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

HRID 1746058ノート

反応式

HRID 1746058 の反応式
[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

参加物

6

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 6212Chloroform溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
2.5 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-97601adef8dd4a8bb2c5f40a228bfc7c
出典データセット
uspto-grants-2015_10
特許番号
US09149038B2

反応ノート

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