Pyridine → HCID 20084618, compound

HRID 615911Notes

Reaction equation

HRID 615911 reaction equation
Cl[C:2]([O:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=[O:3].[C:11]([O:15][CH2:16][CH3:17])(=[O:14])[NH:12][NH2:13].N1C=CC=CC=1>ClCCl>[NH:12]([C:11]([O:15][CH2:16][CH3:17])=[O:14])[NH:13][C:2]([O:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=[O:3]

Participants

5

Reactant 3

HCID 1049PyridineHCID 15891Phenyl chloroformateHCID 20064Hydrazinecarboxylic acid, ethyl ester

Product 1

HCID 20084618HCID 20084618, compoundYield 90.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Phenyl chloroformate (32.34 g, 0.207M) in dichloromethane (100 ml) was reacted with ethyl carbazate (20.8 g, 0.2M) in dichloromethane (150 ml) and pyridine (16.63 g, 0.21M) to give ethyl phenyl hydrazine-1,2-dicarboxylate (40.5 g). After chromatography on silica gel using dichloromethane and ethyl acetate, recrystallization from toluene gave colourless solid m.p. 89.5-90.5. (Found C 53.8%, H 5.5%, N 12.7%; C10H12N2O4 requires C 53.6%, H 5.4%, N 12.5%). The infra-red spectrum (0.5% in dichloromethane) showed bands at 3360 cm-1 (NH), 1775 and 1745 cm-1 (>C=O), and 1600 cm-1 (aromatic ring). Oxidation of the diester (5 g) in dichloromethane (25 ml) with t-butyl hypochlorite and evaporation of the solvent gave a red oil which was extracted with petroleum spirit (b.p. 30°-40° C.) to isolate ethyl phenyl azodicarboxylate (4 g). (Found C 53.9%, H 4.6%, N 12.4%, C10H10N2O4 requires C 54.1%, H 4.5%, N 12.6%). The infra-red spectrum (0.4% in dichloromethane) showed bands at 1792 with a shoulder at circa 1780 cm-1 (>C=O) and 1600 cm-1 (aromatic ring) and no >NH band at 3360 cm-1.

Sources & evidence

ORD record
ord-e9f4213b677c4b2ab526ba4fd6f293ed
Source dataset
uspto-grants-1985_02
Patent number
US04501860

Reaction notes

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