Nitromethane → 7-Chloro-1,3-dihydro-2-nitromethylene-5-phenyl-2H-1,4-benzodiazepine

HRID 649263

Reaction equation

HRID 649263 reaction equation
[N+:1]([CH3:4])([O-:3])=[O:2].[H-].[Na+].[H-].[Cl:8][C:9]1[CH:10]=[CH:11][C:12]2[N:18]=[C:17](OP(N3CCOCC3)(N3CCOCC3)=O)[CH2:16][N:15]=[C:14]([C:34]3[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=3)[C:13]=2[CH:40]=1>CN(C)C=O>[Cl:8][C:9]1[CH:10]=[CH:11][C:12]2[NH:18][C:17](=[CH:4][N+:1]([O-:3])=[O:2])[CH2:16][N:15]=[C:14]([C:34]3[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=3)[C:13]=2[CH:40]=1

Participants

6

Reactant 4

HCID 6375NitromethaneHCID 24758Sodium hydrideHCID 166653HydrideHCID 149078867-chloro-2-di-(morpholino)phosphinyloxy-5-phenyl-3H-1,4-benzodiazepin

Product 1

HCID 700537327-Chloro-1,3-dihydro-2-nitromethylene-5-phenyl-2H-1,4-benzodiazepine

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a mixture of 1.0 ml. of nitromethane and 5 ml. of dry dimethylformamide was added 53 mg. of a 50% dispersion of sodium hydride in mineral oil (1.1 mmole hydride). After 1 hour at room temperature, under nitrogen, 489 mg. (1.0 mmole) of 7-chloro-2-di-(morpholino)phosphinyloxy-5-phenyl-3H-1,4-benzodiazepine was added. After stirring at room temperature for 2 hours, dimethylformamide was evaporated (about 80°). The residue was partitioned between methylene chloride and an aqueous layer which is acidified with a slight excess of acetic acid. The methylene chloride layer was dried (Na2SO4) and evaporated. Separation of the product mixture by preparative tlc (silica gel, developed in 10% methanol in ethylacetate v/v) afforded pure final product, which upon crystallization from methanol, had a m.p. of 178°-180°.

Workup

  1. additionTo a mixture of 1.0 ml
  2. customdimethylformamide was evaporated (about 80°)
  3. customThe residue was partitioned between methylene chloride
  4. dry with materialThe methylene chloride layer was dried (Na2SO4)
  5. customevaporated
  6. customSeparation of the product mixture by preparative tlc (silica gel

Sources & evidence

ORD record
ord-e23de29fe43843a3aa50a16921825b2f
Source dataset
uspto-grants-1988_04
Patent number
US04739049

Linked notes

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