Chloroacetyl chloride → 1-phenyl-2-chloroacetyl-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide

HRID 2058927Notes

Reaction equation

HRID 2058927 reaction equation
[Cl:1][CH2:2][C:3](Cl)=[O:4].[C:6]1([P:12]2(=[O:21])[C:16]3[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=3[CH2:14][NH:13]2)[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.N12CCCCC1C=NCCC2.O1CCCC1>C(OCC)C>[C:6]1([P:12]2(=[O:21])[C:16]3[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=3[CH2:14][N:13]2[C:3](=[O:4])[CH2:2][Cl:1])[CH:7]=[CH:8][CH:9]=[CH:10][CH:11]=1

Participants

6

Reactant 4

HCID 6577Chloroacetyl chlorideHCID 8028TetrahydrofuranHCID 3141121,5-Diazabicyclo(5,4,0)undec-5-eneHCID 130375021-phenyl-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide

Product 1

HCID 130375291-phenyl-2-chloroacetyl-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxideYield 45%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
26 °C

Procedure

Chloroacetyl chloride (0.8 g, 0.0072 mol) was added to a suspension of 1-phenyl-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide (1.5 g, 0.00656 mol) and 1,5-diazabicyclo[5.4.0]undec-5-ene in 25 ml. of tetrahydrofuran with constant stirring. The reaction mixture was heated at reflux for 30 minutes, then stirred for 16 hours at 26° C. The reaction mixture was concentrated using a rotary evaporator and the residue was partitioned between chloroform and water. The chloroform layer was separated, and washed with 5% hydrochloric acid, a 5% sodium bicarbonate solution and then with water. The chloroform layer was dried over magnesium sulfate, concentrated in vacuo and the resulting residue was slurried in anhydrous ether to yield a crystalline solid. The crystalline solid was further purified using a silica gel column with ethyl acetate as the eluant. Fractions containing the benzazaphosphole were combined and concentrated in vacuo to produce a crude product. The crude product was slurried in diethyl ether to yield 1-phenyl-2-chloroacetyl-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide (0.9 g, 45% yield) as a solid having a melting point of 167°-169° C. and the following analysis:

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux for 30 minutes
  3. concentrationThe reaction mixture was concentrated
  4. customa rotary evaporator
  5. customthe residue was partitioned between chloroform and water
  6. customThe chloroform layer was separated
  7. washwashed with 5% hydrochloric acid
  8. dry with materialThe chloroform layer was dried over magnesium sulfate
  9. concentrationconcentrated in vacuo
  10. customto yield a crystalline solid
  11. customThe crystalline solid was further purified
  12. additionFractions containing the benzazaphosphole
  13. concentrationconcentrated in vacuo
  14. customto produce a crude product

Sources & evidence

ORD record
ord-031e67d5505249ceb14cdd69667c2feb
Source dataset
uspto-grants-1982_03
Patent number
US04319913

Reaction notes

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