1,3-Dichloro-5,5-dimethylhydantoin → Methyl 6-(4-chlorophenyl)-5-fluoro-4-((4-oxocyclohexa-2,5-dien-1-ylidene)amino)picolinate

HRID 1774285Notes

Reaction equation

HRID 1774285 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:13]=[C:12]([C:14]([O:16][CH3:17])=[O:15])[CH:11]=[C:10]([NH:18][C:19]3[CH:24]=[CH:23][C:22]([O:25]C)=[CH:21][CH:20]=3)[C:9]=2[F:27])=[CH:4][CH:3]=1.ClN1C(C)(C)C(=O)N(Cl)C1=O>CC#N.O>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[N:13]=[C:12]([C:14]([O:16][CH3:17])=[O:15])[CH:11]=[C:10]([N:18]=[C:19]3[CH:24]=[CH:23][C:22](=[O:25])[CH:21]=[CH:20]3)[C:9]=2[F:27])=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 83601,3-Dichloro-5,5-dimethylhydantoinHCID 86723349Methyl 4-(4-methoxyphenylamino)-5-fluoro-6-(4-chlorophenyl)picolinate

Product 1

HCID 86723350Methyl 6-(4-chlorophenyl)-5-fluoro-4-((4-oxocyclohexa-2,5-dien-1-ylidene)amino)picolinateYield 79%

Reagents, catalysts & solvents 1

HCID 18373917Acetonitrile--water (1/1)Solvent

Procedure

A mixture of methyl 6-(4-chlorophenyl)-5-fluoro-4-((4-methoxyphenyl)amino)-picolinate (0.155 g, 0.400 mmol) and 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione (0.158 g, 0.800 mmol) in 1:1 CH3CN/H2O (5 mL) was stirred at room temperature. After 30 min the suspension of the solid ester dissolved giving a yellow/orange solution, then an orange solid began to form. After stirring at room temperature for 2 h, the reaction solution was decanted, and the orange solid was washed with 1:1 CH3CN/H2O (10 mL). The solid was dissolved in CH2Cl2 and dried (MgSO4), and the solvent was removed to give methyl 6-(4-chlorophenyl)-5-fluoro-4-((4-oxocyclohexa-2,5-dien-l-ylidene)amino)picolinate (0.13 g, 0.316 mmol, 79% yield) as an orange solid: mp 154-156° C.; 1H NMR (400 MHz, CDCl3) δ 7.97 (d, J=7.3 Hz, 2H), 7.65 (d, J=5.4 Hz, 1H), 7.48 (d, J=8.6 Hz, 2H), 7.36 (dd, J=10.1, 2.6 Hz, 1H), 6.87 (d, J=10.3 Hz, 1H), 6.77 (dd, J=10.1, 2.1 Hz, 1H), 6.61 (dd, J=10.2, 2.1 Hz, 1H), 4.02 (s, 3H); 19F NMR (376 MHz, CDCl3) δ −145.68.

Workup

  1. dissolutiondissolved
  2. customgiving a yellow/orange solution
  3. customto form
  4. stirringAfter stirring at room temperature for 2 h
  5. customthe reaction solution was decanted
  6. washthe orange solid was washed with 1:1 CH3CN/H2O (10 mL)
  7. dissolutionThe solid was dissolved in CH2Cl2
  8. dry with materialdried (MgSO4)
  9. customthe solvent was removed

Sources & evidence

ORD record
ord-e536298aa93a43aab3a5bb8e3efc0eca
Source dataset
uspto-grants-2016_02
Patent number
US09260392B2

Reaction notes

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