Sodium hydride → (E,E,E)-7-hydroxymethyl-3,11,15-trimethyl-2,6,10,14-hexadecatetraenoic acid

HRID 26977

反応式

HRID 26977 の反応式
CO[CH:3]([O:17]C)[C:4](=O)[CH2:5][CH2:6]/[CH:7]=[C:8](\[CH3:15])/[CH2:9][CH2:10][CH:11]=[C:12]([CH3:14])[CH3:13].[H-].[Na+].[C:21]([OH:24])(=[O:23])[CH3:22].O.[BH4-].[Na+]>CS(C)=O.C(O)C.O.C(OCC)C>[OH:17][CH2:3]/[C:4](/[CH2:5][CH2:6]/[CH:7]=[C:8](\[CH3:15])/[CH2:9][CH2:10][CH:11]=[C:12]([CH3:13])[CH3:14])=[CH:3]/[CH2:4][CH2:5]/[C:6](/[CH3:7])=[CH:22]/[C:21]([OH:24])=[O:23]

参加物

9

反応物 4

HCID 24758Sodium hydrideHCID 4311764Sodium borohydrideHCID 11139695(E)-1,1-Dimethoxy-6,10-dimethyl-5,9-undecadien-2-oneHCID 21899381Acetic acid--water (1/1)

生成物 1

HCID 86736491(E,E,E)-7-hydroxymethyl-3,11,15-trimethyl-2,6,10,14-hexadecatetraenoic acid

試薬・触媒・溶媒 4

HCID 679Dimethyl Sulfoxide溶媒HCID 702Ethanol溶媒HCID 962Water溶媒HCID 3283Diethyl Ether溶媒

実験手順

A suspension of 14.1 g of (E)-4-methyl-5-carboxy-4-penten-1-yltriphenylphosphonium bromide, 8.4 g of (E)-1,1-dimethoxy-6,10-dimethyl-5,9-undecadien-2-one and 2.5 g of 63.8% sodium hydride in 30 ml of anhydrous dimethyl sulfoxide was stirred at 50°-55° C. for 2.5 hours and 40 ml of acetic acid-water (5:1) was added thereto. The resulting mixture was again stirred at 50°-55° C. for 30 minutes. After completion of the reaction, the reaction mixture was extracted four times with n-hexane and the extracts were washed with water, dried over anhydrous sodium sulfate and then the solvent was distilled off to leave 10.4 g of an yellow oily substance. The resulting oil was dissolved in 50 ml of ethanol, 1.2 g of sodium borohydride was added thereto at 5°-10° C. and the resulting mixture was stirred for 1 hour. To the reaction mixture were added ethyl ether and water and, after stirring, an aqueous layer was separated and neutralized with hydrochloric acid under ice-cooling. The so separated oily substance was extracted with ether and the extract was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off to afford 3.98 g of the end product.

後処理

  1. stirringThe resulting mixture was again stirred at 50°-55° C. for 30 minutes
  2. customAfter completion of the reaction
  3. extractionthe reaction mixture was extracted four times with n-hexane
  4. washthe extracts were washed with water
  5. dry with materialdried over anhydrous sodium sulfate
  6. distillationthe solvent was distilled off
  7. customto leave 10.4 g of an yellow oily substance
  8. stirringat 5°-10° C. and the resulting mixture was stirred for 1 hour
  9. stirringafter stirring
  10. customan aqueous layer was separated
  11. temperaturecooling
  12. customThe so separated oily substance
  13. extractionwas extracted with ether
  14. washthe extract was washed with water
  15. dry with materialdried over anhydrous sodium sulfate
  16. distillationThe solvent was distilled off

出典と根拠

ORDレコード
ord-333981e8b96c46589b0e3762034eaa48
出典データセット
uspto-grants-1979_04
特許番号
US04151357

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