Author Topic: From Pepper to MDA experiments  (Read 8235 times)

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aznxprophetxtasy

  • Guest
From Pepper to MDA experiments
« on: June 15, 2002, 09:26:00 AM »
Hello,


My small (worthless??) contribute to the hive.

I am writing this because the hive as given me so much.  Right now SWIM is out of the country and away from his lab so he wont be able to experiment for a little over a month. When he comes back this is what SWIM plans to do...

SWIM is going to experiment with all his chemistry knowledge and abilites to synthesize MDA from pepper. SWIM knows it can be done, with hard work and lots of experimentation, but since the sources of sassafras oil is diminishing, this has forced myself and other bees to look into other alternatives.

So when SWIM gets back SWIM is going to go to the grocery store to buy a few pounds of black pepper to extract piperine. SWIM would like other bees to suggest and maybe add information for helping him do this project.. It might take a few weeks but it will get done. SWIM is determined to finish it and make MDA from this. This is what SWIM is thinking..

SWIM has gathered sources and he estimates that the average amount of piperine that black pepper has is 5%. So when SWIM buys about 2KG of black pepper he estimates he might get around 90g piperine if his extraction techniques are good. This is what swim understands...

Pepper ---EtOH, MeOH, or CH2CL2--->piperine---Refluxed with 10% alcholic KOH--->  potassium piperinate----HCl---> piperic acid----KMnO4-->piperonal

SWIM is sure there are other things that can change piperic acid into piperonal. SWIM is willing to undergo most experiments people suggest if they are in his abilites.


some other information SWIM has found for the chemicals made in this process....
piperine
From MERCK...
Molecular formula: C17H19NO3
Molecular weight: 285.34
Properties:  Monoclinic prisms from alcohol, mp 130C. Tasteless at first, but burning
  aftertaste. Neutral to litmus. pK (18C: 12.22. Almost insol in water (40 mg/liter at
  18C, in petr ether. One gram dissolves in 15 ml alcohol, 1.7 ml chloroform,
  36 ml ether. Sol in benzene, acetic acid.

Melting Point: 130C

piperidine hydrochloride
Derivative:  Hydrochloride,
Molecular Formula: C5H11N.HCl,
Properties: orthorhombic prisms from alcohol, mp 247C.
   Freely sol in water, alcohol
Melting Point: 247C

piperic acid
Molecular formula: C12H10O4
Molecular weight: 218.21
Properties: Nee dles from alc. Colorless when freshly prepd, rapidly turns
  yellow on exposure to light. mp 216-217C. Sublimes as yellow needles with
  partial decompn. uv max (methanol): 340 nm (epsi 28800) . Sol in 50 parts
  boiling alcohol, 275 parts abs alcohol at 25C Practically insol in water,
  ether, benzene, carbon disulfide.
Melting Point: 216-217C

piperonal
Molecular formula: C8H6O3;
Molecular weight: 150.13.
Properties:  Colorless, lustrous crystals, mp 37C. Heliotrope odor. bp ~263C;
  bp(0.5) 88C Sol in 500 parts water; freely sol in alcohol, ether. Keep in
  cool place protected from light. LD50 orally in rats: 2700 mg/kg (Hagan).

Boiling point: bp ~263C bp(0.5)88C

Melting Point: 37C

Piperonylic Acid
Molecular formula: C8H6O4 ;
Molecular weight: 166.13.
Properties:  Prisms (by sublimation), needles from alc, feathery crys tals
   from water. mp 229C. Sublimes around 210? Slightly sol in
   water, chloroform, cold alcohol, ether. Absorption spectrum: Dobbie,
   Lauder, J. Chem. Soc. 83, 621 (1903)

Melting Point: 229C

MDA Freebase molecular weight= 178.7g/mol
MDA.HCL molecular weight= 215g/mol

Information from Rhodiums site....
Once SWIM gets this PIPERONAL SWIM Plans to use the nitrostyrene method.

Basically piperonal is used as a starting material and condensed with nitroethane to make a nitrostyrene compound which then can later be reduced to MDA.

From "The Complete Book of Ecstasy"
Method 1: To a solution of 15 grams of piperonal in 80 ml glacial acetic acid, add 15 ml nitroethane followed by 10g of cyclohexylamine. The mixture is heated with a boiling water bath for 6 hours. Remove from heat, dilute with 10ml water and cool in an ice bath overnight (place ice bath and reaction mixture in the refrigerator to keep the ice from melting too quick). Bright yellow crystals should precipitate. These are filtered from the cold solution and allowed to dry. Yield ~10g.
A general procedure described by Gairaud and Lappin[45] uses ammonium acetate as the base catalyst for the condensation. It is as follows:

Method 2: 5g of piperonal, 5ml of nitroethane ans 2g of ammonium acetate are added to 20 ml of glacial acetic acid. The resulting solution is refluxed for two hours and then poured into ice-water. The solution is cooled in an ice-bath overnight and the crystals filtered out and allowed to dry.



