تفاعل #2286338

ord-fe666c957aa14a2bbe96669f05457f11

معادلة التفاعل

CN(C)C(=O)Sc1c(Cl)cc([N+](=O)[O-])cc1Cl
dimethyl-thiocarbamic acid S-(2,6-dichloro-4-nitro-phenyl)ester
CN(C)C(=O)Sc1c(Cl)cc([N+](=O)[O-])cc1Cl
Dimethyl-thiocarbamic acid S-(2,6-dichloro-4-nitro-phenyl)ester
O
water
CN(C)C(=O)Sc1c(Cl)cc(N)cc1Cl
dimethyl-thiocarbamic acid S-(4-amino-2,6-dichloro-phenyl)ester
المردود 93.0%
CN(C)C(=O)Sc1c(Cl)cc(N)cc1Cl
Dimethyl-thiocarbamic acid S-(4-amino-2,6-dichloro-phenyl)ester
المردود 93.0%

المذيبات

ظروف التفاعل

درجة الحرارة
50°CELSIUS
الظروف التفصيلية
See reaction.notes.procedure_details.

المعالجة

  1. 1
    درجة الحرارةThe resulting mixture was heated to 95° C. for 2 h
  2. 2
    ترشيحAt this time, the reaction was filtered hot through a pad of celite
  3. 3
    غسيلwas washed with water and ethyl acetate
  4. 4
    تركيزThe filtrates were concentrated
  5. 5
    أخرىto remove the majority of organics
  6. 6
    workup.ADDITIONThe remaining solution was diluted with water (500 mL)
  7. 7
    استخلاصThe solution was extracted with ethyl acetate (3×200 mL)
  8. 8
    تجفيفThe combined organics were dried with magnesium sulfate
  9. 9
    ترشيحfiltered
  10. 10
    تركيزconcentrated under vacuum
  11. 11
    درجة الحرارةwas cooled in the freezer for 30 min
  12. 12
    أخرىThe solid that formed
  13. 13
    ترشيحwas collected by filtration
  14. 14
    غسيلwas washed with cold diethyl ether

الإجراء التجريبي

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

المصدر

DOI: 10.6084/m9.figshare.5104873.v1براءة الاختراع: USRE046024E1uspto-grants-2016_06