N,N,N',N'-Tetramethylethylenediamine → HCID 178444076, 화합물

HRID 582169

반응식

HRID 582169 반응식
[C:1]([N:20]1[CH:24]=[N:23][CH:22]=[N:21]1)([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CN(C)[CH2:27][CH2:28]N(C)C.[CH2:33]([Li])[CH2:34]CC.[O:38]=[CH:39][CH2:40][CH2:41][P:42]([O:47]CC)(=[O:46])[O:43]CC>O1CCCC1.C(O)=O>[PH:42](=[O:43])([OH:47])[OH:46].[CH2:33]([C:40]([CH2:27][CH3:28])([CH:39]([OH:38])[C:24]1[N:20]([C:1]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)([C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=2)[C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[N:21]=[CH:22][N:23]=1)[CH3:41])[CH3:34]

참가 물질

7

반응물 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 46382511-Trityl-1H-1,2,4-triazoleHCID 118163803-(Diethoxyphosphinyl)propanalHCID 178418339Butyllithium

생성물 1

HCID 178444076HCID 178444076, 화합물

시약·촉매·용매 2

HCID 284Formic Acid용매HCID 8028Tetrahydrofuran용매

실험 절차

A solution of 1-trityl-1,2,4-triazole (10.0 g, prepared as described in Example 1) and N,N,N',N'-tetramethylethylenediamine (3.8 g) in dry tetrahydrofuran (250 ml) was cooled to -70° C. under nitrogen. n-Butyllithium (22.2 ml, 1.6M solution in hexane) was added dropwise, with stirring, at such a rate that the internal temperature was maintained below -60° C. The red solution was stirred at -70° C. for twenty-five minutes, then treated dropwise with diethyl 3-oxo-propane phosphonate (6.20 g, prepared by formic acid deacetalisation of the diethyl acetal, DE 2517448, and also described in, for example, Tetrahedron 1981, 37, 1377) whilst maintaining the temperature at that level. The mixture was stirred for two and a half hours at -70° C. then quenched, at that temperature, with saturated aqueous ammonium chloride solution. It was extracted with ethyl acetate and the organic phase washed with brine, dried over magnesium sulphate, and evaporated under reduced pressure to give crude diethyl 3-hydroxy-3(1-trityl-1,2,4-triazol-5-yl)propane phosphonate (10.81 g). Chromatography on silica, using dichloromethane-ethanol (19:1) as eluant, gave pure material, m.p. 154-155° C. NMR (CDCl3): δ 1.3(6H,t), 1.9(2H,m), 1.7(2H,m), 3.1(1H,br), 4.0(4H,m), 4.1(1H,t), 7.1-7.3 (15H,m), 7.9(1H,s). M/S: M+ 505.

후처리

  1. temperatureat such a rate that the internal temperature was maintained below -60° C
  2. stirringThe red solution was stirred at -70° C. for twenty-five minutes
  3. temperaturewhilst maintaining the temperature at that level
  4. stirringThe mixture was stirred for two and a half hours at -70° C.
  5. customthen quenched, at that temperature, with saturated aqueous ammonium chloride solution
  6. extractionIt was extracted with ethyl acetate
  7. washthe organic phase washed with brine
  8. dry with materialdried over magnesium sulphate
  9. customevaporated under reduced pressure

출처 및 근거

ORD 기록
ord-63b8334ef1bd4477aefdd6330f135c48
출처 데이터셋
uspto-grants-1999_07
특허 번호
US05922644

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