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All 26 posts Subject: Electrochemical Reduction of Nitrostyrenes Please login to post Down

uemura
(Hive Bee)
08-31-00 11:06
No 47461
      Electrochemical Reduction of Nitrostyrenes
(Rated as: excellent)

We all heard about or use the modern reduction using LiAlH4, NaBH4 or ones using PdCl2.

Uemura comes up with this thread to bring again attention to procedures, 70ty years old and more, when the first pioneers attempted to reduce the nitro-styrenes to the corresponding amines. All the stuff used should be OTC.

The following is from the paper mentioned in uemuras thread oon 'routes to the 3,4,5trimethoxyphenylethylamine' from 'Journal fuer Praktische Chemie (Vol 137) from the year 1933. Authors K. H. Slotta and G. Szyszka'. Uemura felt free to take the translation (by Dwarfer) available at Rhod's page and corrected some missing thingies and typos. The diagram is now included which seems to be essential.

The authors said: The electrolytical reduction of the corresponding nitro-styrol can be performed in all these cases with high yields if the conditions are choosen properly. The reason that all the valuable <<sic!>> phenyl-ethyl-amines haven't been exclusivly produced via this most simple method is: the yield is highly sensitive to the technical performance of the experiment.

A) Equipment for electrolytic reduction

An anode cell (Z) - a porous cell of Haldenwanger porcellain - was placed in a filter assembly of 500 ccm (F) volume. The anode had measurements of 75mm x 160mm with a 70mm wide glazed edge that prevented the drawing-up and smearing of the liquid to be reduced.

To the anode cell was added a solution of 25ccm concentrated sulfuric acid in 175ccm water. The anode used was lead or carbon rod and was enclosed in a tightly wound, glass spiral cooler. The water in this was conducted to the outer container to help cool the inner tube. By regulating the cooling water it was possible to keep the whole reduction solutionfor the first six hours at 20 degrees Celsius. In the last hours the temperature was allowed to rise to 40 degrees Celsius, to get a nearly quantitative course of the reduction.

The outer container contained a cathode (K) - a lead sheet (200mm x 90mm x 2mm), which before each experiment was coated electrolytically using diluted sulfuric acid, with lead superoxide.

B) Reduction

A solution of 30g 3,4,5-trimethoxy-beta-nitrostyrene in 100ccm glacial acetic acid and 100ccm ethanol was mixed with 50ccm concentrated hydrochloric acid and added to the cathode container. The anode cell was filled with dilute sulfuric acid to the outer level of the cathode cell. Now a current of 5 to 6 amps was passed through the equipment for 12 hours, so that the current density was about 3 amps.

After the finished reduction, the contents of the cathode cell was filtered and dried under vacuum. The remainder was then dissolved in 300ccm water. Any remaining unchanged nitrostyrene was removed by twice shaking it out with ethyl acetate. The ester in the solution was then removed by shaking out once with diethyl ether.

The liquid thus obtained of chloride of mescaline was then put in a separating funnel which had ether added. The amine was freed with a cold concentrated solution of 100g technical sodium hydroxide. The solution obtained, after extracting four times with ether, was dried with calcium carbonate and the amine precipitated with dry hydrochloric acid gas.

After twice dissolving in absolute, dry, non-denatured alcohol, completely pure mescalin hydrochlorid*xH2O was obtained as white leafs with a melting point of 184 degrees Celsius and a yield of 24g (77.3%)

Now some points for discussion:

1) has any bee performed this electrolytical reduction in the described or in any similar form. Report on the experiences are welcome.
2) 'porous cell of Haldenwanger porcellain': what could be used for that, a pourous clay pot? (swim has such a pot which he fills with water and grows orchids on the outside of the pot)
3) Could the glas spiral cooler be replaced with a PVC-tubing cooler?
3) What the opinion of the electrochemical bee-expert. Why is nobody using the above procedure (there are almost nil post on the hive)

Let's start a discussion! The above procedure seems really bee simple! Lets find the proper conditions where it works!

