Water → HCID 19880924, compound

HRID 847345Notes

Reaction equation

HRID 847345 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[NH:11][C:10](=O)[CH2:9][N:8]=[C:7]([C:13]3[NH:14][CH:15]=[CH:16][CH:17]=3)[C:6]=2[CH:18]=1.O.P12(SP3(SP(SP(S3)(S1)=S)(=S)S2)=S)=[S:21]>C1COCC1>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]2[NH:11][C:10](=[S:21])[CH2:9][N:8]=[C:7]([C:13]3[NH:14][CH:15]=[CH:16][CH:17]=3)[C:6]=2[CH:18]=1

Participants

5

Reactant 3

HCID 962WaterHCID 14817Phosphorus sulfide (P2S5)2×HCID 64983Ro 5-3335

Product 1

HCID 19880924HCID 19880924, compoundYield 159.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
40 °C

Procedure

10 g (38.5 mmol) of 7-chloro-1,3-dihydro-5-(1H-pyrrol-2-yl)-1,4-benzodiazepin-2-one were dissolved in anhydrous THF (400 ml) in a 1 litre round-bottom 3-neck flask equipped with a mechanical stirrer. The flask was then placed in the water bath of an ultrasonic apparatus. To the stirred reaction solution was added P4S10 (10 g; 22.5 mmol) and the reaction mixture was irradiated with ultrasound. The temperature was maintained at about 40° C. throughout the reaction. After 2.5 hours, an additional portion of P4S10 (10 g; 22.5 mmol) was added to the mixture and the reaction was continued for an additional 2 hours. The heterogeneous mixture was cooled to ambient temperature and filtered. After washing the solid by-product with several portions of CH2CL2, the filtrates were combined and approximately 80% of the solvent was removed in vacuo. The residual solution was basified with saturated sodium bicarbonate solution until a pH of about 8 was reached. The product which precipitated out was filtered. The filtrate was then extracted with CH2Cl2, followed by concentration in vacuo. The solids were combined and recrystallized in THF/Petroleum ether to give 9.9 g (94% yield) of 7-chloro-1,3-dihydro-5-(1H-pyrrol-2yl)-1,4-benzodiazepin-2-thione as a pale yellow powder having the following characteristics: m.p. 258°-260° C. dec.; IR (KBr) 3450, 3165 cm-1. Anal. Calcd. for C13H10C1N3S: C 56.62; H 3.66; N 15.24. Found: C 56.50; H 3.59; N 15.12.

Workup

  1. customequipped with a mechanical stirrer
  2. customTo the stirred reaction solution
  3. customthe reaction mixture was irradiated with ultrasound
  4. waitthe reaction was continued for an additional 2 hours
  5. temperatureThe heterogeneous mixture was cooled to ambient temperature
  6. filtrationfiltered
  7. washAfter washing the solid by-product with several portions of CH2CL2
  8. customapproximately 80% of the solvent was removed in vacuo
  9. customThe product which precipitated out
  10. filtrationwas filtered
  11. extractionThe filtrate was then extracted with CH2Cl2
  12. concentrationfollowed by concentration in vacuo
  13. customrecrystallized in THF/Petroleum ether

Sources & evidence

ORD record
ord-2e4f44f41a2d460ba1f27a44129d20ec
Source dataset
uspto-grants-1992_08
Patent number
US05141735

Reaction notes

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