盐酸 → 4-(Isopropylthio)-3-methylbenzoic acid

HRID 1908112笔记

反应方程式

HRID 1908112 反应方程式
C([Li])CCC.Br[C:7]1[CH:15]=[CH:14][C:10]([C:11]([OH:13])=[O:12])=[CH:9][C:8]=1[CH3:16].[CH:17]([S:20]SCCC)([CH3:19])[CH3:18].Cl>C1COCC1.[OH-].[Na+]>[CH:17]([S:20][C:7]1[CH:15]=[CH:14][C:10]([C:11]([OH:13])=[O:12])=[CH:9][C:8]=1[CH3:16])([CH3:19])[CH3:18]

参与物

7

反应物 4

HCID 313盐酸HCID 821313-甲基-4-溴苯甲酸HCID 118529Isopropyl propyl disulfideHCID 178418339正丁基锂

产物 1

HCID 585509264-(Isopropylthio)-3-methylbenzoic acid收率 34.5%

试剂、催化剂与溶剂 2

HCID 8028四氢呋喃溶剂2 次HCID 14798氢氧化钠溶剂

反应条件

温度
-78 °C

实验过程

Butyllithium (16 mL of 1.6 M, 26 mmol) was added drop-wise to a mixture of 4-bromo-3-methyl-benzoic acid (2.5 g, 12 mmol) and THF (63 mL) at −78° C. The mixture was allowed to stir at −78° C. for 30 minutes before a solution of 2-isopropyldisulfanylpropane (1.7 g, 12 mmol) in THF (2 mL) was added drop-wise. The mixture was allowed to stir at −78° C. for 30 min, then 30 min at rt. The reaction mixture was then diluted with 100 mL of 1M aqueous sodium hydroxide. The organic layer was discarded and the aqueous layer was made acidic with 4M aqueous hydrochloric acid. The aqueous layer was then extracted 3 times with ethyl acetate. The combined extracts were dried over sodium sulfate and then evaporated to dryness. The crude material was purified by column chromatography using a gradient of 0-5% MeOH in dichloromethane to give 4-(isopropylthio)-3-methylbenzoic acid (870 mg, 18%). MS m/z calc. 210.3. found 211.2 (M+1)+. Retention time: 2.32 minutes (3 min run).

后处理

  1. additionwas added drop-wise
  2. custom30 min
  3. customat rt
  4. extractionThe aqueous layer was then extracted 3 times with ethyl acetate
  5. dry with materialThe combined extracts were dried over sodium sulfate
  6. customevaporated to dryness
  7. customThe crude material was purified by column chromatography

来源与证据

ORD记录
ord-15b5c7efc57445d69a13ce7d01647e70
来源数据集
uspto-grants-2013_12
专利号
US08598164B2

反应笔记

加载中…