"I want to know Gods thoughts, the rest are details" A. Einstein

Sonson
(Stranger)
09-01-00 07:14
No 47756
      Re: electrochemical reduction using lead

It is certainly a very appeling route, but the problem is the mebrane. There are membranes available, like nafion, which is ion-selective, but the question is if they're resistant to the HAc/H2SO4/EtOH mix. Modern membranes comes in sheetform also, making the apparatus design a bit more complicated aswell.
The cooling can probably be done with a PVC tube, but the problem is that PVC is very insulating compared to a glass tubing, but I doubt that is a problem...

uemura
(Hive Bee)
09-02-00 16:37
No 48152
      Re: electrochemical reduction using lead

It is certainly a very appeling route
Thanks for a reply, Sonson!

BUT WHERE ARE ALLL OTHER ELECTROCHEMICAL BEES?????????????????????????///

Bruckner got the 2,4,5 trimethoxy-pheny-ethyl-amin with a similar apparatus. What is is wrong with this approach? Have the oldies been stupid, or what? Why are no bees persueing this method.

Sorry (really) if uemura annoys you.

halfapint
(Hive Bee)
09-10-00 19:58
No 50623
      Re: electrochemical reduction using lead

That is a splendid approach, uemura. The big argument these days is whether the anode must bee pure platinum, as Strike urges, or silver! Mercury is used in one variant, but there is a quasi-religious backlash against this element. It's now pretty clear that lead, or graphite, will give yields comparable to the high-flung theoretical speculations with four-digit calculations of electrochemical overvoltages, oui? I'd like to try palladized graphite, myself, partly because it's what I have available. This approach calls for too much individual tinkering to be popular, because it hasn't been standardized into a formula. Strike made a great advancement in suggesting the sheep gut condom for the membrane, but clay flower pots with the drain hole sealed are the alternative. This particular publication gives the unique contribution of its externally-cooled anode; such fancy glass blowing is not stylish, but plastic tubing, of vinyl or LDPE, would serve as well. Good one.

surroundsoundreverbfuzzbustersleagueresonancemodulation

uemura
(Hive Bee)
09-11-00 07:25
No 50881
      Re: electrochemical reduction using lead

but there is a quasi-religious backlash against this element. It's now pretty clear that lead, or graphite, will give yields comparable to the high-flung theoretical speculations with four-digit calculations of electrochemical overvoltages, oui?
Well spoken, halfapint. It really looks not many bees fly around using lead. At the beginning of last century up to the 40ties, many researches did the reduction to the amin with a similar apparatus as the one shown above.

Uemura thinks he will jump into this experiment when he gets the lead from the divers shop. 2kg for 15$. Gives lot of metal to melt and to make nice anodes/cathodes.

"I want to know God's thoughts, the rest are details" A. Einstein

Antoncho
(Stranger)
09-14-00 03:08
No 51906
      Re: electrochemical reduction using lead

Dear Uemura!
Yesterday as I was digging out my potato crop an idea occured to me that, I gather, may be of interest to you. It's about the membrane for your electrolytic reduction. Take some dry CaSO4 powder, mix it intimately with some (about 20-30 % by weight, i'd guess) fine Al powder (it is used as paint filler), add water and make a thin-walled glass of this mass. When CaSO4 solidifies put your membrane-to-be in conc. soln. of NaOH, Al will dissolve and create precisely those fine pores we're looking for. In case Al powder is unavailable, you can always use smth. like electrolytic iron/HCl or - well, i guess, there are many variants. In any case, CaSO4 is inert to anything. However, this is only a theoretical proposition and, most importantly, proportions of CaSO4/Al should be established experimentally for the best performance of the membrane.

