Tin tetrachloride → 1-(3-Methoxythiophen-2-yl)-3-methylbut-2-en-1-one

HRID 257202Notes

Reaction equation

HRID 257202 reaction equation
[CH3:1][O:2][C:3]1[CH:7]=[CH:6][S:5][CH:4]=1.[CH3:8][C:9]([CH3:14])=[CH:10][C:11](Cl)=[O:12].[Sn](Cl)(Cl)(Cl)Cl.[K+].[Br-]>ClCCl>[CH3:1][O:2][C:3]1[CH:7]=[CH:6][S:5][C:4]=1[C:11](=[O:12])[CH:10]=[C:9]([CH3:14])[CH3:8]

Participants

6

Reactant 4

HCID 24287Tin tetrachlorideHCID 1023943-Methyl-2-butenoyl chlorideHCID 1402493-MethoxythiopheneHCID 253877Potassium Bromide

Product 1

HCID 156438821-(3-Methoxythiophen-2-yl)-3-methylbut-2-en-1-one

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of 3-methoxythiophene (21.3 g, 0.187 mol) [S. Gronowitz, Arkiv. Kemi., 1958, 12, 239] in dichloromethane (50 mL) was slowly added to a solution of 3,3-dimethylacryloyl chloride (22 mL, 0.195 mol) and tin(IV) chloride (23 mL, 0.195 mol) in dichloromethane (350 mL) at 0°-5° C. After stirring at 0°-5° C. an additional 1 h, the solution was poured into ice water (1 L). The organic layer was separated, washed with water, and dried over magnesium sulfate. The solvent was evaporated in vacuo. The resulting oil was purified by flash chromatography using dichloromethane as the eluant to give the product, 29.6 g (81%): mp 49°-51° C.; IR (KBr): 1671, 1628 and 1430 cm-1 ; MS: m/z 197 (MH+); 1H NMR (CDCl3): δ1.98 (d, J=1.2 Hz, 3H), 2.23 (d, J=1.1 Hz, 3H), 3.98 (s, 3H), 6.85 (d, J=5.5 Hz, 1H), 6.89 (dd, J=1.1 Hz, J=1.2 Hz, 1H) and 7.47 (d, J=5.5 Hz, 1H).

Workup

  1. customThe organic layer was separated
  2. washwashed with water
  3. dry with materialdried over magnesium sulfate
  4. customThe solvent was evaporated in vacuo
  5. customThe resulting oil was purified by flash chromatography
  6. customto give the product, 29.6 g (81%)

Sources & evidence

ORD record
ord-7bff982e4be24299aa5a03eb268fb72f
Source dataset
uspto-grants-1993_11
Patent number
US05260453

Reaction notes

Loading…