p-Toluenesulfonic acid → Desmethylnitrazolam

HRID 1764535Notes

Reaction equation

HRID 1764535 reaction equation
[NH:1]([C:3]1[CH2:9][N:8]=[C:7]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[C:6]2[CH:16]=[C:17]([N+:20]([O-:22])=[O:21])[CH:18]=[CH:19][C:5]=2[N:4]=1)[NH2:2].N[C:24]1CN=C(C2C=CC=CC=2)C2C=C([N+]([O-])=O)C=CC=2N=1.C1(C)C=CC(S(O)(=O)=O)=CC=1>C([O-])([O-])OCC.C(Cl)(Cl)Cl>[N+:20]([C:17]1[CH:18]=[CH:19][C:5]2[N:4]3[CH:24]=[N:2][N:1]=[C:3]3[CH2:9][N:8]=[C:7]([C:10]3[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=3)[C:6]=2[CH:16]=1)([O-:22])=[O:21]

Participants

6

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 21265982HCID 21265982, compoundHCID 22768399HCID 22768399, compound

Product 1

HCID 20317280Desmethylnitrazolam

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolventHCID 53630039EthylorthoformateSolvent

Procedure

2-Hydrazino-7-nitro-5-phenyl-3H-1,4-benzodiazepine prepared from 5.6 parts of 2-amino-7-nitro-5-phenyl-3H-1,4-benzodiazepine in a similar manner to Example 7, is dissolved in a mixture of 20 parts by volume of ethyl orthoformate and 100 parts by volume of chloroform, followed by the addition of 10 parts of p-toluenesulfonic acid. The whole mixture is left standing at room temperature for 1 hour with occasional shaking. After completion of the reaction, the solution is washed with a saturated aqueous solution of sodium bicarbonate, then with water, and dried over sodium sulfate. After evaporation of the solvent, the residue is treated with ethyl acetate, whereby 8-nitro-6-phenyl-4H-s-triazolo [4,3-a][1,4] benzodiazepine is yielded as crystals. Recrystallization from tetrahydrofuran yields pale yellow needles melting at 271° C to 272° C.

Workup

  1. waitThe whole mixture is left
  2. customAfter completion of the reaction
  3. washthe solution is washed with a saturated aqueous solution of sodium bicarbonate
  4. dry with materialwith water, and dried over sodium sulfate
  5. customAfter evaporation of the solvent
  6. additionthe residue is treated with ethyl acetate

Sources & evidence

ORD record
ord-533073bec3c2449e8f00ad737e7484a5
Source dataset
uspto-grants-1978_09
Patent number
US04116956

Reaction notes

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