Good luck, Uemura, I will join you by the end of February!

uemura
(Hive Bee)
09-14-00 07:27
No 51977
      Re: electrochemical reduction using lead

Hi Antoncho,
your idea for preparing a membran this way is new to Uemura. He thinks however to make it work (thickness, mounting, etc.) needs a lot of experimentation.

Uemura found in the meantime an hopefully appropiate device for the inner container. It is an unglazed growing pot for orchids. The anode he is going to construct will not be cooled from the outside, but from the inside. Ha! a very clever idea if it works.

Veni, vidi, vici! Julius Caesar

foxy2
(Hive Bee)
10-01-00 02:56
No 56082
      Re: electrochemical reduction using lead

What are your thoughts on a power source??
Will a conventional automotive battery charger work?
Will it generate too much power?
Is a 2amp load way too much?

uemura
(Hive Bee)
10-01-00 09:19
No 56158
      Re: electrochemical reduction using lead

uemura has around a dc variable power supply (these thingies you can buy in electronic shops). The one uemura has allows adjustements for voltage and/or current. Costs should be about 50$ or so.
the electrochmical projects has seezed at the moment due to real-world overload. Hope to activate it end of the year.

Osmium
(Stonium's / Changer)
10-01-00 19:50
No 56226
      Re: electrochemical reduction using lead

> Will a conventional automotive battery charger work?
> Will it generate too much power?

They deliver more than 12V, and any excess current is converted into heat in the electrolysis cell which has to be removed by cooling. This is bad. At least use an old computer power supply (which delivers quite a lot of amperage). Or a regulated power supply. This allows for fine tuning, like current density etc.

> Is a 2amp load way too much?

In most refs no voltage is named, only the amount of Ampères, Faradays or current density. That's the reason why: current is regulated by the resistance of the electrolysis solution and the membrane, and the distance and size of the electrodes. So that question doesn't make much sense. By varying those parameters you can tweak a less-than prefect power supply into something that works, but it's always better to have a real regulatable power supply.

Unobtainium
(Hive Customer Service)
10-01-00 20:36
No 56239
User Picture       Re: electrochemical reduction using lead

You might want to double check that power supply you found. I don't think one costing $50 (new) would be very suitable. A decent regulated variable supply should cost several hundred dollars.

Please Email all complaints of my performance to hive@lycaeum.org

Osmium
(Stonium's / Changer)
10-01-00 22:58
No 56274
      Re: electrochemical reduction using lead

I had one for less than 100$, complete with 2 digital meters for current and voltage, regulatable between 0-3A and 0-30V, so that price is possible.

Unobtainium
(Hive Customer Service)
10-01-00 23:23
No 56280
User Picture       Re: electrochemical reduction using lead

I wish I knew where you bought your power supplies from. My 0-18v/0-3A variable cost over $300.

Please Email all complaints of my performance to hive@lycaeum.org

Osmium
(Stonium's / Changer)
10-02-00 10:18
No 56485
      Re: electrochemical reduction using lead

www.conrad.com is one of the best sources for electronic equipment I know of. At least for Euro bees.

That power supply was bought at a local shop. No way I will tell you bees where I live wink

Unobtainium
(Moderator)
10-02-00 10:23
No 56486
User Picture       Re: electrochemical reduction using lead

Attention USA/Canada
Unfortunately due to high insurance costs and liability reasons, we don´t deliver articles to the U.S.A. or Canada. We do, however send articles to all other countries.
Yes, that will come in quite handy. tongue

Please Email all complaints of my performance to hive@lycaeum.org

uemura
(Hive Bee)
10-02-00 10:48
No 56487
      Re: electrochemical reduction using lead

Good guess Osmium smile
The power supply was a sell-out special offer, that's why is was cheap.

