N,N,N',N'-Tetramethylmethanediamine → 8-Chloro-N,N-dimethyl-β,6-diphenyl-4H-[1,2,4]triazolo[4,3-a][1,4]benzodiazepine-1-ethanamine

HRID 616660Notes

Reaction equation

HRID 616660 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[N:11]3[C:12]([CH2:15][C:16]4[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=4)=[N:13][N:14]=[C:10]3[CH2:9][N:8]=[C:7]([C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)[C:6]=2[CH:28]=1.[CH3:29][N:30]([CH2:32]N(C)C)[CH3:31].C(Cl)(=O)C.C(=O)(O)[O-].[Na+]>CN(C)C=O>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[N:11]3[C:12]([CH:15]([C:16]4[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=4)[CH2:29][N:30]([CH3:32])[CH3:31])=[N:13][N:14]=[C:10]3[CH2:9][N:8]=[C:7]([C:22]3[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=3)[C:6]=2[CH:28]=1

Participants

6

Reactant 4

HCID 5829N,N,N',N'-TetramethylmethanediamineHCID 6367Acetyl chlorideHCID 516892Sodium BicarbonateHCID 12560611HCID 12560611, compound

Product 1

HCID 125606128-Chloro-N,N-dimethyl-β,6-diphenyl-4H-[1,2,4]triazolo[4,3-a][1,4]benzodiazepine-1-ethanamine

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A stirred solution of 8-chloro-1-benzyl-6-phenyl-4H-s-triazolo[4,3-a][1,4]benzodiazepine (3.85 g., 0.01 mole) in dry dimethylformamide (50 ml.) was cooled, under nitrogen, in an ice bath and treated with N,N,N',N',-tetramethyldiaminomethane (1.229 g., 0.012 mole) and then dropwise with acetyl chloride (0.923 ml., 0.013 mole). The mixture was kept in the ice bath for 2 hours, poured into a mixture of ice and saturated aqueous sodium bicarbonate solution and extracted several times with chloroform. The extracts were washed with a dilute aqueous sodium chloride solution, dried over anhydrous sodium sulfate and concentrated in vacuo using xylene and toluene to help remove dimethylformamide. The residue was chromatographed on silica gel (200 g.) with methanol. The product thus obtained was crystallized from diethylether to give 8-chloro-1-[2-(dimethylamino)-1-phenylethyl]-6-phenyl-4H-s-triazolo[4,3-a][1,4]benzodiazepine in six crops; 0.483 g. of melting point 168.5°-170° C; 1.436 g. of melting point 169°-170.5° C. and 0.471 g. of melting point 169°-170.5° C., 0.530 g. of melting point 168.5°-170° C.; 0.231 g. of melting point 169°-170° C. and 0.269 g. of melting point 169°-170.5° C. The analytical sample was crystallized from ethyl acetate-Skellysolve B hexanes and had a melting point of 169.5°-171.5° C.

Workup

  1. extractionextracted several times with chloroform
  2. washThe extracts were washed with a dilute aqueous sodium chloride solution
  3. dry with materialdried over anhydrous sodium sulfate
  4. concentrationconcentrated in vacuo
  5. customto help remove dimethylformamide
  6. customThe residue was chromatographed on silica gel (200 g.) with methanol
  7. customThe product thus obtained
  8. customwas crystallized from diethylether

Sources & evidence

ORD record
ord-2a76a00c805345cc8acbdb4819c00b04
Source dataset
uspto-grants-1978_02
Patent number
US04075221

Reaction notes

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