4-Toluenesulfonyl chloride → HCID 24785948、化合物

HRID 2422934ノート

反応式

HRID 2422934 の反応式
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]([CH2:18][C:19](=[O:27])[NH:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[CH2:9][NH:10]C(=O)OC(C)(C)C)=[CH:4][CH:3]=1.C([O-])([O-])=O.[K+].[K+].[S:34](Cl)([C:37]1[CH:43]=[CH:42][C:40]([CH3:41])=[CH:39][CH:38]=1)(=[O:36])=[O:35]>C(Cl)Cl.O1CCOCC1.O>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH:8]([CH2:9][NH:10][S:34]([C:37]2[CH:43]=[CH:42][C:40]([CH3:41])=[CH:39][CH:38]=2)(=[O:36])=[O:35])[CH2:18][C:19]([NH:20][C:21]2[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=2)=[O:27])=[CH:6][CH:7]=1

参加物

6

反応物 3

HCID 73974-Toluenesulfonyl chlorideHCID 11430Potassium CarbonateHCID 86628706HCID 86628706、化合物

生成物 1

HCID 24785948HCID 24785948、化合物

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 218864351,4-Dioxane--water (1/1)溶媒

実験手順

To a solution of 34 (0.106 g, 0.271 mmol) in DCM (2 ml) TFA (2 ml) was added. After stirring for 2 h at room temperature, the solvent was distilled under reduced pressure to give a brown solid. The crude residue was dissolved as obtained in 1,4-dioxane:H2O 1:1 (5 ml) and K2CO3 (0.225 g, 1.63 mmol, 6 eq) was added followed by tosyl chloride (0.056 g, 0.298 mmol, 1.1 eq) at room temperature. After stirring for 2 h at room temperature, the resulting mixture was evaporated in vacuo to dryness. Water (10 ml) was added and the resulting white solid was separated by filtration and dried. Pure 36 was obtained without further purification (0.079 g, 0.179 mmol, 66%), mp 200-202° C. 1H NMR (400 MHz, CD3OD) δ 2.39 (3H, s, Ar—CH3), 2.56 (1H, dd, J 9.2, 14.4 Hz, H—CHCO), 2.77 (1H, dd, J 6.8, 14.4 Hz, H—CHCO), 3.06 (1H, dd, J 8.2, 13.0 Hz, H—CHNH), 3.15 (1H, dd, J 6.8, 13.2 Hz, H—CHNH) 7.03-7.07 (1H, m, CH, Ar), 7.15 (2H, d, J 8.4 Hz, 2×CH, Ar), 7.21-7.26 (4H, s, 4×CH, Ar), 7.29 (2H, d, J 8.0 Hz, 2×CH, Ar), 7.36-7.38 (2H, m, 2×CH, Ar), 7.62 (2H, d, J 8.8 Hz, 2×CH, Ar). 13C NMR (400 MHz, DMSO-d6) δ21.63 (s) (Ar—CH3), 40.73 (s) (CH2CO), 41.87 (s) (CH2CHCH2), 48.13 (s) (CH2NH), 119.79 (s) (2×CH, Ar), 123.80 (s) (CH, Ar), 127.14 (s) (2×CH, Ar), 128.80 (s) (2×CH, Ar), 129.29 (s) (2×CH, Ar), 130.23 (s) (2×CH, Ar), 130.36 (s) (2×CH, Ar), 131.80 (s) (C, Ar), 138.14 (s) (C, Ar), 139.64 (s) (C, Ar), 141.53 (s) (C, Ar), 143.20 (s) (C, Ar), 169.81 (s) (C═O). νmax (pure sample)/(cm−1) 3340 (md) (N—H), 3141 (md) (N—H), 1665 (st) (C═O), 1598 (st), 1547 (st), 1493 (md), 1444 (st), 1154 (st), 1087 (md). MS (API-ES): m/z 443 [M+H]+ (100%), HRMS (API-ES) m/z found 443.1201 [M+H]+.

後処理

  1. distillationthe solvent was distilled under reduced pressure
  2. customto give a brown solid
  3. stirringAfter stirring for 2 h at room temperature
  4. customthe resulting mixture was evaporated in vacuo to dryness
  5. additionWater (10 ml) was added
  6. customthe resulting white solid was separated by filtration
  7. customdried
  8. customPure 36 was obtained without further purification (0.079 g, 0.179 mmol, 66%), mp 200-202° C

出典と根拠

ORDレコード
ord-a8af23e32a5d4b2688af08408205c191
出典データセット
uspto-grants-2011_06
特許番号
US07960434B2

反応ノート

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