, CDCl3) ? 7.58 (d, J = 7.6 Hz, 4H), 7.55-7.50 (m, 8H), vol.7, p.43
, C NMR (90 MHz, CDCl3)
,
, hydroxy-3-oxoisoindolin-2-yl)-N-phenylacetamide (27k)
, Following the general procedure, the product was obtained as a white solid (242 mg, 86%). (eluent: ethyl acetate/pentane: 3:1)
, 360 MHz, MeOD) ? 7.80 (d, J = 7.5 Hz, 1H), vol.7
, C NMR (91 MHz, MeOD) ? 170.0, 168.9
,
, mg, 88%). (eluent: ethyl acetate/pentane: 2:1)
, 360 MHz, CDCl3) ? 7.81 (dd, J = 7.0, 1.1 Hz, 1H)
,
, C NMR (90 MHz, CDCl3) ? 165.9
, HRMS (ESI) [M+Na + ] calculated for C11H12BrNNaO2 + : 291.9944 and 293.9924. Found: 291.9949 and 293.9921. 4,5, vol.6, pp.7-10
, 94%). (eluent: ethyl acetate/pentane: 2:1)
, 360 MHz, CDCl3) ? 7.92-7.78 (m, 6H), 7.58-7.40 (m, 18H)
, Hz, 14H), 0.97 (t, J = 7.3 Hz, 20H)
, C NMR (90 MHz, CDCl3)
,
, 95%). (eluent: ethyl acetate/pentane: 2:1)
, 300 MHz, CDCl3) ? 7.88-7.77 (m, 1H), vol.7, pp.56-63
, MHz, issue.75
,
, 87%). (eluent: ethyl acetate/pentane: 2:1)