Nitrite → 5-Cyano-4,5-dihydro-3H-pyrazole-3,4-dicarboxylic acid diethyl ester

HRID 329775Notes

Reaction equation

Cl.[NH2:2][CH2:3][C:4]#[N:5].[C:6]([O:15][CH2:16][CH3:17])(=[O:14])/[CH:7]=[CH:8]/[C:9]([O:11][CH2:12][CH3:13])=[O:10].[N:18]([O-])=O.[Na+].N([O-])=O>C(OCC)(=O)C>[CH2:16]([O:15][C:6]([CH:7]1[CH:8]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH:4]([C:3]#[N:2])[N:5]=[N:18]1)=[O:14])[CH3:17]

Participants

Conditions

Temperature: 24 °C

Procedure

To a 500 ml, 3-neck, round bottom flask containing a cold (0° C.) slurry of 46.26 g (0.5 mol) of aminoacetonitrile hydrochloride and 32.74 ml (0.2 mol) of diethyl fumarate in 200 ml of ethyl acetate, were added dropwise, over one hour, an aqueous solution of sodium nitrite (34.5 g of sodium nitrite dissolved in 90 ml of water). The temperature of the reaction mixture was maintained between 0° C. and 5° C. during nitrite addition and then warmed to room temperature (24° C.), where the mixture was stirred for about 3 hours. The organic layer was separated from the aqueous layer and then stirred at room temperature overnight to provide a solution of title compound dissolved in ethyl acetate.

Workup

additionwere added dropwise, over one hour
customThe organic layer was separated from the aqueous layer
stirringstirred at room temperature overnight

Sources & evidence

ORD record: ord-83a2a8f18d74417bba394f8dbc005b17
Source dataset: uspto-grants-1990_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04892956

Reaction notes

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