aznxprophetxtasy (Newbee)
06-15-02 09:26
No 321699
      From Pepper to MDA experiments  Bookmark   


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....
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

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)wink
*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 smile.
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 peppersmile  hehehewink . 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 smile
(Old P2P Cook)
06-15-02 09:54
No 321708
      Nitroethane  Bookmark   

One of your problems is going to be in acquiring the nitroethane.
(Chief Bee)
06-15-02 10:05
No 321715
      Link help  Bookmark   

Piperonal from pepper, extensive reference:
Nitroethane synthesis: ../rhodium/chemistry /nitroalkane.html
(Old P2P Cook)
06-15-02 10:10
No 321719
      Many ways to skin a cat.  Bookmark   

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.
(Official Hive Translator)
06-15-02 11:41
No 321770
      An update, please???  Bookmark   

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!

(Chief Bee)
06-15-02 12:41
No 321792
      gone with the wind  Bookmark   

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?
06-15-02 16:51
No 321881
      piperonal  Bookmark   

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)
06-15-02 18:18
No 321913
      making nitroethane...  Bookmark   

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???
06-15-02 18:22
No 321915
      also...  Bookmark   

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 smile
(Hive Bee)
06-15-02 21:07
No 321946
      I would consider the CuO procedure for getting to ...  Bookmark   

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
(Official Hive Translator)
06-15-02 23:03
No 321977
      Sure!  Bookmark   

Chief: sure, i'll do it ASAP.

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

06-16-02 00:35
No 322001
      Is this for...  Bookmark   

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?
(Hive Bee)
06-16-02 12:24
No 322145
      yes  Bookmark   

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
06-19-02 23:27
No 323277
      from Post 293365 EXAMPLE VII: Syringaldehyde from ...  Bookmark   

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.
06-19-02 23:46
No 323280
      Oh, oh!!, no nevermind  Bookmark   

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 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
(Chief Bee)
06-19-02 23:51
No 323283
      Parts refers to weight parts, as in grams.  Bookmark   

Parts refers to weight parts, as in grams.

You cannot extract an aqueous solution with ethanol, as it is soluble in water.
06-20-02 00:23
No 323288
      Oh bad i dont know what i was thinking.  Bookmark   

Oh 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??

(Chief Bee)
06-20-02 02:22
No 323300
      The solubilities of those in DCM should be very ...  Bookmark   

The solubilities of those in DCM should be very high.
(Hive Bee)
06-24-02 23:46
No 325079
      Nitroethane  Bookmark   

Acquiring nitroethane is easier than getting DCM for swim. Just an email of phone call away for 25.00 a gal he tells me

11-09-02 07:46
No 378067
      iodine oxidation of piperic acid  Bookmark   

is it posible to oxidise piperic acid (to piperonal )
using I2/NaOH ?
what solvent should be used?
(Hive Bee)
11-10-02 16:44
No 378515
      oxidation with KMnO4  Bookmark   

Wouldn't KMnO4 oxidize piperine directly to Benzo[1,3]dioxole-5-carboxylic acid? According to my org chem book, it doesen't metter how long the carbon chain (of alkene) is, KMnO4 will cleave it allways at benzyl-carbon to give corresponding carboxylic acid....

1-2-3 ACiD
(Chief Bee)
11-10-02 17:17
No 378524
      Selectivity  Bookmark   

Under basic conditions, KMnO4 is not as strong as it is under neutral or acid conditions, and the selectivity is increased. Cooling, and the addition of MgSO4 to the reaction mixture also helps. There are examples of this at my page, where propenylbenzenes (like asarone) is oxidized to the corresponding benzaldehyde.

What I don't understand though is how you suggest that LAH can be used to reduce a carboxylic acid to an aldehyde.
(Hive Bee)
11-10-02 18:02
No 378538
      here  Bookmark   

Scroll down to "Reduction of Acyl Compounds Using Various Reducing Agents" on this page:

and you'll see carboxylic acid reduction with LiAlH to aldehyde (a)

I know that most common method is via acylchloride... but after coming across the above described possibility, I figured, why not? Of corse, it can be errorous...

