N,N,N',N'-Tetramethylethylenediamine → HCID 13037521, compound

HRID 2058920Notes

Reaction equation

HRID 2058920 reaction equation
C([Li])CCC.CN(C)CCN(C)C.[CH2:14]([NH:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.[C:28]1([C:34]2[CH:39]=[CH:38][C:37]([P:40](Cl)(Cl)=[O:41])=[CH:36][CH:35]=2)[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1>CCCCCC.C(OCC)C.C1CCCCC1>[C:28]1([C:34]2[CH:39]=[CH:38][C:37]([P:40]3(=[O:41])[C:16]4[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=4[CH2:14][N:21]3[C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)=[CH:36][CH:35]=2)[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=1

Participants

8

Reactant 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 66028BenzylanilineHCID 12670624[1,1'-Biphenyl]-4-ylphosphonic dichlorideHCID 178418339Butyllithium

Product 1

HCID 13037521HCID 13037521, compoundYield 5%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8058HexaneSolventHCID 8078CyclohexaneSolvent3×

Conditions

Temperature
26 °C

Procedure

Under a static nitrogen atmosphere at 0° C., a solution of n-butyllithium (3.94 g, 0.0615 mol) in hexane was added to a solution of tetramethylethylenediamine (1.86 g, 0.016 mol) in 30 ml. of anhydrous cyclohexane with constant stirring. While maintaining the temperature of the reaction at 0° C., a solution of N-benzylaniline (5.5 g, 0.03 mol) in 30 ml. of anhydrous cyclohexane was added to the reaction mixture to produce a suspension containing a dilithio compound which was stirred for an additional 2 hours at 26° C. 4-Phenylphenylphosphonic dichloride (8.7 g, 0.032 mol) was directly added to this suspension followed by 60 ml. of cyclohexane. The resulting mixture was stirred for 16 hours at 26° C. The reaction was quenched with the rapid addition of a solution of acetic acid (6 g, mol) in 30 ml. of anhydrous cyclohexane. After stirring for 30 minutes, the cyclohexane layer was removed under vacuum and the resulting residue was partitioned in methylene chloride and water. The layers were separated and the methylene chloride layer was washed with water, dried over sodium sulfate and concentrated in vacuo to yield an oily residue. The oily residue was chromatographically separated 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 anhydrous diethyl ether to yield 1-(4-phenylphenyl)-2-phenyl-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide (0.55 g, 5% yield) as a white solid having a melting point of 259°-261° C. and the following analysis:

Workup

  1. temperatureWhile maintaining
  2. customthe temperature of the reaction at 0° C.
  3. customto produce a suspension
  4. stirringThe resulting mixture was stirred for 16 hours at 26° C
  5. customThe reaction was quenched with the rapid addition of a solution of acetic acid (6 g, mol) in 30 ml
  6. stirringAfter stirring for 30 minutes
  7. customthe cyclohexane layer was removed under vacuum
  8. customthe resulting residue was partitioned in methylene chloride
  9. customThe layers were separated
  10. washthe methylene chloride layer was washed with water
  11. dry with materialdried over sodium sulfate
  12. concentrationconcentrated in vacuo
  13. customto yield an oily residue
  14. customThe oily residue was chromatographically separated on a silica gel column
  15. additionFractions containing the benzazaphosphole
  16. concentrationconcentrated in vacuo
  17. customto produce a crude product

Sources & evidence

ORD record
ord-f59a1cedb6c9401182be887131a94a47
Source dataset
uspto-grants-1982_03
Patent number
US04319913

Reaction notes

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