Chlorotrimethylsilane → HCID 54268405, compound

HRID 728744Notes

Reaction equation

HRID 728744 reaction equation
[CH:1](=[O:21])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20].Br[CH:23]([CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH3:41])[C:24]([O:26][CH3:27])=[O:25].C[Si](C)(C)Cl>[Zn].S(=O)(=O)(O)O>[OH:21][CH:1]([CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20])[CH:23]([CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH3:41])[C:24]([O:26][CH3:27])=[O:25]

Participants

6

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 75458IcosanalHCID 13706912Methyl 2-bromohexadecanoate

Product 1

HCID 54268405HCID 54268405, compoundYield 51.2%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 1118Sulfuric AcidSolvent

Conditions

Temperature
85 °C

Procedure

Icosanal (1 g, 3.37 millimole) and methyl 2-bromohexadecanoate (977.8 mg, 2.80 millimole) were dissolved in the same mixed solvent (30 ml). The obtained solution (4 ml) was added dropwise to the reaction vessel containing zinc activated by trimethylchlorosilane as described above, and the mixture was stirred at 85° C. for 1 hour. The progress of reaction was confirmed through thin layer chromatography, and the rest of the solution (26 ml) was gradually added under the same conditions and the mixture was stirred for 8 hours. After cooling the reaction mixture with ice, 20% sulfuric acid (50 ml) was added thereto, and the, mixture,, was stirred for 15 minutes. Then the mixture was extracted twice with benzene, and the organic phase was washed twice with 10% sulfuric acid, and successively washed once with saturated aqueous sodium bicarbonate solution, once with 10% sulfuric acid, then twice with water, and dried over anhydrous sodium sulfate. The solvent was distilled off from the organic phase, and the obtained residue was dissolved in a developing solvent (n-hexane:ether=8:2) and fractionated through silicagel column chromatography (n-hexane:ether=8:2). The fourth and fifth fractions were pooled and the solvent was distilled off to give methyl 3-hydroxy-2-n-tetradecyl-docosanoate (III) (812.8 mg, yield 51%) in the form of white crystals.

Workup

  1. customThe progress of reaction
  2. stirringthe mixture was stirred for 8 hours
  3. additionwas added
  4. stirringthe, mixture,, was stirred for 15 minutes
  5. extractionThen the mixture was extracted twice with benzene
  6. washthe organic phase was washed twice with 10% sulfuric acid
  7. washsuccessively washed once with saturated aqueous sodium bicarbonate solution, once with 10% sulfuric acid
  8. dry with materialtwice with water, and dried over anhydrous sodium sulfate
  9. distillationThe solvent was distilled off from the organic phase
  10. dissolutionthe obtained residue was dissolved in a developing solvent (n-hexane:ether=8:2)
  11. distillationthe solvent was distilled off

Sources & evidence

ORD record
ord-6117ed55ccc24a06b4844d3f9904211b
Source dataset
uspto-grants-1991_09
Patent number
US05049664

Reaction notes

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