2-(4-Chloro-2-iodophenyl)-4,4-dimethyl-4,5-dihydrooxazole → tert-Butyl 3-(5-chloro-2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)phenyl)-3-oxopropyl(methyl)carbamate

HRID 426065노트

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HRID 426065 반응식
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[O:9][CH2:10][C:11]([CH3:14])([CH3:13])[N:12]=2)=[C:4](I)[CH:3]=1.C([Li])CCC.CON(C)[C:24](=[O:36])[CH2:25][CH2:26][N:27]([CH3:35])[C:28](=[O:34])[O:29][C:30]([CH3:33])([CH3:32])[CH3:31]>C1COCC1>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[O:9][CH2:10][C:11]([CH3:14])([CH3:13])[N:12]=2)=[C:4]([C:24](=[O:36])[CH2:25][CH2:26][N:27]([CH3:35])[C:28](=[O:34])[O:29][C:30]([CH3:31])([CH3:32])[CH3:33])[CH:3]=1

참가 물질

5

반응물 3

HCID 122201312-(4-Chloro-2-iodophenyl)-4,4-dimethyl-4,5-dihydrooxazoleHCID 59364357Tert-butyl 3-(methoxy(methyl)amino)-3-oxopropyl(methyl)carbamateHCID 178418339Butyllithium

생성물 1

HCID 59364350tert-Butyl 3-(5-chloro-2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)phenyl)-3-oxopropyl(methyl)carbamate수율 38%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

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온도
0 °C

실험 절차

To a solution of 2-(4-chloro-2-iodophenyl)-4,4-dimethyl-4,5-dihydrooxazole (3.3 g, 9.7 mmol) in dry THF (30 mL) at −78° C. was added n-butyl lithium (2.5 M in hexane, 4.0 mL, 10.0 mmol) drop wise. After stirring for 30 min, a solution of tert-butyl 3-(methoxy(methyl)amino)-3-oxopropyl(methyl)carbamate (2.0 g, 8.1 mmol) in dry THF (5 mL) was added. The reaction mixture was warmed slowly to 0° C. then stored in refrigerator (4° C.) over night. The reaction was then warmed to room temperature and stirred 7 h. The reaction was quenched with 1N HCl, diluted with brine and ethyl acetate. After separation, the organic phases were dried over sodium sulfate, filtered and concentrated. The residue was purified by column chromatography on silica gel (120 g column, 0% ethyl acetate in hexanes to 50% ethyl acetate in hexanes) to give product (1.2 g, 38%). 1H NMR (CD3OD) δ 7.75 (d, J=7.6 Hz, 1H), 7.55-7.60 (m, 2H), 4.10-4.20 (m, 2H), 3.58 (t, J=6.8 Hz, 2H), 3.05-3.15 (m, 2H), 2.88 (s, 3H), 1.43 (s, 9H), 1.35 (s, 6H); MS EI m/z 395 (M+H)+.

후처리

  1. waitthen stored in refrigerator (4° C.) over night
  2. temperatureThe reaction was then warmed to room temperature
  3. stirringstirred 7 h
  4. customThe reaction was quenched with 1N HCl
  5. additiondiluted with brine and ethyl acetate
  6. customAfter separation
  7. dry with materialthe organic phases were dried over sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe residue was purified by column chromatography on silica gel (120 g column, 0% ethyl acetate in hexanes to 50% ethyl acetate in hexanes)

출처 및 근거

ORD 기록
ord-05e1eeac0cee4f008139101d36b181d6
출처 데이터셋
uspto-grants-2012_01
특허 번호
US08106221B2

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