Hydrochloric Acid → 1,1,3-Trichloropropene

HRID 485143

Reaction equation

HRID 485143 reaction equation
[Cl:1][C:2]([Cl:6])([Cl:5])[CH:3]=[CH2:4].[Cl:7][C:8]([Cl:12])=[CH:9][CH2:10][Cl:11].[Sb](F)(F)F.[ClH:17].S(=O)(=O)(O)O.[Cl-:23].[Al+3].[Cl-].[Cl-].[OH-].[K+].F>>[Cl:7][C:8]([Cl:12])=[CH:9][CH2:10][Cl:11].[Cl:1][C:2]([Cl:6])([Cl:5])[CH:3]([Cl:23])[CH2:4][Cl:17]

Participants

10

Reactant 8

HCID 313Hydrochloric AcidHCID 1118Sulfuric AcidHCID 14797Potassium HydroxideHCID 14917Hydrofluoric AcidHCID 166901-Propene, 3,3,3-trichloro-HCID 173781,1,3-TrichloropropeneHCID 24554Antimony trifluorideHCID 6451240Aluminum(III) Chloride

Product 2

HCID 173781,1,3-TrichloropropeneHCID 134544911,1,1,2,3-Pentachloropropane

Procedure

An earlier reference by Haszeldine, "Fluoro-olefins. Part II. Synthesis and Reaction of Some 3,3,3-Trihalogenopropenes" Journal of the Chemical Society [1953] pp. 3371-3378, describes a plethora of reactions of products derived from 1,1,1,3-tetrachloropropane. The reference describes preparation of this intermediate by reaction of carbon tetrachloride with ethylene in the presence of benzoyl peroxide. Among the numerous syntheses carried out by Haszeldine with 1,1,1,3-tetrachloropropane as the starting material are: dehydrochlorination of this starting material with 10% ethanolic potassium hydroxide to produce a mixture of 3,3,3- and 1,1,3-trichloropropene; isomerization of 3,3,3-trichloropropene to 1,1,3-trichloropropene using a variety of allylic rearrangement catalysts including antimony fluoride, concentrated hydrochloric acid, concentrated sulfuric acid, aluminum chloride, ferric chloride, ethanolic KOH and anhydrous hydrogen fluoride; chlorination of 1,1,3-trichloropropene in the presence of light to produce 1,1,1,2,3-pentachloropropane; chlorination of 3,3,3-trichloropropene to produce 1,1,1,2,3-pentachloropropane; dehydrochlorination of 1,1,1,2,3-pentachloropropane with ethanolic potassium hydroxide to produce a mixture of 2,3,3,3-tetrachloropropene and 1,1,2,3-tetrachloropropene; separation of 2,3,3,3-tetrachloropropene from 1,1,2,3-tetrachloropropene by distillation; and isomerization of 2,3,3,3-tetrachloropropene in the presence of aluminum chloride to produce 1,1,2,3-tetrachloropropene in 51% yield. Alternatively, Haszeldine discloses thermal isomerization of 2,3,3,3-tetrachloropropene to 1,1,2,3 tetrachloropropene at 180° C. in 45% yield. Based on the yields reported by Haszeldine for the above described series of steps, the overall yield obtained with his syntheses can be computed as 41.8% based on 1,1,1,3-tetrachloropropane, 10.4% based on carbon tetrachloride.

Sources & evidence

ORD record
ord-21438eff58cc4589855ad3b83173a572
Source dataset
uspto-grants-1985_08
Patent number
US04535194

Linked notes

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