Triphenylphosphine → (+/-)-7-(3-Chloropyridazin-6-yl)-8-methyl-5-(4-nitrophenyl)-8,9-dihydro-7H-1,3-dioxolo[4,5-h][2,3]benzodiazepine

HRID 25088Notes

Reaction equation

HRID 25088 reaction equation
[Cl:1][C:2]1[N:7]=[N:6][C:5]([NH:8][N:9]=[C:10]([C:24]2[CH:29]=[CH:28][C:27]([N+:30]([O-:32])=[O:31])=[CH:26][CH:25]=2)[C:11]2[C:12]([CH2:20][CH:21](O)[CH3:22])=[CH:13][C:14]3[O:18][CH2:17][O:16][C:15]=3[CH:19]=2)=[CH:4][CH:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>CN(C)C=O>[Cl:1][C:2]1[N:7]=[N:6][C:5]([N:8]2[CH:21]([CH3:22])[CH2:20][C:12]3[CH:13]=[C:14]4[O:18][CH2:17][O:16][C:15]4=[CH:19][C:11]=3[C:10]([C:24]3[CH:25]=[CH:26][C:27]([N+:30]([O-:32])=[O:31])=[CH:28][CH:29]=3)=[N:9]2)=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 865938171-(6-[(6-Chloropyridazin-3-yl)-hydrazono-(4-nitrophenyl)-methyl]-(benzo-1,3-dioxol-5-yl)}-propan-2-ol

Product 1

HCID 22565518(+/-)-7-(3-Chloropyridazin-6-yl)-8-methyl-5-(4-nitrophenyl)-8,9-dihydro-7H-1,3-dioxolo[4,5-h][2,3]benzodiazepineYield 42%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A mixture of 0.3 g (0.66 mmol) of the compound prepared in Step A, 10 ml of dimethylformamide and 0.34 g (1.30 mmol) of triphenyiphosphine was stirred at room temperature for 5 min, then 0.20 ml (1.27 mmol) of diethyl azodicarboxylate was added and stirring was continued for 24 h. After dilution with sodium chloride solution the precipitated product was filtered off, dried and purified by column chromatography using silica gel (MN Kieselgel 60) as adsorbent and a mixture of chloroform-methanol (99:1) as eluent. The residue obtained on concentration was crystallized by refluxing in ethanol to yield 0.12 g (42%) of the title compound; Mp.: 254-255° C.

Workup

  1. stirringstirring
  2. waitwas continued for 24 h
  3. filtrationAfter dilution with sodium chloride solution the precipitated product was filtered off
  4. customdried
  5. custompurified by column chromatography
  6. additiona mixture of chloroform-methanol (99:1) as eluent
  7. customThe residue obtained on concentration
  8. customwas crystallized
  9. temperatureby refluxing in ethanol

Sources & evidence

ORD record
ord-695c86f66ffc4bbdaaff243f5c4f5faf
Source dataset
uspto-grants-2005_02
Patent number
US06858605B2

Reaction notes

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