3,4-(METHYLENEDIOXY)BUTYROPHENONE synthesis
- Product Name:3,4-(METHYLENEDIOXY)BUTYROPHENONE
- CAS Number:63740-97-6
- Molecular formula:C11H12O3
- Molecular Weight:192.21
106-31-0
274-09-9
63740-97-6
To a pre-dried two-necked round-bottomed flask were added 1,2-methylenedioxybenzene (piperylene ring, 2.0 g, 16.37 mmol), 1,2-dichloroethane (7 mL) and n-butyric anhydride (3.2 mL, 19.6 mmol). The reaction mixture was cooled to -10 °C and boron trifluoride ethyl ether complex (BF3-Et2O, 6.78 g, 47.7 mmol) was slowly added dropwise over 15 min while keeping the reaction temperature between -5 °C and 0 °C. After the dropwise addition, the reaction mixture was continued to be stirred at -5 °C for 3 hours. Upon completion of the reaction, the reaction was quenched with saturated aqueous sodium acetate solution, and the organic layer was separated and washed sequentially with 5% aqueous sodium hydroxide solution (7 mL) and deionized water. The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography with hexane/ethyl acetate (10:1, v/v) as eluent to afford the target compound 3,4-(methylenedioxy)phenylbutanone (1.34 g, 85% yield). 1H NMR (400 MHz, CDCl3) δ: 7.52 (dd, J = 8.1, 1.6 Hz, 1H), 7.40 (d, J = 8.1 Hz, 1H), 6.80 (d, J = 8.1 Hz, 1H), 5.99 (s, 1H), 2.82 (t, J = 7.3 Hz, 2H), 1.70 (h, J = 7.4 Hz, 2H ), 0.95 (t, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ: 198.4, 151.5, 148.1, 132.0, 124.1, 107.8, 107.7, 101.7, 40.2, 18.0, 13.8. HRMS-ESI-MS (m/z) [M + H]+: calculated value C11H13O3: 193.0865; measured value: 193.0867.
Yield:63740-97-6 75 g
Reaction Conditions:
with zinc(II) oxide;zinc(II) chloride in dichloromethane at 0 - 5; for 5 h;
Steps:
7 Preparation of 5-butyl-l,3-Benzodioxole (using 0.5 moles of Zinc oxide and 0.05 moles of Zinc chloride per mole of acyl chloride using dichloromethane as solvent)
122 g of 1,3-benzodioxole and 190 g of dichloromethane were charged into a 1 litre reaction flask and the mixture was cooled to 0°C under stirring. 41 g of Zinc oxide and 7 g of Zinc chloride were added under stirring. Subsequently, 106.5 g of butanoyl chloride was added to the above mixture in 4 hours maintaining the temperature of the reaction medium between 0°C and 5°C under stirring. The reaction medium was stirred for another 1 hour until the acylation reaction was substantially completed. The reaction mass was subjected to aqueous workup to remove Zinc chloride and butanoic acid and the organic layer was separated and distilled to recover 65 g of unreacted 1,3-benzodioxole and 75 g of l-(l,3-benzodioxol-5-yl)-l-butanone with a GC purity of > 99%. The l-(l,3-benzodioxol-5-yl)-l-butanone was subjected to selective reduction and dehydration as discussed in Example 2 to obtain 66 g of 5-butyl-l,3-benzodioxole with a yield of 115.8% (wt./wt. on 1,3-benzodioxole consumed) and purity of > 99% by GC analysis.
References:
ANTHEA AROMATICS PRIVATE LIMITED;MOHAPATRA, Manoj Kumar;BENDAPUDI, Ramamohanrao;MENACHERRY, Paul Vincent;PAUL, Vincent WO2018/150230, 2018, A1 Location in patent:Paragraph 0077; 0078
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