Hydrochloric Acid → phenyl 3-(1-methyl-1H-tetraazol-5-yl)phenylcarbamate

HRID 1454245Notes

Reaction equation

HRID 1454245 reaction equation
[CH3:1][N:2]1[C:6]([C:7]2[CH:12]=[CH:11][CH:10]=[C:9]([NH2:13])[CH:8]=2)=[N:5][N:4]=[N:3]1.N1C(C)=CC=CC=1C.Cl[C:23]([O:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)=[O:24].Cl>ClCCl.C1(C)C=CC=CC=1>[C:26]1([O:25][C:23](=[O:24])[NH:13][C:9]2[CH:10]=[CH:11][CH:12]=[C:7]([C:6]3[N:2]([CH3:1])[N:3]=[N:4][N:5]=3)[CH:8]=2)[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 79372,6-LutidineHCID 15891Phenyl chloroformateHCID 144576753-(1-methyl-1H-1,2,3,4-tetrazol-5-yl)aniline

Product 1

HCID 22252681phenyl 3-(1-methyl-1H-tetraazol-5-yl)phenylcarbamateYield 84.9%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Procedure

1-Methyl-5-(3-aminophenyl)-tetrazole (24.0 g, 137 mmol) was dissolved in dichloromethane (1.4 L) and 2,6-lutidine (44.1 g, 411 mmol) was added. Phenyl chloroformate (21.2 g, 136 mmol) was added in 4 portions over 15 minutes, and the mixture was stirred for 1.5 hours. The mixture was poured into 1N aqueous hydrochloric acid (200 mL) and the mixture was extracted three times with dichloromethane (200 mL). The combined organic layers were washed with saturated aqueous sodium chloride, dried over sodium sulfate, and concentrated under vacuum to give a crude brown material. The crude brown material was dissolved in hot toluene, filtered, and allowed to precipitate at 0° C. to give a white solid (34.1 g). The filtrate was concentrated and recrystallized again from toluene to give an additional crop of off-white crystals (3.44 g, 93% total). 1H NMR (300 MHz, CDCl3), δ10.51 (bs, 1H), 8.01 (s, 1H), 7.71 (dt, J=7, 2 Hz, 1H), 7.55 (m, 2H), 7.41 (m, 2H), 7.24 (m, 2H), 4.14 (s, 3H).

Workup

  1. extractionthe mixture was extracted three times with dichloromethane (200 mL)
  2. washThe combined organic layers were washed with saturated aqueous sodium chloride
  3. dry with materialdried over sodium sulfate
  4. concentrationconcentrated under vacuum
  5. customto give a crude brown material
  6. filtrationfiltered
  7. customto precipitate at 0° C.

Sources & evidence

ORD record
ord-30539cb15e714fac8876f03b25a24daa
Source dataset
uspto-grants-2009_01
Patent number
US07479496B2

Reaction notes

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