2-Chloroaniline → 2-Chloro-6-[1-(4,6-dimethoxypyrimidin-2-yl)-1-methylthiomethyl]aniline

HRID 1454762Notes

Reaction equation

HRID 1454762 reaction equation
[Cl:1][C:2]1[CH:8]=[CH:7][CH:6]=[CH:5][C:3]=1[NH2:4].ClOC(C)(C)C.[CH3:15][S:16][CH2:17][C:18]1[N:23]=[C:22]([O:24][CH3:25])[CH:21]=[C:20]([O:26][CH3:27])[N:19]=1.CO.C[O-].[Na+]>ClCCl.O>[Cl:1][C:2]1[CH:8]=[CH:7][CH:6]=[C:5]([CH:17]([C:18]2[N:19]=[C:20]([O:26][CH3:27])[CH:21]=[C:22]([O:24][CH3:25])[N:23]=2)[S:16][CH3:15])[C:3]=1[NH2:4]

Participants

7

Reactant 4

HCID 72402-ChloroanilineHCID 521297Tert-Butyl hypochloriteHCID 23694274Sodium methanolate methanolHCID 574281232-Methylthiomethyl-4,6-dimethoxypyrimidine

Product 1

HCID 575309642-Chloro-6-[1-(4,6-dimethoxypyrimidin-2-yl)-1-methylthiomethyl]anilineYield 83%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-70 °C

Procedure

2-Chloroaniline 5.2 g (26.0 mmol) was dissolved in dichloromethane (200 ml) and the solution was cooled to −70° C. To the cooled solution a dichloromethane (10 ml) solution of tert-butyl hypochlorite 2.82 g (26.0 mmol) was added dropwise and the solution was stirred at −70° C. for 10 minutes. To the obtained reaction solution a dichloromethane (20 ml) solution of 2-methylthiomethyl-4,6-dimethoxypyrimidine 3.38 g (26.0 mmol) was added dropwise and the solution was stirred at −70° C. for 40 minutes. To the obtained reaction solution 28% sodium methoxide methanol solution (9 ml) was added and the solution was stirred until it came to room temperature. Water was added to the reaction solution and the organic layer was separated. The water layer was further extracted twice with dichloromethane. After the organic layer had been washed with water and dried, dichloromethane was distilled off under reduced pressure and the objective 2-chloro-6-[1-(4,6-dimethoxypyrimidin-2-yl)-1-methylthiomethyl]aniline 7.00 g (yield 83%) was obtained as oily substance from the obtained oily substance by column chromatography using 1:8 mixed solvent of ethyl acetate and hexane as eluent.

Workup

  1. additionwas added dropwise
  2. stirringthe solution was stirred at −70° C. for 40 minutes
  3. additionwas added
  4. stirringthe solution was stirred until it
  5. customcame to room temperature
  6. customthe organic layer was separated
  7. extractionThe water layer was further extracted twice with dichloromethane
  8. washAfter the organic layer had been washed with water
  9. customdried
  10. distillationdichloromethane was distilled off under reduced pressure

Sources & evidence

ORD record
ord-cf091f460dac441c86f8847ed8694bc1
Source dataset
uspto-grants-2009_01
Patent number
US07482308B2

Reaction notes

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