Ethyl diazoacetate → Ethyl 2-chloro-2-fluorocyclopropanecarboxylate

HRID 1358732Notes

Reaction equation

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]

Participants

Conditions

Temperature: 10 °C

Procedure

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.

Workup

additionwas charged under elevated pressure over five hours

Sources & evidence

ORD record: ord-4295cb6c851f49a89054239d146eecaf
Source dataset: uspto-grants-2003_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06596898B2

Reaction notes

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