2-[3,5-Dichloro-4-(1-cyano-1-methylethyl)phenyl]-2,3,4,5-tetrahydro-3,5-dioxo-1,2,4-triazine-6-carboxylic acid → 2,6-dichloro-4-(4,5-dihydro-3,5-dioxo-1,2,4-triazin-2(3H)-yl)-alpha,alpha-dimethylbenzeneacetonitrile

HRID 1072478Notes

Reaction equation

HRID 1072478 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([N:14]2[C:19](=[O:20])[NH:18][C:17](=[O:21])[C:16](C(O)=O)=[N:15]2)[CH:5]=[C:6]([Cl:13])[C:7]=1[C:8]([C:11]#[N:12])([CH3:10])[CH3:9]>SCC(O)=O>[Cl:13][C:6]1[CH:5]=[C:4]([N:14]2[C:19](=[O:20])[NH:18][C:17](=[O:21])[CH:16]=[N:15]2)[CH:3]=[C:2]([Cl:1])[C:7]=1[C:8]([CH3:10])([CH3:9])[C:11]#[N:12]

Participants

3

Reactant 1

HCID 111528672-[3,5-Dichloro-4-(1-cyano-1-methylethyl)phenyl]-2,3,4,5-tetrahydro-3,5-dioxo-1,2,4-triazine-6-carboxylic acid

Product 1

HCID 114841762,6-dichloro-4-(4,5-dihydro-3,5-dioxo-1,2,4-triazin-2(3H)-yl)-alpha,alpha-dimethylbenzeneacetonitrileYield 41%

Reagents, catalysts & solvents 1

HCID 1133Thioglycolic AcidSolvent

Conditions

Temperature
100 °C

Procedure

A suspension of intermediate (6) (0.28 mole) in mercaptoacetic acid (250 ml) was stirred for 4 hours at 100° C., then allowed to cool to RT and stirred overnight. The reaction mixture was poured out onto crushed ice and this mixture was extracted with CH2Cl2. The separated organic layer was dried, filtered and the solvent evaporated. Toluene was added and azeotroped on the rotary evaporator. The residue was purified by short column chromatography over silica gel (eluent: CH2Cl2/CH3OH 98/2). The pure fractions were collected and the solvent was evaporated. The residue was stirred in DIPE, filtered off, washed with DIPE, then dried, yielding 36.8 g (41%) of 2,6-dichloro-4-(4,5-dihydro-3,5-dioxo-1,2,4-triazin-2(3H)-yl)-α,α-dimethylbenzeneacetonitrile. The filtrate was stirred in DIPE and the resulting precipitate was filtered off, washed with DIPE, and dried, yielding 2.5 g (3%) of 2,6-dichloro-4-(4,5-dihydro-3,5-dioxo-1,2,4-triazin-2(3H)-yl)-α,α-dimethylbenzeneacetonitrile (intermediate 7).

Workup

  1. temperatureto cool to RT
  2. stirringstirred overnight
  3. additionThe reaction mixture was poured out
  4. customonto crushed ice
  5. extractionthis mixture was extracted with CH2Cl2
  6. customThe separated organic layer was dried
  7. filtrationfiltered
  8. customthe solvent evaporated
  9. additionToluene was added
  10. customazeotroped on the rotary evaporator
  11. customThe residue was purified by short column chromatography over silica gel (eluent: CH2Cl2/CH3OH 98/2)
  12. customThe pure fractions were collected
  13. customthe solvent was evaporated
  14. stirringThe residue was stirred in DIPE
  15. filtrationfiltered off
  16. washwashed with DIPE
  17. customdried

Sources & evidence

ORD record
ord-1d9415d10f724aebaf2f0b096bf3f370
Source dataset
uspto-grants-2005_06
Patent number
US06911444B2

Reaction notes

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