Benzene → HCID 57315705, compound

HRID 442462Notes

Reaction equation

HRID 442462 reaction equation
C([Li])CCC.[C:6]([O:10][C:11](=[O:15])[CH2:12][N+:13]#[C-:14])([CH3:9])([CH3:8])[CH3:7].[P:16](Cl)(=[O:23])([O:20][CH2:21][CH3:22])[O:17][CH2:18][CH3:19].C1C=CC=CC=1>CCCCCC.O>[C:6]([O:10][C:11](=[O:15])[CH:12]([P:16]([O:20][CH2:21][CH3:22])([O:17][CH2:18][CH3:19])=[O:23])[N+:13]#[C-:14])([CH3:9])([CH3:8])[CH3:7]

Participants

7

Reactant 4

HCID 241BenzeneHCID 13139Diethyl chlorophosphateHCID 2759404tert-Butyl isocyanoacetateHCID 178418339Butyllithium

Product 1

HCID 57315705HCID 57315705, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8058HexaneSolvent3×

Procedure

1 ml of an approximately 2 molar solution of butyllithium in hexane is added over a period of 15 minutes to a solution, cooled to -10° C., of 282 mg (2 mmols) of isocyanoacetic acid tert.-butyl ester in 3 ml of dry hexane (distilled over sodium), whilst stirring vigorously and in a nitrogen atmosphere. The suspension which forms is stirred for a further 10 minutes and a solution of 413 μl (2 mmols) of diethyl phosphorochloridate in 5 ml of dry hexane is then added over a period of 15 minutes. The reaction mixture is stirred for a further 30 minutes, then treated with 20 ml of benzene and 5 ml of water and stirred vigorously for a further 10 minutes. The organic phase is washed with 3 times 5 ml of saturated aqueous sodium chloride solution, dried over sodium sulphate and evaporated in vacuo. The residue is chromatographed on silica gel. Benzene/ethyl acetate, 3:1, elutes diethylphosphono-isocyanoacetic acid tert.-butyl ester as a pale yellow oil; IR spectrum (in methylene chloride): characteristic bands at 3.4; 4.64; 5.70; 7.30; 8.00; 8.70 and 9.80μ.

Workup

  1. stirringThe suspension which forms is stirred for a further 10 minutes
  2. stirringThe reaction mixture is stirred for a further 30 minutes
  3. stirringstirred vigorously for a further 10 minutes
  4. washThe organic phase is washed with 3 times 5 ml of saturated aqueous sodium chloride solution
  5. dry with materialdried over sodium sulphate
  6. customevaporated in vacuo
  7. customThe residue is chromatographed on silica gel

Sources & evidence

ORD record
ord-d1598b234bdc4ceda7ce8db8a4285bdc
Source dataset
uspto-grants-1977_08
Patent number
US04045520

Reaction notes

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