Hydrazine → 2-(2-Nitrophenyl)propoxycarbonyl hydrazine

HRID 658515Notes

Reaction equation

HRID 658515 reaction equation
Cl[C:2]([O:4][CH2:5][CH:6]([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][C:9]=1[N+:14]([O-:16])=[O:15])[CH3:7])=[O:3].[NH2:17][NH2:18]>C(Cl)Cl>[N+:14]([C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][C:8]=1[CH:6]([CH3:7])[CH2:5][O:4][C:2]([NH:17][NH2:18])=[O:3])([O-:16])=[O:15]

Participants

4

Reactant 2

HCID 9321HydrazineHCID 114479052-(2-Nitrophenyl)propyl chloroformate

Product 1

HCID 116083982-(2-Nitrophenyl)propoxycarbonyl hydrazineYield 57%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of 2-(2-nitrophenyl)propyl chloroformate (6.0 g, 24.6 mmol) in methylene chloride (20 mL) was added dropwise to a solution of hydrazine (3.0 mL, 98 mmol) in methylene chloride (50 mL) over a period of 30 min. The reaction mixture was stirred at room temperature for an additional 15 min. The solvent was evaporated to afford light brown oil. The residue was purified on a silica gel column. Elution of the column with 20% ethyl acetate in hexanes gave 3.35 g (14 mmol, 57% yield) of 2-(2-nitrophenyl)propoxycarbonyl hydrazine. 1H-NMR (600 MHz, DMSO-d6): δ 8.10 (s, 2H, CONH), 7.82 (d, J=7.5 Hz, 1H, Ar—H), 7.67 (m, 2H, Ar—H), 7.47 (m, 1H, Ar—H), 4.15 (d, J=7.2 Hz, 2H, CH2), 3.9 (s, 2H, NH2), 3.39 (m, 1H, CH), 1.25 (d, J=6.9 Hz, 3H, CH3). 13C-NMR (150 MHz, DMSO-d6): δ 157.99 (OCOR), 150.00 (C ipso to NO2), 136.72 (C ipso to CH(CH3)CH2OCOR), 132.86 (C para to NO2), 128.55 (C para to CH(CH3)CH2OCOR), 127.69 (C ortho to CH(CH3)CH2OCOR), 123.68 (C ortho to NO2), 67.49 (CH2OCOR), 33.36 (CH), 17.93 (CH3). Mass analysis (MALDI-TOF): calculated for C10H13N3O4 239.23, found 239.20 (C10H13N3O4Na 262.18 is the major peak). TLC: 5% methanol in chloroform, Rf=0.5.

Workup

  1. customThe solvent was evaporated
  2. customto afford light brown oil
  3. customThe residue was purified on a silica gel column
  4. washElution of the column with 20% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-bef67af226bc4d5cb4c6ae0f9815cd07
Source dataset
uspto-grants-2011_12
Patent number
US08076501B2

Reaction notes

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