Dichloromethane → HCID 13037526, compound

HRID 2058924Notes

Reaction equation

HRID 2058924 reaction equation
[C:1]1([P:7]2(=[O:22])[C:11]3[CH:12]=[CH:13][CH:14]=[CH:15][C:10]=3[CH2:9][N:8]2[C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C(Cl)Cl.F[B-](F)(F)F.[O:31]=[N+:32]=[O:33]>C(OCC)C>[C:1]1([P:7]2(=[O:22])[C:11]3[CH:12]=[CH:13][CH:14]=[CH:15][C:10]=3[CH2:9][N:8]2[C:16]2[CH:17]=[CH:18][C:19]([N+:32]([O-:33])=[O:31])=[CH:20][CH:21]=2)[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

5

Reactant 3

HCID 6344Dichloromethane2×HCID 11073463Nitronium tetrafluoroborateHCID 13037520HCID 13037520, compound

Product 1

HCID 13037526HCID 13037526, compoundYield 78%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
26 °C

Procedure

Under a static nitrogen atmosphere, a solution of 1,2-diphenyl-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide (1.0 g, 0.0033 mol) in 10 ml. of methylene chloride was dropwise added to a constantly stirred suspension of nitronium tetrafluoroborate (0.47 g, 0.0035 mol) in 25 ml. of methylene chloride while maintaining the temperature between -5° C. and 5° C. The reaction mixture was stirred for 3 hours at 26° C. and then added to 40 ml. of ice water. The layers were separated and the aqueous layer was extracted with methylene chloride. The methylene chloride layers were combined, dried over magnesium sulfate, and concentrated in vacuo to yield a residue which was purified on a silica gel column using 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-(4-nitrophenyl)-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide (0.9 g, 78% yield) as a yellow solid having a melting point of 255°-257° C. and the following analysis:

Workup

  1. additionadded to 40 ml
  2. customThe layers were separated
  3. extractionthe aqueous layer was extracted with methylene chloride
  4. dry with materialdried over magnesium sulfate
  5. concentrationconcentrated in vacuo
  6. customto yield a residue which
  7. customwas purified on a silica gel column
  8. additionFractions containing the benzazaphosphole
  9. concentrationconcentrated in vacuo
  10. customto produce a crude product

Sources & evidence

ORD record
ord-61f88d86c5904f76a4902ea731ab9e14
Source dataset
uspto-grants-1982_03
Patent number
US04319913

Reaction notes

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