Water → (4-Diethoxyphosphoryloxyimino-cyclohexa-2,5-dienylidene)-2,4-dichlorophenyl-acetonitrile

HRID 1018893Notes

Reaction equation

HRID 1018893 reaction equation
[OH:1][N:2]=[C:3]1[CH:8]=[CH:7][C:6](=[C:9]([C:12]2[CH:17]=[CH:16][C:15]([Cl:18])=[CH:14][C:13]=2[Cl:19])[C:10]#[N:11])[CH:5]=[CH:4]1.C(N([CH2:25][CH3:26])CC)C.C([P:29](Cl)(CC)=[O:30])C.[OH2:34].C1C[O:38][CH2:37][CH2:36]1>C(OCC)(=O)C>[CH2:37]([O:38][P:29]([O:1][N:2]=[C:3]1[CH:8]=[CH:7][C:6](=[C:9]([C:12]2[CH:17]=[CH:16][C:15]([Cl:18])=[CH:14][C:13]=2[Cl:19])[C:10]#[N:11])[CH:5]=[CH:4]1)([O:30][CH2:25][CH3:26])=[O:34])[CH3:36]

Participants

7

Reactant 5

HCID 962WaterHCID 8028TetrahydrofuranHCID 8471TriethylamineHCID 5195381Diethylphosphinoyl chlorideHCID 18398532(4-Hydroxyimino-cyclohexa-2,5-dienylidene)-2,4-dichlorphenyl-acetonitrile

Product 1

HCID 18398561(4-Diethoxyphosphoryloxyimino-cyclohexa-2,5-dienylidene)-2,4-dichlorophenyl-acetonitrile

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

20.4 g (0.07 mol) of (4-hydroxyimino-cyclohexa-2,5-dienylidene)-2,4-dichlorphenyl-acetonitrile, 7.1 g (0.07 mol) of triethylamine and a catalytic amount of N,N-dimethylaminopyridine are dissolved in 270 ml of THF. This solution is cooled in an ice bath, and 12.1 g (0.07 mol) of diethylphosphoryl chloride are added dropwise while stirring. When the addition is complete, the orange solution is warmed to room temperature and stirred overnight. Water and ethyl acetate are subsequently added, and the organic layer is washed several times with saturated sodium chloride solution and water and dried over magnesium sulfate. Evaporation of the solvent gives 30.4 g of a viscous yellowish oil, which is further purified by filtration over silica gel (eluent: hexane/ethyl acetate 9:1). Yield: 25.5 g (85%). 31P-NMR (CDCl3; δ relative to H3PO4 as external reference): 0.132 and 0.003 ppm (P(V) of the (E) and (Z)-isomers). 1H-NMR (CDCl3, δ [ppm]): 7.60-7.15 (m, 7H); 7.0-6.55 (m, 2H), 4.35-4.15, (m, 4H-C(1′)); 1.38 and 1.35 (t, 3H-C(2′)).

Workup

  1. temperatureThis solution is cooled in an ice bath
  2. additionWhen the addition
  3. stirringstirred overnight
  4. washthe organic layer is washed several times with saturated sodium chloride solution and water
  5. dry with materialdried over magnesium sulfate
  6. customEvaporation of the solvent

Sources & evidence

ORD record
ord-e24bb00e0949495faef2497c675f9a16
Source dataset
uspto-grants-2002_11
Patent number
US06485886B1

Reaction notes

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