Veni, vidi, vici! Julius Caesar

improv_chem
(Stranger)
10-02-00 18:55
No 56596
      Re: electrochemical reduction using lead

membranes>>> check out the crystal meth forum >>meth from hotdogs.
I think this is the same stuff used in dialasis(sp?) tubing. Still havn't tested it for durability with the acids and solvents you mentioned for this process though.
Power supplies>>>> Use a 12 volt battery charger and put a potentiometer that can handle the power you are expecting in series with the cell. By increasing the potentiometer resistance you can decrease the current. If you put a volt meter across the cell then you will read the proper voltage to run it at for that particular current. Can't find a potentiometer>> use some nicrome wire as a resistor. The length of the wire is proportional to the resistance.
Stay tuned for dream results...........
You have got some good shit going here, keep up the electrical cell discussions!!! smile

You don't need a fucking lab!!!

uemura
(Hive Bee)
10-04-00 11:52
No 57199
      Re: electrochemical reduction using lead

improv_chem!
You have got some good shit going here, keep up the electrical cell discussions!!!
Bee sure Uemura will pursue this topic definitely. It's a matter of time. Fot the time beeing:
here is a picture of uemura's lab-power-supply. It provides 0-30 Volts, 0-2Ampere. There is a switchable analog meter for current or voltage.

Cave canem, Latin!

ragga
(Hive Bee)
10-27-00 23:31
No 64126
      Re: electrochemical reduction using lead

could you post that pic once again for us?

PVnRT_NC8
(FMAN / Eraser)
10-28-00 02:52
No 64178
      Re: electrochemical reduction using lead

Delux is ready for as to power it up, gona use a different catalyst for mine tahnks----> Diproplyene glycol monomethyl ether will also try the acedic acid for cusshioning effects, these all this solvent would be good at decarboxylation if heat was applied I think RIGHT?

Thus any clorinated saturated solvent might be mich except radical haloid interaction.....Um stuff like 111-triclorethane proally IS it flamable? NO um it is going to make you pass out if concentrated no could fuck up your dope most definatly can

Um ather things decarboxyle stuff, ussually coo2 is given off as a gas or product it seems the co bond is a dam hard cross do not entertain it so there.

So um stuff that could back bone a cooh, um carbon, ummm other stuff best would proally be an unsaturated carbon this drive a metal reation right? -c-c-c-c-c-this keeps the ring from hydrogen ballance or buffer it?

Thus um as metals flow into solution some free radicaily natured carbons enterinto the solution DUH?
now the free metals can do a few things if they need to like um become electrode meterial um carries from hydrogen and likely haloids as well as oxygen, some oxygen is transformed in such reactions and made into electrodde meterial etc etc....the most important thing happening here with haloids is the formations of interesting salts that are not soluable, as well as that these resulting salts really fuck shit up for the amine and at times it salts out

Finally I DONT BELIVE IN YOUR METH AS IT IS SCIENTIFICALLY DISPROVED AGAIN NA D AGAIN AND I AM WANTING A PUBLIC SEAT.

So somehow the meths are magically ellicticatedfrom the reaction?? prally so yes

But these things if left to theyre own devices would most often fail due to lack of ed it seems yes

So um concerning the metal salts these rock out are insoluable to a percentage near the point of colapse and thus get spent as cruciable ellectrode meterial thus iron/pt/etc etc......Finally si has an effect in tighting the coo bonds to co bonds somae salt proalyy in paticuliar as evidenced to this mind the silica haloid salts most are familiar with at this day and age.....howver a mydriad of possibiliaties exist and I now enter into an undiscovered paradigm......Shuligans beware.....unsaturated carbon compounds are active also, and your compounds might not have been delivered in the optimial manner as this was not compleatly grasped at that time or more interesting objectives were added to the unordinary looking therums.

Thus if I halogenaed to foram a metal salt, there must be some meatl for this to be conected into such as alum would work.....or silical each seperate salt preferential to certain sites upon the building structure as well many such salts are polymers of themselves, water is not frozen into or outof suck theyre pretty stable,,,in the TRANSITION STATE THIS INVOLVING BIND FORMATIONS FROM SAT TO UNSATURATED COMPOUNDS CAPABLE OF CYCLIZATION one hydrogen oxygen or element proally working on it self.

