Thiophosgene → 6-Bromo-4-fluorobenzo[d][1,3]dioxole-2-thione

HRID 1746058노트

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HRID 1746058 반응식
[Br:1][C:2]1[CH:7]=[C:6]([OH:8])[C:5]([OH:9])=[C:4]([F:10])[CH:3]=1.[C:11](Cl)(Cl)=[S:12].[OH-].[Na+]>C(Cl)(Cl)Cl.C(OCC)(=O)C>[Br:1][C:2]1[CH:3]=[C:4]([F:10])[C:5]2[O:9][C:11](=[S:12])[O:8][C:6]=2[CH:7]=1

참가 물질

6

반응물 3

HCID 10040ThiophosgeneHCID 14798Sodium HydroxideHCID 115793565-Bromo-3-fluorobenzene-1,2-diol

생성물 1

HCID 904155846-Bromo-4-fluorobenzo[d][1,3]dioxole-2-thione수율 62.1%

시약·촉매·용매 2

HCID 6212Chloroform용매HCID 8857Ethyl Acetate용매

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온도
2.5 °C

실험 절차

5-Bromo-3-fluorobenzene-1,2-diol (2.0 g, 9.7 mmol, prepared according to Lu, Hejun; Tang, Peng Cho; Chen, Yiqian; Wang, Shenglan; Wang, Hua; Zhang, Lei; Li, Jun, WO 2011140936 A1) was dissolved in chloroform (25 mL), treated with thiophosgene (1.2 g, 11 mmol) and cooled to 0-5° C. Sodium hydroxide (10% aqueous, 8.9 g, 22 mmol) was added dropwise with vigorous stirring over 30 min. After 1 h, the chloroform was removed under vacuum and the pH was adjusted to 2 by addition of 6 M HCl. The solid that was formed was taken up in ethyl acetate (120 mL), washed with saturated NaCl (30 mL), dried (Na2SO4) and evaporated. The material was purified by flash chromatography using a 0-30% ethyl acetate-hexane gradient to give the title compound as a tan solid (1.5 g, 62%): mp 41-42° C.; 1H NMR (400 MHz, CDCl3) δ 7.35-7.30 (m, 1H), 7.29 (d, J=1.6 Hz, 1H); 19F NMR (376 MHz, CDCl3) δ −128.93; EIMS m/z 248/250.

후처리

  1. waitAfter 1 h
  2. customthe chloroform was removed under vacuum
  3. additionthe pH was adjusted to 2 by addition of 6 M HCl
  4. customThe solid that was formed
  5. washwashed with saturated NaCl (30 mL)
  6. dry with materialdried (Na2SO4)
  7. customevaporated
  8. customThe material was purified by flash chromatography

출처 및 근거

ORD 기록
ord-97601adef8dd4a8bb2c5f40a228bfc7c
출처 데이터셋
uspto-grants-2015_10
특허 번호
US09149038B2

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