Here is goess...


Step 1.

a. pepper + pet ether -> piperine

b. piperine + NaOH in MeOH -> piperic acid

c. piperic acid + KMnO4 -> pipernol


Step 2.

a. ethanol + HCl -> ethyl chloride

b. ethyl chloride + NaNO2 -> EtNO2


Step 3.

a. pipernol + EtNO2 + NaOH + HCl in MeOH -> MDP2NP

b. MDP2NP + Fe + HCl -> MDP2P

c. reductively aminate!


Thoughts? Suggestions? Worries? Most of the reactions are as mild as possible, the chems as limited and as otc as possible, and yields as high as possible. That being said, it's quite a bit of work and it's still far a from perfect synth.

Alternately, for the second step one could just react ethylamine with KMnO4. Less otc, but a helluva lot easier for the chemist that has access to ethylamine. Any thoughts there? Ethanol and ammonia and a hydrogenation catalyst maybe?

Refs obviously available on any part of the reaction upon request.

Enjoy!


-F☺rd

BFD, however; INb4SdeH

curious about the hydrochloric acid and ethanol step. got a ref?

BFD, however; INb4SdeH

FUCK! :mad:

BFD? Do you ever contribute to something? :(

curious about the hydrochloric acid and ethanol step. got a ref?

Same for me!

Here is goess...


Step 1.

a. pepper + pet ether -> piperine

b. piperine + NaOH in MeOH -> piperic acid

c. piperic acid + KMnO4 -> pipernol


Step 2.

a. ethanol + HCl -> ethyl chloride

b. ethyl chloride + NaNO2 -> EtNO2


Step 3.

a. pipernol + EtNO2 + NaOH + HCl in MeOH -> MDP2NP

b. MDP2NP + Fe + HCl -> MDP2P

c. reductively aminate!


Thoughts? Suggestions? Worries? Most of the reactions are as mild as possible, the chems as limited and as otc as possible, and yields as high as possible. That being said, it's quite a bit of work and it's still far a from perfect synth.

Alternately, for the second step one could just react ethylamine with KMnO4. Less otc, but a helluva lot easier for the chemist that has access to ethylamine. Any thoughts there? Ethanol and ammonia and a hydrogenation catalyst maybe?

Refs obviously available on any part of the reaction upon request.

Enjoy!


-F☺rd

I like the way you think! I can tell you the Step 1 B & C is a bitch! Annoying to clean and if not done correctly fucks up everything! Both of them, althought i will be honest C is the most likely where your too fuck up, your ratios and temp better be fucking correct or you will get nada!

I have seen ethylamine at photo chem supllies...don't know what it is used for in photo chem tho' :(

Oh and you can buy piperine in bulk non supcioulsy, serioulsy! Last time i checked it was at around 10 euros for 1 KG, not too bad :)

I would like some ref or proof for:

-2a & 2b
-3a

First time i see that step 3a, never heard of it, and the big "cock block" is usually using nitroethane in that step...so yeah :(

Ethylamine doesn't seem to be too OTC unfortunately, however is it possible to make it from acetonenitrile with LiAlH4 in dry ether I think. If NaBH4 could be used to replace the LiAlH4 this would be relatively OTC but it might not be 'reducing' enough. :(

CH3CN + 4[H] --> CH3CH2NH2

BFD = big fucking deal
yeah only if I actually know.
Unlike this cut and paste BS , or theories that have never been done.Or the I was going to but.......
Or stolen answers from others work.
here ya go a way to mdma:
For the tosylation of alkohol, the base is pyridine, because

1. It neutralizes the HCl
2. Very important: it form a complex with tosyl chloride which make the attack by the alkohol on the sulfur more easily .

For the hydratation of the alkene, acid medium is not good because the 1-aryl-2 propanol first formed is rapidly deshydrated to the stabilized isosafrole wich is hydrated to the 1-aryl-1-propanol. The result is:

1. very poor yield in 1-aryl-2-propanol
2. mixture of 1-aryl-2-propanol and 1-aryl-2- propanol which are not easy to separate ( must use distillation ) .

