Dimethyl Disulfide → 3-Methylthio-4-hydroxy-5-benzyloxybenzaldehyde

HRID 1110819ノート

反応式

HRID 1110819 の反応式
Br[C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([O:11][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[C:9]=1[OH:10])[CH:5]=[O:6].[CH3:19][S:20]SC>[Cu].N1C=CC=CC=1>[CH3:19][S:20][C:2]1[CH:3]=[C:4]([CH:7]=[C:8]([O:11][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[C:9]=1[OH:10])[CH:5]=[O:6]

参加物

5

反応物 2

HCID 12232Dimethyl DisulfideHCID 150782813-Bromo-4-hydroxy-5-benzyloxybenzaldehyde

生成物 1

HCID 117781083-Methylthio-4-hydroxy-5-benzyloxybenzaldehyde収率 76%

試薬・触媒・溶媒 2

HCID 23978Copper触媒HCID 1049Pyridine溶媒

反応条件

温度
95 °C

実験手順

In an alternative procedure a 50-L flask equipped with a mechanical stirrer was charged with 3-bromo-4-hydroxy-5-benzyloxybenzaldehyde (1.332 kg, 4.34 mol), Copper powder (1.068 kg, 16.82 mol), dimethyldisulfide (1.068 kg, 11.36 mol) and pyridine (23 L). The mixture was heated at 95° C. overnight with gentle stirring, filtered, and the filtered cake was washed with dichloromethane (30 L). The pyridine filtrate was distilled off to leave a black residue, from which the product was extracted with the dichloromethane washes. The combined organic extracts were washed with 2N HCl until it became light brown and the acidic aqueous layer was clear. The organic layer was dried (MgSO4), filtered, and the filtrate was evaporated to dryness. Crystallization from dichloromethane-hexane gave the title compound (900 g, 76%): mp 117°-119° C.; NMR (CDCl3) δ 2.50 (s, SCH3), 5.20 (s, OCH2Ar), 6.72 (s, OH), 7.34-7.46 (m, ArH), 9.78 (s, ArCHO)

後処理

  1. customIn an alternative procedure a 50-L flask equipped with a mechanical stirrer
  2. filtrationfiltered
  3. washthe filtered cake was washed with dichloromethane (30 L)
  4. distillationThe pyridine filtrate was distilled off
  5. customto leave a black residue
  6. extractionfrom which the product was extracted with the dichloromethane
  7. washThe combined organic extracts were washed with 2N HCl until it
  8. dry with materialThe organic layer was dried (MgSO4)
  9. filtrationfiltered
  10. customthe filtrate was evaporated to dryness
  11. customCrystallization from dichloromethane-hexane

出典と根拠

ORDレコード
ord-d55cb4eadbec4f4ca34f934e2b6b3dd5
出典データセット
uspto-grants-1990_12
特許番号
US04977146

反応ノート

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