Ethyl Bromide → 6(R),10-dimethyl-undecan-2-yn-4(R,S)-ol

HRID 26991

反応式

HRID 26991 の反応式
C([Br:3])C.[Mg:4].[CH3:5][C:6]#[CH:7].[CH3:8][C@H:9]([CH2:13][CH2:14][CH2:15][CH:16]([CH3:18])[CH3:17])[CH2:10][CH:11]=[O:12].[NH4+].[Cl-]>C(OCC)C.O>[C:7]([Mg:4][Br:3])#[C:6][CH3:5].[CH3:8][C@H:9]([CH2:13][CH2:14][CH2:15][CH:16]([CH3:18])[CH3:17])[CH2:10][CH:11]([OH:12])[C:5]#[C:6][CH3:7]

参加物

9

反応物 5

HCID 6332Ethyl BromideHCID 6335PropyneHCID 25517Ammonium ChlorideHCID 5462224MagnesiumHCID 12266719(3r)-3,7-Dimethyloctanal

生成物 2

HCID 1317114886(R),10-dimethyl-undecan-2-yn-4(R,S)-ol収率 100%HCID 178419101HCID 178419101、化合物

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 3283Diethyl Ether溶媒2 回

実験手順

Propynyl magnesium bromide was prepared as described earlier from ethyl bromide (77 g, 0.405 mol, freshly distilled), magnesium (10.8 g 0.4455 mol) and methyl acetylene (approximately 100 ml at -70°) in 400 ml of absolute diethyl ether. To this well stirred mixture was added dropwise 26.4 g (0.169 mol) of 3(R),7-dimethyloctanal (R-(+)-dihydrocitronellal) in 500 ml of dry ether while the reaction temperature was maintained between 0°-5° C. with external cooling. After 45 min. all aldehyde had been added and the reaction was allowed to warm to 30° and stirred at this temperature for 1.0 hr. Thin layer chromatography analysis of the reaction mixture at this point showed the disappearance of starting material. The flask was then cooled in an ice-bath and 100 g of NH4Cl in 600 ml of water was added slowly. The content was transferred to a separatory funnel and the layers separated. The aqueous phase was further extracted with ether (3×250 ml). The combined ether extract was filtered quickly through Celite and washed with saturated brine (3×500 ml) and dried over MgSO4. After filtration the solvent was evaporated to dryness in a rotary evaporator (40°/25 mmHg) to give 33.1 g (100%) of crude 6(R),10-dimethyl-undecan-2-yn-4(R,S)-ol as a clear light amber oil.

後処理

  1. temperaturewas maintained between 0°-5° C. with external cooling
  2. temperatureto warm to 30°
  3. stirringstirred at this temperature for 1.0 hr
  4. temperatureThe flask was then cooled in an ice-bath
  5. customThe content was transferred to a separatory funnel
  6. customthe layers separated
  7. extractionThe aqueous phase was further extracted with ether (3×250 ml)
  8. extractionThe combined ether extract
  9. filtrationwas filtered quickly through Celite
  10. washwashed with saturated brine (3×500 ml)
  11. dry with materialdried over MgSO4
  12. filtrationAfter filtration the solvent
  13. customwas evaporated to dryness in a rotary evaporator (40°/25 mmHg)

出典と根拠

ORDレコード
ord-8c318fe5e20f44a49c4e80b93ea77d95
出典データセット
uspto-grants-1979_04
特許番号
US04151360

関連ノート

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