Triethylamine → 4-(5-Chloro-2-methylphenyl)-2-ethyl-3-thioxo-[1,2,4]oxadiazinan-5-one

HRID 411975Notes

Reaction equation

HRID 411975 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:11])=[C:6]([N:8]=[C:9]=[S:10])[CH:7]=1.Cl.[CH3:13][NH:14][O:15][CH2:16][C:17]([OH:19])=O.[CH2:20](N(CC)CC)C>C(Cl)(Cl)Cl>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([CH3:11])=[C:6]([N:8]2[C:17](=[O:19])[CH2:16][O:15][N:14]([CH2:13][CH3:20])[C:9]2=[S:10])[CH:7]=1

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 295195-Chloro-2-methylphenyl isothiocyanateHCID 85852466N-methyl aminooxy acetic acid hydrochloride

Product 1

HCID 98143904-(5-Chloro-2-methylphenyl)-2-ethyl-3-thioxo-[1,2,4]oxadiazinan-5-oneYield 14.8%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

A mixture of 5-chloro-2-methylphenyl-isothiocyanate (9.18 g), N-methyl aminooxy acetic acid hydrochloride (7.78 g), triethylamine (20 g) and chloroform (200 mL) was heated at reflux for one hour, stirred at ambient temperature for one hour, then evaporated to dryness. The residue was dissolved in ethyl acetate (400 mL) and washed with 2N HCl (2×200 mL) then with water (200 mL). The organic phase was dried over anhydrous magnesium sulfate and evaporated to dryness The residue (8 g) was dissolved in benzene (150 mL). Phosphorus pentachloride (7 g) was added in portions. The mixture was heated at reflux for one hour then evaporated to dryness. The residue was dissolved in ethyl acetate (300 mL) and washed with sodium bicarbonate saturated solution (2×200 mL) then with water (200 mL). The organic phase was dried over anhydrous magnesium sulfate and evaporated to dryness. The residue was chromatographed on silica gel (10-20% ethyl acetate in hexane). Crystallization from ethyl acetate/hexane afforded the title compound (2.1 g) as a solid, m.p. 119-121° C. Mass spectrum (El, M.+) m/z 282/284. 1H-NMR (CDCl3; 400 MHz) δ7.32 (d, 1H), 7.23 (d, 1H), 7.13 (s, 1H), 4.81 (ABq, 2H), 4.26 (m, 2H), 2.13 (s, 3H), and 1.40 ppm (t, 3H).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for one hour
  3. customevaporated to dryness
  4. dissolutionThe residue was dissolved in ethyl acetate (400 mL)
  5. washwashed with 2N HCl (2×200 mL)
  6. dry with materialThe organic phase was dried over anhydrous magnesium sulfate
  7. customevaporated to dryness The residue (8 g)
  8. dissolutionwas dissolved in benzene (150 mL)
  9. additionPhosphorus pentachloride (7 g) was added in portions
  10. temperatureThe mixture was heated
  11. temperatureat reflux for one hour
  12. customthen evaporated to dryness
  13. dissolutionThe residue was dissolved in ethyl acetate (300 mL)
  14. washwashed with sodium bicarbonate saturated solution (2×200 mL)
  15. dry with materialThe organic phase was dried over anhydrous magnesium sulfate
  16. customevaporated to dryness
  17. customThe residue was chromatographed on silica gel (10-20% ethyl acetate in hexane)
  18. customCrystallization from ethyl acetate/hexane

Sources & evidence

ORD record
ord-091449bb24404dbe84f9016250c7a52b
Source dataset
uspto-grants-2003_05
Patent number
US06562814B2

Reaction notes

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