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

HRID 1755172ノート

反応式

HRID 1755172 の反応式
[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

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒3 回

反応条件

温度
0 °C

実験手順

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]+.

後処理

  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

出典と根拠

ORDレコード
ord-99f41fe1d255429a869264c4c4b6c0f4
出典データセット
uspto-grants-2015_10
特許番号
US09169201B2

反応ノート

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