Diphenylacetylene → 1,1-Dimethyl 2,3-diphenyl-2-cyclopropene-1,1-dicarboxylate

HRID 487022

Reaction equation

[C:1]1([C:7]#[C:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[N+](=[C:17]([C:22]([O:24][CH3:25])=[O:23])[C:18]([O:20][CH3:21])=[O:19])=[N-]>CC(CC(C)=O)=O.CC(CC(C)=O)=O.[Cu]>[C:1]1([C:7]2[C:17]([C:22]([O:24][CH3:25])=[O:23])([C:18]([O:20][CH3:21])=[O:19])[C:8]=2[C:9]2[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

Conditions

Temperature: 120 °C

Procedure

A 100 millilater round-bottom flask was equipped with a magnetic stirrer and reflux condenser with N2 inlet. The flask was charged with 25.0 grams (0.140 mole) of diphenylacetylene and 140 milligrams of cupric acetylacetonate. The mixture was heated to 120° C. using an oil bath and 8.85 grams (0.056 mole) of dimethyl diazomalonate was added over 24 hours using a syringe pump. When all of the dimethyl diazomalonate had been added, heating at 120° C. was continued for 8 hours. The diphenylacetylene was distilled off under vacuum, boiling point 170° C./19 Mm. The residue was purified by flash chromatography eluting with 75:25 hexane-ethyl acetate to give 4.65 grams (0.015 mole) of the desired product as a white solid. NMR analysis of the product indicated the following:

Workup

customA 100 millilater round-bottom flask was equipped with a magnetic stirrer
temperaturereflux condenser with N2 inlet
temperatureheating at 120° C.
distillationThe diphenylacetylene was distilled off under vacuum, boiling point 170° C./19 Mm
customThe residue was purified by flash chromatography
washeluting with 75:25 hexane-ethyl acetate

Sources & evidence

ORD record: ord-66d65d320ac04264a52aa06affbf25cc
Source dataset: uspto-grants-1994_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05292937

Linked notes

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