posted 12-11-1999 04:18 PM         

Piperonal transformed into the MD2Nitropropene by the action of NaOH in methanol looks straightforward and high-yeilding enuf. However, the LAH reduction of the nitropropene sounds a little scary... LAH in THF under reflux sounds like something to try after a little more lab experience. Red-AL or aluminum amalgam or zinc/nickel etc sounds a little friendlier. The elf in question is scratching his head pretty hard right now, as he started thinking about MDP2P routes and their relative simplicity.

The elf in question continued to think about MDP2P routes such as Leukart or Aluminum amalgam with nitromethane and felt like he was cursed to have piperonal as a starting material... He then remembered a method of converting piperonal into MDP2P and began scratching his head even more... He did some searching and seemed to find a Fe/HCL or FeCl based reduction of the nitropropene would yield MDP2P

posted 12-12-1999 10:59 AM         

Lino

posted 12-12-1999 04:14 PM         

I don't agree, when I tried this (half-full, plugged 100ml RB) long ago it turned black after a week. No product at all.

posted 12-14-1999 03:45 PM         

Yes its turns dark oily liquid. If you have saved this, shake it (if it is not enough, scrach it w. glass rod, agitate w. different temperatures but if you did all right it is not nessesary) and wath one of the miracles of chemistry. If you want good visual effect (I bet you should) snip your flask with finger and wath crystals grow from snip point. Yield of bright yellow crystals IS 90% <, after purification, if it is not, you should NOT be satisfied. If you get your results please let us know.

posted 12-18-1999 04:39 AM         

Sparks, woud you look around to find your notes, no matter how long it takes ?

There must be such details as currents, voltage, preparation of cathode surface, maesurments of apparatus and so on without what you could spend significant amount of your rest life to get some results.

posted 01-13-2000 02:21 PM         

Then I catched you right.
Actually we are exactly from opposite sides of the earth. It sounds philosophic but it is just as simple.

posted 01-20-2000 03:55 PM         

Theoretically add it to some nitropropane plus a little ammonium acetate or hexamine (in THF is it?) and reduce to get MBDB or "J."

posted 01-25-2000 03:16 AM         

100g. bensaldehyde, 40g. ammoniumacetate, 100 ml. nitroethane, 400 ml. GAA.
Reflux 2-3 hours (60-80c?)

Pour in big glasscontainer (should look like red wine now) and add 200 ml. denaturated etOH.
Cover and put in the freezer for at least 3 hours.
Filter and rinse crystals (phenylnitropropene) with etOH.

Cover the bottom of a beaker with 0.5-1 cm mercury.
Mix 600ml. 24% acetic acid, 400ml. dH2O and 600ml. denaturated ethanole.
Pour 1l. of the mixture in the beaker.

Plug the hole in a unglased cheramic flowerpot with a rubberstopper.
Mix 100ml. conc. H2SO4 and 400ml. dH2O.
Pour the diluted acid in the flowerpot.
Place the flowerpot in the beaker.

Now the electrical connections has to be made.
Remember, NO uninsulated copperwire must EVER come in contact with the electrolytes during the process.
This means the insulation must be below the surface of the mercury.
The electrode in the flowerpot is leadplate, as big as you can fit in the flowerpot.
The leadplate is the anode and the mercury is the cathode.

Add 20g. nitropropene to the mixture in the beaker (will probably not dissolve).
Connect the wires to a battery charger (I would use a regulated powersupply)
If the amperemeter reading is low (what is a low reading?), add a few drops of acid from the pot to the beaker slow and with stirring.
Kepp the temp below 50c.
About 2-3 hours after all nitropropene has disappeared and lots of hydrogen bubbles evolve from the surface of the Hg, the process is done.
Disconnect the wires and remove the flowerpot.
Decant the liquid from the mercury and boil to remove the ethanole.
Basify with NaOH and extract 3 times with ether (or toluene).

posted 01-26-2000 03:47 AM         

Is'nt it simple ? As non-chemist opinion familiar with above procedure - it sounds like it should work. Some notes to have keep in mind shoul be also: Purify P2NP carefully before use, also keep in mind to use purified Hg (if you get it from waste exhange somewhere) Voltage should be 12V as it was mentioned car battery charger, try runs with different currents per/cm2 may give different results as different reaction times. Also you must be creative with reaction cell design and try to understand/feel the process. Never tried with above catholyte solvent combination, more like with GAA and Ethanol/no H2O at all but who knows ? Also the reaction times varied 12-24 hours. Prepare make multiple differenced experiment runs to get results.

Who will try it out first ?

Sad I have no time to do it now.

Thank you sparks !

posted 01-26-2000 04:25 AM         

In Psychedelic Chemistry they use a slightly different method.
-Add 4g. P2NP to 100ml. etOH and 50ml. GAA.
Then add 10ml conc. HCl or 50ml. sulfuric acid for the catholyte in a 40cm2 Hg-cathode in a porous cell surrounded by 3N sulfuric acid anolyte with a water cooled lead anode (leadpipe with running water) and reduce at 4 Amps. (about 0.07amps./cm2 cathode surface) at 30-40c for twenty hours or until solution is colourless.
Evaporate in vacuum to about 20ml. cool with ice basify with NaOH and extract with ether.

posted 01-27-2000 08:57 PM         

However and that the basic ingredients would be benzene and or the pyradine type stuff and or acetone and methanol and ammonia,,,,

posted 02-03-2000 09:08 PM         

first ya proally need to have info that be decent ot there to be worhty of collection and distribution?