1-2-3 ACiD
(Chief Bee)
11-10-02 18:07
No 378539
      I've never seen that before.  Bookmark   

I've never seen that before. It seems to me it would be very hard to not overreduce to the alcohol.
(Hive Bee)
11-10-02 18:10
No 378541
      indeed  Bookmark   

I know, it looked wierd to me 2, since i know that LAH will continue reducing no matter what... strange... it could be an error on that page huh?

1-2-3 ACiD
(Chief Bee)
11-10-02 18:38
No 378550
      At least an additional reagent or other vital ...  Bookmark   

At least an additional reagent or other vital information is left out. It is not possible to do using standard methods.
(Hive Bee)
12-09-02 18:06
No 387976
      Can someone confirm that copper sulfate under ...  Bookmark   

Can someone confirm that copper sulfate under basic conditions would oxidize piperic acid into piperonal with higher yields then KMnO4?

The method seems simple. Just throw in your piperic acid, NaOH, CuSO4, and water. Reflux for 8hours, then filter through a buchner funnel, wash the filter cake, and acidifiy filtrate with HCl. Then extract with DCM and remove DCM to leave impure piperonal crystals? Is that method doable?

If the DCM contained unreacted piperic acid or piperidine, and piperonal, then couldnt a bee do a bisulfite adduct to purify piperonal purification??

Seems like a good route if one cannot find safrole!

Sink or SWIM
(Official Hive Translator)
12-10-02 05:39
No 388093
      Can someone confirm that copper sulfate under ...  Bookmark   

Can someone confirm that copper sulfate under basic conditions would oxidize piperic acid into piperonal with higher yields then KMnO4?

Well, that's a strange question - go ahead, try this yourself and post the results!

It IS very easy.

BTW - you can PM me for help if you ever get to this in practice.

(Hive Bee)
12-10-02 16:38
No 388244
      And I WILL! Piperine---> Piperonal via CuSO4 ...  Bookmark   

And I WILL! Piperine---> Piperonal via CuSO4 experiments coming within the next two weeks....

Sink or SWIM
(Official Hive Translator)
12-10-02 23:09
No 388328
      Wishing you the best of luck!  Bookmark   

And, to make the road easier for you, let me give you a coupla advices (just in case you don't know):

a) DO NOT try to perform oxidation directly on piperine, hydrolyze to acid 1st. The thing is, in chemistry, ESPECIALLY when you're travelling on an unexplored ground, nothing ever works the 1st time you do it - no matter how simple it seemssmile To get a positive result, you have to derive conclusions from the preceding negative results, and with piperine no negative result you get (i'll promise you negative resultswink) will bee conclusive - there's just too many variables involved.

Only IF you succeed in pulling this w/piperic acid, you might want to try this w/piperine - in fact, that would bee a great idea IF you succeed.

b) Don't try to modify the hydrolysis procedure. That piperinic amide bond is very hard to break - bee sure to use KOH (not NaOH) in MeOH or EtOH.

c) Search for the best piperine extraction techniques - there's been posted quite a number of it, decide which one to use depending on your most available solvt. I might add that acetone works well too - if you just leave it in a bottle to SLOWLY evaporate, piperine will xtallize out as beautiful needles.

To all said above i want to add that you may always count on my help in your experiments, if you should need anywink

(Hive Addict)
02-11-03 20:44
No 406910
      need help!  Bookmark   

First off, If something is chemically wrong here its because I am teaching myself organic chemistry.

I have been researching using Benedict's reagent for synthesis of piperonal from piperic acid. But upon reading it seems Benedict's Reagent is used only to oxidize aldehydes into carboxylic acids. 

You would have to reduce piperic acid into piperonal by removing an oxygen, not oxidize it.

I have been reading the post Post 293365 (Antoncho: "Double bond ox. cleavage (to aldehyde) with CuO", Chemistry Discourse) on the oxidation of vanillin to its aldehyde, but the bonds on vanillin and piperic acid are different. I cant seem to figure out if Benedict's Reagent is oxidizing or reducing.

If Benedict's Reagent wont work to reduce piperic acid to piperonal then could you use al/hg to reduce?

