Nitric Acid → 6-(2,3,5-Trichlorophenyl)-1,2,4-triazine-3,5-diamine

HRID 745912Notes

Reaction equation

HRID 745912 reaction equation
[Cl:1][C:2]1[C:11]([Cl:12])=[CH:10][C:9]([Cl:13])=[CH:8][C:3]=1[C:4]([C:6]#[N:7])=O.C(=O)(O)O.[NH2:18][NH:19][C:20]([NH2:22])=[NH:21].[N+]([O-])(O)=O>CS(C)=O>[NH2:21][C:20]1[N:19]=[N:18][C:4]([C:3]2[CH:8]=[C:9]([Cl:13])[CH:10]=[C:11]([Cl:12])[C:2]=2[Cl:1])=[C:6]([NH2:7])[N:22]=1

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 185491782,3,5-Trichlorobenzoyl cyanideHCID 178513185HCID 178513185, compound

Product 1

HCID 64190366-(2,3,5-Trichlorophenyl)-1,2,4-triazine-3,5-diamine

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

A solution of 2,3,5-trichlorobenzoyl cyanide (38.5 g, 0.16M) in dimethylsulphoxide (80 ml) was added dropwise to a stirred suspension of aminoguanidine bicarbonate (65.76 g, 0.32M) which had been treated with 8N aqueous nitric acid (560 ml). The mixture was stirred for 3 hours and then was left to stand at room temperature for 21 days. The solid was filtered off, washed with water (2×100 ml) and dried in vacuo. A suspension of the dried solid in a 10% solution of potassium hydroxide pellets in methanol (320 ml) was heated to reflux for 1 hour, the mixture was cooled and evaporated down in vacuo. The residue was treated with ice/water (200 ml), the resultant solid was filtered off and dried in vacuo. This dried solid was put on top of a dry column (25 mm diameter, 200 g of MFC silica gel) and eluted with a solution of ethyl acetate/methanol/acetic acid (90:2.5:2.5). Fractions 50 to 80 (900 drops per fraction) were collected, combined and evaporated down in vacuo. The resultant solid was recrystallised from ispropanol to give 3,5-diamino-6-(2,3,5-trichlorophenyl)-1,2,4 -triazine. Yield 0.77 g (1.6%), m.p. 232°-235° C. (uncorrected).

Workup

  1. waitwas left
  2. waitto stand at room temperature for 21 days
  3. filtrationThe solid was filtered off
  4. washwashed with water (2×100 ml)
  5. customdried in vacuo
  6. additionA suspension of the dried solid in a 10% solution of potassium hydroxide pellets in methanol (320 ml)
  7. temperaturewas heated
  8. temperatureto reflux for 1 hour
  9. temperaturethe mixture was cooled
  10. customevaporated down in vacuo
  11. additionThe residue was treated with ice/water (200 ml)
  12. filtrationthe resultant solid was filtered off
  13. customdried in vacuo
  14. washeluted with a solution of ethyl acetate/methanol/acetic acid (90:2.5:2.5)
  15. customFractions 50 to 80 (900 drops per fraction) were collected
  16. customevaporated down in vacuo
  17. customThe resultant solid was recrystallised from ispropanol

Sources & evidence

ORD record
ord-f3c5605bd45c4b34ad1711172efe94fc
Source dataset
uspto-grants-1986_07
Patent number
US04602017

Reaction notes

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