Water → HCID 69876625, compound

HRID 1838116Notes

Reaction equation

HRID 1838116 reaction equation
Cl.[CH3:2][O:3][C:4](=[O:29])[C:5]1[CH:10]=[CH:9][CH:8]=[C:7](/[CH:11]=[C:12]2/[CH:13]=[C:14]([C:22]3[CH:27]=[CH:26][CH:25]=[C:24]([OH:28])[CH:23]=3)[CH:15]([CH2:18][N:19]([CH3:21])[CH3:20])[CH2:16][CH2:17]/2)[CH:6]=1.C[Si](C)(C)[Cl:32].O>CC(C)=O>[ClH:32].[CH3:2][O:3][C:4](=[O:29])[C:5]1[CH:10]=[CH:9][CH:8]=[C:7](/[CH:11]=[C:12]2\[CH:13]=[C:14]([C:22]3[CH:27]=[CH:26][CH:25]=[C:24]([OH:28])[CH:23]=3)[CH:15]([CH2:18][N:19]([CH3:21])[CH3:20])[CH2:16][CH2:17]\2)[CH:6]=1

Participants

5

Reactant 3

HCID 962WaterHCID 6397ChlorotrimethylsilaneHCID 69876549HCID 69876549, compound

Product 1

HCID 69876625HCID 69876625, compoundYield 27.6%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

8.1 g potassium tert-butylate and 35.4 g 3-(benzoic acid methyl ester)-methyltriphenylphosphonium chloride were suspended in 800 ml analytical grade toluene under a nitrogen atmosphere at room temperature and the suspension was then stirred at 70° C. for one hour. 7 g 3-(3-(tert-butyl-diphenyl-silanyloxy)-cyclohex-2-enone in 100 ml analytical grade toluene were added at this temperature and the mixture was stirred at 70° C. for 3 days. The mixture was quenched with 500 ml water. The phases were separated and the aqueous phase was washed 3 times with 200 ml ethyl acetate each time. The combined organic phases were dried over magnesium sulfate and then freed from solvent in vacuo. The residue obtained in this way was taken up in a mixture of 150 ml ethyl acetate and 150 ml diiso-ether. The solid which had precipitated out was filtered off and washed with diiso-ether. The combined organic phases were freed from the solvent in vacuo. The residue (16.7 g) was dissolved in 70 ml tetrahydrofuran, and 16.7 ml tetrabutylammonium fluoride were added. After a reaction time of 10 minutes the reaction solution was quenched with 50 ml water and extracted three times with 50 ml ethyl acetate each time. The combined organic phases were dried over magnesium sulfate and then freed from the solvent in vacuo. The residue was purified by column chromatography on silica gel with ethyl acetate/methanol=9/1. 2.5 g E-3-[4-dimethylaminomethyl-3-(3-hydroxy-phenyl)-cyclohex-2-enylidenemethyl]-benzoic acid methyl ester base were obtained as the first product fraction. To liberate the hydrochloride, the base was dissolved in 50 ml acetone, and an equimolar amount of trimethylchlorosilane and water was added. 2 g (36.8% of theory) E-3-[4-dimethylaminomethyl-3-(3-hydroxy-phenyl)-cyclohex-2-enylidenemethyl]-benzoic acid methyl ester hydrochloride (37) were obtained in this way. 1.8 g (27.6% of theory) Z-3 [4-Dimethylaminomethyl-3-(3-hydroxy-phenyl)-cyclohex-2-enylidenemethyl]-benzoic acid methyl ester were obtained as the second product fraction. To liberate the hydrochloride, the base was dissolved in 50 ml acetone, and an equimolar amount of trimethylchlorosilane and water was added. 1.5 g (27.6% of theory) Z-3-[4-dimethylaminomethyl-3-(3-hydroxy-phenyl)-cyclohex-2-enylidenemethyl]-benzoic acid methyl ester hydrochloride (38) were obtained in this way.

Sources & evidence

ORD record
ord-8a41e4e1f9494bfc82579dad0314481e
Source dataset
uspto-grants-2004_01
Patent number
US06673794B2

Reaction notes

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