Carbamate → tert-Butyl [2-(3-acetyl-5-chloro-6-cyano-2-ethoxyphenyl)-2-hydroxyethyl]carbamate

HRID 1499936노트

반응식

HRID 1499936 반응식
ClC1C=CC(C(O[NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=O)=CC=1.[C:19]([C:22]1[CH:29]=[C:28]([Cl:30])[C:25]([C:26]#[N:27])=[C:24]([CH:31]=[CH2:32])[C:23]=1[O:33][CH2:34][CH3:35])(=[O:21])[CH3:20].C(=O)([O-:38])N>O.C(#N)C.[Os](=O)(=O)(=O)=O>[C:19]([C:22]1[C:23]([O:33][CH2:34][CH3:35])=[C:24]([CH:31]([OH:38])[CH2:32][NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])[C:25]([C:26]#[N:27])=[C:28]([Cl:30])[CH:29]=1)(=[O:21])[CH3:20]

참가 물질

7

반응물 3

HCID 276CarbamateHCID 23655003tert-Butyl (4-Chlorobenzoyl)oxycarbamateHCID 866778524-Acetyl-6-chloro-3-ethoxy-2-vinylbenzonitrile

생성물 1

HCID 86677853tert-Butyl [2-(3-acetyl-5-chloro-6-cyano-2-ethoxyphenyl)-2-hydroxyethyl]carbamate

시약·촉매·용매 3

HCID 30318Osmium Tetroxide촉매HCID 962Water용매2회HCID 6342Acetonitrile용매2회

실험 절차

0.2 M Osmium tetraoxide in water (0.5 mL) was added to a solution of tert-butyl [(4-chlorobenzoyl)oxy]carbamate (Ref. Lawrence Harris, J. Org. Chem., 2011, 76, 358-372). (0.91 g, 3.3 mmol) in acetonitrile (10 mL) and stirred for 10 minutes. 4-Acetyl-6-chloro-3-ethoxy-2-vinylbenzonitrile (0.56 g, 2.2 mmol) as a solution in acetonitrile (10 mL) was added to the carbamate solution followed by the addition of water (2 mL) and the reaction was stirred for 3 hours at room temperature. The reaction was quenched with saturated 10 M dipotassium disulfite in water (12 mL) and stirred for 5 minutes. Water was added and the reaction mixture was extracted with ethyl acetate. The extracts were washed with saturated sodium bicarbonate solution, brine and dried over sodium sulfate, filtered and evaporated. Purification on silica gel using ethyl acetate in hexane (0-100%) gave the desired compound as a racemic mixture, 610 mg, 72%. LCMS calculated for C18H24ClN2O5 (M+H)+: m/z=383.1; found: 383.1. 1H NMR (400 MHz, DMSO-d6): δ 7.62 (s, 1 H), 7.03 (br s, 1 H), 5.68 (br s, 1 H), 3.96 (m, 1 H), 3.69 (m, 1 H), 3.31 (m, 1 H), 3.19 (m, 1 H), 2.60 (s, 3 H), 1.30 (m, 12 H).

후처리

  1. customThe reaction was quenched with saturated 10 M dipotassium disulfite in water (12 mL)
  2. stirringstirred for 5 minutes
  3. additionWater was added
  4. extractionthe reaction mixture was extracted with ethyl acetate
  5. washThe extracts were washed with saturated sodium bicarbonate solution, brine
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. customevaporated
  9. customPurification on silica gel

출처 및 근거

ORD 기록
ord-d88372ec5c6244d5a8f97628dafe9795
출처 데이터셋
uspto-grants-2015_12
특허 번호
US09199982B2

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