Preparation method of piperonal

[Chemtrail]

Preparation method of piperonal​

CN108752310B patent​

China

The current methods for preparing piperonal are as follows:

CN108752310B - Preparation method of piperonal - Google Patents

The invention provides a preparation method of piperonal, which comprises the following steps: the piperonyl, the catalyst and the urotropine react in an alcohol solvent at 50-120 ℃ for 1-10 h to obtain the piperonal. The whole process only needs one-step reaction, the process is simplified, the...

patents.google.com

Enjoy this sexy little patent

 

[Chemtrail]

*safrole *

Swim could do a synthesis :

5-bromo-1,3-benzodioxole (methylene benzene "honey comb" with a bromine -arm) --->
safrole

Eugenol oil --->
Safrole

*That sesemol molecule seems to have potential .. *

Or

Just distill from sassafras oil ~80% at ~140C w/ vacuum pump ~4 hours


...-erowid has some clever ideas of a safrole synthesis

 

[Chemtrail]

Swim had noticed piperonal (heliotropin) CSA# 120-57-0

Has been sold in perfume stores in 20% - 50% concentration ratios for legal reasons

with Benzyl Benzoate (BB)

DiPropylene Glycol (DPG)

TriEthyl Citrate (TEC)



The question is how could Swim extract the piperonal (or heliotropin) ; from the other Non Polar solubility additives ?

 

[Chemtrail]

There is a ~60° Boiling Point difference with

Piperonal 264C

and

Benzyl Benzoate 324C


The solubility are basically the same , as well as the dipropylene glycol and TriEthyl Citrate

 

[Chemtrail]

Swim hit the jackpot

BAM !


2.4. Piperonal from pepper

2.4.1. Oxidative cleavage of piperine by ozonolysis
A stream of ozone gas, generated by a HAILEA HLO-100 Ozone Steriliser
(-
100 mg of ozone per hour), was passed through a solution of piperine (1.00 g,
3.51 mmol) in a 5% solution of water in acetone. After 8 h, the ozone generator was
switched off and the solution extracted with two 10 mL portions of diethyl ether.
The combined ether extracts were dried over anhydrous sodium sulphate and the
solvent evaporated in vacuo yielding bright yellow oil. Yield: 508 mg (97%). 1
H
NMR: see Fig. S13. GC–MS: see Fig. 2.

2.4.2. Oxidative cleavage of piperine with aqueous KMnO4 in THF

An aqueous solution of KMnO4 (2.00 g, 12.6 mmol in 40 mL of water) was added
dropwise over a period of 4 h to a solution of piperine (1.00 g, 3.51 mmol in 40 mL of
THF) at 60 8C. After the solution had been added, the mixture was stirred for 4 h
before the MnO2 precipitate that had formed was filtered off leaving a pale yellow
solution.
The sample was extracted with diethyl ether and the combined extracts
were dried over anhydrous sodium sulphate. The ether was evaporated in vacuo to
yield a dark yellow-orange oil that solidified on cooling. Yield: 340 mg (65%). 1
H
NMR: see Fig. S14. GC–MS: see Fig. 2.


2.5. Piperonal from vanillin

2.5.1. 3,4-Dihydroxybenzaldehyde from vanillin

A solution of vanillin (1.00 g, 6.58 mmol) in 100 mL of toluene was added to
aluminium chloride (1.15 g, 8.65 mmol) in a two-neck 250 mL round bottom flask.
Pyridine (2.50 mL, 31.1 mmol) was added dropwise and the resulting mixture was
stirred at reflux for 6 h. Next, 100 mL of dilute hydrochloric acid (15–20%) was
added. The organic layer was separated from the aqueous layer, which was then
extracted with three 20 mL portions of diethyl ether. The combined ether extracts
were dried over anhydrous sodium sulphate and the solvent evaporated in vacuo to
yield a pale brown solid. Yield: 798 mg (88%). 1
H NMR: see Fig. S15.

2.5.2. Piperonal from 3,4-dihydroxybenzaldehyde

To a suspension of K2CO3 in 10 mL of N-methyl-pyrrolidinone, a solution of 3,4-
dihydroxybenzaldehyde (500 mg, 3.62 mmol) and CH2Cl2 (5 mL, 78.3 mmol) in
5 mL of N-methyl-pyrrolidinone was added. The resulting brown mixture was
stirred at 120 C for 3 h. The mixture was allowed to cool and water was added. The
sample was extracted with two 20 mL portions of toluene and the combined
toluene layers were washed with brine and dried over anhydrous sodium sulphate.
The solvent was evaporated in vacuo to yield a brown oil. Yield: 452 mg (83%). 1
H
NMR: see Fig. S17.

2.6. MDMA from piperonal

 

[Chemtrail]

2.3.2.6 4-Allylcatechol from eugenol (Route 3)

Eugenol (8.0 g), aluminium chloride (8.6 g, 64 mmol) and 250 mL of toluene were cooled in an
ice bath. Pyridine (18.5 mL, 230 mmol) was added dropwise and the mixture heated under reflux
for 5 hrs. The resulting mixture was left to cool, and the clear, yellow organic layer was decanted.
The remaining solid was dissolved in hydrochloric acid (300 mL, 6.4 M) and extracted with diethyl
ether (3 x 100 mL). The organic extracts were washed with water (3 x 100 mL), dried over
anhydrous sodium sulfate, decanted and the solvent was removed with a rotary evaporator, to
give a black liquid. Yield: 6.4 g.
GC-MS: Figure 4-14.
1H NMR (500MHz, CDCl3): Figure 4-15.

2.3.2.7 Safrole from 4-allylcatechol
(Route 2 and 3)

A solution containing dichloromethane (5.0 mL, 78 mmol) and 50 mL of dimethyl sulfoxide were
heated at 120 – 130 °C. Sodium hydroxide (2.5 g, 63 mmol) was added to the solution. 4- Allylcatechol (4.0 g) was dissolved in 10 mL of dimethyl sulfoxide and added dropwise to the
mixture, which was heated at 120 – 130 °C for 45 mins. The resulting mixture was decanted and
water(50 mL) was added and left to cool. The resulting solution was extracted with diethyl ether
(3 x 25 mL) and the organic layer was washed with water (3 x 25 mL). The organic extracts were
dried over anhydrous sodium sulfate, decanted and the solvent was removed with a rotary
evaporator, producing brown liquid.

Route 2 – Yield: 3.4 g. GC-MS: Figure 4-11;
1H NMR (500MHz, CDCl3): Figure 4-12.
Route 3 – Yield: 3.7 g. GC-MS: Figure 4-16.
1H NMR (500MHz, CDCl3): Figure 4-17.

2.3.3 MDMA
2.3.3.1 MDP2P from safrole (Route A)



...

... This recipe uses DMSO instead of dimethyl sulfoxide
AND
Uses potassium carbonate instead of NaOH

Credit goes to cycloknight on science madness and Chemdelic

Another relative Reference with loads !!! Of info

vanillin.eugenol.demethylation.methylenation