1-Methyl-4-iodo-1H-pyrazole → di-tert-butyl 1-(1-methyl-1H-pyrazol-4-yl)hydrazine-1,2-dicarboxylate

HRID 82316Notes

Reaction equation

I[C:2]1[CH:3]=[N:4][N:5]([CH3:7])[CH:6]=1.[Li]CCCC.[N:13](/[C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])=[N:14]/[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16]>CCOCC.CCCCCC>[CH3:7][N:5]1[CH:6]=[C:2]([N:13]([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[NH:14][C:15]([O:17][C:18]([CH3:19])([CH3:20])[CH3:21])=[O:16])[CH:3]=[N:4]1

Participants

Conditions

Temperature: 0 °C

Procedure

To a solution of 4-iodo-1-methyl-1H-pyrazole (21 g, 0.12 mol) in dry ether (200 mL) at −78° C. was added n-BuLi (84.5 mL of a 2.5 M solution in hexane, 0.18 mol) over a period of 30 min and the mixture stirred for a further 30 min. A solution of di-tert-butyl(Z)-diazene-1,2-dicarboxylate (30.4 g, 0.12 mol) in ether (100 ml) was added to the reaction mixture over a period of 10 min and the resultant mixture stirred at −78° C. for 1 hour. The reaction was warmed to 0° C. and quenched with ice-water and extracted with ether (3×100 mL). The organic layer was separated, dried (Na2SO4) and evaporated in vacuo. The crude material was washed with hexane and then dried under vacuum to give the title compound in 30% yield, 11.2 g.

Workup

customquenched with ice-water
extractionextracted with ether (3×100 mL)
customThe organic layer was separated
dry with materialdried (Na2SO4)
customevaporated in vacuo
washThe crude material was washed with hexane
customdried under vacuum

Sources & evidence

ORD record: ord-0ea4a0d685bf4ce392de4e4073d00fc2
Source dataset: uspto-grants-2014_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08846698B2

Reaction notes

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