Chlorotrimethylsilane → HCID 67079336, compound

HRID 1753204Notes

Reaction equation

HRID 1753204 reaction equation
[CH3:1][Si:2]([CH3:28])([CH3:27])[O:3][CH:4]1[CH:9]([O:10][Si:11]([CH3:14])([CH3:13])[CH3:12])[CH:8]([O:15][Si:16]([CH3:19])([CH3:18])[CH3:17])[CH:7]([CH2:20][O:21][Si:22]([CH3:25])([CH3:24])[CH3:23])[O:6][C:5]1=[O:26].C(N(CC)CC)C.[CH3:36][Si:37](Cl)([CH3:39])[CH3:38].C[Si](C)(C)O[C:44]1([C:71]2[CH:76]=[C:75](Br)[CH:74]=[CH:73][C:72]=2[CH:78]([O:81][CH:82]([CH3:84])[CH3:83])[O:79][CH3:80])C(O[Si](C)(C)C)C(O[Si](C)(C)C)C(O[Si](C)(C)C)C(CO[Si](C)(C)C)[O:45]1.C([Li])CCC.CCCCCC.[CH2:98]([C:100]1[CH:107]=[CH:106][C:103](C=O)=[CH:102][CH:101]=1)[CH3:99].[Cl-].[NH4+]>O1CCCC1>[CH3:36][Si:37]([CH3:39])([CH3:38])[O:26][C:5]1([C:73]2[CH:74]=[C:75]([C:103]3[CH:106]=[CH:107][C:100]([CH2:98][CH3:99])=[CH:101][CH:102]=3)[CH:76]=[C:71]([CH2:44][OH:45])[C:72]=2[CH:78]([O:81][CH:82]([CH3:83])[CH3:84])[O:79][CH3:80])[CH:4]([O:3][Si:2]([CH3:28])([CH3:27])[CH3:1])[CH:9]([O:10][Si:11]([CH3:12])([CH3:13])[CH3:14])[CH:8]([O:15][Si:16]([CH3:19])([CH3:18])[CH3:17])[CH:7]([CH2:20][O:21][Si:22]([CH3:25])([CH3:24])[CH3:23])[O:6]1

Participants

10

Reactant 8

HCID 6397ChlorotrimethylsilaneHCID 8058HexaneHCID 8471TriethylamineHCID 208614-EthylbenzaldehydeHCID 25517Ammonium ChlorideHCID 523407HCID 523407, compoundHCID 67079154HCID 67079154, compoundHCID 178418339Butyllithium

Product 1

HCID 67079336HCID 67079336, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-48 °C

Procedure

After the reaction mixture was cooled to −48° C., the mixture was added dropwise to a solution of 3,4,5-tris(trimethylsilyloxy)-6-trimethylsilyloxymethyl-tetrahydropyran-2-one (402 g, 862 mmol) in tetrahydrofuran (2012 ml) at −77° C., and the reaction mixture was stirred at −70° C. for 1.5 hours. Triethylamine (24 ml, 172 mmol) and trimethylsilyl chloride (98 g, 903 mmol) were added thereto, and the mixture was warmed to 0° C. to give a solution containing 2,3,4,5-tetrakis(trimethylsilyloxy)-6-trimethylsilyloxymethyl-2-(5-bromo-2-(1-methoxy-1-methylethoxymethyl)phenyl)tetrahydropyran. The resulting solution was cooled to −78° C., and n-butyllithium in hexane (1.54 M, 1119 ml, 1724 mmol) was added dropwise thereto at the same temperature. After the mixture was stirred for 1 hour, 4-ethylbenzaldehyde (242 g, 1806 mmol) was added dropwise at −78° C., and the mixture was stirred at the same temperature for 2.5 hours. The reaction mixture was poured into an aqueous solution of 20% ammonium chloride, and the organic layer was separated, and washed with water. The solvent was evaporated under reduced pressure to give a product containing the titled compound as an oil (879 g). The product was used in the next step without further purification.

Workup

  1. temperaturethe mixture was warmed to 0° C.
  2. customto give a solution
  3. temperatureThe resulting solution was cooled to −78° C.
  4. stirringAfter the mixture was stirred for 1 hour
  5. stirringthe mixture was stirred at the same temperature for 2.5 hours
  6. customthe organic layer was separated
  7. washwashed with water
  8. customThe solvent was evaporated under reduced pressure
  9. customto give a product

Sources & evidence

ORD record
ord-423e1ecb2abf4822ad41e4d1f496717f
Source dataset
uspto-grants-2015_10
Patent number
US09163051B2

Reaction notes

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