Ethyl Bromide → (9Z)-2,7-dimethyltridec-9-en-3-yne-2,5-diol

HRID 1799153노트

반응식

HRID 1799153 반응식
C(Br)C.[Mg].[CH3:5][C:6]([OH:10])([C:8]#[CH:9])[CH3:7].[CH3:11][CH:12]([CH2:16]/[CH:17]=[CH:18]\[CH2:19][CH2:20][CH3:21])[CH2:13][CH2:14][OH:15]>O1CCCC1>[CH3:5][C:6]([OH:10])([C:8]#[C:9][CH:14]([OH:15])[CH2:13][CH:12]([CH3:11])[CH2:16]/[CH:17]=[CH:18]\[CH2:19][CH2:20][CH3:21])[CH3:7]

참가 물질

6

반응물 4

HCID 6332Ethyl BromideHCID 82582-Methyl-3-butyn-2-olHCID 5462224MagnesiumHCID 86625207(5Z)-3-methylnon-5-en-1-ol

생성물 1

HCID 86625208(9Z)-2,7-dimethyltridec-9-en-3-yne-2,5-diol수율 77.1%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매4회

실험 절차

A solution of 10.4 g (95.6 mmol) of ethyl bromide in 40 mL of dry tetrahydrofuran was added dropwise over a period of 30 min to a vigorously stirred suspension of 2.32 g (95.6 mmol) of magnesium turnings in 15 mL of dry tetrahydrofuran, with the reaction being initiated by occasional heating with a heat gun. After stirring the reaction mixture for 90 min under reflux, it was allowed to cool down to room temp., and a solution of 3.54 g (42.2 mmol) of 2-methylbut-3-yn-2-ol in 40 mL of dry tetrahydrofuran was added dropwise with stirring. The reaction mixture was then again refluxed for 3 h, the heating bath removed and a solution of 6.50 g (42.2 mmol) of (5Z)-3-methylnon-5-en-1-ol in 40 mL of dry tetrahydrofuran added at room temp. with stirring over a period of 30 min. The reaction mixture was refluxed with stirring overnight, allowed to cool to room temp., and quenched by pouring into 100 mL of an aqueous satd. NH4Cl solution. The organic layer was separated, and the aqueous one extracted three times with 500 mL of ether each. The combined organic extracts were dried with sodium sulphate, and concentrated to dryness in a rotary evaporator. The resulting residue (10.8 g) was purified by flash chromatography (200 g of silica gel, pentane/ether, 1:1, Rf=0.22) to furnish 7.76 g (77%) of (9Z)-2,7-dimethyltridec-9-en-3-yne-2,5-diol as a colourless oil.

후처리

  1. temperatureby occasional heating with a heat gun
  2. temperatureunder reflux
  3. temperatureto cool down to room temp.
  4. stirringwith stirring
  5. temperatureThe reaction mixture was then again refluxed for 3 h
  6. customthe heating bath removed
  7. stirringwith stirring over a period of 30 min
  8. temperatureThe reaction mixture was refluxed
  9. stirringwith stirring overnight
  10. temperatureto cool to room temp.
  11. customquenched
  12. additionby pouring into 100 mL of an aqueous satd
  13. customThe organic layer was separated
  14. extractionthe aqueous one extracted three times with 500 mL of ether each
  15. dry with materialThe combined organic extracts were dried with sodium sulphate
  16. concentrationconcentrated to dryness in a rotary evaporator
  17. customThe resulting residue (10.8 g) was purified by flash chromatography (200 g of silica gel, pentane/ether, 1:1, Rf=0.22)

출처 및 근거

ORD 기록
ord-3506a7a68ec247ddaa8a815d0708ef86
출처 데이터셋
uspto-grants-2013_01
특허 번호
US08344023B2

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