1,1,2,2-Tetrachloroethane → HCID 13695067, compound

HRID 596683Notes

Reaction equation

HRID 596683 reaction equation
[Cl-].[Al+3].[Cl-].[Cl-].[Cl:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=1[OH:12].[C:13]1(=[O:19])[O:18][C:16](=[O:17])[CH2:15][CH2:14]1.[CH:20](Cl)(Cl)C(Cl)Cl.[Cl:26][C:27]1[C:28]([OH:40])=[C:29]([CH:37]=[CH:38][CH:39]=1)[C:30]([CH2:32][CH2:33][C:34]([OH:36])=[O:35])=[O:31]>Cl>[Cl:26][C:27]1[C:28]([OH:40])=[C:29]([CH:37]=[CH:38][CH:39]=1)[C:30]([CH2:32][CH2:33][C:34]([O:36][CH3:6])=[O:35])=[O:31].[Cl:5][C:6]1[CH:11]=[C:10]([CH:9]=[CH:8][C:7]=1[OH:12])[C:16]([CH2:15][CH2:14][C:13]([O:18][CH3:20])=[O:19])=[O:17]

Participants

8

Reactant 5

HCID 65911,1,2,2-TetrachloroethaneHCID 72452-ChlorophenolHCID 7922Succinic anhydrideHCID 6451240Aluminum(III) ChlorideHCID 54446402HCID 54446402, compound

Product 2

HCID 13695067HCID 13695067, compoundHCID 20309575Methyl 3-chloro-2-hydroxy-γ-oxobenzenebutanoate

Reagents, catalysts & solvents 1

HCID 313Hydrochloric AcidSolvent

Procedure

Aluminium chloride powder (66.75g, 0.5 mole) was added during one hour to a stirred mixture of dry 2-chlorophenol (27.3g, 0.22 mole), powdered succinic anhydride (20g, 0.2 mole) and dry sym-tetrachlorethane (150 ml) while the temperature was allowed to rise from 20° C to 40° C. The resultant mixture was heated in an oil bath at 135° C for 2 hours, then cooled in ice and hydrolysed with cold 10% hydrochloric acid solution (100 ml). Tetrachloroethane was removed by steam distillation and the aqueous residue precipitated a gum which was purified by standard procedures to give 31.97g, 70%, of a mixture of 3-(3-chloro-2-hydroxybenzoyl) propionic acid and 3-(3-chloro-4-hydroxybenzoyl)propionic acids. Esterification of the mixed acids with methanol - hydrogen chloride and separation of the products by column chromatography (silica, 5/1 chloroform/petroleum ether B.p. 60°-80° C) gave methyl 3-(3-chloro-2-hydroxybenzoyl)propionate (m.p. 60°-62° C) and methyl 3-(3-chloro-4-hydroxybenzoyl)propionate (m.p. 85°-89° C). Hydrolysis of the latter ester with dilute sodium hydroxide solution gave 3-(3-chloro-4-hydroxybenzoyl)propionic acid (m.p. 155°-160° C). The pure acid, on recrystallisation from water, had m.p. 160°-162° C.

Workup

  1. customto rise from 20° C to 40° C
  2. customTetrachloroethane was removed by steam distillation
  3. customthe aqueous residue precipitated a gum which
  4. customwas purified by standard procedures
  5. customto give 31.97g, 70%
  6. customEsterification of the mixed acids with methanol - hydrogen chloride and separation of the products by column chromatography (silica, 5/1 chloroform/petroleum ether B.p. 60°-80° C)

Sources & evidence

ORD record
ord-43a9e73bd4244befa8601aef3a856687
Source dataset
uspto-grants-1977_03
Patent number
US04011321

Reaction notes

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