Again, forgive me If I totally screwed up on the oxidation/reduction reactions.

Sink or SWIM
(Chief Bee)
02-12-03 14:29
No 407183
      the oxidation of vanillin to its aldehyde That  Bookmark   

the oxidation of vanillin to its aldehyde

That makes no sense, vanillin is already an aldehyde (3-Methoxy-4-Hydroxybenzaldehyde).

The conversion of piperic acid to piperonal is an oxidation, as you are adding an oxygen atom on each of the carbon fragments you create in the reaction (one on the piperonal, and one on the remaining carbon chain (you can disregard the "acid" part of piperic acid, that end of the molecule is not participating in the reaction).
(Hive Addict)
02-12-03 16:08
No 407211
      I feel like an idiot  Bookmark   

I really need to learn more organic chemistry!!

Thanks a bunch for clarifying this for me!

Sink or SWIM
(Hive Addict)
02-16-03 15:15
No 408697
      A clever route to nitroethane.  Bookmark   

Starting with alanine, you can oxidize to a nitro acid using potassium permanganate, you then decarboxylate the nitro-acid to nitroethane by forming a sodium ester of the nitroacid and heat this with water, the result is nitroethane and an alkali bicarbonate on reaction with water, I wonder if it would be smarter to acidify the mixture of alanine/KMnO4 and water to more effectively oxidize the amino acid to a nitroacid? Aurelius came up with this idea and it's posted as such:
Method 18:  Oxidation of alanine with permanganate followed by decarboxylation

Nitroethane via oxidation of alanine? 
MeCH(NH2).COOH + 3(O) --> MeCH(NO2).COOH + H2O.
MeCH(NO2).COOH + NaOH --> MeCH(NO2).COONa.
MeCH(NO2).COONa + H2O --> MeCH2(NO2) + NaHCO3.
A solution of potassium permanganate (0.3 mol) in water was made by dissolving 47.41 g KMnO4 in 400 mL hot water in a 1 L 3-necked flask fitted with a reflux condenser, a stirbar[note 1], thermometer, and a 100-mL addition funnel. As the solution cools to room temperature fine crystals of KMnO4 crystallise out of solution[note 2]. A solution of alanine (0.1 mol, 8.91 g) in 65 mL of water was placed in the addition funnel and added dropwise with stirring over a 20 minute period. The temperature slowly rose. When the addition was complete, the reaction mixture was heated to 60º over a period of approximately 2 hours. 40 mL of acetone was added [note 3] and then the reaction mixture maintained at 70-85º [the sludge was extremely viscous and the stirbar was of no use] for 2 hours. 0.1 mol sodium hydroxide in 20 mL of water was then added through the addition funnel.
Pause (to be completed).
The flask showed no sign of heating up after addition of the NaOH. By now the black/brown sludge will not mix (with the stir-bar). The next step is to heat to 80-100C to
decarboxylate any nitro-propionic acid and then to steam distil.
1. An overhead stirrer is essential - the stirbar will get clogged with MnO2.
2. KMnO4 solubility is 1 in 3.5 parts of hot water and 1 in 14 parts of cold water.
3. The acetone was added to try to clear the sludge. I would have added more but I had second thoughts.
1. Synthesis Of Aliphatic And Alicyclic Nitro Compounds; Org. Syn. p 131-132 [The Oxidation of Amines]

Post 238118 (Aurelius: "Re: What can be done to improve the performance of clandestine nitroethane synth?", Chemistry Discourse)
(Hive Addict)
02-16-03 20:19
No 408765
      Hmm.. alanine. Where can I get this OTC?  Bookmark   

Hmm.. alanine. Where can I get this OTC?

I am still doing the pepper-->piperonal experiments. After more reading, I have found alot of sources confirming piperic acid does oxidize to piperonal (not like I didnt believe you Rhodium...I DID...I just needed proof wink).

