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2-((2-Benzoylphenylthio)methyl)-2-ethylhexanal → 3-Butyl-3-ethyl-5-phenyl-2,3-dihydrobenzothiepine

HRID 1604492
Notes
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Reaction equation

HRID 1604492 reaction equation
[C:1]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[S:15][CH2:16][C:17]([CH2:24][CH3:25])([CH2:20][CH2:21][CH2:22][CH3:23])[CH:18]=O)(=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1>COCCOC.[Cl-].[Na+].O.[Zn]>[CH2:20]([C:17]1([CH2:24][CH3:25])[CH:18]=[C:1]([C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=2[S:15][CH2:16]1)[CH2:21][CH2:22][CH3:23]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 1

HCID 116028262-((2-Benzoylphenylthio)methyl)-2-ethylhexanal

Product 1

HCID 223252133-Butyl-3-ethyl-5-phenyl-2,3-dihydrobenzothiepineYield 52.7%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 80711,2-DimethoxyethaneSolvent2×HCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
5 °C

Procedure

A mixture of 2.6 g (0.04 mole) of zinc dust, 7.2 g (0.047 mole) of TiCl3 and 80 mL of anhydrous ethylene glycol dimethyl ether (DME) was held at reflux for 2 h. The reaction mixture was cooled to 5° C. To the reaction mixture was added dropwise a solution of 3.54 g (0.01 mole) of 2 in 30 mL of DME in 40 min. The reaction mixture was stirred at room temperature for 16 h and then was held at reflux for 2 h and cooled before being poured into brine. The organic was extract into methylene chloride. The methylene chloride extract was dried over MgSO4 and concentrated in vacuo. The residue was purified by HPLC (hexane) to give 1.7 g (43%) of 3 as an oil in the first fraction. The second fraction was discarded and the third fraction was further purified by HPLC (hexane) to give 0.07 g (2%) of 4a in the earlier fraction and 0.1 g (3%) of 4b in the later fraction.

Workup

  1. temperatureat reflux for 2 h
  2. temperatureat reflux for 2 h
  3. temperaturecooled
  4. extractionThe organic was extract into methylene chloride
  5. extractionThe methylene chloride extract
  6. dry with materialwas dried over MgSO4
  7. concentrationconcentrated in vacuo
  8. customThe residue was purified by HPLC (hexane)

Sources & evidence

ORD record
ord-47f00853ebe04568a1d3a8a67e3e8592
Source dataset
uspto-grants-1999_11
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US05994391

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes