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

HRID 417812

반응식

HRID 417812 반응식
[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].[Cl:24][CH2:25][CH2:26][N:27]([CH2:38][CH2:39][Cl:40])[P:28](Cl)([N:30]([CH2:34][CH2:35][Cl:36])[CH2:31][CH2:32][Cl:33])=[O:29].CC(C)([O-])C.[K+]>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:28]([N:27]([CH2:26][CH2:25][Cl:24])[CH2:38][CH2:39][Cl:40])([N:30]([CH2:31][CH2:32][Cl:33])[CH2:34][CH2:35][Cl:36])=[O:29])=[O:13])[CH2:21][CH2:22][Cl:23]

참가 물질

6

반응물 3

HCID 428391N,N,N',N'-Tetrakis(2-chloroethyl)phosphorodiamidic Chloride2회HCID 23665647Potassium tert-butoxide2회HCID 591649705-Hydroxy-3-thiapentyl N,N,N',N'-tetrakis(2-chloroethyl)phosphorodiamidate

생성물 1

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

시약·촉매·용매 2

HCID 8028Tetrahydrofuran용매2회HCID 8857Ethyl Acetate용매

반응 조건

온도
2.5 °C

실험 절차

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+).

후처리

  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

출처 및 근거

ORD 기록
ord-cef3643e234e471fbb2deb5a26020afb
출처 데이터셋
uspto-grants-2012_01
특허 번호
US08093231B2

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