N,N-Dimethylaniline → 8,5-Dichloro-5H-dibenzo[b,e][1,4]diazepine

HRID 1986572Notes

Reaction equation

HRID 1986572 reaction equation
CN(C)C1C=CC=CC=1.P(Cl)(Cl)([Cl:12])=O.[Cl:15][C:16]1[CH:17]=[CH:18][C:19]2[NH:25][C:24]3[CH:26]=[CH:27][CH:28]=[CH:29][C:23]=3[C:22](=O)[NH:21][C:20]=2[CH:31]=1>C1(C)C=CC=CC=1>[Cl:15][C:16]1[CH:17]=[CH:18][C:19]2[N:25]([Cl:12])[C:24]3[CH:26]=[CH:27][CH:28]=[CH:29][C:23]=3[CH:22]=[N:21][C:20]=2[CH:31]=1

Participants

5

Reactant 3

HCID 949N,N-DimethylanilineHCID 24813Phosphorus oxychlorideHCID 36531168-chloro-5,10-dihydro-11H-dibenzo[b,e][1,4]diazepin-11-one

Product 1

HCID 574854318,5-Dichloro-5H-dibenzo[b,e][1,4]diazepineYield 69%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
95 °C

Procedure

N,N-dimethylaniline (5.1 ml, 40 mmol) and phosphorus oxychloride (2.8 ml, 30 mmol) was added to a mixture of 8-chloro-5,10-dihydro-dibenzo[b,e][1,4]diazepine-11-one (2.45 g, 10 mmol) in dry toluene (20 ml). The mixture was shaken at 95° C. for 2 h. The temperature was then decreased and the excess N,N-dimethylaniline and phosphorus oxychloride were removed at reduced pressure using an oil pump. The remaining oil was dissolved in dioxane (20 ml) and aqueous Na2CO3-solution (10 ml, 2 M) was added. The two-phase mixture was shaken at 80° C. for 30 min. The temperature was then decreased and ether was added to the reaction mixture. The ethereal phase was washed with saturated aqueous NaCl-solution, dried (Na2SO4) and finally concentrated at reduced pressure. The obtained oil crystallized upon standing at room temperature. Recrystallization (heptane-ether) gave 1.8 g (69%) of the title compound (160FE64). 1H NMR (CDCl3) d 7.61 (dd, 1H, J=1.4, 7.8 Hz), 7.31 (dt, 1H, J=1.5, 8.0 Hz), 7.15 (d, 1H, J=2.5 Hz), 7.02 (m 2H), 6.66 (dd, 1H, J=1.0, 7.8 Hz), 6.58 (d, 1H, J=8.4 Hz), 4.94 (bs, 1H). 13C NMR (CDCl3) d 157.2, 152.4, 140.3, 138.9, 134.0, 131.9, 129.7, 128.5, 128.0, 127.0, 123.5, 121.0, 119.8.

Workup

  1. customthe excess N,N-dimethylaniline and phosphorus oxychloride were removed at reduced pressure
  2. dissolutionThe remaining oil was dissolved in dioxane (20 ml)
  3. additionaqueous Na2CO3-solution (10 ml, 2 M) was added
  4. stirringThe two-phase mixture was shaken at 80° C. for 30 min
  5. additionether was added to the reaction mixture
  6. washThe ethereal phase was washed with saturated aqueous NaCl-solution
  7. dry with materialdried (Na2SO4)
  8. concentrationfinally concentrated at reduced pressure
  9. customThe obtained oil crystallized
  10. customupon standing at room temperature
  11. customRecrystallization (heptane-ether)

Sources & evidence

ORD record
ord-64cc16d592c849f5873f075785f18958
Source dataset
uspto-grants-2009_06
Patent number
US07550454B2

Reaction notes

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