Ethyl diazoacetate → Ethyl 2-chloro-2-fluorocyclopropanecarboxylate

HRID 1358732ノート

反応式

HRID 1358732 の反応式
C(C1OC[C@H](C(C)(C)C)N=1)(C1OC[C@H](C(C)(C)C)N=1)(C)C.[Cl:22][C:23]([F:25])=[CH2:24].[N+](=[CH:28][C:29]([O:31][CH2:32][CH3:33])=[O:30])=[N-]>C1CCCCC1.FC(F)(F)S([O-])(=O)=O.[Cu+2].FC(F)(F)S([O-])(=O)=O>[Cl:22][C:23]1([F:25])[CH2:24][CH:28]1[C:29]([O:31][CH2:32][CH3:33])=[O:30]

参加物

6

反応物 3

HCID 12192Ethyl diazoacetateHCID 753441-Chloro-1-fluoroetheneHCID 688208t-Bu-box, (S,S)-

生成物 1

HCID 9793930Ethyl 2-chloro-2-fluorocyclopropanecarboxylate

試薬・触媒・溶媒 2

HCID 2734996copper(II) trifluoromethanesulfonate触媒HCID 8078Cyclohexane溶媒4 回

反応条件

温度
10 °C

実験手順

Cyclohexane (76.6 g), 2,2′-isopropylidenebis[(4S)-4-tert-butyl-2-oxazoline] (64.8 mg, 0.22 mmol), and copper (II) trifluoromethanesulfonate (72.1 mg, 0.20 mmol) were charged in an autoclave, and then 1-chloro-1-fluoroethylene (76.8 g, 0.95 mol) was charged under elevated pressure. After the mixed solution was cooled to 10° C., a mixed solution containing 95% of ethyl diazoacetate (12.0 g, 100 mmol) and cyclohexane (50 g) was charged under elevated pressure over five hours. Cyclohexane (20 ml) was further charged under elevated pressure and stirring was continued at the same temperature for 1 hour, and then the internal pressure was released to give a solution of ethyl 2-chloro-2-fluorocyclopropanecarboxylate in cyclohexane (179.3 g). This solution was analyzed by gas chromatography to find that the content of the ethyl 2-chloro-2-fluorocyclopropanecarboxylate was 6.52% (yield based on ethyl diazoacetate: 70.1%), and the ratio of cis-isomer/trans-isomer was 64.4/35.6.

後処理

  1. additionwas charged under elevated pressure over five hours

出典と根拠

ORDレコード
ord-4295cb6c851f49a89054239d146eecaf
出典データセット
uspto-grants-2003_07
特許番号
US06596898B2

反応ノート

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