Hydrochloric Acid → Ethyl 4-amino-3-nitrobenzimidate hydrochloride

HRID 712933Notes

Reaction equation

HRID 712933 reaction equation
NC1C=CC(C#N)=CC=1[N+]([O-])=O.[ClH:13].[CH2:14]([O:16][C:17](=[NH:28])[C:18]1[CH:23]=[CH:22][C:21]([NH2:24])=[C:20]([N+:25]([O-:27])=[O:26])[CH:19]=1)[CH3:15]>O1CCOCC1.C(O)C.C(OCC)C>[ClH:13].[CH2:14]([O:16][C:17](=[NH:28])[C:18]1[CH:23]=[CH:22][C:21]([NH2:24])=[C:20]([N+:25]([O-:27])=[O:26])[CH:19]=1)[CH3:15]

Participants

7

Reactant 3

HCID 313Hydrochloric AcidHCID 5959014-Amino-3-nitrobenzonitrileHCID 53872271Ethyl 4-amino-3-nitrobenzimidate

Product 1

HCID 67073287Ethyl 4-amino-3-nitrobenzimidate hydrochloride

Reagents, catalysts & solvents 3

HCID 702EthanolSolvent2×HCID 3283Diethyl EtherSolvent2×HCID 312751,4-DioxaneSolvent

Conditions

Temperature
2.5 °C

Procedure

A mixture of 4-amino-3-nitrobenzonitrile (63.3 g, 388 mmol) in 1,4-dioxane (600 mL) and anhydrous ethanol (600 mL) was cooled in an ice water bath to 0-5° C. and treated with gaseous HCl for 1.5 h. The reaction mixture was tightly sealed and allowed to warm up to room temperature with stirring for 18 h. The flask was then carefully unsealed and the reaction mixture was diluted with anhydrous diethyl ether (about 2.4 L) until a cloudy solution was obtained. A minimum amount of absolute ethanol required to give a clear solution was then added, and the resulting solution stirred until crystals of 4-amino-3-nitro-benzimidic acid ethyl ester were observed. Ether was then cautiously added to complete the crystallization process and the suspension was allowed to stand for about 30 minutes. The crystals were filtered and washed with dry diethyl ether, then allowed to dry under aspirator vacuum. The crystals were dried in vacuo to give 4-amino-3-nitro-benzimidic acid ethyl ester hydrochloride (84.6 g) as off-white crystals.

Workup

  1. customThe reaction mixture was tightly sealed
  2. temperatureto warm up to room temperature
  3. customwas obtained
  4. customto give a clear solution
  5. additionwas then added
  6. waitto stand for about 30 minutes
  7. filtrationThe crystals were filtered
  8. washwashed with dry diethyl ether
  9. customto dry under aspirator vacuum
  10. customThe crystals were dried in vacuo

Sources & evidence

ORD record
ord-bbe581a8ae7e409caf6629e36a1adfe9
Source dataset
uspto-grants-2015_11
Patent number
US09181280B2

Reaction notes

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