N,N,N',N'-Tetrakis(2-chloroethyl)phosphorodiamidic Chloride → Di[2-[[bis[bis(2-chloroethyl)amino]phosphinyl]oxy]ethyl]sulfide

HRID 855525

反応式

HRID 855525 の反応式
[Cl:1][CH2:2][CH2:3][N:4]([CH2:21][CH2:22][Cl:23])[P:5]([N:14]([CH2:18][CH2:19][Cl:20])[CH2:15][CH2:16][Cl:17])(=[O:13])[O:6][CH2:7][CH2:8][S:9][CH2:10][CH2:11][OH:12].CC(C)([O-])C.[K+].[Cl:30][CH2:31][CH2:32][N:33]([CH2:44][CH2:45][Cl:46])[P:34](Cl)([N:36]([CH2:40][CH2:41][Cl:42])[CH2:37][CH2:38][Cl:39])=[O:35]>O1CCCC1.C(OCC)(=O)C>[Cl:1][CH2:2][CH2:3][N:4]([P:5]([N:14]([CH2:15][CH2:16][Cl:17])[CH2:18][CH2:19][Cl:20])([O:6][CH2:7][CH2:8][S:9][CH2:10][CH2:11][O:12][P:34]([N:33]([CH2:32][CH2:31][Cl:30])[CH2:44][CH2:45][Cl:46])([N:36]([CH2:37][CH2:38][Cl:39])[CH2:40][CH2:41][Cl:42])=[O:35])=[O:13])[CH2:21][CH2:22][Cl:23]

参加物

6

反応物 3

HCID 428391N,N,N',N'-Tetrakis(2-chloroethyl)phosphorodiamidic ChlorideHCID 23665647Potassium tert-butoxide2 回HCID 591649705-Hydroxy-3-thiapentyl N,N,N',N'-tetrakis(2-chloroethyl)phosphorodiamidate

生成物 1

HCID 86601855Di[2-[[bis[bis(2-chloroethyl)amino]phosphinyl]oxy]ethyl]sulfide収率 18%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒

反応条件

温度
2.5 °C

実験手順

5-Hydroxy-3-thiapentyl N,N,N′,N′-tetrakis(2-chloroethyl)phosphorodiamidate, 174 mg (0.387 mmol), and N,N,N′N′-tetrakis(2-chloroethyl)phosphorodiamidoyl chloride, 363 mg (0.996 mmol), were dissolved in 15 mL anhydrous tetrahydrofuran and cooled to 0-5° C. in an ice-water bath. Potassium tert-butoxide, 0.4 mL of 1 M solution in tetrahydrofuran (0.4 mmol), was added over a 10-15 minute period, and the reaction mixture kept at 0-5° C. for another 30 minutes under nitrogen. The reaction mixture was allowed to warm to room temperature and stirred at room temperature for 43 hours. Additional potassium tert-butoxide and N,N,N′,N′-tetrakis(2-chloroethyl)phosphorodiamidoyl chloride were added over the next 4 days to drive the reaction to completion. After 4.5 days, the reaction mixture was diluted with ethyl acetate; and the ethyl acetate layer separated, washed with water and brine, then dried over anhydrous magnesium sulfate, and the ethyl acetate removed under vacuum. The crude di[2-[[bis[bis(2-chloroethyl)amino]phosphinyl]oxy]ethyl]sulfide, 630 mg, was twice purified by preparative HPLC, and the product fractions combined and lyophilized, giving di[2-[[bis[bis(2-chloroethyl)amino]phosphinyl]oxy]ethyl]sulfide, compound 1CC, as a colorless oil, compound 1CC, 56 mg (18% yield), identified by HPLC and 1H and 31P NMR. Mass spectrum: 779 (C20H40Cl8N4O4P2S+4+H+).

後処理

  1. temperatureto warm to room temperature
  2. customthe reaction to completion
  3. waitAfter 4.5 days
  4. customand the ethyl acetate layer separated
  5. washwashed with water and brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. customthe ethyl acetate removed under vacuum
  8. customThe crude di[2-[[bis[bis(2-chloroethyl)amino]phosphinyl]oxy]ethyl]sulfide, 630 mg, was twice purified by preparative HPLC

出典と根拠

ORDレコード
ord-a9b8f3fc2e6c4993b410040a2f8c955a
出典データセット
uspto-grants-2007_08
特許番号
US07262182B2

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