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

HRID 2371785Notes

Reaction equation

HRID 2371785 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-difluoro-cyclopropanecarbonyl 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 in succession with dilute aqueous hydrochloric acid and water and concentrated under reduced pressure. 19.2 g of a dark oil remain, which is distilled using a bulb tube. At 0.1 mbar and a jacket temperature of 120° C., a yellow oil passes over which solidifies on standing. 8.4 g (33% of theory) of 2-(4-chlorophenyl)-ethin-1-yl 2,2-difluoro-1-methylcycloprop-1-yl ketone of melting point 67°-68° C. are obtained. ##STR65##

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 in succession with dilute aqueous hydrochloric acid and water
  6. concentrationconcentrated under reduced pressure
  7. distillationwhich is distilled
  8. customa jacket temperature of 120° C.

Sources & evidence

ORD record
ord-fab03f94dd1b4684a0fb8746bfff9d2c
Source dataset
uspto-grants-1992_03
Patent number
US05095147

Reaction notes

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