The oxymercuration process give only the 1-aryl -2-propanol intermediate without rearrangement in about 20min with >95% yield but HgCl2 can not be used, sorry. HgAc2 or Hg(NO3)2 or Hg(ClO4)2 or Hg(CF3COO)2 can be used. You must use Hg2+ (mercuric) and not Hg+ ion (mercurous). You can make HgAc2 from HgCl2+CH3COOH but you must purify it. Anyway HgAc2 can easily be purchased.

on wikipedia it says "At various times in the past, ethyl chloride has also been produced from ethanol and hydrochloric acid."

having said that, one can simply buy nitroethane pure and use it

I like the way you think! I can tell you the Step 1 B & C is a bitch! Annoying to clean and if not done correctly fucks up everything! Both of them, althought i will be honest C is the most likely where your too fuck up, your ratios and temp better be fucking correct or you will get nada!


The cleanliness of the reaction larger depends on the solvent. It's a MESS with alcohols but with ethers, much cleaner. Microwave it then toss it in some pet ether and your yields'll be exponentially better.

Edit: I see now that you were referring to b and c ;) yes, those reactions are a bitch, but still quite doable. I'dd venture to saw that your average kitchen chemist would have little trouble if (s)he was careful, patient, and had a digital hotplate and sep funnel.


Oh and you can buy piperine in bulk non supcioulsy, serioulsy! Last time i checked it was at around 10 euros for 1 KG, not too bad :)


That'd make everything much easier. Thanks!


I would like some ref or proof for:

-2a & 2b
-3a


Step two's out of one of my textbooks, I'll edit in the info when I find time to find the page. Probably after work.

As for 3a, it's a nice clean reaction written up by Rhodium himself. Here ya go:

hxxp://www.erowid.org/archive/rhodium/chemistry/mdp2np.html

-F☺rd

c. piperic acid + KMnO4 -> pipernol

That's "piperonal." As in "piperonylic aldehyde.

The boys in the hive (who are always hard) note that you have to babysit the fuck out of the reaction and still note that it can all turn into the more-logical piperonylic acid.

Alternately, for the second step one could just react ethylamine with KMnO4. Less otc, but a helluva lot easier for the chemist that has access to ethylamine. Any thoughts there? Ethanol and ammonia and a hydrogenation catalyst maybe?

The fuck? Ever heard of the reduction of acetamide?

I don't know why that didn't immediately occur to you. Of course, if your goal is EtNO2, formation of the ethanal oxime and treatment with H2O2 or any peracid would be easier... but how can you NOT know amides reduce to amine?

Read more, copypasta less... but it's better than some of the things that have been posted... 'n to answer your question, yes, it could theoretically be done.

The fuck? Ever heard of the reduction of acetamide?

I don't know why that didn't immediately occur to you. Of course, if your goal is EtNO2, formation of the ethanal oxime and treatment with H2O2 or any peracid would be easier... but how can you NOT know amides reduce to amine?

Read more, copypasta less... but it's better than some of the things that have been posted... 'n to answer your question, yes, it could theoretically be done.

Thanks for the tips! :) I like the acetamide reaction a lot.

Wish I could blame the oversights on the how long ago I wrote this up, but mostly it's just that I'm still learning. Slowly. ;)

-F☺rd

The fuck? Ever heard of the reduction of acetamide?

I don't know why that didn't immediately occur to you but how can you NOT know amides reduce to amine?

Then you should quote a reduction of acetamide to ethylamine from a journal, using PRACTICAL reagents.

Then you should quote a reduction of acetamide to ethylamine from a journal, using PRACTICAL reagents.

It's all well and good saying that but, firstly, if someone doesn't know that an amide can be reduced to the corresponding amide, a reference wouldn't help.

Secondly, if you do know that acetamide can be reduced to ethylamine, but you can't go and find your own reference for the procedure with such simpe substrates, you shouldn't be doing it...

Some spoon-feeding is beneficial, or even necessary. Spoon feeding a 3-course meal doesn't help anyone though...