So maybe if in finality I decided my compounds were more potent when XTYLIZATION was prefored here at this point and not over another point in my sceem would in fact be better than the reported paridigm? Thus you might have a bunch of metal haloid amine meterial however as the metal plates out the amine is freed inot the freebase or transitory phase....

This amine being studdied at pre

111-tri ethanes UNSATURATE CARBINYL COMPOUNDS IN TRANSITORY STATES SALTS OF SUCH USUALLY EMPLOYING HALOIDS AND METAL COMBINATIONS.....

Amine amine amine joined togeter a ch2 mitigating for them
keeps all hell from busting loose by the way I did study shuligian and to his CREDIT NOT MY OWN I VOW THIS DANGEROUS COMPOUND IS SOMEWAHT DANGEROUS????? NOT my IDEA OK IT WORKS ITS THE ONLY THING I LIKED ABOUT THIS GUY HE SAID THIS STUFF WORKS TO STABALIZE STUFF IN MINNI AMOUNTS

One drop added to reaction as like it was a religious practice I thought

So them amines situated can be so saturate as to basically pry themselves apart upon any signifiant addation from and only from this paticuliar angle in paticulliar

THIS IS THE TRANSITORY STATE I DO NOT BELIVE IN PURE COMPOUNDS ONLY POLY COMPOUNDS I AM A POLYSUBSTANCE ABUSER etc.

SO,,,Then the amine is protected by varios co- bonds simmiliar to a nylon or plastic....yes

thus such bonds must suck up oxygen to be collapsed an in the oposite direction.....

as coo

As well it goes deeper so I stop here for now for more precise info?

Um I do belive there is something important being overlooked as per ussual? RIGHT

ONe thing was very close "key" alleadyin hand "yours"
Now new key in my hand " do not understand key" is now revoked permenantly and presently I will not comment further

This thread invokes my seence of freedom as well as individuallity as i belive this is censored at large?

NO NOT YOU THEM EVERTHING AT LAGE AVERYWHERE ALL AT ONCE TRANSCENDING TIME AND SPACE? PROALY

I wouldent eraese it if I was in control I would paraphrase or edit it though. I am Einstien I did not appreciate the effort to communicate with moderate and tollerate much of anything I was a nervous individual.

uemura
(Hive Bee)
10-28-00 08:20
No 64278
      Re: electrochemical reduction using lead

here we go

ragga
(Hive Bee)
11-01-00 21:23
No 65724
      Re: electrochemical reduction using lead

uemura...
could you send me a private messaage or post a clarification to my private message?
maby i should post it?

Rhodium
(Chief Bee)
01-31-04 22:50
No 485734
User Picture       Electrochemical Nitrostyrene Reduction
(Rated as: excellent)

The article mentioned and partially translated in Post 47461 (uemura: "Electrochemical Reduction of Nitrostyrenes", Novel Discourse)

Über -Phenyl-äthylamine. III. Neue Darstellung von Mescalin
K. H. Slotta & G. Szyszka
J. Prakt. Chem. 137, 339-350 (1933) (https://www.rhodium.ws/pdf/mescaline.slotta-szyszka.pdf)

^{The Hive - Clandestine Chemists Without Borders}

Rhodium
(Chief Bee)
02-05-04 14:43
No 486580
User Picture       More German Mescaline Chemistry
(Rated as: excellent)

Here are the other parts in the same series:

Über -Phenyl-äthylamine. I. Mescalin und Mescalin-ähnliche Substanzen.
K. H. Slotta & H. Heller
Chem. Ber. 63, 3029-3044 (1930) (https://www.rhodium.ws/pdf/mescaline.slotta-heller.pdf)

Über -Phenyl-äthylamine. II. Eine Neue Tyramin-Synthese
K. H. Slotta & W. Altner, Chem. Ber. 64, 1510-1520 (1931)
Posted in Post 477747 (lugh: "Tyramine Preparations", Chemicals & Equipment)