Today Ive just processed oleoresin from blackpepper. This stuff is cool. From reading its a matrix of turpenes and about 70% crystalline piperine. The hard part is isolating the piperine from the turpenes and oil...but after experimentation 10mL of boiling 70% Isopropyl alcohol to 7g of oleoresin produced 5g of crude piperine after cooling the IPA. Letting it stand for 48hours left a layer of nice dark yellow crystals. After recrystalization from ethanol...little clear yellow crystal shards weighed out at approx 4g.

Im going for the route from post Post 293365 (Antoncho: "Double bond ox. cleavage (to aldehyde) with CuO", Chemistry Discourse) from Antoncho. Hopefully, piperic acid can be oxidizied into piperonal.

Im trying this at a smaller scale. This is my plan (which will be performed VERY SOON):

5g Piperic acid
25.6g Hydrated Copper Sulfate
16.9g Sodium Hydroxide
205g H2O

This will be placed in a 500mL RB flask refluxed for 8hours with good magnetic stirring.

After the solution cools, I vacuum filter it. This should leave precipatated red cupric oxide because the action of the Benedicts reagent oxidizing the carboxylic acid into the corresponding aldehyde. I will wash the cupric oxide through the filter with warm ethanol and add this to the mother solution.

After that I throw everything into a 1L sep funnel and acidify until neutral. I then extract 3x 50mL DCM. Pool the DCM and evaporate to leave something....

Perhaps bisulifte/metabisulfite could purify piperonal. Destruction could be done with sodium carbonate or NaOH.

These are just thoughts. Anyone care to mention a better idea?

I know it probably needs alot of tinkering before it can work but does piperic acid need to be in suspension or does it need to be dissolved in the solution to work?

Chemistry is hard to learn, but its worth it.
(Hive Addict)
02-17-03 12:01
No 409048
      Hey Spisshak  Bookmark   

Hey Spisshak, thanks for the credit, but aurelius did not come up with the idea for the alanine oxidation procedure.  I found that in a search of the older materials on the hive. I can't remember who the credit goes to, but if you do a search i'm sure it'll be easy to find.  I did a search, Cherrie Baby was the original poster.  credit goes to CB. 

BTW: alanine is sold all over the internet and in health stores such as G*C. 
(Hive Bee)
02-17-03 12:46
No 409057
      Part two !  Bookmark   

SPISSHAK, please complete  and post the experiment, EtNO2 from alanine, GREAT !!!!

A really clever route
(Hive Bee)
02-17-03 13:26
No 409074
      Pssst!  Bookmark   

That's not the only possibility, see Post 264850 (ChemicalSolution: "space efficient, easy 2-Br-propionic acid prep", Methods Discourse) & Post 396684 (Aurelius: "Patent References  US patent 4319059", Chemistry Discourse).
05-06-03 00:31
No 431690
      What about nitromethane?  Bookmark   

I read somewhere that Nitro RC Fuel contains nitromethane...  What would using nitromethane instead of nitroethane change in the rxn? would it change the rxn or are they "interchangeable" (for lack of a better word)?

thanks for your time!
05-06-03 08:39
No 431737
      One of my favourite compounds...  Bookmark   

Nitromethane is present in model plane fuel and similar products, generally at around 20% concentration. It is mixed with castor oil (non-polar) and methanol (polar), which means extraction can be harder than you might at first think. It can be extracted by fractional distillation though.
Or, if you search a little harder, then in many places you can find PURE, 99+% NM at a reasonable price. But in some areas you cannot buy this lovelly product frown.
Anyway, where was I... ah yes, I remember. NM cannot be substituted for NE here. As I understand it, using NM would lead to (in the case of using piperonal) 3,4-methylenedioxyphenylethylamine - MDA but without the methyl group on the carbon that's bonded to the -NH2. PIHKAL states that this compound is not active, at least not at 300mg.
I have an idea for you to think about/laugh at though...
CH3-NO2 + CH2O --> HO-CH2-CH2-NO2
IIRC this reaction happens quickly in slightly alkaline solution at around 50*C... the orgsyn database has a procedure if you want to have a look.
Would this not condense with piperonal just as NE does? Then if you could get rid of the -OH... (I'm not sure how to do that!) Or maybe the "MDA-ol" would be interesting as it is? I dunno.
It would be nice if this worked, making NE is a pain in the ass compared to buying a gallon of NM...