Reduction is the tricky part. There are several ways to reduce the nitrostyrene material into MDA.

*Lithium Aluminum Hydride (maybe easy)
*electrochemical cell (i have some experience with these) ;)
*possibilty to reduction using metals such as zinc powder and acetic acid, tin powder and hydrochloric acid, or iron powder and hydrochloric acid may work. (downside might not work)

The general method of using these reagents is covered in Robert L. Augustine, Reduction: Techniques and Application in Organic Synthesis under the chapter Dissolving Metal Reductions.

SWIM plans to experiment with all those methods to see which one works and which one can give me the best yields..

Nitrostyrene preperation uses piperonal, nitroethane, and a catalyst for the condensation. Some catalysts are cyclohexylamine (hard to get??) or ammonium acetate.

For the reduction of the nitrostyrene to MDA the LAH seems to be a good option as it is more experimented with than metal and acid. LAH method needs THF(tetrahydrofuran)(substitute maybe???) so that might be a little tricky to get... There is not much information on reduction so SWIMS going to have to tediously do his own experimentation (any good tips on this???) After reduction is complete, extract the oils, do A/B seperation, do some washings, and probably want to distill the MDA freebase then crystalize  :) .
Reduction of nitrostyrene with electrochemical cell seems easy enough....

copied from "The Complete Book Of Ecstacy"..
The cells are basically a container divided by some material which will allow charged ions to pass and therefore allow electricity to flow. The membrane also halts the flow (or reduces it considerably) of the material being reduced. This is necessary because if the membrane wasn't there, the reduced product could travel to the other electrode and become oxidized. The membranes are made of such materials as sintered glass, cellophane, porous ceramic plates etc.
This procedure was written for the analogous nitrostyrene which would lead to amphetamine. It should work equally well for MDA[46].

207g (1 mole) of the nitrostyrene is dissolved with a solvent prepared by mixing one liter of ethanol with 500ml of acetic acid and 500ml of 12N sulfuric acid. The solution is placed in the cathode compartment of a divided electrolytic cell containing a mercury, copper or metal of similar nature as the cathode electrode. The anode can be made of lead. 3N sulfuric acid is placed in the anode compartment. Current is passed equaling ~0.2 amperes/cm2 of cathode surface. The temperature is kept between 30-40°C during the electrolysis until at least 8 Faradays of electricity have passed through the solution.

The number of square centimeters of your cathode surface (count both sides if both sides are in contact with the solution) times 0.2 is the amount of current you need flowing through your cell. 1 Faraday is equal to 96485.309 coulombs/mole of electrons and 1 Ampere is equal to 1 coulomb/second. The amount of time in hours the reaction should be run is then 771882.5 divided by the number of Amperes divided by 3600. If you have a total cathode electrode area of 40 cm2 then you need 8 Amperes running through your cell for 26.8 hours.

Remove the ethanol and ethyl acetate present through distillation (quit distilling when the temperature approaches 100C). Basify the remaining solution with 25% NaOH and extract the MDA from the solution with 3 portions of ether (or toluene or methylene chloride). Wash the extract with several portions of calcium carbonate solution, water and then dry with magnesium sulfate. Filter out the drying agent. Pass HCl gas through the solution until no more precipitate is formed. Filter the crystals and wash with ether and allow to dry.



There you have it complete hypothesis from piperonal to MDA.HCL


Oh yeah, also SWIM will try to give much information as possible when doing these experiments. SWIM can distill, fractionally distill, reflux, and do tritrations and just the basic stuff but SWIM cant do TLC analysis or any of that advanced organic chemistry stuff. SWIM wants to help out the hive as much as possible because the ability to get certain precursors are diminishing. SWIMS dream is if this synth/experimenting is successful, I will write a detailed write-up and everyone will be making mda from pepper :)   hehehe ;)  . What can they do now, put pepper as a List I precursor?? LoL

If possible and if interested other bees can join SWIM and combine data so future bees can easily make MDA from pepper
More detailed information can be obtained at Rhodiums site if interested and more information needed.



In my opinion MDA is just as great as MDMA so this might be worth it to make for me at least :)

terbium

  • Guest
Nitroethane
« Reply #1 on: June 15, 2002, 09:54:00 AM »
One of your problems is going to be in acquiring the nitroethane.

