Methylhydrazine → HCID 12515151, compound

HRID 2082780Notes

Reaction equation

HRID 2082780 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[NH:11][C:10](=S)[CH2:9][N:8]=[C:7]([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)[C:6]=2[CH:19]=1.[CH3:20][NH:21][NH2:22]>CO>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[N:11]=[C:10]([N:21]([CH3:20])[NH2:22])[CH2:9][N:8]=[C:7]([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)[C:6]=2[CH:19]=1

Participants

4

Reactant 2

HCID 6061MethylhydrazineHCID 826706Thionordiazepam

Product 1

HCID 12515151HCID 12515151, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A suspension of 8.6 g. (0.03 mole) of 7-chloro-1,3-dihydro-5-phenyl-2H-1,4-benzodiazepine-2-thione (I) (prepared as in U.S. Pat. No. 3,422,091) in 600 ml. of methanol; is treated with 5.53 g. (0.12 mole) of methylhydrazine (II) and stirred at room temperature for about 2.5 hours. A vigorous stream of nitrogen is bubbled through the mixture during this period to remove liberated hydrogen sulfide. The mixture is concentrated under vacuum to a small volume, diluted with ice water and extracted with chloroform. The extract is washed with cold, dilute sodium chloride solution, dried with sodium sulfate and concentrated under vacuum. The residue is chromatographed on 400 g. of silica gel with a mixture of 1.5% methanol-98.5% chloroform. The product is crystallized on a rotary evaporator at about 25° C. by replacing the chloroform of a methanolchloroform solution, first with ethyl acetate and then with Skellysolve B. The yields of 7-chloro-2-(1-methylhydrazino)-5-phenyl-3H-1,4-benzodiazepine (III) are 5.07 g. having a melting point of 166.6° to 173° C. and 0.52 g. having a melting point of 175° to 176° C. The analytical sample is recrystallized from ethyl acetate-Skellysolve B having a melting point of 178.5° to 179.5° C.; ultraviolet (EtOH) end absorption, λmax. 232mμ (ε=21,400), 269 (18,300), 352 (2920); infrared absorption (Nujol) 3290, 3180 cm-1 (NH), 1645, 1590, 1575, 1565 (C=N/C=C).

Workup

  1. additionA suspension of 8.6 g
  2. additionis treated with 5.53 g
  3. customA vigorous stream of nitrogen is bubbled through the mixture during this period
  4. customto remove liberated hydrogen sulfide
  5. concentrationThe mixture is concentrated under vacuum to a small volume
  6. additiondiluted with ice water
  7. extractionextracted with chloroform
  8. washThe extract is washed with cold, dilute sodium chloride solution
  9. dry with materialdried with sodium sulfate
  10. concentrationconcentrated under vacuum
  11. customThe residue is chromatographed on 400 g
  12. additionof silica gel with a mixture of 1.5% methanol-98.5% chloroform
  13. customThe product is crystallized on a rotary evaporator at about 25° C.

Sources & evidence

ORD record
ord-ecfa20a37764421b99bab9fda686f7c0
Source dataset
uspto-grants-1978_04
Patent number
US04082761

Reaction notes

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