Hydrochloric Acid → 4-(Isopropylthio)-3-methylbenzoic acid

HRID 1478459

反応式

HRID 1478459 の反応式
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]

参加物

7

反応物 4

HCID 313Hydrochloric AcidHCID 821314-Bromo-3-methylbenzoic acidHCID 118529Isopropyl propyl disulfideHCID 178418339Butyllithium

生成物 1

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

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 14798Sodium Hydroxide溶媒

反応条件

温度
-78 °C

実験手順

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 dichloromthane 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).

後処理

  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

出典と根拠

ORDレコード
ord-7d32caeb20864eaaaac5dd12b5dfed08
出典データセット
uspto-grants-2016_08
特許番号
US09403839B2

関連ノート

読み込み中…