1,3-benzodioxole from piperonal

[ketonechaser]

Is there way to synthesize 1,3-benzodioxole from piperonal?

 

[ketonechaser]

Found some synthesis can someone tell me is it valid or not?

1. Start with 10 grams of piperonal and dissolve it in about 100 mL of a suitable solvent such as dichloromethane or ethyl acetate.
2. Add a catalytic amount (e.g., 0.1-0.5 mol%) of a Lewis acid, such as aluminum chloride (AlCl3) or boron trifluoride (BF3). For 10 grams of piperonal, you can use approximately 10-50 mg of the catalyst.
3. Heat the reaction mixture under reflux at around 60-70°C for approximately 4-6 hours. Ensure the reaction flask is properly equipped with a reflux condenser and a heating mantle.
4. After reflux, cool the reaction mixture and carefully add a diluted solution of sodium hydroxide (NaOH) to hydrolyze the cyclic acetal. Use a solution of about 5-10% NaOH and add it dropwise until pH reaches around 7-8. Keep the temperature around 0-5°C.
5. Acidify the reaction mixture with hydrochloric acid (HCl) to protonate the hydrolyzed product. Use approximate 5-10 mL of concentrated HCl solution while maintaining the temperature around 0-5°C.
6. Extract the resulting mixture with a non-polar solvent (e.g., diethyl ether or dichloromethane) by performing multiple extractions with about 50-100 mL of the solvent each time until the organic layer is clear and colorless.
7. Dry the organic layer with anhydrous magnesium sulfate (MgSO4) by adding about 5-10 grams of MgSO4 to absorb any remaining water. Allow it to sit for approximately 30 minutes and then filter the mixture to remove the drying agent.
8. Remove the solvent under reduced pressure using a rotary evaporator or by simple evaporation at a temperature range of 40-50°C. The residue should provide you with the desired 1,3-benzodioxole.

 

[The-Hive]

youtube.com/@TOXXIE

 

[Mr Gonzo]

This kicks the hell out of making piperonal via the method I have been looking at, can anyone give a yield expectancy for this route. And bro where the heck did you find this out? I was looking at maybe ozone doped with O2 to oxidize from piperine.

 

[The-Hive]

This kicks the hell out of making piperonal via the method I have been looking at, can anyone give a yield expectancy for this route. And bro where the heck did you find this out? I was looking at maybe ozone doped with O2 to oxidize from piperine.

Mr GonzoAdding 500g of phosphoric acid catalyst into a 2000ml three-neck flask, adding 150ml of methanol under stirring, heating to 55 ℃, slowly adding 50g of piperonyl, dropping after 0.5 hour, adding 82g (0.59mol) of urotropine, starting to heat to 80 ℃, preserving heat for 7 hours, sampling, carrying out liquid phase analysis, cooling to 60-70 ℃, adding 700ml of water, stirring for 3 hours, adding ethyl acetate for two-time extraction, combining organic phases, adding saturated salt solution for washing, separating out the organic phase, adding 40g of anhydrous sodium sulfate for drying, filtering, concentrating ethyl acetate at 40 ℃ of filtrate, and carrying out reduced pressure distillation on residual oil pump to obtain 31g of piperonal with the purity of 9

 

[Mr Gonzo]

Adding 500g of phosphoric acid catalyst into a 2000ml three-neck flask, adding 150ml of methanol under stirring, heating to 55 ℃, slowly adding 50g of piperonyl, dropping after 0.5 hour, adding 82g (0.59mol) of urotropine, starting to heat to 80 ℃, preserving heat for 7 hours, sampling, carrying out liquid phase analysis, cooling to 60-70 ℃, adding 700ml of water, stirring for 3 hours, adding ethyl acetate for two-time extraction, combining organic phases, adding saturated salt solution for washing, separating out the organic phase, adding 40g of anhydrous sodium sulfate for drying, filtering, concentrating ethyl acetate at 40 ℃ of filtrate, and carrying out reduced pressure distillation on residual oil pump to obtain 31g of piperonal with the purity of 9

The-HiveI need to rewrite my entire notes I made starting with just black pepper, take it all my piperinic acid is now a pointless mass of stuff that only smells nice.

 

[The-Hive]

This kicks the hell out of making piperonal via the method I have been looking at, can anyone give a yield expectancy for this route. And bro where the heck did you find this out? I was looking at maybe ozone doped with O2 to oxidize from piperine.

Mr GonzoAdding 300ml of acetic acid, 50g of urotropine and 100ml of water into a 2000ml three-opening reaction bottle in sequence under stirring, dripping 90g of piperonyl chloride at the temperature of 20 ℃, keeping the temperature not more than 35 ℃, continuing to react for 1 hour at the temperature of 40-42 ℃ after the addition is finished, then adding 1000ml of water, heating to 100-102 ℃, refluxing and hydrolyzing for 2.5 hours, sampling and monitoring the reaction, cooling to 40 ℃ after the reaction is finished, extracting with dichloromethane for 4 times (400 ml each time), combining, concentrating dichloromethane, and distilling residual liquid under reduced pressure by an oil pump to obtain 30g of piperonal with the purity of 96 percent.

 

[The-Hive]

This kicks the hell out of making piperonal via the method I have been looking at, can anyone give a yield expectancy for this route. And bro where the heck did you find this out? I was looking at maybe ozone doped with O2 to oxidize from piperine.

Mr GonzoAdding 300ml of acetic acid, 50g of urotropine and 100ml of water into a 2000ml three-opening reaction bottle in sequence under stirring, dripping 90g of piperonyl chloride at the temperature of 20 ℃, keeping the temperature not more than 35 ℃, continuing to react for 1 hour at the temperature of 40-42 ℃ after the addition is finished, adding 1000ml of water and 0.5g of tetrabutylammonium bromide, heating to 100-102 ℃, performing reflux hydrolysis for 2 hours, cooling, concentrating 300ml of half water, cooling to 40 ℃, extracting for 4 times by using dichloromethane, extracting 400ml each time, combining, concentrating the dichloromethane, and performing reduced pressure distillation by using a residual oil pump to obtain 55g of piperonal with the purity of 98%.

 

[The-Hive]

This kicks the hell out of making piperonal via the method I have been looking at, can anyone give a yield expectancy for this route. And bro where the heck did you find this out? I was looking at maybe ozone doped with O2 to oxidize from piperine.

Mr GonzoWear a full face respirator if you are doing it the black pepper route

 

[Mr Gonzo]

Wear a full face respirator if you are doing it the black pepper route

The-HiveI've got the one the SAS wore in the Iranian Embassy siege in London, and extra cans to put on it. And Bro I can not thank you enough on these synths. Been banging my head of a wall for a while now over the ways to oxidize piperine. Even the sites like sciencemadness people are talking about either Chemplayers vid or the ozone route.

All so, I noticed that the use of the IUPAC nomenclature was used and giving a quick look on google got a load of stuff I haven't read, I'll keep that in mind as this chem has about 4 common names alone!

 

[The-Hive]

Happy to help