Dimethyl methylphosphonate → HCID 87946522, compound

HRID 2304987Notes

Reaction equation

HRID 2304987 reaction equation
C([Li])CCC.[CH3:6][P:7](=[O:12])([O:10][CH3:11])[O:8][CH3:9].[CH3:13][C:14]1[O:15][CH2:16][C:17]([CH:35]=[O:36])([CH2:19][CH2:20][C:21]2[CH:26]=[CH:25][C:24]([CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH3:34])=[CH:23][CH:22]=2)[N:18]=1.[CH:37]1[CH:42]=[CH:41][C:40]([O:43][C:44](Cl)=[S:45])=[CH:39][CH:38]=1>C1COCC1>[O:43]([C:44]([O:36][CH:35]([C:17]1([CH2:19][CH2:20][C:21]2[CH:26]=[CH:25][C:24]([CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH3:34])=[CH:23][CH:22]=2)[CH2:16][O:15][C:14]([CH3:13])=[N:18]1)[CH2:6][P:7](=[O:12])([O:10][CH3:11])[O:8][CH3:9])=[S:45])[C:40]1[CH:41]=[CH:42][CH:37]=[CH:38][CH:39]=1

Participants

6

Reactant 4

HCID 12958Dimethyl methylphosphonateHCID 70498Phenyl thioxochloroformateHCID 86585467HCID 86585467, compoundHCID 178418339Butyllithium

Product 1

HCID 87946522HCID 87946522, compoundYield 17%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 0.46 mL of 2 M n-butyllithium in hexanes in 4 mL of THF at −78° C. was treated with 0.10 mL (0.92 mmol) dimethyl methylphosphonate and strirred cold for 50 min. (+/−)-2-Methyl-4-formyl-4-(2-(4-octylphenyl)ethyl)oxazoline (252 mg, 0.76 mmol, from EXAMPLE 2, Step B) was added and the resulting solution was stirred cold for 5 h. The mixture was treated with 0.32 mL (2.3 mmol) of phenyl chlorothionoformate and stirred cold for 1 h. The reaction was quenched with 2 mL of sat'd NH4Cl, then extracted with 30 mL of CH2Cl2. The organic layer was separated, washed with sat'd NaHCO3, dried and concentrated. Flash chromatography on silica gel using hexanes/EtOAc/CH3CN as the eluant afforded 75 mg (17%) of the title compound as a mixture of isomers: Mass spectrum (NH3—CI) 590 (M+H).

Workup

  1. stirringstirred cold for 1 h
  2. customThe reaction was quenched with 2 mL of sat'd NH4Cl
  3. extractionextracted with 30 mL of CH2Cl2
  4. customThe organic layer was separated
  5. washwashed with sat'd NaHCO3
  6. customdried
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-977a2971c4344ca49c3f9fb2cbeae179
Source dataset
uspto-grants-2002_08
Patent number
US06437165B1

Reaction notes

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