Potassium Hydroxide → HCID 53638311, compound

HRID 2081816Notes

Reaction equation

HRID 2081816 reaction equation
[Cl:1][CH:2]([C:10]([CH3:31])=[CH:11][CH:12]([C:22]1[C:27]([CH3:29])([CH3:28])[CH2:26][CH2:25][CH2:24][C:23]=1[CH3:30])[S:13]([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)(=[O:15])=[O:14])[CH2:3][CH2:4][C:5]([CH3:9])=[CH:6][CH:7]=O.[OH-].[K+]>O.C(Cl)Cl>[C:16]1([S:13]([CH:12]([C:22]2[C:27]([CH3:29])([CH3:28])[CH2:26][CH2:25][CH2:24][C:23]=2[CH3:30])[CH:11]=[C:10]([CH3:31])[CH:2]([Cl:1])[CH2:3][CH2:4][C:5]([CH3:9])=[CH:6][CH:7]=[CH:7][CH:6]=[C:5]([CH3:9])[CH:4]=[CH:3][CH:2]=[C:10]([CH3:31])[CH:11]=[CH:12][C:22]2[C:27]([CH3:29])([CH3:28])[CH2:26][CH2:25][CH2:24][C:23]=2[CH3:30])(=[O:15])=[O:14])[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1

Participants

5

Reactant 2

HCID 14797Potassium HydroxideHCID 57158643HCID 57158643, compound

Product 1

HCID 53638311HCID 53638311, compoundYield 89.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

A 100-ml round-bottom flask was charged with a solution of 2.14 g (6.4 mmoles) of vitamin A acetate, 1.68 g (6.4 mmoles) of triphenylphosphine and 0.64 g (6.4 mmoles) of concentrated sulfuric acid in 10 g of methanol, and the contents were stirred at 25° C. for 3 hours. Thereafter, methanol was removed by distillation in vacuo from the reaction mixture to obtain a tar-like vitamin A phosphonium salt. This was dissolved in 10 g of water and to the solution was added 10 ml of a solution of 3.0 g (6.4 mmoles) of 6-chloro-3,7-dimethyl-9-(2,6,6-trimethyl-1-cyclohexen-1-yl)-9-phenylsulfonyl-2,7-nonadien-1-al in methylene chloride. To this mixture was added gradually 10.84 g (12.8 mmoles) of a 7.7% aqueous solution of potassium hydroxide at 8° C., and the resulting mixture was stirred for 30 minutes. After completion of the reaction, an organic layer was separated from an aqueous layer and washed with water, followed by distilling off of the solvent, to give 6.72 g (purity: 40.9%, 3.85 mmoles, yield: 60.2%) of an oily substance. This substance was purified by silica gel chromatography (hexane/ethyl acetate=85/15) to give 2.05 g of 1-phenylsulfonyl-4-chloro-1,18-di(2,6,6-trimethyl-1-cyclohexen-1-yl)-3,7,12,16-tetramethyloctadeca-2,7,9,11,13,15,17-heptaene.

Workup

  1. customAfter completion of the reaction
  2. customan organic layer was separated from an aqueous layer
  3. washwashed with water
  4. distillationby distilling off of the solvent
  5. customto give 6.72 g (purity: 40.9%, 3.85 mmoles, yield: 60.2%) of an oily substance
  6. customThis substance was purified by silica gel chromatography (hexane/ethyl acetate=85/15)

Sources & evidence

ORD record
ord-e08f7cca616d4cff8928a08d66647346
Source dataset
uspto-grants-1993_02
Patent number
US05185468

Reaction notes

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