N,N,N',N'-Tetramethylethylenediamine → HCID 13037520, compound

HRID 2058919Notes

Reaction equation

HRID 2058919 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([P:34](Cl)(Cl)=[O:35])[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1>CCCCCC.C1CCCCC1>[C:28]1([P:34]2(=[O:35])[C:16]3[CH:17]=[CH:18][CH:19]=[CH:20][C:15]=3[CH2:14][N:21]2[C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1

Participants

7

Reactant 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 66028BenzylanilineHCID 69990Phenylphosphonic dichlorideHCID 178418339Butyllithium

Product 1

HCID 13037520HCID 13037520, compound

Reagents, catalysts & solvents 2

HCID 8058HexaneSolventHCID 8078CyclohexaneSolvent3×

Conditions

Temperature
26 °C

Procedure

Under a static nitrogen atmosphere at 0° C., a solution of n-butyllithium (3.90 g, 0.061 mol) in hexane was added to a solution of tetramethylethylenediamine (1.8 g, 0.0155 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. This suspension was stirred for 2 hours at 26° C. and then cooled to 0° C. A solution of phenylphosphonic dichloride (6.25 g, 0.032 mol) in 30 ml. of anhydrous cyclohexane was added dropwise to the suspension over a period of 15 minutes and the resulting mixture was stirred for 0.5 hours at 0° C., then for 2.5 hours at 26° C. The reaction was quenched with the rapid addition of 6 ml. of acetic acid. The reaction mixture was concentrated in vacuo and the residue partitioned in methylene chloride and water. The layers were separated and the methylene chloride layer was washed with 5% hydrochloric acid, sodium bicarbonate, then water. The methylene chloride layer was dried over magnesium sulfate, concentrated in vacuo and the resulting residue was slurried in anhydrous diethyl ether and allowed to stand at 0° C. for 40 hours. The slurry was filtered and the resulting yellow precipitate was dissolved in a minimal amount of hot ethyl alcohol. The ethyl alcohol solution was diluted with petroleum ether to yield 1,2-diphenyl-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide as white fluffy crystals. A second crop was obtained and the combined product yield was recrystallized from ethanol to yield 1,2-diphenyl-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide (3.0 g, 33% yield) as fluffy needles having a melting point of 227°-229° C. and the following analysis:

Workup

  1. temperatureWhile maintaining
  2. customthe temperature of the reaction at 0° C.
  3. customto produce a suspension
  4. temperaturecooled to 0° C
  5. stirringthe resulting mixture was stirred for 0.5 hours at 0° C.
  6. waitfor 2.5 hours at 26° C
  7. customThe reaction was quenched with the rapid addition of 6 ml
  8. concentrationThe reaction mixture was concentrated in vacuo
  9. customthe residue partitioned in methylene chloride
  10. customThe layers were separated
  11. washthe methylene chloride layer was washed with 5% hydrochloric acid, sodium bicarbonate
  12. dry with materialThe methylene chloride layer was dried over magnesium sulfate
  13. concentrationconcentrated in vacuo
  14. waitto stand at 0° C. for 40 hours
  15. filtrationThe slurry was filtered
  16. dissolutionthe resulting yellow precipitate was dissolved in a minimal amount of hot ethyl alcohol
  17. additionThe ethyl alcohol solution was diluted with petroleum ether

Sources & evidence

ORD record
ord-44ca12f8eaa94c9386c76771839154b7
Source dataset
uspto-grants-1982_03
Patent number
US04319913

Reaction notes

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