Stannous chloride dihydrate → 1-(3-Amino-4-Methylphenyl)Ethanone

HRID 1945358

反応式

HRID 1945358 の反応式
O.O.[Sn](Cl)Cl.[CH3:6][C:7]1[CH:12]=[CH:11][C:10]([C:13]([CH3:15])=[O:14])=[CH:9][C:8]=1[N+:16]([O-])=O>CO>[NH2:16][C:8]1[CH:9]=[C:10]([C:13](=[O:14])[CH3:15])[CH:11]=[CH:12][C:7]=1[CH3:6]

参加物

4

反応物 2

HCID 61436Stannous chloride dihydrateHCID 792463'-Nitro-4'-methylacetophenone

生成物 1

HCID 3429141-(3-Amino-4-Methylphenyl)Ethanone

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

反応条件

温度
60 °C

実験手順

Tin(II)dichloride dihydrate (37 g, 168 mmol) was added to 4-methyl-3-nitroacetophenone (10 g, 56 mmol) dissolved in methanol (350 mL). The reaction mixture was heated at 60° C. for 18 h, concentrated, and dried under high vacuum to give to 1-(3-amino-4-methylphenyl)ethanone which contained tin salts. LC (Cond.-J1): 0.73 min; LC/MS: Anal. Calcd. for [M+H]+ C9H11NO: 150.08; found: 150. The material was used without purification. HATU (10.6 g, 28 mmol) was added in one portion to a stirred solution of 1-(3-amino-4-methylphenyl)ethanone (4.1 g, 28 mmol), N-Boc-L-proline (6 g, 28 mmol), and Hunig's base (25 mL) in DMF (225 mL) and the reaction mixture was stirred 18 h. The solvent was removed in vacuo and the residue was taken up in ethyl acetate/methanol (1:1) and applied to a flash SiO2 column. A step elution by gradient 20%; 50%; 75%; 100% B (total elution vol 1500 mL); A=hexanes; B=ethyl acetate; and a final elution with; 10% methanol/ethyl acetate was conducted to give J.38, 4.4 g (46%). 1H NMR (300 MHz, DMSO-d6) δ: 9.51/9.45 (s, 1H), 7.95-7.92 (m, 1H), 7.70 (d, J=8.0 Hz, 1H), 7.37 (d, J=7.7 Hz, 1H), 4.33-4.29 (m, 1H), 3.48-3.29 (m, 2H), 2.50 (s, 3H), 2.26 (s, 3H), 1.98-1.80 (m, 4H), 1.41/1.36 (m, 9H). LC (Cond.-J1): 1.70 min; LRMS: Anal. Calcd. for [M+H]+ C19H27N2O4: 347.20; found 347.41.

後処理

  1. concentrationconcentrated
  2. customdried under high vacuum

出典と根拠

ORDレコード
ord-50c045c9a34b415dac082da606d508bd
出典データセット
uspto-grants-2013_03
特許番号
US08394968B2

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