Toluene → 2-Cyclopropyl-7-methyl-5-methylthio-3-[(2'-nitrobiphen-4-yl)methyl]pyrazolo[1,5-a]pyrimidine

HRID 1655520Notes

Reaction equation

HRID 1655520 reaction equation
[CH:1]1([C:4](=O)[CH:5]([CH2:8][C:9]2[CH:14]=[CH:13][C:12]([C:15]3[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=3[N+:21]([O-:23])=[O:22])=[CH:11][CH:10]=2)[C:6]#[N:7])[CH2:3][CH2:2]1.[NH2:25][NH2:26].[CH3:27][S:28][C:29](SC)=[CH:30][C:31](=O)[CH3:32].C1(C)C=CC=CC=1>C(O)C.C(O)(=O)C.N1CCCCC1>[CH:1]1([C:4]2[C:5]([CH2:8][C:9]3[CH:14]=[CH:13][C:12]([C:15]4[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=4[N+:21]([O-:23])=[O:22])=[CH:11][CH:10]=3)=[C:6]3[N:7]=[C:29]([S:28][CH3:27])[CH:30]=[C:31]([CH3:32])[N:26]3[N:25]=2)[CH2:3][CH2:2]1

Participants

8

Reactant 4

HCID 1140TolueneHCID 9321HydrazineHCID 109427784,4-Bis(methylsulfanyl)but-3-en-2-oneHCID 1317181973-Cyclopropyl-3-oxo-2-[(2'-nitrobiphen-4-yl)methyl]propanenitrile

Product 1

HCID 1317181982-Cyclopropyl-7-methyl-5-methylthio-3-[(2'-nitrobiphen-4-yl)methyl]pyrazolo[1,5-a]pyrimidineYield 17%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 702EthanolSolventHCID 8082PiperidineSolvent

Procedure

A solution of 11.1 g (34.7 mmol) 3-cyclopropyl-3-oxo-2-[(2'-nitrobiphen-4-yl)methyl]propanenitrile and 4.0 mL (126 mmol) hydrazine in 400 mL dry ethanol was refluxed for 4 hours. The mixture was cooled to room temperature then stripped of solvent in vacuo. The resulting foam was kept under vacuum overnight (final weight 11.8 g) then was redissolved in 600 mL acetic acid along with 1 mL piperidine and 9.14 g (56.4 mmol) 1,1-bis(methylthio)but-1-en-3-one. The mixture was heated to 90° C. for 5 hours, was cooled to room temperature, was stripped of solvent in vacuo, then was stripped from toluene. The crude material was chromatographed on silica gel under medium pressure using 10% ethyl acetate in hexanes to give 2.50 g (17% yield) of the title compound as a light yellow crystalline solid. Rf 0.24 in 20% EtOAc/hexane, visualized by UV, iodine, and ammonium molybdate/ceric sulfate stain.

Workup

  1. customwas kept under vacuum overnight
  2. temperatureThe mixture was heated to 90° C. for 5 hours
  3. temperaturewas cooled to room temperature
  4. customThe crude material was chromatographed on silica gel under medium pressure

Sources & evidence

ORD record
ord-0aeac6d5e53d4e1d9e21543d2be3e000
Source dataset
uspto-grants-1993_10
Patent number
US05250521

Reaction notes

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