1,3-Dichloroacetone → 3-Chloro-2-oxopropyl triphenylphosphonium chloride

HRID 2306096Notes

Reaction equation

HRID 2306096 reaction equation
[Cl:1][CH2:2][C:3]([CH2:5]Cl)=[O:4].[CH:7]1[CH:12]=[CH:11][C:10]([P:13]([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[CH:9][CH:8]=1>C1COCC1.CCOCC>[Cl-:1].[Cl:1][CH2:2][C:3](=[O:4])[CH2:5][P+:13]([C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1)([C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[C:10]1[CH:9]=[CH:8][CH:7]=[CH:12][CH:11]=1

Participants

5

Reactant 2

HCID 107931,3-DichloroacetoneHCID 11776Triphenylphosphine

Product 1

HCID 27736283-Chloro-2-oxopropyl triphenylphosphonium chlorideYield 170.1%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

The procedure of Tome et al., Tetrahedron Letters, Volume 37, pp 6951-6954 (1996), was followed. 1,3-Dichloroacetone (8.0 g) and Ph3P (15.0 g) were stirred in THF (38 mL) at reflux for 4 h. The cooled suspension was diluted with ether, filtered and the solid was washed with ether and dried to give (3-chloro-2-oxopropyl)triphenylphosphonium chloride (20.86 g) as a white solid. This material was dissolved in a mixture of water (110 mL) and MeOH (110 mL) and treated with NaHCO3 (10.3 g). The resulting white precipitate was collected by filtration, washed with water and dried in vacuo to give 1-chloro-3-(triphenylphosphanylidene)-2-propanone (18.25 g). A solution of this phosphorane (18.2 g) and 3-chlorophenol (7.28 g) was stirred with K2CO3 (28.57 g) in DMSO (91 mL) at 62° C. for 18 then diluted with water (2 L), extracted with ether (3×1 L), dried (MgSO4), filtered and concentrated to give 1-(3-chlorophenoxy)-3-(triphenylphosphanylidene)-2-propanone (21.7 g) as a tan solid. 1H NMR (CDCl3): δ 4.02 (s, 2H), 4.23-4.35 (d, 1H), 7.42-7.72 (m, 15H).

Workup

  1. temperatureat reflux for 4 h
  2. filtrationfiltered
  3. washthe solid was washed with ether
  4. customdried

Sources & evidence

ORD record
ord-71959183cebf4f3789423b3a0496872f
Source dataset
uspto-grants-2002_08
Patent number
US06441196B2

Reaction notes

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