Triethylamine → HCID 376100、化合物

HRID 1899059ノート

反応式

HRID 1899059 の反応式
O[CH2:2][CH2:3][N:4]([C:8]1[C:9]([N+:21]([O-:23])=[O:22])=[CH:10][C:11]([N+:18]([O-:20])=[O:19])=[C:12]([S:14]([NH2:17])(=[O:16])=[O:15])[CH:13]=1)[CH2:5][CH2:6]O.CCN(CC)CC.CS([Cl:35])(=O)=O.[Li+].[Cl-:37]>C1COCC1.CCOC(C)=O.CN(C=O)C>[Cl:37][CH2:2][CH2:3][N:4]([C:8]1[C:9]([N+:21]([O-:23])=[O:22])=[CH:10][C:11]([N+:18]([O-:20])=[O:19])=[C:12]([S:14]([NH2:17])(=[O:16])=[O:15])[CH:13]=1)[CH2:5][CH2:6][Cl:35]

参加物

8

反応物 4

HCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 433294Lithium ChlorideHCID 10360491HCID 10360491、化合物

生成物 1

HCID 376100HCID 376100、化合物収率 69.9%

試薬・触媒・溶媒 3

HCID 6228Dimethylformamide溶媒HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
130 °C

実験手順

A stirred solution of the above diol (IX) (1.90 g, 5.43 mmol) and Et3N (1.90 mL, 14 mmol) in dry THF (60 mL) was treated dropwise at 0° C. with methanesulfonyl chloride (0.89 mL, 11 mmol). After a further 15 min, the solution was diluted with EtOAc, washed well with water, and worked up to give the crude dimesylate (Id: X=OSO2Me, R=SO2NH2). This was immediately dissolved in DMF (50 mL) containing LiCl (20 g), and the mixture stirred at 130° C. for 15 min before solvent was removed under reduced pressure. The residue was partitioned between EtOAc and water, and the organic layer was worked up and chromatographed on silica gel. Elution with EtOAc gave 5-[N,N-bis(2-chloroethyl)amino]-2,4-dinitrobenzenesulfonamide (18) (Id: X=Cl, R=SO2NH2) (1.47 g, 64%), mp 153°-154° C. (EtOAc/petroleum ether). 1H NMR ((CD3)2CO) δ 8.54. (S, 1H, H-3), 7.99 (br, 2H, SO2NH2), 7.91 (S, 1H, H-6), 3.84 (t, J=5.6 Hz, 4H, CH2Cl), 3.67 (t, J=5.6 Hz, 4H, CH2N). 13C NMR ((CD3)2CO) δ 146.13 (C-5), 140.64 (C-1), 138.86, 136.93 (C-2,4), 124.95, 121.77 (C-3,6), 52.47 (CH2N), 41.62 (CH2Cl). Anal. (C10H12Cl2N4O6S) C,H,N,S.

後処理

  1. washwashed well with water
  2. customto give the crude dimesylate (Id: X=OSO2Me, R=SO2NH2)
  3. customwas removed under reduced pressure
  4. customThe residue was partitioned between EtOAc and water
  5. customchromatographed on silica gel
  6. washElution with EtOAc

出典と根拠

ORDレコード
ord-58e099cbe67b4c2babec4188316728f8
出典データセット
uspto-grants-1996_11
特許番号
US05571845

反応ノート

読み込み中…