Hydrochloric Acid → HCID 12232925, compound

HRID 1439542Notes

Reaction equation

HRID 1439542 reaction equation
[S:1]1[CH:5]=[CH:4][CH:3]=[CH:2]1.[Cl:6][C:7]1[CH:15]=[C:14]([F:16])[CH:13]=[CH:12][C:8]=1[C:9](Cl)=[O:10].Cl>C1C=CC=CC=1>[S:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[C:9]([C:8]1[CH:12]=[CH:13][C:14]([F:16])=[CH:15][C:7]=1[Cl:6])=[O:10]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 8030ThiopheneHCID 27365462-Chloro-4-fluorobenzoyl chloride

Product 1

HCID 12232925HCID 12232925, compound

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

To a stirred mixture of 25.25 parts of thiophene, 58.1 parts of 2-chloro-4-fluorobenzoyl chloride and 200 parts of anhydrous benzene are added dropwise 78.16 parts of stannic chloride (fuming) at room temperature (slightly exothermic reaction: the temperature is kept for 3 hours at 25° C). The reaction mixture is poured onto a mixture of crushed ice and concentrated hydrochloric acid solution. The whole is stirred for a few minutes and the layers are separated. The organic layer is diluted with 80 parts of toluene, washed successively with 200 parts of sodium hydroxide solution 5% and with 200 parts of water, dried and evaporated. The residue is distilled, yielding 2-chloro-4-fluorophenyl 2-thienyl ketone; bp. 129°-130° C at 0.5 mm pressure. 7.2 parts of sodium hydride dispersion 55% are suspended three times in benzene and the latter is decanted each time. Then there are added successively 150 parts of hexamethylphosphoramide and dropwise 26.1 parts of diethyl 2-methylmalonate. The mixture is slightly heated and when the reaction is ceased, there are added 36.1 parts of 2-chloro-4-fluorophenyl 2-thienyl ketone. The whole is stirred for 6 hours at 100° C. The reaction mixture is cooled and 320 parts of benzene are added. The organic phase is washed twice with water, dried and evaporated. The residue is distilled, yielding diethyl 2-[3-chloro-4-(2-thenoyl)phenyl]-2-methylmalonate; bp. 225°-235° C at 0.6-0.8 mm pressure.

Workup

  1. customslightly exothermic reaction
  2. customthe layers are separated
  3. additionThe organic layer is diluted with 80 parts of toluene
  4. washwashed successively with 200 parts of sodium hydroxide solution 5% and with 200 parts of water
  5. customdried
  6. customevaporated
  7. distillationThe residue is distilled

Sources & evidence

ORD record
ord-326d2b84b75d4204ad9290d79770a4e4
Source dataset
uspto-grants-1977_11
Patent number
US04060528

Reaction notes

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