Sodium Chloride → HCID 178490609、化合物

HRID 66637

反応式

HRID 66637 の反応式
[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([CH:14]=[CH:15][C:16]=1[O:17][CH3:18])[CH2:12]Cl)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Mg:19].FCC#N.[C-]#N.[Na+].[Cl-:27].[NH4+].[Cl-].[Na+]>O1CCCC1.O>[CH2:1]([O:8][C:9]1[CH:10]=[C:11]([CH:14]=[CH:15][C:16]=1[O:17][CH3:18])[CH2:12][Mg:19][Cl:27])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

参加物

9

反応物 6

HCID 5234Sodium ChlorideHCID 8929Sodium CyanideHCID 10420Acetonitrile, fluoro-HCID 25517Ammonium ChlorideHCID 2802242-(Benzyloxy)-4-(chloromethyl)-1-methoxybenzeneHCID 5462224Magnesium

生成物 1

HCID 178490609HCID 178490609、化合物

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-30 °C

実験手順

Under an atmosphere of nitrogen, 3-benzyloxy-4-methoxybenzyl magnesium chloride is prepared from 3-benzyloxy-4-methoxybenzylchloride (C. Schopf and L. Winterhalder, Ann. 544, 62 (1940) (22.0 g, 84 mmol) and magnesium turnings (4.1 g) in tetrahydrofuran (THF) (100 ml) at room temperature (about 2 hours). After cooling to -30° C., a solution of fluoroacetonitrile (4.94 g) in THF (40 ml) is added dropwise, maintaining the temperature between -30° C. and -40° C. Stirring is continued at this temperature for another 30 minutes, then the mixture is poured into a solution of sodium cyanide (12.3 g) and ammonium chloride (17.9 g) in water (150 ml), previously cooled with ice. After stirring for 30 minutes, the mixture is saturated with sodium chloride whereupon the phases separate. After extracting the aqueous phase two more times with diethyl ether, the combined THF and ether phases are dried (Na2SO4) and evaporated to give the crude aminonitrile (25.9 g) as a brown oil. The oil is dissolved in ether and treated with HCl gas to prepare the hydrochloride as an oil. This oil is recrystallized twice from ethanol/ether to give 2-fluoromethyl-2-amino-3-(3'-benzyloxy-4'-methoxyphenyl)propionitrile as the hydrochloride as a slightly colored solid; NMR (CD3OC): 3.47 ppm (3H, s), 4.32 ppm (2H, d, JH--F =46 Hz), 4.73 ppm (2H, s), 6.60 ppm (3H, m), 6.97 ppm (5H, m).

後処理

  1. customat room temperature
  2. custom(about 2 hours)
  3. temperaturemaintaining the temperature between -30° C. and -40° C
  4. temperaturepreviously cooled with ice
  5. stirringAfter stirring for 30 minutes
  6. customseparate
  7. extractionAfter extracting the aqueous phase two more times with diethyl ether
  8. dry with materialthe combined THF and ether phases are dried (Na2SO4)
  9. customevaporated
  10. customto give the crude aminonitrile (25.9 g) as a brown oil

出典と根拠

ORDレコード
ord-a3ef8b34366e4a66a317bdcc6edb8c68
出典データセット
uspto-grants-1982_08
特許番号
US04342780

関連ノート

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