Ammonium Chloride → HCID 178435655, compound

HRID 275572Notes

Reaction equation

HRID 275572 reaction equation
[CH:1]([N-]C(C)C)(C)C.[Li+].[PH:9](=[O:12])([OH:11])[OH:10].[CH2:13]([C:15]([CH2:43][CH3:44])([CH:17](F)[C:18]1[N:22]=[CH:21][N:20]([C:23]([C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[N:19]=1)C)[CH3:14].[Cl-].[NH4+]>>[PH:9](=[O:10])([OH:12])[OH:11].[CH2:13]([CH:15]1[CH:43]([CH2:44][CH3:1])[CH:17]1[C:18]1[N:22]=[CH:21][N:20]([C:23]([C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)([C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=2)[C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=2)[N:19]=1)[CH3:14]

Participants

4

Reactant 3

HCID 25517Ammonium ChlorideHCID 2724682Lithium diisopropylamideHCID 178443894HCID 178443894, compound

Product 1

HCID 178435655HCID 178435655, compound

Procedure

Lithium diisopropylamide (0.91 ml, 1.5M in cyclohexane) was added dropwise under nitrogen to a stirred solution of diethyl 3-fluoro-3(1-trityl-1,2,4-triazol-3-yl)propane phosphonate (0.35 g, prepared as described in Example 27) whilst maintaining the temperature below -60° C. After five hours, the mixture was allowed to warm then stand at room temperature overnight. It was then poured on to saturated ammonium chloride solution and extracted with ethyl acetate. The extracts were dried over magnesium sulphate and evaporated under reduced pressure. The residue was chromatographed on silica, using dichloromethane-ethanol (19:1) as eluant, to give diethyl 2(1-trityl-1,2,4-triazol-3-yl)cyclopropane phosphonate (0.18 g). NMR (CDCl3): δ1.3(6H,2xt), 1.4-1.5(3H,m), 2.6-2.7(1H,m), 4.05-4.2(4H,m), 7.1-7.3(15H,m), 7.8(1H,s). M/S: M+ 487. The basic structure was confirmed by 13C, 19F, 31P, COSY and NOESY experiments but stereochemistry could not be assigned. Theoretical calculations suggested that the trans (1RS,2RS) isomer is likely to be much more stable and thus preferred.

Workup

  1. temperaturewhilst maintaining the temperature below -60° C
  2. temperatureto warm
  3. waitthen stand at room temperature overnight
  4. extractionextracted with ethyl acetate
  5. dry with materialThe extracts were dried over magnesium sulphate
  6. customevaporated under reduced pressure
  7. customThe residue was chromatographed on silica

Sources & evidence

ORD record
ord-0ca8bfbb931d4499bb9d08710d461483
Source dataset
uspto-grants-1995_02
Patent number
US05393732

Reaction notes

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