Tris(trimethylsilyl)silane → HCID 178497966, compound

HRID 1861612Notes

Reaction equation

HRID 1861612 reaction equation
Cl[C:2]([F:26])([F:25])[C:3]1[N:8]=[C:7]([CH3:9])[C:6]([C:10]([C:12]2[C:17](=[O:18])[CH2:16][CH2:15][C:14]([CH3:23])([C:19]([O:21][CH3:22])=[O:20])[C:13]=2[OH:24])=[O:11])=[CH:5][CH:4]=1.C[Si]([SiH]([Si](C)(C)C)[Si](C)(C)C)(C)C>C1(C)C=CC=CC=1>[F:26][CH:2]([F:25])[C:3]1[N:8]=[C:7]([CH3:9])[C:6]([C:10]([C:12]2[C:17](=[O:18])[CH2:16][CH2:15][C:14]([CH3:23])([C:19]([O:21][CH3:22])=[O:20])[C:13]=2[OH:24])=[O:11])=[CH:5][CH:4]=1

Participants

4

Reactant 2

HCID 123134Tris(trimethylsilyl)silaneHCID 178497965HCID 178497965, compound

Product 1

HCID 178497966HCID 178497966, compoundYield 76.8%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

200 mg (0.516 mmol) of methyl 3-[6-(chlorodifluoromethyl)-2-methylpyridine-3-carbonyl]-2-hydroxy-1-methyl-4-oxocyclohex-2-enecarboxylate (compound A94-B34) is heated for 3 hours at a temperature of 120° C. in 8 ml of toluene in the presence of 0.18 ml (0.62 mmol) tris(trimethylsilyl)silane. The viscous residue which remains is chromatographed on silica gel. The pale yellow viscous oil which is obtained by eluting with a mixture of toluene, ethyl alcohol, dioxane, triethylamine and water (100:40:20:20:5 by volume) is dissolved in dichloromethane and washed in succession with aqueous hydrochloric acid and water. Evaporation of the organic solution which has been dried with Na2SO4 yields 140 mg (73%) of pure methyl 3-(6-difluoromethyl-2-methylpyridine-3-carbonyl)-2-hydroxy-1-methyl-4-oxocyclohex-2-enecarboxylate in the form of a pale yellow oil. 1H-NMR (CDCl3): 1.28, s, 3H; 1.79-1.97, m, 1H; 2.39-2.46, m, 1H; 2.43, s, 3H; 2.69, dt (J, 19.2 and 4.8 Hz), 1H; 2.82-2.92, m, 1H; 3.67, s, 3H; 6.55, t, (J, 55.5 Hz), 1H; 7.43, d (J, 7.8 Hz), 1H; 7.49, d (J, 7.8 Hz), 1H; 17.20 ppm, br s, 1H.

Workup

  1. customThe viscous residue which remains is chromatographed on silica gel
  2. customThe pale yellow viscous oil which is obtained
  3. washby eluting with a mixture of toluene, ethyl alcohol, dioxane, triethylamine and water (100:40:20:20:5 by volume)
  4. dissolutionis dissolved in dichloromethane
  5. washwashed in succession with aqueous hydrochloric acid and water
  6. customEvaporation of the organic solution which
  7. dry with materialhas been dried with Na2SO4

Sources & evidence

ORD record
ord-b19edf74fe244c5d90a008a7248ed374
Source dataset
uspto-grants-2003_03
Patent number
US06534445B1

Reaction notes

Loading…