Hydrochloric Acid → 3-Butyl-3-ethyl-2,3-dihydrobenzothiepine

HRID 1935571Notes

Reaction equation

HRID 1935571 reaction equation
[CH2:1]([C:3]([CH2:10][S:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[CH:18]=O)([CH:6]=[CH:7][CH2:8][CH3:9])[CH:4]=O)[CH3:2].Cl.C(Cl)Cl>COCCOC.[Zn]>[CH2:6]([C:3]1([CH2:1][CH3:2])[CH:4]=[CH:18][C:13]2[CH:14]=[CH:15][CH:16]=[CH:17][C:12]=2[S:11][CH2:10]1)[CH2:7][CH2:8][CH3:9]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 6344DichloromethaneHCID 537561052-Ethyl-2-((2-formylphenyl)thiomethyl)hexenal

Product 1

HCID 223252483-Butyl-3-ethyl-2,3-dihydrobenzothiepineYield 141.6%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 80711,2-DimethoxyethaneSolvent2×

Procedure

A mixture of 2.6 g (0.04 mole) of zinc dust, 7.2 g (0.047 mole) of TiCl3, and 50 mL of DME was held at reflux for 2 h and cooled to room temperature. To this mixture was added 2.4 g (8.6 mmole) of 17 in 20 mL of DME in 10 min. The reaction mixture was stirred at room temperature for 2 h and held at reflux for 1 h then was let standing at room temperature over weekend. The reaction mixture was poured into dilute HCl and was stirred with methylene chloride. The methylene chloride-water mixture was filtered through Celite. The methylene chloride layer was washed with brine, dried over MgSO4, and concentrated in vacuo to give 3.0 g of a residue. Purification by HPLC gave 0.41 g (20%) of 18 as an oil in the early fraction.

Workup

  1. temperatureat reflux for 2 h
  2. temperatureat reflux for 1 h
  3. waitthen was let standing at room temperature over weekend
  4. filtrationThe methylene chloride-water mixture was filtered through Celite
  5. washThe methylene chloride layer was washed with brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-9e4e605de92747e787f651301f004b7d
Source dataset
uspto-grants-2002_05
Patent number
US06387924B2

Reaction notes

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