3-Chlorotoluene → HCID 71078040, compound

HRID 2175472Notes

Reaction equation

HRID 2175472 reaction equation
[CH3:1][N:2]1[C:9]([CH3:10])=[CH:8][C:6](=[O:7])[N:5]([CH3:11])[C:3]1=[O:4].ClC1C=CC=CC=1.[C:19]1([CH3:26])[CH:24]=[CH:23][CH:22]=[C:21](Cl)[CH:20]=1>[Cl-].[Zn+2].[Cl-].O>[C:19]1([CH3:26])[CH:24]=[CH:23][CH:22]=[C:21]([C:8]2[C:6](=[O:7])[N:5]([CH3:11])[C:3](=[O:4])[N:2]([CH3:1])[C:9]=2[CH3:10])[CH:20]=1

Participants

6

Reactant 3

HCID 79313-ChlorotolueneHCID 7964ChlorobenzeneHCID 260751,3,6-Trimethyl-2,4(1H,3H)-pyrimidinedione

Product 1

HCID 71078040HCID 71078040, compoundYield 26.3%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 962WaterSolvent

Procedure

In a 100 mL round bottom flask equipped with a condenser and an air lock was placed compound 2 (see FIG. 3) (5.00 g, 32.4 mmol), anhydrous zinc chloride 3 (4.45 g, 32.6 mmol), dry chlorobenzene (20 mL) and m-tolyl chloride (4.6 mL, 5.38 g, 34.8 mmol). The reaction was brought to reflux in an oil bath and vigorously stirred for 3 h. After cooling, water (40 mL) was added through the condenser, dropwise at first and then with increasing speed. The condenser was then rearranged for distillation and the chlorobenzene was removed by azeotropic distillation. The solution was then cooled in an ice bath, and diethyl ether (30 mL) was added while stirring to give a precipitate. The precipitate was filtered and recrystallized from 2-propanol to yield 3d (1.11 g, 26.3%); m.p. 136.8-139° C. 1H NMR (600 MHz, CD2Cl2) δ 7.68-7.66 (m, 1H), 7.65-7.62 (m, 1H), 7.44-7.40 (m, 1H), 7.35 (t, J=7.6, 1H), 3.46 (s, 3H), 3.30 (s, 3H), 2.40 (s, 3H), 2.18 (s, 3H). 13C NMR (151 MHz, CD2Cl2) δ 194.00, 161.07, 152.22, 151.98, 139.22, 138.16, 134.94, 130.03, 129.01, 126.93, 113.36, 32.36, 28.32, 21.54, 17.99. MS (ES+) (m/z): [M+1]+ calculated for C15H17N2O3, 273.12. found 237.10.

Workup

  1. customIn a 100 mL round bottom flask equipped with a condenser
  2. temperatureto reflux in an oil bath
  3. temperatureAfter cooling
  4. temperaturedropwise at first and then with increasing speed
  5. distillationThe condenser was then rearranged for distillation
  6. customthe chlorobenzene was removed by azeotropic distillation
  7. temperatureThe solution was then cooled in an ice bath
  8. additiondiethyl ether (30 mL) was added
  9. stirringwhile stirring
  10. customto give a precipitate
  11. filtrationThe precipitate was filtered
  12. customrecrystallized from 2-propanol

Sources & evidence

ORD record
ord-d4fc89014e804973bad791798e49b430
Source dataset
uspto-grants-2015_06
Patent number
US09062073B2

Reaction notes

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