"Simplicity is the ultimate sophistication."
05-06-03 10:27
No 431752
      Very depressing.... let me clarify, using...  Bookmark   

Very depressing.... let me clarify, using  nitromethane/cyclohexylamine to do Piperonal->MDP2P will not work?  I dont know if it helps, but Ive read that you can substitute cyclohexylamine with methylamine... is this reaction still undooable?

Thank you for your time!
(Hive Addict)
05-06-03 11:34
No 431761
      you will get a nitro styrene  Bookmark   

not a nitro-propene, if you converted to aldoxime and hydrolized a nitro-styrene you will get MDPAA methylenedioxyl-phenyl-acetaldehyde, not the methyl ketone.
Yes those amines will work in the condensation reaction.
05-06-03 11:43
No 431762
      MDP2P?  Bookmark   

let me clarify, using nitromethane/cyclohexylamine to do Piperonal->MDP2P will not work?

Well, I'm still new to all this, I'm sure a more experienced bee will come along and tell you for certain soon...

But, I fail to see how that could form MDP2P, which as far as I'm aware is (methylenedioxyphenyl)propanone. Did you just get your abbreviations mixed up? I know that happens to me a lot frown.

I drew a little diagram to illustrate the problem:

"Simplicity is the ultimate sophistication."
05-06-03 12:13
No 431763
      Oh..  Bookmark   

Well its good that methylamine can be a replacement!

Ya, I think I was actually talking about nitroalkene.

I like the nitroethanol idea.. but I dont know whether the results can be reduced to MDA

Over and Out.
05-06-03 12:26
No 431764
      Sorry about the multiple posts..  Bookmark   

I think that the nitroethanol idea will work acording to

../rhodium/chemistry /nitro2amine.zn-formate.html

"Aliphatic and aromatic nitro compounds are selectively and rapidly reduced to their corresponding amino derivatives in good yields using Ammonium Formate and commercial Zinc dust. This system is found to be compatible with several sensitive functionalities including halogens, -OH, -OCH3, -CHO, -COCH3, COC6H5, -COOH, -CO2C6H5, -CONH2, -CN, -CH:CHCOOH, -NHCOCH3. The reduction can be carried out not only with HCOONH4 but also with HCOOH. "

Hope it helps
(Hive Addict)
05-06-03 13:36
No 431776
      I don't think it will work  Bookmark   

if you use nitro ethanol.
That merely says you can reduce the nitro group without affecting other functional groups using that system.
You may end up with the amine or oxime but you will probably have a terminal alcohol grouping on the end of the propyl chain.
They aren't so easily reduced.
05-06-03 14:23
No 431785
      Hrm...  Bookmark   

So the procedure in ( ../rhodium/chemistry /nitro2amine.zn-formate.html ) wont remove the  terminal alcohol grouping?

If this is not possible, do you know of any other ways to go from piperonal to MDA without using nitroethane? or other watched precursors?

Thank you for you time!
(Chief Bee)
05-06-03 18:19
No 431813
      Unfortunately not  Bookmark   

No, it will not remove the terminal alcohol grouping, for that you need drastic conditions like in these docs:

../rhodium/chemistry /amphetamine.phenylalanine.html
../rhodium/chemistry /amph.phenylalanine.html
(Hive Addict)
05-06-03 19:07
No 431822
      Nitroethane the easy way.  Bookmark   

If you cannot find nitroethane (its hard to find in some places) I suggest synthesizing nitroethane using Sodium Ethyl Sulfate and Sodium Nitrite. Sodium Ethyl Sulfate can easily bee made and sodium nitrite is easily obtained. Yields are OK so you can get a nice sum of nitroethane if you are working on the 1-2L scale.

If you dont want to go through the trouble of extracting piperine from pepper, there ARE suppliers selling bulk piperine for cheap.
05-06-03 21:11
No 431852
      Thanks  Bookmark   

Thank you Rhodium and hCiLdOdUeDn!
(Hive Addict)
05-07-03 21:49
No 432048
      Your Welcome!  Bookmark   

Your Welcome!~

Good luck to you in the future!