N,N,N',N'-Tetramethylethylenediamine → HCID 13037514, compound

HRID 2058914Notes

Reaction equation

HRID 2058914 reaction equation
C([Li])CCC.CN(C)CCN(C)C.[CH:14]([NH:17][CH2:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)([CH3:16])[CH3:15].[C:25]1([P:31](Cl)(Cl)=[O:32])[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1>CCCCCC.C1CCCCC1>[CH:14]([N:17]1[CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=2[P:31]1(=[O:32])[C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)([CH3:16])[CH3:15]

Participants

7

Reactant 4

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 66024IsopropylbenzylamineHCID 69990Phenylphosphonic dichlorideHCID 178418339Butyllithium

Product 1

HCID 13037514HCID 13037514, compoundYield 28%

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 (7.87 g, 0.123 mol) in hexane was added to a solution of tetramethylethylenediamine (14.3 g, 0.123 mol) in 60 ml. of anhydrous cyclohexane with constant stirring. While maintaining the temperature of the reaction at 0° C., a solution of N-isopropylbenzylamine (9 g, 0.06 mol) in 60 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 -40° C. using a solid carbon dioxide-acetone bath. A solution of phenylphosphonic dichloride (12.5 g, 0.064 mol) in 60 ml. of anhydrous cyclohexane was rapidly added to the suspension causing the temperature of the reaction to increase to 10° C. The reaction mixture was stirred for 1.5 hours at 26° C., after which time the reaction mixture was cooled to 0° C. and then quenched with the rapid addition of 12 ml. of acetic acid. After stirring for 15 minutes, the cyclohexane was removed on a rotary evaporator, and the resulting residue was partitioned between methylene chloride and water. The layers were separated and the methylene chloride layer was washed with water, dried over magnesium sulfate and concentrated in vacuo to yield an oil. This oil was distilled at 160° C. and 0.2 torr and the resulting residue was crystallized at 0° C. from diethyl ether and petroleum ether to yield 2-(1-isopropyl)-1-phenyl-2,3-dihydro-1H-2,1-benzazaphosphole-1-oxide (4.5 g, 28% yield) having a melting point of 92°-94° 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 -40° C.
  5. customthe temperature of the reaction
  6. temperatureto increase to 10° C
  7. stirringThe reaction mixture was stirred for 1.5 hours at 26° C.
  8. temperatureafter which time the reaction mixture was cooled to 0° C.
  9. customquenched with the rapid addition of 12 ml
  10. stirringAfter stirring for 15 minutes
  11. customthe cyclohexane was removed on a rotary evaporator
  12. customthe resulting residue was partitioned between methylene chloride and water
  13. customThe layers were separated
  14. washthe methylene chloride layer was washed with water
  15. dry with materialdried over magnesium sulfate
  16. concentrationconcentrated in vacuo
  17. customto yield an oil
  18. distillationThis oil was distilled at 160° C.
  19. custom0.2 torr and the resulting residue was crystallized at 0° C. from diethyl ether and petroleum ether

Sources & evidence

ORD record
ord-09857cba9f6245b2982e44052c7b6884
Source dataset
uspto-grants-1982_03
Patent number
US04319913

Reaction notes

Loading…