It's all well and good saying that but, firstly, if someone doesn't know that an amide can be reduced to the corresponding amide, a reference wouldn't help.

Secondly, if you do know that acetamide can be reduced to ethylamine, but you can't go and find your own reference for the procedure with such simpe substrates, you shouldn't be doing it...

Some spoon-feeding is beneficial, or even necessary. Spoon feeding a 3-course meal doesn't help anyone though...

Saying basically "hey you fucking idiot, you're too fucking stupid to realize that you could make it real easy from acetamide with LAH" isn't very helpful either, since
He probably doesn't have LAH or an account with Aldrich.
It would be stupid to waste LAH in this way.

Assume that there is a reason for saying what I did. JP seems to think that there is a practical way for us mortals to reduce acetamide to ethylamine. Let's see it.

Wish I could blame the oversights on the how long ago I wrote this up, but mostly it's just that I'm still learning. Slowly. ;)

No problem... one of the things you'll wanna get quick, though, is knowing which functional groups you're working with. Piperonol (an alcohol) won't react with nitroalkanes in the fashion you hoped, while piperonal - like most aldehydes - will do better...

He probably doesn't have LAH or an account with Aldrich.
It would be stupid to waste LAH in this way.


3. LAH is pathetically simple (albeit slightly dangerous) to make.

4. LAH isn't near the only generic reducing agent.

Some spoon-feeding is beneficial, or even necessary. Spoon feeding a 3-course meal doesn't help anyone though...

No kidding.

...having to get into a trollfest just to document in triplicate shit like 'zinc is a reducing agent' (http://www.springerlink.com/content/g363r271t7450656/) or that amides reduce to amines (http://jan.ucc.nau.edu/~jmaxka/chm238/materials/Class_notes/CH%2024.pdf) would be the death of this forum.

~sigh~

3. LAH is pathetically simple (albeit slightly dangerous) to make.

I have yet to see a synthesis for LAH that didn't use a small amount of LAH in the synth itself. :(

http://designer-drugs.com/pte/12.162.180.114/dcd/chemistry/lah.synthesis.html For example.

Fancy being so kind as to enlighten me as to the other method you have up your sleeve?

im still waiting on the ethanol to chloride thing, im wondering what conditions are required.

I have yet to see a synthesis for LAH that didn't use a small amount of LAH in the synth itself. :(

http://designer-drugs.com/pte/12.162.180.114/dcd/chemistry/lah.synthesis.html For example.

Fancy being so kind as to enlighten me as to the other method you have up your sleeve?



The prep you linked to does describe the synthesis of low purity LiAlH4 useful for initiating larger scale reactions...

im still waiting on the ethanol to chloride thing, im wondering what conditions are required.

http://en.wikipedia.org/wiki/Ethanol#Halogenation



If I had to guess, I would say that the Lewis acidity of the Zinc chloride and it's realtively oxophilic nature serve to effectively activate the protonated hydroxyl group to nucleophilic substituion by chloride anion.

3. LAH is pathetically simple (albeit slightly dangerous) to make.

And I bet he has so much anhydrous AlCl3 and LiH that he just didn't know what to do with it. Don't we all. Brilliant!


4. LAH isn't near the only generic reducing agent.



Since sodium bisulfite is a reducing agent, does that mean that he can just mix some up with some acetamide, then? Brilliant! You fucking dipshit, even Pt catalysts require extreme conditions to reduce amides to amines.


'zinc is a reducing agent' (http://www.springerlink.com/content/g363r271t7450656/)

And what does the link really say? "The reaction of Vilsmeier complexes of primary, secondary and tertiary amides..." Oh, now you've got POCl3 involved too. WOW OTC ETHYLAMINE! You fucking reject.


amides reduce to amines (http://jan.ucc.nau.edu/~jmaxka/chm238/materials/Class_notes/CH%2024.pdf)

What the hell is that link supposed to do? "acetamide + LAH" So what? Why should we give a shit what LAH does when WE DON'T HAVE ANY. And neither do you. You even think that making ethylamine is a great use of LAH, because you can only pretend to have a clue.

