Triethylamine → [[[[(2-Chloro-6-ethylphenyl)amino]thioxomethyl]methylamino]oxy]acetic acid

HRID 411978Notes

Reaction equation

HRID 411978 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([CH3:8])[C:3]=1[N:9]=[C:10]=[S:11].Cl.[CH3:13][NH:14][O:15][CH2:16][C:17]([OH:19])=[O:18].[CH2:20](N(CC)CC)C>C(Cl)(Cl)Cl>[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([CH2:8][CH3:20])[C:3]=1[NH:9][C:10]([N:14]([CH3:13])[O:15][CH2:16][C:17]([OH:19])=[O:18])=[S:11]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 37317252-Chloro-6-Methylphenyl IsothiocyanateHCID 85852466N-methyl aminooxy acetic acid hydrochloride

Product 1

HCID 86585213[[[[(2-Chloro-6-ethylphenyl)amino]thioxomethyl]methylamino]oxy]acetic acidYield 92.8%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

A mixture of 2-chloro-6-methylphenyl-isothiocyanate (18.3 g), N-methyl aminooxy acetic acid hydrochloride (15.5 g), triethylamine (30 g) and chloroform (300 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 (500 mL) and washed with 2N HCl (2×300 mL) then with water (300 mL). The organic phase was dried over anhydrous magnesium sulfate and evaporated to dryness affording (28 g) of [[[[(2-Chloro-6-ethylphenyl)amino]thioxomethyl]methylamino]oxy]acetic acid as a semi solid. 1H-NMR (DMSO-d6; 300 Mhz) δ12.8 (br s, 1H), 10.04 (s, 1H), 7.38-7.20 (m, 3H), 4.61 (s, 2H), 3.58 (s, 3H), and 2.20 ppm (s, 3H). The acid (26.8 g) was dissolved in benzene (300 mL). Phosphorus pentachloride (18 g) was added in portions. The mixture was heated at reflux for one half hour then evaporated to dryness. The residue was dissolved in ethyl acetate (500 mL) and washed with sodium bicarbonate saturated solution (2×300 mL) then with water (300 mL). The organic phase was dried over anhydrous magnesium sulfate and evaporated to dryness. Crystallization from ethanol afforded the title compound (10.5 g) as a solid, m.p. 176-178° C. Mass spectrum (ESl, [M+H]+) m/z 271/273. 1H-NMR (CDCl3; 400 MHz) δ7.37 (d, 1H), 7.29 (t, 1H), 7.22 (d, 1H), 4.86 (ABq, 2H), 3.76 (s, 3H), and 2.21 ppm (s, 3H).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for one hour
  3. customevaporated to dryness
  4. dissolutionThe residue was dissolved in ethyl acetate (500 mL)
  5. washwashed with 2N HCl (2×300 mL)
  6. dry with materialThe organic phase was dried over anhydrous magnesium sulfate
  7. customevaporated to dryness

Sources & evidence

ORD record
ord-60326332a4e945c9b57cec3281e9fbd8
Source dataset
uspto-grants-2003_05
Patent number
US06562814B2

Reaction notes

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