1-({5-Chloro-2-[(phenylmethyl)oxy]phenyl}methyl)-4-nitro-1H-pyrazole → 1-({5-Chloro-2-[(phenylmethyl)oxy]phenyl}methyl)-1H-pyrazol-4-amine

HRID 1746103Notes

Reaction equation

[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([O:17][CH2:18][C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[C:6]([CH2:8][N:9]2[CH:13]=[C:12]([N+:14]([O-])=O)[CH:11]=[N:10]2)[CH:7]=1>C(O)C>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([O:17][CH2:18][C:19]2[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=2)=[C:6]([CH2:8][N:9]2[CH:13]=[C:12]([NH2:14])[CH:11]=[N:10]2)[CH:7]=1

Participants

Conditions

Temperature: 85 °C

Procedure

To a solution of 1-({5-chloro-2-[(phenylmethyl)oxy]phenyl}methyl)-4-nitro-1H-pyrazole (for a preparation see intermediate 8; 476 mg, 1.39 mmol) in ethanol (15 ml) was added stannous chloride (hydrated) (1.59 g, 7.03 mmol) and the reaction stirred at 85° C. overnight, under nitrogen. The reaction mixture was applied to a 20 g SCX-2 cartridge (pre-washed with MeOH) and the cartridge washed with methanol (6 column volumes). The product was eluted with 10% NH3 (aqueous) in MeOH (4 column volumes). The combined basic fractions were concentrated in vacuo. The residue was loaded in dichloromethane and purified on silica (50 g) using 0-100% ethyl acetate-cyclohexane. The appropriate fractions were combined and evaporated in vacuo to give the title compound (191 mg) as a red gum; LCMS (System 1): MH+=314, tRET=2.69 min.

Workup

washThe reaction mixture was applied to a 20 g SCX-2 cartridge (pre-washed with MeOH)
washthe cartridge washed with methanol (6 column volumes)
washThe product was eluted with 10% NH3 (aqueous) in MeOH (4 column volumes)
concentrationThe combined basic fractions were concentrated in vacuo
custompurified on silica (50 g)
customevaporated in vacuo

Sources & evidence

ORD record: ord-05913cbe04fc45659213b15cce14fd5a
Source dataset: uspto-grants-2015_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09149462B2

Reaction notes

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