Water → Dimethyl-thiocarbamic acid S-(4-amino-2,6-dichloro-phenyl)ester

HRID 271209Notes

Reaction equation

HRID 271209 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([N+:8]([O-])=O)[CH:5]=[C:4]([Cl:11])[C:3]=1[S:12][C:13](=[O:17])[N:14]([CH3:16])[CH3:15].O>C(O)(=O)C.CC(O)C.[Fe]>[NH2:8][C:6]1[CH:5]=[C:4]([Cl:11])[C:3]([S:12][C:13](=[O:17])[N:14]([CH3:16])[CH3:15])=[C:2]([Cl:1])[CH:7]=1

Participants

6

Reactant 2

HCID 962WaterHCID 12661483S-(2,6-Dichloro-4-nitrophenyl) dimethylcarbamothioate

Product 1

HCID 59834498Dimethyl-thiocarbamic acid S-(4-amino-2,6-dichloro-phenyl)esterYield 93%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 176Acetic AcidSolventHCID 3776IsopropanolSolvent

Conditions

Temperature
50 °C

Procedure

A mixture of dimethyl-thiocarbamic acid S-(2,6-dichloro-4-nitro-phenyl) ester (80) (1.6 g, 5.4 mmol) in glacial acetic acid (24 mL), 2-propanol (48 mL), and water (24 mL) heated to 50° C. was treated with iron powder (2.1 g, 37.8 mmol). The resulting mixture was heated to 95° C. for 2 h. At this time, the reaction was filtered hot through a pad of celite and was washed with water and ethyl acetate. The filtrates were concentrated to remove the majority of organics. The remaining solution was diluted with water (500 mL) and was then brought to pH=8 with a concentrated ammonium hydroxide solution. The solution was extracted with ethyl acetate (3×200 mL). The combined organics were dried with magnesium sulfate, filtered and concentrated under vacuum. The resulting residue was slurried with diethyl ether and was cooled in the freezer for 30 min. The solid that formed was collected by filtration and was washed with cold diethyl ether to afford dimethyl-thiocarbamic acid S-(4-amino-2,6-dichloro-phenyl) ester (81) (1.33 g, 93%) as a white solid; EI(+)-HRMS m/e calcd for C9H10Cl2N2OS (M+H)+ 264.9964, found 264.9964. Exact Mass=263.9891; Molecular weight=265.16

Workup

  1. temperatureThe resulting mixture was heated to 95° C. for 2 h
  2. filtrationAt this time, the reaction was filtered hot through a pad of celite
  3. washwas washed with water and ethyl acetate
  4. concentrationThe filtrates were concentrated
  5. customto remove the majority of organics
  6. additionThe remaining solution was diluted with water (500 mL)
  7. extractionThe solution was extracted with ethyl acetate (3×200 mL)
  8. dry with materialThe combined organics were dried with magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated under vacuum
  11. temperaturewas cooled in the freezer for 30 min
  12. customThe solid that formed
  13. filtrationwas collected by filtration
  14. washwas washed with cold diethyl ether

Sources & evidence

ORD record
ord-a4f16f420c1443bdacc03e2256b76909
Source dataset
uspto-grants-2008_11
Patent number
US07452882B2

Reaction notes

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