Propargyl bromide → 3,7-Dimethyl-(2-propynyloxy)-octanal

HRID 1576989

반응식

HRID 1576989 반응식
[NH2-].[Na+].CO[CH:5]([O:16]C)[CH2:6][CH:7]([CH3:15])[CH2:8][CH2:9][CH2:10][C:11]([CH3:14])(O)[CH3:12].[CH2:18](Br)[C:19]#[CH:20].C[O:23]CCOC>>[CH3:15][CH:7]([CH2:8][CH2:9][CH2:10][CH:11]([CH3:12])[CH3:14])[CH:6]([O:23][CH2:18][C:19]#[CH:20])[CH:5]=[O:16]

참가 물질

5

반응물 4

HCID 7842Propargyl bromideHCID 80711,2-Dimethoxyethane3회HCID 8863Hydroxycitronellal dimethyl acetalHCID 24533Sodium amide

생성물 1

HCID 538731643,7-Dimethyl-(2-propynyloxy)-octanal

반응 조건

온도
85 °C

실험 절차

59 g. of sodium amide (50% suspension in benzene) are placed in 1 liter of 1,2-dimethoxyethane and treated dropwise, while cooling with ice, with 109.2 g. of 1,1-dimethoxy-3,7-dimethyl-7-octanol in 400 ml. of 1,2-dimethoxyethane. The mixture is left to stir under a nitrogen atmosphere for 15 hours at 85°C. The mixture is then again cooled and treated dropwise with a solution of 89.3 g. of propargyl bromide in 250 ml. of 1,2-dimethoxyethane. The mixture is then left to stir at 40°C. until the reaction is complete. The mixture is poured on to 4 liters of ice-water and extracted twice with 2.5 liters of ether. The extracts are washed with 10% sodium hydroxide, water and saturated sodium chloride solution, dried over sodium sulphate and evaporated. By distillation or chromatography, there is obtained pure dimethylacetal of 3,7-dimethyl-(2-propynyloxy)-octanal; boiling point (bulb-tube) = 70°C/0.03 mmHg; nD25 = 1.4491. 65 g. of the dimethylacetal of 3,7-dimethyl-7-(2-propynyloxy)-octanal are heated at 40°C. for 16 hours with a mixture of 300 ml. of 2-N hydrochloric acid, 700 ml. of water and 1 liter of tetrahydrofuran while stirring well. For the working up, the mixture is poured on to 1 liter of ice-water and extracted twice with 1.5 liters of ether. The extracts are washed with 10% sodium carbonate solution, water and saturated sodium chloride solution, dried over sodium sulphate and evaporated. By distillation, there is obtained pure 3,7-dimethyl-7-(2-propynyloxy)-octanal; boiling point = 113°C/1 mmHg; nD25 = 1.4553.

후처리

  1. additiontreated dropwise
  2. temperaturewhile cooling with ice, with 109.2 g
  3. waitThe mixture is left
  4. temperatureThe mixture is then again cooled
  5. additiontreated dropwise with a solution of 89.3 g
  6. waitThe mixture is then left
  7. stirringto stir at 40°C. until the reaction
  8. extractionextracted twice with 2.5 liters of ether
  9. washThe extracts are washed with 10% sodium hydroxide, water and saturated sodium chloride solution
  10. dry with materialdried over sodium sulphate
  11. customevaporated
  12. distillationBy distillation or chromatography

출처 및 근거

ORD 기록
ord-c807b501878f4f309f2e232235eba7bc
출처 데이터셋
uspto-grants-1976_09
특허 번호
US03983247

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