Hydrochloric Acid → Gossyplure

HRID 64597

反応式

HRID 64597 の反応式
[CH2:1]=[CH:2][CH2:3][CH2:4][CH:5]=[CH:6][CH2:7][CH2:8][CH:9]=[CH:10][CH2:11][CH2:12][CH2:13][CH3:14].C([Mg]Cl)CCC.[C:21]([O:24][CH2:25][CH2:26]Br)(=[O:23])[CH3:22].Cl>[Ti](Cl)(Cl)(Cl)Cl>[CH3:14][CH2:13][CH2:12][CH2:11]/[CH:10]=[CH:9]\[CH2:8][CH2:7]/[CH:6]=[CH:5]\[CH2:4][CH2:3][CH2:2][CH2:1][CH2:26][CH2:25][O:24][C:21]([CH3:22])=[O:23]

参加物

6

反応物 4

HCID 313Hydrochloric AcidHCID 135641-Acetoxy-2-bromoethaneHCID 54124585Tetradeca-1,5,9-trieneHCID 178418265HCID 178418265、化合物

生成物 1

HCID 5363265Gossyplure収率 11%

試薬・触媒・溶媒 1

HCID 24193Titanium Tetrachloride触媒

反応条件

温度
0 °C

実験手順

1,5,9-Tetradecatriene (10 g, 0.052 mol), n-butylmagnesium chloride (24.8 mL of 2.5M in tetrahydrofuran; 0.062 mol) and titanium tetrachloride (0.52 g, 0.0027 mol) were stirred under an inert atmosphere at about 65° C. for about 4.5 hours. The reaction mixture was then cooled to 0° C. and cuprous bromide (0.14 g, 1.0 mmol) was added. 2-Bromoethyl acetate (6.9 mL, 0.063 mol) was then added dropwise and the mixture allowed to warm slowly to room temperature and stirred for several hours at room temperature. Reaction temperature was then raised to 60° C. for 4 hours before the mixture was cooled, acidified with aqueous HCl, then extracted with hexane. The hexane extract was washed with saturated sodium bicarbonate solution, dried over MgSO4, filtered and solvent removed on the rotary evaporator. GLC analysis of this crude reaction product indicated an 11% yield of gossyplure. It should be recognized that while this reaction represents successful production of gossyplure from 1,5,9 -tetradecatriene in one reaction vessel, the reaction parameters have not been optimized. Consequently, significantly improved yields of gossyplure can be expected upon optimization of various reaction parameters.

後処理

  1. temperatureto warm slowly to room temperature
  2. customReaction temperature
  3. temperaturewas then raised to 60° C. for 4 hours before the mixture
  4. temperaturewas cooled
  5. extractionextracted with hexane
  6. extractionThe hexane extract
  7. washwas washed with saturated sodium bicarbonate solution
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. customsolvent removed on the rotary evaporator
  11. customGLC analysis of this crude reaction product

出典と根拠

ORDレコード
ord-84f5d1ced4764e9682f1afa69091250d
出典データセット
uspto-grants-1986_09
特許番号
US04609498

関連ノート

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