p-Toluenesulfonic acid → (+/-)-8-Methyl-7-(5-methyl-1,3,4-thiadiazol-2-yl)-5-(4-nitrophenyl)-8,9-dihydro-7H-1,3-dioxolo[4,5-h][2,3]benzodiazepine

HRID 25073Notes

Reaction equation

HRID 25073 reaction equation
[CH3:1][CH:2]1[CH2:8][C:7]2[CH:9]=[C:10]3[O:15][CH2:14][O:13][C:11]3=[CH:12][C:6]=2[C:5]([C:16]2[CH:21]=[CH:20][C:19]([N+:22]([O-:24])=[O:23])=[CH:18][CH:17]=2)=[N:4][N:3]1[C:25](=[S:28])[NH:26][NH2:27].[CH2:29](N(CC)CC)[CH3:30].C(Cl)(=O)C.C1(C)C=CC(S(O)(=O)=O)=CC=1>ClCCl>[CH3:1][CH:2]1[CH2:8][C:7]2[CH:9]=[C:10]3[O:15][CH2:14][O:13][C:11]3=[CH:12][C:6]=2[C:5]([C:16]2[CH:17]=[CH:18][C:19]([N+:22]([O-:24])=[O:23])=[CH:20][CH:21]=2)=[N:4][N:3]1[C:25]1[S:28][C:29]([CH3:30])=[N:27][N:26]=1

Participants

6

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 6367Acetyl chlorideHCID 8471TriethylamineHCID 12137411(+/-)-8-Methyl-5-(4-nitrophenyl)-8,9-dihydro-7H-1,3-dioxolo[4,5-h][2,3]benzodiazepine-7-carbothiohydrazide

Product 1

HCID 22565477(+/-)-8-Methyl-7-(5-methyl-1,3,4-thiadiazol-2-yl)-5-(4-nitrophenyl)-8,9-dihydro-7H-1,3-dioxolo[4,5-h][2,3]benzodiazepineYield 93.5%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To an ice cooled stirred mixture of 1.0 g (2.50 mmol) of the starting material XVIII, 35 ml of dichloromethane, 0.40 ml (2.75 mmol) of triethylamine and 0.22 ml (2.80 mmol) of acetyl chloride was added. The so obtained solution was left at room temperature for 16 h, then 0.6 g of p-toluenesulfonic acid was added and the mire was stirred at 40° C. for 2 h. Then the reaction mixture was washed with sodium hydrogen carbonate solution and water until neutrality, dried and concentrated. The crude product was treated with methanol, then recrystallized from ethanol to yield 0.99 g (91%) of the title compound. Mp.: 213-215° C.

Workup

  1. additionwas added
  2. customThe so obtained solution
  3. stirringthe mire was stirred at 40° C. for 2 h
  4. washThen the reaction mixture was washed with sodium hydrogen carbonate solution and water until neutrality
  5. customdried
  6. concentrationconcentrated
  7. additionThe crude product was treated with methanol
  8. customrecrystallized from ethanol

Sources & evidence

ORD record
ord-2952dc3ce583405b8c5ff043d76c4f1e
Source dataset
uspto-grants-2005_02
Patent number
US06858605B2

Reaction notes

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