Methyl 4-Formylbenzoate → 4-(2-Benzyloxycarbonyl-2-bromo-vinyl)-benzoic acid methyl ester

HRID 1755172노트

반응식

HRID 1755172 반응식
[CH2:1]([O:8][C:9](=[O:18])[CH:10]([Br:17])P(OC)(OC)=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Li+].C[Si]([N-][Si](C)(C)C)(C)C.[CH3:29][O:30][C:31](=[O:40])[C:32]1[CH:37]=[CH:36][C:35]([CH:38]=O)=[CH:34][CH:33]=1>C1COCC1>[CH3:29][O:30][C:31](=[O:40])[C:32]1[CH:37]=[CH:36][C:35]([CH:38]=[C:10]([C:9]([O:8][CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)=[O:18])[Br:17])=[CH:34][CH:33]=1

참가 물질

5

반응물 3

HCID 15294Methyl 4-FormylbenzoateHCID 2733832Lithium HexamethyldisilazideHCID 86669789Bromo-(dimethoxy-phosphoryl)-acetic acid benzyl ester

생성물 1

HCID 866697884-(2-Benzyloxycarbonyl-2-bromo-vinyl)-benzoic acid methyl ester수율 95.4%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매3회

반응 조건

온도
0 °C

실험 절차

To a cooled (−78° C.) solution of bromo-(dimethoxy-phosphoryl)-acetic acid benzyl ester (500 mg, 1.5 mmol) in THF (10 mL) was added LHMDS (1.2 mL of a 1M solution in THF, 1.2 mmol). The reaction was warmed to 0° C. and stirred for 30 minutes, then recooled to −78° C. 4-Formyl-benzoic acid methyl ester (163 mg, 1.0 mmol) in THF (2 mL) was added dropwise, and the reaction was allowed to warm to room temperature and stirred for 18 hours. The reaction was evaporated to dryness by rotary evaporator and purified by column chromatography on silica gel eluting with 50% ethyl acetate in hexanes to yield 4-(2-Benzyloxycarbonyl-2-bromo-vinyl)-benzoic acid methyl ester (358 mg, 64%) as a mixture of E and Z isomers. 1H NMR (300 MHz, CDCl3): δ 8.33 (s, 1H), 8.05 (d, J=7.5 Hz, 1H), 7.88 (m, 2H), 7.4-7.2 (m, 7H), 5.33 (s, 1H), 5.16 (s, 2H), 3.93-3.91 (s, 3H). LC-MS m/z=376 [C18H15BrO4+H]+.

후처리

  1. customrecooled to −78° C
  2. temperatureto warm to room temperature
  3. stirringstirred for 18 hours
  4. customThe reaction was evaporated to dryness by rotary evaporator
  5. custompurified by column chromatography on silica gel eluting with 50% ethyl acetate in hexanes

출처 및 근거

ORD 기록
ord-99f41fe1d255429a869264c4c4b6c0f4
출처 데이터셋
uspto-grants-2015_10
특허 번호
US09169201B2

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