Ammonium Chloride → Benzyl {2-[3,5-bis(trifluoromethyl)phenyl]-2-hydroxy-1,1-dimethylethyl}carbamate

HRID 607040노트

반응식

HRID 607040 반응식
C([Mg]Br)C.I[C:6]1[CH:11]=[C:10]([C:12]([F:15])([F:14])[F:13])[CH:9]=[C:8]([C:16]([F:19])([F:18])[F:17])[CH:7]=1.[CH3:20][C:21]([NH:25][C:26](=[O:35])[O:27][CH2:28][C:29]1[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1)([CH3:24])[CH:22]=[O:23].[NH4+].[Cl-]>C1COCC1.O>[F:17][C:16]([F:19])([F:18])[C:8]1[CH:7]=[C:6]([CH:22]([OH:23])[C:21]([NH:25][C:26](=[O:35])[O:27][CH2:28][C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)([CH3:24])[CH3:20])[CH:11]=[C:10]([C:12]([F:15])([F:14])[F:13])[CH:9]=1

참가 물질

7

반응물 4

HCID 25517Ammonium ChlorideHCID 6309701-Iodo-3,5-bis(trifluoromethyl)benzeneHCID 14578675(1,1-Dimethyl-2-oxoethyl)carbamic acid benzyl esterHCID 178418443HCID 178418443, 화합물

생성물 1

HCID 53363830Benzyl {2-[3,5-bis(trifluoromethyl)phenyl]-2-hydroxy-1,1-dimethylethyl}carbamate

시약·촉매·용매 2

HCID 962Water용매HCID 8028Tetrahydrofuran용매2회

실험 절차

Ethylmagnesium bromide (1.63 mL, 1M in THF, 1.63 mmol) was added dropwise to a stirred solution of 1-iodo-3,5-bis(trifluoromethyl)benzene (608 mg, 317 μL, 1.79 mmol) in dry THF (1 mL) at room temperature under N2 and the reaction was stirred for 30 min. The resulting solution was added to a stirred solution of benzyl (1,1-dimethyl-2-oxoethyl)carbamate (163.5 mg, 0.739 mmol) in dry THF (1 mL) at −20° C. and reaction was allowed to warn to room temperature over 3 h. Saturated NH4Cl (10 mL) and water (10 mL) were added and the mixture was extracted with EtOAc (3×20 mL). The combined extracts were dried (Na2SO4) and concentrated in vacuo to give the crude product. This was purified by flash chromatography (Si, 25×160 mm, 0-40% EtOAc in hexanes gradient) to afford benzyl {2-[3,5-bis(trifluoromethyl)phenyl]-2-hydroxy-1,1-dimethylethyl}carbamate. Rf=0.40 (20% EtOAc in hexanes). LCMS calc.=436.1; found=436.0 (M+1)+. 1H NMR (600 MHz, CDCl3) δ 7.80 (s, 1H), 7.77 (s, 2H), 7.39-7.33 (m, 5H), 5.12-5.08 (m, 2H), 1.36 (s, 1H), 4.90 (d, J=4.4 Hz, 1H), 4.81 (s, 1H), 1.36 (s, 3H), 1.23 (s, 3H).

후처리

  1. customreaction
  2. waitto warn to room temperature over 3 h
  3. extractionthe mixture was extracted with EtOAc (3×20 mL)
  4. dry with materialThe combined extracts were dried (Na2SO4)
  5. concentrationconcentrated in vacuo
  6. customto give the crude product
  7. customThis was purified by flash chromatography (Si, 25×160 mm, 0-40% EtOAc in hexanes gradient)

출처 및 근거

ORD 기록
ord-7ac17aab30434b40a3ad17defd6eb4c0
출처 데이터셋
uspto-grants-2011_03
특허 번호
US07915271B2

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