Reaction #2286338

Reaction equation

dimethyl-thiocarbamic acid S-(2,6-dichloro-4-nitro-phenyl)ester

Dimethyl-thiocarbamic acid S-(2,6-dichloro-4-nitro-phenyl)ester

water

→

dimethyl-thiocarbamic acid S-(4-amino-2,6-dichloro-phenyl)ester

Yield 93.0%

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

Yield 93.0%

Solvents

acetic acid

2-propanol

Conditions

Workup

1. 1
   TemperatureThe resulting mixture was heated to 95° C. for 2 h
2. 2
   FiltrationAt this time, the reaction was filtered hot through a pad of celite
3. 3
   Washwas washed with water and ethyl acetate
4. 4
   ConcentrationThe filtrates were concentrated
5. 5
   Otherto remove the majority of organics
6. 6
   workup.ADDITIONThe remaining solution was diluted with water (500 mL)
7. 7
   ExtractionThe solution was extracted with ethyl acetate (3×200 mL)
8. 8
   DryingThe combined organics were dried with magnesium sulfate
9. 9
   Filtrationfiltered
10. 10
    Concentrationconcentrated under vacuum
11. 11
    Temperaturewas cooled in the freezer for 30 min
12. 12
    OtherThe solid that formed
13. 13
    Filtrationwas collected by filtration
14. 14
    Washwas washed with cold diethyl ether

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

Source