Tetrahydrofuran → Anitrazafen

HRID 2397449Notes

Reaction equation

HRID 2397449 reaction equation
O1CCC[CH2:2]1.C([Li])CCC.Cl[C:12]1[N:13]=[N:14][C:15]([C:26]2[CH:31]=[CH:30][C:29]([O:32][CH3:33])=[CH:28][CH:27]=2)=[C:16]([C:18]2[CH:23]=[CH:22][C:21]([O:24][CH3:25])=[CH:20][CH:19]=2)[N:17]=1.C(=O)([O-])[O-].[Na+].[Na+]>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.O>[CH3:25][O:24][C:21]1[CH:22]=[CH:23][C:18]([C:16]2[N:17]=[C:12]([CH3:2])[N:13]=[N:14][C:15]=2[C:26]2[CH:31]=[CH:30][C:29]([O:32][CH3:33])=[CH:28][CH:27]=2)=[CH:19][CH:20]=1

Participants

7

Reactant 4

HCID 8028Tetrahydrofuran2×HCID 10340Sodium CarbonateHCID 155715943-Chloro-5,6-bis(4-methoxyphenyl)-1,2,4-triazineHCID 178418339Butyllithium

Product 1

HCID 44410Anitrazafen

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 962WaterSolvent

Procedure

To a slurry of 11.7 g. (0.33 mole) of methyltriphenylphosphonium bromide in 150 ml. of dry tetrahydrofuran at -35° C. was added, over a 15-minute period, 20 ml. (0.033 mole) of n-butyl lithium. The reaction mixture was stirred for one hour. To the reaction mixture at -35° to -40° C. was added over a 10-minute period a solution of 5.7 g. (0.0165 mole) of 3-chloro-5,6-bis(4-methoxyphenyl)-1,2,4-triazine in 50 ml. of tetrahydrofuran. The reaction mixture was allowed to warm to ambient temperature and was stirred overnight. A solution of 1.05 g. (0.0165 mole) of sodium carbonate in 50 ml. of water was added dropwise to the reaction mixture which then was heated at reflux for 3 hours. The reaction mixture was cooled, poured over ice, and extracted with diethyl ether. The diethyl ether extract was washed with water, dried over anhydrous sodium sulfate, and concentrated. The concentrate was chromatographed over silica gel, with three fractions being collected. After evaporation of solvent, the third fraction solidified, m.p. about 109°-113° C. The solid was identified as 5,6-bis(4-methoxyphenyl)-3-methyl-1,2,4-triazine by nuclear magnetic resonance analysis, mass spectrographic analysis, and elemental micro-analysis.

Workup

  1. additionTo the reaction mixture at -35° to -40° C. was added over a 10-minute period a solution of 5.7 g
  2. stirringwas stirred overnight
  3. temperaturethen was heated
  4. temperatureat reflux for 3 hours
  5. temperatureThe reaction mixture was cooled
  6. additionpoured over ice
  7. extractionextracted with diethyl ether
  8. extractionThe diethyl ether extract
  9. washwas washed with water
  10. dry with materialdried over anhydrous sodium sulfate
  11. concentrationconcentrated
  12. customThe concentrate was chromatographed over silica gel, with three fractions
  13. custombeing collected
  14. customAfter evaporation of solvent

Sources & evidence

ORD record
ord-6f47cd5fee2b463193c8bdc00842288d
Source dataset
uspto-grants-1977_05
Patent number
US04021553

Reaction notes

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