Phosphorus trichloride → Phosphine, tert-butylbis(dimethylamino)-

HRID 1107226

反応式

HRID 1107226 の反応式
[C:1]([Li])([CH3:4])([CH3:3])[CH3:2].[CH3:6][N:7]([P:9](Cl)[N:10]([CH3:12])[CH3:11])[CH3:8].P(Cl)(Cl)Cl.C[N-]C.[Li+]>C(OCC)C.CCCCCC.CN(P(N(C)C)N(C)C)C>[C:1]([P:9]([N:10]([CH3:12])[CH3:11])[N:7]([CH3:8])[CH3:6])([CH3:4])([CH3:3])[CH3:2]

参加物

8

反応物 4

HCID 24387Phosphorus trichloride3 回HCID 76872Chlorobis(dimethylamino)phosphineHCID 5152226Lithium N-methylmethanaminideHCID 178418306HCID 178418306、化合物2 回

生成物 1

HCID 576682Phosphine, tert-butylbis(dimethylamino)-収率 69%

試薬・触媒・溶媒 3

HCID 3283Diethyl Ether溶媒3 回HCID 8058Hexane溶媒HCID 15355Hexamethylphosphorous triamide溶媒2 回

反応条件

温度
0 °C

実験手順

Tertiarybutylbis(dimethylamino)phosphine was prepared according to Reaction Scheme #2 by reaction of tertiarybutyllithium with bis(dimethylamino)phosphoruschloride which had been prepared from the reaction of neat trisdimethylaminophosphine and phosphorustrichloride. Trisdimethylaminophosphine was prepared from the reaction of phosphorus trichloride with three equivalents of lithium dimethylamide in diethylether at 0° C. A solution of 88.4 g (0.64 mol) PCl3 in 50 ml diethylether was added dropwise to a stirred suspension of 105 g (2.06 mol) LiNMe2 in 1.5 liters diethylether at 0° C. The resulting mixture was filtered and the P(NMe2)3 product, 0.444 mol, 72.5 g (69% yield based on PCl3), was fractionally distilled from the filtrate at 45° C./9.5 torr. PCl3, 0.222 mol (30.5 g) was added slowly to the purified P(NMe2)3 with stirring at 0° C. The resulting P(NMe2)2Cl compound was heated to 35° C. for one hour then diluted with 1 liter of hexane and cooled to -78° C. A 400 ml aliquot (0.68 mol) of tertiarybutyl lithium, ((CH3)3C)Li, in hexane was added dropwise over a two hour period with stirring. The mixture was allowed to warm, filtered and the tertiarybutyl-bis(dimethylamino)phosphine, ((CH3)3C)P(NMe2)2, product, 55 g, 0.31 mol (45% yield based on P(NMe2)2Cl), was purified by repeated fractional distillation of the filtrate.

後処理

  1. filtrationThe resulting mixture was filtered
  2. distillationthe P(NMe2)3 product, 0.444 mol, 72.5 g (69% yield based on PCl3), was fractionally distilled from the filtrate at 45° C./9.5 torr
  3. additionPCl3, 0.222 mol (30.5 g) was added slowly to the purified P(NMe2)3
  4. temperatureThe resulting P(NMe2)2Cl compound was heated to 35° C. for one hour
  5. additionthen diluted with 1 liter of hexane
  6. temperaturecooled to -78° C
  7. stirringwith stirring
  8. temperatureto warm
  9. filtrationfiltered
  10. customthe tertiarybutyl-bis(dimethylamino)phosphine, ((CH3)3C)P(NMe2)2, product, 55 g, 0.31 mol (45% yield based on P(NMe2)2Cl), was purified
  11. distillationdistillation of the filtrate

出典と根拠

ORDレコード
ord-6998d31fd98b4979aa53799f5921bdfe
出典データセット
uspto-grants-2000_05
特許番号
US06060119

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