Carbofuran → Ethyl N-{[{[(2,2-dimethyl-2,3-dihydro-1-benzofuran-7-yl)oxy]carbonyl}(methyl)amino]sulfanyl}-N-phenylglycinate

HRID 1648759ノート

反応式

HRID 1648759 の反応式
[CH3:1][NH:2][C:3](=[O:16])[O:4][C:5]1[C:13]2[O:12][C:11]([CH3:15])([CH3:14])[CH2:10][C:9]=2[CH:8]=[CH:7][CH:6]=1.[S:17](Cl)Cl.C(N(CC)CC)C.[CH2:27]([O:29][C:30](=[O:39])[CH2:31][NH:32][C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[CH3:28]>C(Cl)Cl.C1C=CC=CC=1.CCCCCC>[C:33]1([N:32]([CH2:31][C:30]([O:29][CH2:27][CH3:28])=[O:39])[S:17][N:2]([CH3:1])[C:3](=[O:16])[O:4][C:5]2[C:13]3[O:12][C:11]([CH3:14])([CH3:15])[CH2:10][C:9]=3[CH:8]=[CH:7][CH:6]=2)[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1

参加物

7

反応物 4

HCID 2566CarbofuranHCID 8471Triethylamine2 回HCID 25353Sulfur dichlorideHCID 75190N-Phenylglycine ethyl ester

生成物 1

HCID 3067960Ethyl N-{[{[(2,2-dimethyl-2,3-dihydro-1-benzofuran-7-yl)oxy]carbonyl}(methyl)amino]sulfanyl}-N-phenylglycinate収率 62.3%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒2 回HCID 110624Benzene hexane溶媒

反応条件

温度
0 °C

実験手順

A 11 g quantity (0.05 mole) of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methyl-carbamate was dissolved in 70 ml of methylene chloride, 5.2 g (0.05 mole) of sulfur dichloride was added to the solution with cooling, and 5 g (0.05 mole) of triethylamine was further added dropwise to the solution at -10° to -5° C. The mixture was stirred at 0° C. for one hour and further at room temperature for 2 hours. After cooling to -10° to -5° C., 9 g (0.05 mole) of N-phenylglycine ethyl ester was then added dropwise to the mixture, and 5 g (0.05 mole) of triethylamine was further added dropwise to the mixture. The resulting mixture was stirred at 0° C. for 2 hours and thereafter allowed to stand overnight at room temperature. With addition of 100 ml of methylene chloride, the reaction mixture was washed with 100 ml of water three times. The methylene chloride layer was dried and then concentrated in a vacuum to give an oily product. A benzene-hexane (1:1) mixture was added to the oily product, whereby crystals were precipitated. The thus-precipitated crystals were then filtered off, and the mother liquor was concentrated to give an oily product, which was subsequently cooled to obtain crystals. The thus-obtained crystals were recrystallized from diethyl ether to obtain 13.4 g (yield: 62.3%) of white crystals having a melting point of 92° to 93° C.

後処理

  1. temperaturewith cooling
  2. temperatureAfter cooling to -10° to -5° C.
  3. additionwas further added dropwise to the mixture
  4. stirringThe resulting mixture was stirred at 0° C. for 2 hours
  5. waitto stand overnight at room temperature
  6. washthe reaction mixture was washed with 100 ml of water three times
  7. dry with materialThe methylene chloride layer was dried
  8. concentrationconcentrated in a vacuum
  9. customto give an oily product
  10. customwere precipitated
  11. filtrationThe thus-precipitated crystals were then filtered off
  12. concentrationthe mother liquor was concentrated
  13. customto give an oily product, which
  14. temperaturewas subsequently cooled
  15. customto obtain crystals
  16. customThe thus-obtained crystals were recrystallized from diethyl ether

出典と根拠

ORDレコード
ord-50a176214522476e91a7ee4472f21f45
出典データセット
uspto-grants-1983_11
特許番号
US04413005

反応ノート

読み込み中…