Tin tetrachloride → HCID 23445655, compound

HRID 1069229Notes

Reaction equation

HRID 1069229 reaction equation
[CH:1]1([C:6]2[CH:7]=[C:8]([CH:12]=[CH:13][C:14]=2[O:15][CH3:16])[C:9]([OH:11])=O)[CH2:5][CH2:4][CH2:3][CH2:2]1.C(Cl)(=O)C(Cl)=O.[CH3:23][C:24]1[S:25][C:26]([CH2:30][C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)=[CH:27][C:28]=1[CH3:29].[Sn](Cl)(Cl)(Cl)Cl>C(Cl)Cl.CN(C)C=O.O>[CH2:30]([C:26]1[S:25][C:24]([CH3:23])=[C:28]([CH3:29])[C:27]=1[C:9]([C:8]1[CH:12]=[CH:13][C:14]([O:15][CH3:16])=[C:6]([CH:1]2[CH2:2][CH2:3][CH2:4][CH2:5]2)[CH:7]=1)=[O:11])[C:31]1[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=1

Participants

8

Reactant 4

HCID 24287Tin tetrachlorideHCID 65578Oxalyl chlorideHCID 102419632,3-Dimethyl-5-benzylthiopheneHCID 15895034HCID 15895034, compound

Product 1

HCID 23445655HCID 23445655, compoundYield 52.3%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

To a slurry of 3-cyclopentyl-p-anisic acid (5.0 g, 22.7 mmol, RN-59216-82-9) in anhydrous methylene chloride (60 mL) was added oxalyl chloride (2.4 mL, 27.2 mmol) and N,N-dimethylformamide (2 drops) at room temperature under nitrogen. After stirring for 1.5 h the reaction mixture was concentrated under reduced pressure. The residue was dissolved in carbon disulfide (32 mL) and the resulting solution was added to 2,3-dimethyl-5-benzylthiophene (5.1 g, 25.0 mmol). At −78° C. under nitrogen, tin(IV) chloride (2.9 mL, 25.0 mmol) was added, and the reaction mixture was then stirred at room temperature for 4 h. The solution was poured onto a mixture of ice and water (200 mL) and extracted with diethyl ether (200 mL). The diethyl ether layer was washed twice with sodium bicarbonate (50 mL) and once with brine (50 mL). Concentration under reduced pressure and chromatography with petroleum ether:ethyl acetate (95:5) gave the title compound as an amber oil (4.8 g, 52%): (DMSO-d6): δ7.61-7.54 (m, 2H), 7.24-7.14 (m, 3H), 7.08-7.02 (m, 3H), 3.87 (s, 3H), 3.84 (s, 2H), 3.42-3.30 (m, 1H), 2.26 (s, 3H), 2.00-1.85 (m, 2H), 1.81 (s, 3H), 1.74-1.58 (m, 4H), 1.48-1.36 (m, 2H); MS(EI): [M+] 404; Anal. Calc. for C26H28O2S: C, 77.19; H, 6.98; N, 0.00. Found: C, 76.26; H, 7.24; N, 0.04.

Workup

  1. concentrationwas concentrated under reduced pressure
  2. dissolutionThe residue was dissolved in carbon disulfide (32 mL)
  3. stirringthe reaction mixture was then stirred at room temperature for 4 h
  4. extractionextracted with diethyl ether (200 mL)
  5. washThe diethyl ether layer was washed twice with sodium bicarbonate (50 mL) and once with brine (50 mL)
  6. concentrationConcentration under reduced pressure and chromatography with petroleum ether:ethyl acetate (95:5)

Sources & evidence

ORD record
ord-8cc6345da4d74f9f91701fc9c7024866
Source dataset
uspto-grants-2001_06
Patent number
US06251936B1

Reaction notes

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