And I bet he has so much anhydrous AlCl3 and LiH that he just didn't know what to do with it. Don't we all. Brilliant!

http://www.made-in-china.com/image/2f0j00dPEathTqmuzVM/Reinforced-Aluminum-Foil.jpg

+

http://www.lifehack.org/wp-content/files/2007/06/20070625-c-to-d-battery.jpg

+

http://www.plumbing.sg/Kohler%20Bathroom%20Faucet(sink).jpg

Since sodium bisulfite is a reducing agent, does that mean that he can just mix some up with some acetamide, then?

Certainly worth a try. Why don't you try it, trap some, and find your yields? Y'know, do something useful and creative, rather than troll shit and try to get people killed?

Brilliant! You fucking dipshit, even Pt catalysts require extreme conditions to reduce amides to amines.

And what does the link really say? "The reaction of Vilsmeier complexes of primary, secondary and tertiary amides..." Oh, now you've got POCl3 involved too. WOW OTC ETHYLAMINE! You fucking reject.

POCl3 has never been used for reducing amides.

Can anyone in the class tell us what POCl3 has to do with amides?

As to what the link says, it says that... zinc... is... a... reducing... agent.

That particular one? Mentions the reductive powers of zinc metal in ethanol. Another (http://www.rsc.org/publishing/journals/_denial.asp) might mention zinc chloride, and amusingly, one of the earlier reducing agents for amide->amine conversion was potassium bromide (http://www.1911encyclopedia.org/Amines), unless this was just an in-situ hoffman rearrangement - another valid route to ethylamine.

Of course, as already noted, the ethoxime is a much easier route and one which allows one to skip several steps if one didn't want ethylamine on the road to nitroethane - but you didn't care about that, did you?

This is the last time you will be spoonfed. Your insistance on choosing helplessness as a vehicle of trolling and harassment happens to run directly counter to the ethos of this forum, and from henceforth, if you choose to be incompetent or otherwise helpless, the rest of the forum will continue without you. Good day.

Can anyone in the class tell us what POCl3 has to do with amides?

This is the last time you will be spoonfed.

http://en.wikipedia.org/wiki/Vilsmeier-Haack_reaction
"The Vilsmeier-Haack reaction (also called the Vilsmeier reaction) is the chemical reaction of a substituted amide with phosphorus oxychloride and an activated arene."

You're the one who gave the link to the abstract "The reaction of Vilsmeier complexes of primary, secondary and tertiary amides with zinc-ethanol affords the corresponding amines in high yields.", and I have to spoonfeed its meaning to you! But you're so dense, you probably still don't get it.

I have to spoonfeed its meaning to you! But you're so dense, you probably still don't get it.

Speaking of dense.... notice that all the V-H products tend to be, umm, methyl aldehydes?

Curiouser and curiouser.

Here is goess...


Step 1.

a. pepper + pet ether -> piperine


-F☺rd

Pet ether isn't the best solvent to use to extract from Pepper.
Meths (denatured ethanol) works well.

Leave the Pet ether for the cleanup of the extracted piperine.

SwIm has tried this & got nice crystals.

Tried both the KmNo4 (made a nice smell) & CuSo4 sulphate (ended up with nice crystals that were not much different from the starting crystal) ideas.

SwIm intends to do it all again soon, bigger volumes.
--------------
Oh swIm found out that the main chemical (except maybe water) in the coolant used for Lathes & other Milling machinery is Triethanolamine.

Is that helpfull? swIms not sure 'imself

Pet ether isn't the best solvent to use to extract from Pepper.
Meths (denatured ethanol) works well.

Leave the Pet ether for the cleanup of the extracted piperine.

SwIm has tried this & got nice crystals.

http://i190.photobucket.com/albums/z132/benzowarrior/Piperine%20Extraction/33.jpg

This was before a recrystallisation, and I have to agree, you can get some nice crystals. Sorry about the quality of the photograph, but it at least shows that it will work.

Recrystalise it again, thats almost a powder, a nice powder though.

The crystals are almost seethru, same colour, it'd be worth doing.

Nice results....