Piperine,C17H1903N occure in the unripe fruit [black pepper], in the kernal of the ripe fruit [white pepper] of piper nigrum, and in the fruit of Ascanti [P.clusii C. DC 5%] It is also found in long pepper [P. longum L. 4.98%] and in the seeds of Cebeba censii. The piperine content of black pepper varies from 6-9% although some contains as much as 11%.

Piperine is prepared by extraction of the ground pepper and evaporation of the extract. After removal of the resin (see chavicine) in aqueous sodium hydroxide, the residue is disolved in hot ethanol form which the base crystalizes on cooling. Although the solid is tasteless an ethanolic solution of the base has quite a sharp taste. This alkaloid is a very weak base and forms ssalts with one mole of strong mineral acid. The hydrocloride is yellow crystaline solid soluable in ethanol, cloroform, and hot benzene while the hydrobromide is a yellow crystaline powder melting to a red liquid at ca. 170*. Underspecial conditions a dihydrocloride can be obtained as an orange powder which decomposes spontaniously, loosing hydrogen cloride in the air. All these salts are readilly hydrolyzed by water. With 1,2,5,- trinitrobenzene, piperine forms a compound which crystalizes as red needles, m.p. 130*.

As early as 1849, piperine was hydrolyzed with aqueous sodium hydroxide or nitric acid to a new volitile base, piperidine C5H11N. the acidic product of hydrolysis, piperic acid[C12H10O4 m.p.216-217*], when fused with potasium hydroxide, gave protocatechuic acid, while addation occurred when bromine was added to the C-12 acid. One mole of bromine entered the molecule [C12H10BR2O4] by direct addation of the regent, while tetrabromopiperic acid [C12H10BR4)4 m.p. 160-165*,dec] resulted when bromine in carbon disulfide was the regent. Further evidence for the presence of the two ethylenic linkages in piperic acid was derived from its reduction [NaHg] to a dihydropiperic acid [m.p. 70.5-71.5*] , which in turn absorbed one mole of bromine. Moreover, piperic acid was regenerated by the action of potasium hydroxide on this dibromodihydropiperic acid [C12H12BR2O4 m.p.1350136*]. Tetrahydropiperic acid resulted from the catalytic reduction of either piperic acid or its dihydroderivative. Furthermore, tetrahydropiperine was obtained by the catalytic hydrogenation of piperine. Hot sodium hydroxide converted the tetrabromo acid to piperonal while replacement of two bromines by hydroxyls and subsequent elemination of water to yield a lactide-anhydride is introduced either by boiling water alone or in combination with sodium carbonate.

The structure of piperic acid was deduced from oxidative experiments. Piperic acid when oxidized with potasium pergermate gave oxalic acid and two new products, piperonal and piperonylic acid the structures of which as subsequently etablished by the following equation: C12H10O4 [(2)C2H2O4] + (0-CH2-0)-benz-COH +(0-CH2-0)-benz-CO2
Piperic acid Oxalic acid + Piperonal + Piperonylic acid………

From this, piperic acid was considered to be represented by(0-CH2-0)-benz-CH=CH-CH=CH-CO2H, a structure accomidated by the subesequent observation that the acid is converted by careful oxidation [KMnO4 in basic solution] to piperonal, piperonylic acid and tartaric acid. The acid structure of [above] "(0-CH2-0)-benz-CH=CH-CH=CH-CO2H " obtained by condensing piperonal with acetaldehyde followed by the action of sodium acetate and acetic anhydride on the resulting aldehyde (0-CH2-0)-benz-CH=CH-CHO, was identical with piperic acid.

After the structure of the piperidine had been established, it was possible to confirm the early assumption that piperine is the piperidineamide of the piperic acid. Piperine resulted when the acid cloride of (0-CH2-0)-benz-CH=CH-CH=CH-CO2H*(PCl5) was treated with piperidine. Hence, piperine must be represented by !!!. Methyl, ethyl and phenyl analogs of piperine have been prepared by simmiliar synthesis [M. Scholtz, Ber.,56,711(1923)] structure of !!! (0-CH2-0)-[benz]-CH=CH-CH=CH-CON[pyridine]!!!

By comparison of several compounds closely related to piperine it has been concluded that the paticuliar taste of the alcholic solution of piperine is dependent upon the presence of the phenyl group, the 4-carbon chain, and the amide group of piperine, but is independent of the methylenedioxy group, the double bonds, and the piperidine nucleus.

Patr two: CHAVICINE

Since piperine is tasteless, pelletier and later Bucheim concluded that the component [chavicine C17H19O3N], responsible for the paculiar taste of the peper must be in the resin. Chavicine was isolated as follows:

Ground pepper was extracted with ethanol and the extract evaporateed to dryness. The residue was thoughly extracted with ether and the etheral solution washed sucessively with 10% potasium hydroxide and with water. Removal of the ether and steam distillation of the residue expelled the essential oils. The nonvolitile residue was disolved in ether, the solution filtered to remove small amounts of piperine which seperated, and the filtrate evaporated to dryness. Subsequent digestion of the residuewith petrolium ether, solution in ethanol, and decoloration with carcoal afforded the amorphous chavicine.