Rhodium

  • Guest
Link help
« Reply #2 on: June 15, 2002, 10:05:00 AM »
Piperonal from pepper, extensive reference:

http://www.3base.i-p.com/


Nitroethane synthesis:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/nitroalkane.html


terbium

  • Guest
Many ways to skin a cat.
« Reply #3 on: June 15, 2002, 10:10:00 AM »
But if someone is willing to go to that much effort I would think that isosafrole via alkali fusion of eugenol would be much more facile.

Antoncho

  • Guest
An update, please???
« Reply #4 on: June 15, 2002, 11:41:00 AM »
Rhodium, would you bee so kind to update your site w/a much-shorter, much-simpler version of Vitsh/SWIA to make nitroethane from EtOH, H2SO4 and NaNO2??

I mean - not very many people would wnat to go into THAT much trouble to make EtNO2 - as described on your site, but w/our w/Vitsh's modifications it's quite worth the effort.

If you have any doubts - SWIA personally performed this proc for specifically nitroethane and got a result much similar to the one stated by Vitsh. There also was one report on HyperLab from Ennarkont who'd also done it w/success. All bp's correct.

I mean, why in the fucking world isolate that pure ethylsulfate thru its calcium salt while one can do 3x times faster w/out doing this?

Seems to me that most bees are still pretty confused about doing that - but, i swear, it's quite viable!



Antoncho

Rhodium

  • Guest
gone with the wind
« Reply #5 on: June 15, 2002, 12:41:00 PM »
Sure, Antoncho - but I cannot find it. You have a lot of scattered notes in a dozen threads in the making of nitroethane (and one by Vitsh, but that one is for nitromethane), but I cannot find a simple step-by-step (or journal style) writeup I can just cut and paste onto my site...

Could you perhaps PM me what you have, in a format that is ready for publication?

aznxprophetxtasy

  • Guest
piperonal
« Reply #6 on: June 15, 2002, 04:51:00 PM »
But if you get can get piperonal from black pepper first, the steps to condense it and reduce it is fairly simple. Probably just as easy as synthesizing mdma from safrole. All you need is nitroethane, ammmonium acetate as catalyst, and depends on the method of reduction it could be a electrochemical cell or ever dissolved metal acids?? If we can find an easy way or find a source of nitroethane it will defintely be worth it IMO. I searched the fuckin search engine and found that some bee has found nitroethane at a performance fuel supplier with nitromethane.

Also here is something interesting....

Post 318184

(3base: "nitroethane from ethanol / new hope", Novel Discourse)

Post 319775

(3base: "DANGERS - nitroethane from ethanol", Novel Discourse)


aznxprophetxtasy

  • Guest
making nitroethane...
« Reply #7 on: June 15, 2002, 06:18:00 PM »
Looking at rhodiums site again for nitroalkane synthesis under nitroethane the procedure doesnt sound too complex if SWIM cant get a source of nitroethane in town. All it uses is ethyl bromide (which can be made) DMF as solvent and NaNO2. One concern i have though is how safe is it to distill this crude nitroethane???

aznxprophetxtasy

  • Guest
also...
« Reply #8 on: June 15, 2002, 06:22:00 PM »
If swim decides to make nitroethane then he will have to make ethyl bromide which is an easy process. On the other hand, ethyl bromide seems kinda dangerous- its boiling point is 38C!! boils lower than DCM. Also ethyl bromide is highly flamable but its stable. If i can find a source of nitroethane then all my worries are over  :)

El_Zorro

  • Guest
I would consider the CuO procedure for getting to ...
« Reply #9 on: June 15, 2002, 09:07:00 PM »
I would consider the CuO procedure for getting to piperonal, it'd be cheaper, and probably give higher yeilds.

Do not go gentle into that good night.  Rage, Rage, against the dying of the light.  --Dylan Thomas

Antoncho

  • Guest
Sure!
« Reply #10 on: June 15, 2002, 11:03:00 PM »
Chief: sure, i'll do it ASAP.

El_Zorro: yep, i agree, that sounds very promising.



Antoncho

aznxprophetxtasy

  • Guest
Is this for...
« Reply #11 on: June 16, 2002, 12:35:00 AM »
Is the Cupric Oxide used to oxidize piperic acid to piperonal? Is that what you are talking about "for getting to piperonal" Any simple procedure for this?

El_Zorro

  • Guest
yes
« Reply #12 on: June 16, 2002, 12:24:00 PM »
I'm sorry I wasn't clearer.  The CuO method of oxidizing piperic acid to piperonal should give higher yeilds than the KMnO4 route.  (The KMnO4 gives mostly the MDbenzoic acid, with little if any piperonal.)  And besides, it looks FUCKING cheap!  Just throw the CuSO4(and it's hydrated, to boot!), NaOH, water, and piperic acid in a flask and reflux for eight hours!

