Chlorotrimethylsilane → HCID 14715012, compound

HRID 1681171Notes

Reaction equation

HRID 1681171 reaction equation
C(N(CC)CC)C.Cl[Si:9]([CH3:12])([CH3:11])[CH3:10].[CH:13]([O:16][C:17]1[C:18]([OH:27])([CH3:26])[C:19](=[O:25])[C:20]=1[O:21][CH:22]([CH3:24])[CH3:23])([CH3:15])[CH3:14]>C(OCC)C>[CH:13]([O:16][C:17]1[C:18]([O:27][Si:9]([CH3:12])([CH3:11])[CH3:10])([CH3:26])[C:19](=[O:25])[C:20]=1[O:21][CH:22]([CH3:23])[CH3:24])([CH3:15])[CH3:14]

Participants

5

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 8471TriethylamineHCID 14140277HCID 14140277, compound

Product 1

HCID 14715012HCID 14715012, compoundYield 94.2%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

Triethylamine (28 mL, 0.20 mol) and chlorotrimethylsilane (13 mL, 0.10 mol) were successively added to a stirred solution of 3,4-diisopropoxy-2-hydroxy-2-methylcyclobut-3-ene-1-one (14.3 g, 0.0667 mol) in diethyl ether (250 mL). The mixture was allowed to stir at ambient temperatures for 18 hrs. The mixture was filtered through SiO2 contained in a sintered glass funnel. The filter cake was washed with additional diethyl ether. The ether was removed to leave 3,4-diisopropoxy-2-trimethylsilyloxy-2-methylcyclobut-3-ene-1-one (18 g, 94% yield) as a clear oil. Trimethylsilyl trifluoromethanesulfonate (150 μL, 0.78 mmol) was added to a stirred solution of the silyl ether (18 g, 0.0628 mol) and 1,2-bis(trimethylsilyloxy)ethane (16.2 mL, 0.066 mmol) in tetrahydrofuran (36 mL). The solution was stirred for 1 hr at 22° C. and additional trimethylsilyl trifluoromethanesulfonate (150 μL) was then added. The solution was stirred for an additional 0.25 hr and was concentrated to dryness The residue was flash chromatographed on SiO2 (200 g) with diethyl etherhexanes (1:1) to afford 2,2-ethylenedioxy-3-isopropoxy-4-methylcyclobut-3-ene-1-one (9 g, 73% yield) as a colorless crystalline solid. A solution of n-Bu4N+CN- (140 mg, 0.52 mmol) in tetrahydrofuran (4 mL) was added dropwise to a stirred solution of the ketal (2.0 g, 0.010 mol) and n-Bu3SnSi(CH3)3 (4.03 g, 0.011 mol) in tetrahydrofuran (60 mL) at 22° C. Stirring was continued for 0.66 hr, and the dark solution was concentrated to dryness. The residue was flash chromatographed on SiO2 (80 g) with hexane and then with diethyl ether-hexane (25:75) to afford the title compound as a yellow oil (4.11 g, 95% yield).

Workup

  1. filtrationThe mixture was filtered through SiO2
  2. customcontained in a sintered glass funnel
  3. washThe filter cake was washed with additional diethyl ether
  4. customThe ether was removed

Sources & evidence

ORD record
ord-2f09b106e66b482eab19ece8b6b7623c
Source dataset
uspto-grants-1992_12
Patent number
US05169843

Reaction notes

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