Water → HCID 178443900、化合物

HRID 247683

反応式

HRID 247683 の反応式
[C:1]([C:3]1[CH:8]=[CH:7][C:6]([C@H:9]2[CH2:14][CH2:13][C@H:12]([CH2:15][CH2:16][CH2:17][CH:18]=O)[CH2:11][CH2:10]2)=[CH:5][CH:4]=1)#[N:2].O.CO[C:23](C)(C)[CH3:24]>[Br-].C([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)C>[CH2:15]([C@H:12]1[CH2:13][CH2:14][C@H:9]([C:6]2[CH:7]=[CH:8][C:3]([C:1]#[N:2])=[CH:4][CH:5]=2)[CH2:10][CH2:11]1)[CH2:16][CH2:17][CH:18]=[CH:23][CH3:24]

参加物

5

反応物 3

HCID 962WaterHCID 15413tert-Butyl methyl ether2 回HCID 178509796HCID 178509796、化合物

生成物 1

HCID 178443900HCID 178443900、化合物

試薬・触媒・溶媒 1

HCID 73727Phosphonium, ethyltriphenyl-, bromide (1:1)触媒

反応条件

温度
0 °C

実験手順

A suspension of 3.16 g of ethyl-triphenylphosphonium bromide in 50 ml of dry t-butyl methyl ether was treated with 960 mg of potassium t-butylate while gassing with argon at -10° C. and the mixture was stirred for a further 45 minutes at 0° C. Thereafter, the mixture was cooled to -20° C., treated within 5 minutes with a solution of 1.45 g of 4-[trans-4-(p-cyanophenyl)cyclohexyl]butyraldehyde (purity 90%) in 20 ml of t-butyl methyl ether and the mixture was stirred for a further 30 minutes while warming to room temperature. The reaction mixture was subsequently poured into 100 ml of water and extracted three times with 100 ml of diethyl ether each time. The organic phases were washed with 100 ml of water, dried over magnesium sulphate and concentrated. Low-pressure chromatography (0.5 bar) of the residue on silica gel with ethyl acetate/petroleum ether (vol. 3:97) gave p-[trans-4-(4-hexenyl)cyclohexyl]benzonitrile (4Z: 4E=88:12) as a colourless oil. Additional low-pressure chromatography (0.5 bar) of this material on 140 g of silver nitrate-coated silica gel (prepared according to Example 2) with hexane/diethyl ether (vol. 3:1) yielded 750 mg of p-[trans-4-(4Z-hexenyl)cyclohexyl]benzonitrile. Two-fold recrystallization from methanol finally gave 468 mg of colourless crystals with m.p. (C-I) 27.4° C. and cl.p. (N-I) 4.5° C.

後処理

  1. customwhile gassing with argon at -10° C.
  2. temperatureThereafter, the mixture was cooled to -20° C.
  3. stirringthe mixture was stirred for a further 30 minutes
  4. temperaturewhile warming to room temperature
  5. extractionextracted three times with 100 ml of diethyl ether each time
  6. washThe organic phases were washed with 100 ml of water
  7. dry with materialdried over magnesium sulphate
  8. concentrationconcentrated

出典と根拠

ORDレコード
ord-d08c5725593e43fa8a2d6c3202e7a7b2
出典データセット
uspto-grants-1987_11
特許番号
US04709030

関連ノート

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