반응 #2286338

ord-fe666c957aa14a2bbe96669f05457f11

반응 방정식

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
수율 93.0%
CN(C)C(=O)Sc1c(Cl)cc(N)cc1Cl
Dimethyl-thiocarbamic acid S-(4-amino-2,6-dichloro-phenyl)ester
수율 93.0%

반응 조건

온도
50°CELSIUS
상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    온도The resulting mixture was heated to 95° C. for 2 h
  2. 2
    여과At this time, the reaction was filtered hot through a pad of celite
  3. 3
    세척was washed with water and ethyl acetate
  4. 4
    농축The filtrates were concentrated
  5. 5
    기타to remove the majority of organics
  6. 6
    workup.ADDITIONThe remaining solution was diluted with water (500 mL)
  7. 7
    추출The solution was extracted with ethyl acetate (3×200 mL)
  8. 8
    건조The combined organics were dried with magnesium sulfate
  9. 9
    여과filtered
  10. 10
    농축concentrated under vacuum
  11. 11
    온도was cooled in the freezer for 30 min
  12. 12
    기타The solid that formed
  13. 13
    여과was collected by filtration
  14. 14
    세척was washed with cold diethyl ether

실험 절차

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

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: USRE046024E1uspto-grants-2016_06