Pyridine → HCID 178521904, compound

HRID 1492445Notes

Reaction equation

HRID 1492445 reaction equation
[NH:1]1[C:5]([C:6]2[CH:11]=[CH:10][C:9]([NH2:12])=[CH:8][CH:7]=2)=[N:4][N:3]=[N:2]1.CN(C)C=O.N1C=CC=CC=1.Cl[C:25]([O:27][C:28]1[CH:33]=[CH:32][C:31]([N+:34]([O-:36])=[O:35])=[CH:30][CH:29]=1)=[O:26]>C(#N)C>[NH:4]1[C:5]([C:6]2[CH:11]=[CH:10][C:9]([NH:12][C:25](=[O:26])[O:27][C:28]3[CH:29]=[CH:30][C:31]([N+:34]([O-:36])=[O:35])=[CH:32][CH:33]=3)=[CH:8][CH:7]=2)=[N:1][N:2]=[N:3]1

Participants

6

Reactant 4

HCID 1049PyridineHCID 6228DimethylformamideHCID 821294-Nitrophenyl chloroformateHCID 178507471HCID 178507471, compound

Product 1

HCID 178521904HCID 178521904, compound

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A solution of [4-(1H-tetrazol-5-yl)phenyl]amine (0.97 g, 0.006 mol, prepared in sequence by the procedures described by W. G. Finnegan et al., J. Amer. Chem. Soc, 1958, 80, 3908 and McManus and Herbst, J. Amer. Chem. Soc,, 1959, 24, 1044) in acetonitrile (30 mL), dimethylformamide (7 mL) and pyridine (0.97 mL, 0.95 g, 0.012 mol) under argon at 0° C. was treated with p-nitrophenyl chloroformate (1.21 g, 0.006 mol) and stirred at room temperature overnight. The reaction mixture was concentrated in vacuo and an effort was made to partition the remaining oil between ethyl acetate and 1M HCl, resulting in separation of product insoluble in either phase. This was collected, triturated with wet ether and dried in vacuo overnight to yield 1.37 g of [4-(1H-tetrazol-5-yl)phenyl]carbamic acid, 4-nitrophenyl ester, m.p. >260° C. TLC, silica gel, EtOAc/MeOH/HOAc (20:1:0.2), Rf =0.63; 1H-NMR (DMSO-d6 ) δ7.6 (d, J=8.8 Hz, 2H), 7.7 (d, J=8.8 Hz, 2H), 8.1 (d, J=8.8 Hz, 2H) 8.3 (d, J=8.8 Hz, 2H); 13C-NMR (DMSO-d6) δ150.6, 144.7, 140.9, 128.0, 125.3, 123.0, 118.9, 118.2. M.S., (M+H)+ at 327, M.W. 326.

Workup

  1. concentrationThe reaction mixture was concentrated in vacuo
  2. customto partition the remaining oil between ethyl acetate and 1M HCl
  3. customresulting in separation of product insoluble in either phase
  4. customThis was collected
  5. customtriturated with wet ether
  6. customdried in vacuo overnight

Sources & evidence

ORD record
ord-0af060e945bd48849c65f753a5a9471b
Source dataset
uspto-grants-1994_12
Patent number
US05374643

Reaction notes

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