Water → (5-Diethoxyphosphoryloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile

HRID 1018889Notes

Reaction equation

HRID 1018889 reaction equation
[OH:1][N:2]=[C:3]1[S:7][C:6](=[C:8]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=2[CH3:17])[C:9]#[N:10])[CH:5]=[CH:4]1.C([P:20](Cl)(CC)=[O:21])C.C(N([CH2:30][CH3:31])CC)C.[OH2:32].[O:33]1CC[CH2:35][CH2:34]1>>[CH2:34]([O:33][P:20]([O:1][N:2]=[C:3]1[S:7][C:6](=[C:8]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=2[CH3:17])[C:9]#[N:10])[CH:5]=[CH:4]1)([O:21][CH2:30][CH3:31])=[O:32])[CH3:35]

Participants

6

Reactant 5

HCID 962WaterHCID 8028TetrahydrofuranHCID 8471TriethylamineHCID 5195381Diethylphosphinoyl chlorideHCID 86758612HCID 86758612, compound

Product 1

HCID 53810703(5-Diethoxyphosphoryloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile

Conditions

Temperature
5 °C

Procedure

8 g (33 mmol) of (5-Hydroxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile are dissolved in 90 ml of tetrahydrofuran (THF) and cooled in an ice bath. After adding 6.3 g (36 mmol) of diethylphosphoryl chloride to the solution, 5.0 g (50 mmol) of triethylamine are added dropwise, keeping the temperature below 50° C. The reaction mixture is stirred at 5° C. for 60 min., then poured into 100 ml of water, and extracted with ethyl acetate. The organic phase is washed with 0.1N hydrochloric acid solution, water, and sodium chloride solution. The organic phase is dried over MgSO4, the solvent is distilled off, and the residue is purified by flash chromatography on silica gel with ethyl acetate—hexane (1:1) as eluent. The product is obtained in the form of a yellow solid, melting point 90-91° C. The structure is confirmed by the 1H-NMR spectrum (CDCl3). δ [ppm]: 1.43 (t, 6H), 2.37 (s, 3H), 4.36-4.47 (m, 4H), 6.13 (d, 1H), 6.86 (d, 1H), 7.19-7.39 (m, 4H).

Workup

  1. temperaturecooled in an ice bath
  2. additionare added dropwise
  3. customthe temperature below 50° C
  4. extractionextracted with ethyl acetate
  5. washThe organic phase is washed with 0.1N hydrochloric acid solution, water, and sodium chloride solution
  6. dry with materialThe organic phase is dried over MgSO4
  7. distillationthe solvent is distilled off
  8. customthe residue is purified by flash chromatography on silica gel with ethyl acetate—hexane (1:1) as eluent
  9. customThe product is obtained in the form of a yellow solid, melting point 90-91° C

Sources & evidence

ORD record
ord-93baef1de423460c9cf0587cecb58c3f
Source dataset
uspto-grants-2002_11
Patent number
US06485886B1

Reaction notes

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