Dimethyl Sulfoxide → HCID 178444074, compound

HRID 582182Notes

Reaction equation

HRID 582182 reaction equation
CS(C)=O.C(Cl)(=O)C(Cl)=O.[PH:11](=[O:14])([OH:13])[OH:12].[CH2:15]([C:17]([CH2:45][CH3:46])([CH:19]([OH:44])[C:20]1[N:24]=[CH:23][N:22]([C:25]([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)([C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[N:21]=1)[CH3:18])[CH3:16].C(N(CC)CC)C>ClCCl.C(OCC)(=O)C.O.CCOCC>[PH:11](=[O:12])([OH:14])[OH:13].[CH2:45]([C:17]([CH2:15][CH3:16])([C:19](=[O:44])[C:20]1[N:24]=[CH:23][N:22]([C:25]([C:32]2[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=2)([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[N:21]=1)[CH3:18])[CH3:46]

Participants

9

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 178444075HCID 178444075, compound

Product 1

HCID 178444074HCID 178444074, compoundYield 73.4%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent3×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-60 °C

Procedure

A solution of dimethylsulphoxide (0.46 g) in dichloromethane (3 ml) was added dropwise to a stirred solution of oxalyl chloride (0.36 g) in dichloromethane (15 ml), maintaining the temperature below -60° C. After fifteen minutes, a solution of diethyl 3-hydroxy-3(1-trityl-1,2,4-triazol-3-yl)propane phosphonate (1.19 g, prepared as described in Example 24) in dichloromethane (5 ml) was added, dropwise with stirring, at -60° C. After a further one hour, triethylamine (4.0 ml) was added. The stirred reaction mixture was allowed to warm to -25° C. over fifteen minutes, maintained at that temperature for fifteen minutes, then treated with ether (25 ml) and water (25 ml). The aqueous phase was reextracted twice with ethyl acetate and the combined organic layers washed with water and brine, 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 3-oxo-3(1-trityl-1,2,4-triazol-3-yl)propane phosphonate (0.87 g, m.p. 99-100° C). NMR (CDCl3): δ 1.25(6H,t), 2.1-2.25(2H,m), 3.35(2H,m), 4.1(4H,m), 7.1-7.35(15H,m), 8.05(1H,s). M/S: M+ 503. IR: 1712 cm-1.

Workup

  1. temperaturemaintaining the temperature below -60° C
  2. waitAfter fifteen minutes
  3. customThe stirred reaction mixture
  4. temperatureto warm to -25° C. over fifteen minutes
  5. temperaturemaintained at that temperature for fifteen minutes
  6. washthe combined organic layers washed with water and brine
  7. dry with materialdried over magnesium sulphate
  8. customevaporated under reduced pressure
  9. customThe residue was chromatographed on silica

Sources & evidence

ORD record
ord-3f9371731873441391c3ff96125a9733
Source dataset
uspto-grants-1999_07
Patent number
US05922644

Reaction notes

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