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

HRID 1945358

반응식

HRID 1945358 반응식
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]

참가 물질

4

반응물 2

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

생성물 1

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

시약·촉매·용매 1

HCID 887Methanol용매

반응 조건

온도
60 °C

실험 절차

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.

후처리

  1. concentrationconcentrated
  2. customdried under high vacuum

출처 및 근거

ORD 기록
ord-50c045c9a34b415dac082da606d508bd
출처 데이터셋
uspto-grants-2013_03
특허 번호
US08394968B2

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