Dimethyl Sulfoxide → HCID 21717629, compound

HRID 1386483Notes

Reaction equation

HRID 1386483 reaction equation
[Br-].[CH3:2][C:3]1([CH3:35])[CH2:12][CH2:11][C:10]([CH3:14])([CH3:13])[C:9]2[CH:8]=[C:7]([CH2:15][P+](C3C=CC=CC=3)(C3C=CC=CC=3)C3C=CC=CC=3)[CH:6]=[CH:5][C:4]1=2.[H-].[Na+].[CH3:38][C:39]([C:41]1[CH:46]=[CH:45][C:44]([C:47]#[N:48])=[CH:43][CH:42]=1)=O.[CH3:49]S(C)=O>>[CH3:15][C:7]1[C:6]([CH:39]([C:41]2[CH:46]=[CH:45][C:44]([C:47]#[N:48])=[CH:43][CH:42]=2)[CH:38]=[CH2:49])=[CH:5][C:4]2[C:3]([CH3:35])([CH3:2])[CH2:12][CH2:11][C:10]([CH3:13])([CH3:14])[C:9]=2[CH:8]=1

Participants

5

Reactant 4

HCID 679Dimethyl Sulfoxide2×HCID 24758Sodium hydride2×HCID 740444'-CyanoacetophenoneHCID 11353265HCID 11353265, compound

Product 1

HCID 21717629HCID 21717629, compound

Procedure

A solution of (5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthalenyl)methyl-triphenyl-phosphonium bromide (6.25 g, 11.5 mmol) and NaH (10.5 mmol), coming from 0.42 g of a dispersion of 60% NaH in oil, in 35 ml of anhydrous DMSO is agitated under argon for 20 minutes, during which a solution of 4-cyanoacetophenone (1.45 g, 10.0 mmol) in 15 ml of DMSO is added. The solution is agitated for 6 hours at ambient temperature then poured over ice (150 g). This was then extracted with ether (125 ml, 3×50 ml). The raw product is then purified by three successive flash chromatographies on silica (1st eluent hexane:acetone=5:95, 2nd eluent hexane:acetone=4:96, 3rd eluent hexane:acetone=2.5:97.5) so as to separate the (E) and the (Z) 4-[1-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-naphthalenyl)-2-propenyl]benzonitriles. In order to obtain the pure (Z) isomer (less polar than the (E)isomer), the different fractions are verified by HPLC. The (E)isomer crystallises in the fractions coming from the flash chromatography. It is filtered, washed with hexane and dried at the palette pump. Its purity is determined by HPLC analysis.

Workup

  1. additionis added
  2. extractionThis was then extracted with ether (125 ml, 3×50 ml)
  3. customThe raw product is then purified by three successive flash chromatographies on silica (1st eluent hexane:acetone=5:95, 2nd eluent hexane:acetone=4:96, 3rd eluent hexane:acetone=2.5:97.5) so as
  4. customto separate the (E)

Sources & evidence

ORD record
ord-10db7ff87d2f4832bbe3dd1ba1c2e007
Source dataset
uspto-grants-2001_07
Patent number
US06265423B1

Reaction notes

Loading…