Sodium borohydride → HCID 18362118, compound

HRID 382852Notes

Reaction equation

HRID 382852 reaction equation
[CH2:1]=[C:2]([CH:6]([O:11][C:12](=[O:14])[CH3:13])[C:7]([Cl:10])([Cl:9])[Cl:8])[C:3]([O-:5])=[O:4].[CH2:15]=[C:16]([CH:20](O)[C:21](Cl)(Cl)Cl)C([O-])=O.[BH4-].[Na+].CC(=CC(Cl)(Cl)Cl)C(OCCCC)=O>O1CCCC1>[CH3:1][CH:2]([CH:6]([O:11][C:12](=[O:14])[CH3:13])[C:7]([Cl:9])([Cl:10])[Cl:8])[C:3]([O:5][CH2:15][CH2:16][CH2:20][CH3:21])=[O:4]

Participants

6

Reactant 4

HCID 4311764Sodium borohydrideHCID 18362105HCID 18362105, compoundHCID 18362119HCID 18362119, compoundHCID 545132692-Butenoic acid, 4,4,4-trichloro-2-methyl-, butyl ester

Product 1

HCID 18362118HCID 18362118, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
70 °C

Procedure

1236.1 g of crude 2-methylene-3-acetoxy-4,4,4-trichlorobutyrate (91.3%) containing about 2.5% 2-methylene-3-hydroxy-4,4,4-trichlorobutyrate and 747 ml of tetrahydrofuran was charged to a 2-liter flask equipped with a reflux condenser, magnetic stir bar, and a thermometer. 38.0 g of sodium borohydride was added in three portions to the stirred solution. The reaction temperature rose to 32° C. The reaction was heated slowly to 70° C. for three hours. NMR indicated 80% of the starting material was converted into product, butyl 2-methyl-4,4,4-trichlorobut-2-enoate. The reaction was heated for another six hours at 80° C. and the reaction was quenched by removal of tetrahydrofuran and addition of water. The organic layer was separated and GC analysis showed the presence of 79.2% butyl 2-methyl-4,4,4-trichlorobut-2-enoate, 1% butyl 2-methyl-2,4,4-trichlorobut-3-enoate, 6.6% unreacted starting material, butyl 2-methylene-3-acetoxy-4,4,4-trichlorobutyrate, 3% butyl 2-methyl-3-acetoxy-4,4,4-trichlorobutyrate, and 0.5% butyl 2-methylene-3-hydroxy-4,4,4-trichlorobutyrate. Hydrogenated product, butyl 2-methyl-3-acetoxy-4,4,4-trichlorobutyrate, was formed owing to the presence of water or traces of other protonic solvents in the reaction system.

Workup

  1. additionwas charged to a 2-liter flask
  2. customequipped with a reflux condenser, magnetic stir bar
  3. customrose to 32° C
  4. temperatureThe reaction was heated for another six hours at 80° C.
  5. customthe reaction was quenched by removal of tetrahydrofuran and addition of water
  6. customThe organic layer was separated

Sources & evidence

ORD record
ord-2f08c8ce51514785a7b6efd25eef7da4
Source dataset
uspto-grants-2001_10
Patent number
US06310237B1

Reaction notes

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