Silane, (chloromethyl)trimethyl- → HCID 18370002, compound

HRID 1532501Notes

Reaction equation

HRID 1532501 reaction equation
Cl[CH2:2][Si:3]([CH3:6])([CH3:5])[CH3:4].[Li].C[Si](C[Li])(C)C.[CH3:14][C:15]1[C:16](=[O:26])[C:17]([CH3:25])([CH3:24])[CH2:18][CH:19]2[C:23]=1[O:22][CH2:21][O:20]2>CCCCC.O1CCCC1.O>[CH3:14][C:15]1[C:16]([CH2:2][Si:3]([CH3:6])([CH3:5])[CH3:4])([OH:26])[C:17]([CH3:25])([CH3:24])[CH2:18][CH:19]2[C:23]=1[O:22][CH2:21][O:20]2

Participants

8

Reactant 4

HCID 75361Silane, (chloromethyl)trimethyl-HCID 3028194LithiumHCID 18370006HCID 18370006, compoundHCID 178418939HCID 178418939, compound

Product 1

HCID 18370002HCID 18370002, compoundYield 100%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8003PentaneSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

24.7 ml (20.6 g, 0.17 mol) of chloromethyltrimethylsilane were reacted with 2.92 g (0.42 mol) of lithium powder in 150 ml of pentane (according to the method described in Example 3). The resulting solution of trimethylsilylmethyllithium (about 0.14 mol) in pentane was placed in a 500 ml flask under argon gasification. A solution of 20 g (0.11 mol) of 4,6,6-trimethyl-5,6,7,7a-tetrahydro-1,3-benzodioxol-5-one in 25 ml of tetrahydrofuran was added thereto at −20° C. within about 20 minutes. After a further 20 minutes, the mixture was warmed slowly to room temperature and then cooled to 0° C. Thereafter, 90 ml of water were added dropwise thereto. Subsequently, the water was separated in a water separator and extracted twice with 100 ml of pentane each time. The pentane phases were washed in succession with sodium bicarbonate solution and sodium chloride solution, dried over anhydrous sodium sulphate and concentrated. The crude product (31.9 g) was then crystallized in 60 ml of pentane and cooled to −25° C. The resulting white crystals were filtered off, washed with a small amount of pentane at −20° C. and dried at room temperature under a high vacuum. This gave 30.5 g (almost 100% yield) of 4,6,6-trimethyl-5,6,7,7a-tetrahydro-5-trimethylsilylmethyl-1,3-benzodioxol-5-ol as white crystals, m.p. 63-64.5° C. IR (Nujol, cm−1): 3510 (OH); mass spectrum: 253 (M+—OH, 5), 214 (M—C4H8); 1H-NMR (C6D6, 400 MHz): inter alia 0.27 (s, 9H), 4.9 (s, 1H), 5.19 (s, 1H).

Workup

  1. waitAfter a further 20 minutes
  2. temperaturecooled to 0° C
  3. customSubsequently, the water was separated in a water separator
  4. extractionextracted twice with 100 ml of pentane each time
  5. washThe pentane phases were washed in succession with sodium bicarbonate solution and sodium chloride solution
  6. dry with materialdried over anhydrous sodium sulphate
  7. concentrationconcentrated
  8. customThe crude product (31.9 g) was then crystallized in 60 ml of pentane
  9. temperaturecooled to −25° C
  10. filtrationThe resulting white crystals were filtered off
  11. washwashed with a small amount of pentane at −20° C.
  12. customdried at room temperature under a high vacuum

Sources & evidence

ORD record
ord-178ce067cccb4c17b6a47f2d2b5584e8
Source dataset
uspto-grants-2001_03
Patent number
US06201155B1

Reaction notes

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