Triethylamine → [[[[(2,5-Dimethylphenyl)amino]thioxomethyl]methylamino]oxy]acetic acid

HRID 411977

反応式

HRID 411977 の反応式
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][C:3]=1[N:9]=[C:10]=[S:11].Cl.[CH3:13][NH:14][O:15][CH2:16][C:17]([OH:19])=[O:18].C(N(CC)CC)C>C(Cl)(Cl)Cl>[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][C:3]=1[NH:9][C:10]([N:14]([CH3:13])[O:15][CH2:16][C:17]([OH:19])=[O:18])=[S:11]

参加物

5

反応物 3

HCID 8471TriethylamineHCID 1404992,5-Dimethylphenyl isothiocyanateHCID 85852466N-methyl aminooxy acetic acid hydrochloride

生成物 1

HCID 86585212[[[[(2,5-Dimethylphenyl)amino]thioxomethyl]methylamino]oxy]acetic acid収率 93.3%

試薬・触媒・溶媒 1

HCID 6212Chloroform溶媒

実験手順

A mixture of 2,5-dimethylphenyl-isothiocyanate (16.3 g), N-methyl aminooxy acetic acid hydrochloride (15.55 g), triethylamine (30 g) and chloroform (250 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 (2×200 mL) then with water (200 mL). The organic phase was dried over anhydrous magnesium sulfate and evaporated to dryness affording (25 g) of [[[[(2,5-dimethylphenyl)amino]thioxomethyl]methylamino]oxy]acetic acid as an oil. 1H-NMR (DMSO-d6; 300 Mhz) δ13.25 (br s, 1H), 10.08 (s, 1H), 7.15-6.94 (m, 3H), 4.62 (s, 2H), 3.52 (s, 3H), 2.24 ppm (s, 3H and 2.10 ppm (s, 3H). The acid (24.1 g) was dissolved in benzene (250 mL). Phosphorus pentachloride (18.7 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 (600 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. The residual oily substance crystallized upon standing. The solid mass was stirred in methanol (100 mL). The solid was collected by filtration and air dried to give the title compound (11.2 g), m.p. 104-106° C. Mass spectrum (El, M.+) m/z 250. 1H-NMR (CDCl3; 400 MHz) δ7.21-7.17 (m, 2H), 6.92 (s, 1H), 4.84 (ABq, 2H), 3.75 (s, 3H), 2.35 (s, 3H), and 2.12 ppm (s, 3H).

後処理

  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 (2×200 mL)
  6. dry with materialThe organic phase was dried over anhydrous magnesium sulfate
  7. customevaporated to dryness

出典と根拠

ORDレコード
ord-8c2c0380c4364cb49779eb636ba3821c
出典データセット
uspto-grants-2003_05
特許番号
US06562814B2

関連ノート

読み込み中…