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

HRID 1648759Notes

Reaction equation

HRID 1648759 reaction equation
[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

Participants

7

Reactant 4

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

Product 1

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

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 110624Benzene hexaneSolvent

Conditions

Temperature
0 °C

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-50a176214522476e91a7ee4472f21f45
Source dataset
uspto-grants-1983_11
Patent number
US04413005

Reaction notes

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