[No 293365]

Do not go gentle into that good night.  Rage, Rage, against the dying of the light.  --Dylan Thomas

aznxprophetxtasy

  • Guest
from Post 293365 EXAMPLE VII: Syringaldehyde from ...
« Reply #13 on: June 19, 2002, 11:27:00 PM »
from

Post 293365

(Antoncho: "Double bond ox. cleavage (to aldehyde) with CuO", Chemistry Discourse)


EXAMPLE VII: Syringaldehyde from the isolated intermediate

Syringaldehyde may also be prepared by oxidizing the isolated 3,5-dimethoxy-4-hydroxypropenylbenzene of Example V with nitrobenzene in alkali or other low potential oxidizing agents.
Thus 195 parts 3,5-dimethoxy-4-hydroxypropenylbenzene are added to a cupric oxide mixture freshly prepared from 1000 parts hydrated copper sulfate, 660 parts sodium hydroxide, and 8000 parts of water and the resulting mixture is
heated to boiling under reflux for eight hours. The separated red cuprous oxide is filtered and washed with water. The alkaline filtrate and washings are acidified and extracted with ether.
Bisulfite purification of the ether extract should yield approximately 155 parts or 90% syringaldehyde.
Other alkaline copper oxidizing agents such as Fehling's Solution, Benedict’s Solution, may be used with the same results. An alkaline copper oxidizing agent is particularly advantageous for replacing the propenyl group with the aldehyde group because the strength of its action in changing from a cupric to a cuprous compound is definitely adequate to oxidize to the aldehyde, and at the same time insufficient to continue the oxidation to the acid further or to destruction. However, in large scale operation, it will be obvious that oxidizing agents having no such automatic action may be employed for reasons of economy, and the extent of the reaction controlled by controlling the amount of the reagent.


Very interesting stuff. Seems very simple and cheap and yet have very good yields compared to the potassium permangante method. Thanks for this info.

One question though on the parts. it says 1000 parts hydrated copper sulfate to 660 parts sodium hydroxide. Does this mean in grams or is it molar?

Just reflux the filtered homemade Cupric Oxide with the piperic acid in ethanol solution or what? Or is that something SWIM will have to experiment with??

Very good, thanks for the link.

aznxprophetxtasy

  • Guest
Oh, oh!!, no nevermind
« Reply #14 on: June 19, 2002, 11:46:00 PM »
Oh didnt read the article thoroughly. It says to reflux the "3,5-dimethoxy-4-hydroxypropenylbenzene" with coppersulfate, sodium hydroxide and water for 8 hours.

Should SWIM experiment with this??

218g piperic acid added to 1000g hydrated copper sulfate 660g Sodium Hydroxide, and 8L of water,  boiled under reflux for 8hours, filter the cupric oxide crap, acidify the filtrate, extract with ether (will ethanol work since piperonal is soluble in it?) then evaporate the ethanol to leave (hopefully) lustrous piperonal crystals??

SWIMs idea is that the piperonal can be further purified because if any byproducts are made..or not converted..it can be seperated. Piperic acid is only soluble in 275 parts of alcohol at 25C and piperonylic acid is only slightly soluble in cold alcohol, yet piperonal is 'soluble' in alcohol according to MERCK....does anyone have the exact solubilities of these substances.

Thanks everyone for your help...when SWIM gets back to the lab he will experiment with this and write a report on it..SWIM will return

Rhodium

  • Guest
Parts refers to weight parts, as in grams.
« Reply #15 on: June 19, 2002, 11:51:00 PM »
Parts refers to weight parts, as in grams.

You cannot extract an aqueous solution with ethanol, as it is soluble in water.

aznxprophetxtasy

  • Guest
Oh yeah...my bad i dont know what i was thinking.
« Reply #16 on: June 20, 2002, 12:23:00 AM »
Oh yeah...my bad i dont know what i was thinking. DCM will probably be the method of choice then. Does anyone know the solubilities of piperonal, piperic acid, or piperonylic acid in DCM??

thanx

Rhodium

  • Guest
The solubilities of those in DCM should be very ...
« Reply #17 on: June 20, 2002, 02:22:00 AM »
The solubilities of those in DCM should be very high.

sYnThOmAtIc

  • Guest
Nitroethane
« Reply #18 on: June 24, 2002, 11:46:00 PM »
Acquiring nitroethane is easier than getting DCM for swim. Just an email of phone call away for 25.00 a gal he tells me


senzualus

  • Guest
iodine oxidation of piperic acid
« Reply #19 on: November 09, 2002, 07:46:00 AM »
is it posible to oxidise piperic acid (to piperonal )
using I2/NaOH ?
what solvent should be used?