Triethylamine → 2-(4-Chlorophenyl)-ethin-1-yl 2,2-difluoro-1-methyl-cycloprop-1-yl ketone

HRID 2372037Notes

Reaction equation

HRID 2372037 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]#[CH:9])=[CH:4][CH:3]=1.C(N(CC)CC)C.[CH3:17][C:18]1([C:23](Cl)=[O:24])[CH2:20][C:19]1([F:22])[F:21]>[Cu]Br.C1(C)C=CC=CC=1>[F:21][C:19]1([F:22])[CH2:20][C:18]1([C:23]([C:9]#[C:8][C:5]1[CH:6]=[CH:7][C:2]([Cl:1])=[CH:3][CH:4]=1)=[O:24])[CH3:17]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 70118Benzene, 1-chloro-4-ethynyl-HCID 146952322,2-Difluoro-1-methylcyclopropane-1-carbonyl chloride

Product 1

HCID 146952462-(4-Chlorophenyl)-ethin-1-yl 2,2-difluoro-1-methyl-cycloprop-1-yl ketoneYield 33%

Reagents, catalysts & solvents 2

HCID 24593copper(I) bromideCatalystHCID 1140TolueneSolvent

Procedure

13.7 g (0.1 mol) of p-chlorophenyl-acetylene are added to a mixture of 10.1 g (0.1 mol) of triethylamine, 1.4 g (0.01 mol) of copper(I) bromide and 55 ml of toluene, and the mixture is stirred for 30 minutes at room temperature under argon. After the reaction mixture has been heated to 55° C., 15.5 g (0.1 mol) of 1-methyl-2,2-difluorocyclopropanecarbonyl chloride are added dropwise. After this, the mixture is stirred for 8 hours at 90° C., and then cooled and filtered. The filtrate is washed with dilute aqueous hydrochloric acid and water in succession and concentrated under reduced pressure. 19.2 g of a dark oil remain which is distilled using a bulb tube. A yellow oil, which solidifies on standing, distils over at 0.1 mbar and a jacket temperature of 120° C. 8.4 g (33% of theory) of 2-(4-chlorophenyl)-ethin-1-yl 2,2-difluoro-1-methyl-cycloprop-1-yl ketone of melting point 67°-68° C. are obtained. ##STR54##

Workup

  1. temperatureAfter the reaction mixture has been heated to 55° C.
  2. stirringAfter this, the mixture is stirred for 8 hours at 90° C.
  3. temperaturecooled
  4. filtrationfiltered
  5. washThe filtrate is washed with dilute aqueous hydrochloric acid and water in succession
  6. concentrationconcentrated under reduced pressure
  7. distillationis distilled
  8. customdistils over at 0.1 mbar
  9. customa jacket temperature of 120° C

Sources & evidence

ORD record
ord-5c373b9639264bc5aa5f24defd99b52f
Source dataset
uspto-grants-1992_03
Patent number
US05097050

Reaction notes

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