Tributylstannane → 5-[[3,5-Bis(1,1-dimethylethyl)-4-hydroxyphenyl]methylene]-3-[2-(acetyloxy)ethyl]-4-thiazolidinone

HRID 2943

Reaction equation

HRID 2943 reaction equation
[CH3:1][C:2]([C:5]1[CH:6]=[C:7]([CH:16]=[C:17]2[S:21][C:20](=S)[N:19]([CH2:23][CH2:24][O:25][C:26](=[O:28])[CH3:27])[C:18]2=[O:29])[CH:8]=[C:9]([C:12]([CH3:15])([CH3:14])[CH3:13])[C:10]=1[OH:11])([CH3:4])[CH3:3].C([SnH](CCCC)CCCC)CCC.CC(N=NC(C#N)(C)C)(C#N)C>C1(C)C=CC=CC=1>[CH3:4][C:2]([C:5]1[CH:6]=[C:7]([CH:16]=[C:17]2[S:21][CH2:20][N:19]([CH2:23][CH2:24][O:25][C:26](=[O:28])[CH3:27])[C:18]2=[O:29])[CH:8]=[C:9]([C:12]([CH3:13])([CH3:14])[CH3:15])[C:10]=1[OH:11])([CH3:1])[CH3:3]

Participants

5

Reactant 3

HCID 5948TributylstannaneHCID 6547AzobisisobutyronitrileHCID 541262165-{[3,5-Bis(1,1-dimethylethyl)-4-hydroxyphenyl]methylene}-3-[2-(acetyloxy)ethyl]-2-thioxo-4-thiazolidinone

Product 1

HCID 538671995-[[3,5-Bis(1,1-dimethylethyl)-4-hydroxyphenyl]methylene]-3-[2-(acetyloxy)ethyl]-4-thiazolidinoneYield 59.7%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

Under a nitrogen atmosphere, 82.2 g of 5-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methylene]-3-[2-(acetyloxy) ethyl]-2-thioxo-4-thiazolidinone in 950 ml of toluene was heated to 65° C. Tri-n-butyl tin hydride (219.7 g) and AIBN (4.65 g) were added and the solution heated at reflux temperature for an additional 10 minutes. After cooling, the mixture was washed with 1.25l of 1N hydrochloric acid followed by 500 ml of a saturated sodium chloride solution. The organic layer was stripped and allowed to stand overnight, during which time a precipitate separated. The liquid portion was decanted off, and the resulting residue was purified by chromatography over silica gel, eluting with a gradient of 25-50% of ethyl acetate in hexane. The appropriate fractions were combined and concentrated in vacuo to provide 45.7 g of the desired titled compound, m.p.=152°-155° C.

Workup

  1. temperaturethe solution heated
  2. temperatureat reflux temperature for an additional 10 minutes
  3. temperatureAfter cooling
  4. washthe mixture was washed with 1.25l of 1N hydrochloric acid
  5. customa precipitate separated
  6. customThe liquid portion was decanted off
  7. customthe resulting residue was purified by chromatography over silica gel
  8. washeluting with a gradient of 25-50% of ethyl acetate in hexane
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-3db3491868884e35b394ce60e7488946
Source dataset
uspto-grants-1998_03
Patent number
US05731336

Linked notes

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