Über -Phenyl-äthylamine. IV. Darstellung von -[Amino-phenyl]-äthylaminen.
K. H. Slotta & G. Szyszka
Chem. Ber. 68, 184-192 (1935) (https://www.rhodium.ws/pdf/pea-4.slotta-szyszka.pdf)

...and here the poor chemists are flamed by a colleague for saying in Part 3 above that their synthesis of mescaline was better than his... crazy

Synthese des Mescalins (Entgegnung auf die "Berichtigung" von K.H. Slotta und G. Szyszka)
Georg Hahn
Chem. Ber. 67, 1210-1211 (1934) (https://www.rhodium.ws/pdf/mescaline-flame.pdf)

Here are his own contributions to mescaline chemistry - you can judge yourself:

Über -[Oxy-phenyl]-äthylamine und Ihre Umwandlungen. I. Synthese des Mescalins.
Georg Hahn und H. Wassmuth
Chem. Ber. 67, 696-708 (1934) (https://www.rhodium.ws/pdf/mescaline-hahn.pdf)
____ ___ __ _

Über -[Oxy-phenyl]-äthylamine und Ihre Umwandlungen. II.
Synthese weiterer Amine und der entsprechenden [Oxy-phenyl]-essigsäuren aus naürlichen Allylverbindungen.
Georg Hahn und Otto Schales
Chem. Ber. 67, 1486-1493 (1934) (https://www.rhodium.ws/pdf/allyl2paa2pea.pdf)

And finally, some further elaborations on phenethylamine syntheses by his collaborator on the second paper:

Über -Substituierte Äthylamine. I.
Ein einfaches Verfahren zur Darstellung von -Phenyl-äthylaminen aus -Nitro-styrolen.
Otto Schales
Chem. Ber. 68, 1579-1581 (1935) (https://www.rhodium.ws/pdf/schales.ns2pea.pdf)
____ ___ __ _

Über -Substituierte Äthylamine. II. Die katalytische Hydrierung von Oximen.
Otto Schales
Chem. Ber. 68, 1943-1945 (1935) (https://www.rhodium.ws/pdf/schales.oxime2pea.pdf)

^{The Hive - Clandestine Chemists Without Borders}

Rhodium
(Chief Bee)
05-13-04 23:34
No 506993
User Picture       Mescaline, Amphetamine etc. by LAH reduction
(Rated as: good read)

Ueber die Reduktion von β-Nitrostyrolen mit Lithiumaluminiumhydrid
M. Erne & F. Ramirez
Helv. Chim. Acta 33, 912-916 (1950) (https://www.rhodium.ws/pdf/nitrostyrene.lah.erne-ramirez.pdf)

Summary
The following phenethylamines were prepared by reduction of the corresponding β-nitrostyrenes: 3,4,5-Trimethoxyphenethylamine (Mescaline, 77%), 2,3,4-Trimethoxyphenethylamine (Isomescaline, 80%), DL-Amphetamine (87%), 3,4-Methylenedioxyphenethylamine (MDPEA, 86%), as well as 5-Bromo-3,4-Methylenedioxyphenethylamine (dehalogenation could be controlled by adjusting the reaction conditions). The required nitrostyrene was made by bromination of protocatechualdehyde, methylenation with methylene sulfate and NaOH-catalyzed condensation with nitromethane. Myristicinaldehyde (5-Methoxy-3,4-methylenedioxybenzaldehyde) was also prepared in 17% yield by methylenation of 5-Methoxy-3,4-dihydroxybenzaldehyde with methylene sulfate.

^{The Hive - Clandestine Chemists Without Borders}

Rhodium
(Chief Bee)
09-14-04 16:36
No 531289
User Picture       α-Diazoacetophenone Mescaline Synthesis
(Rated as: good read)

Notiz über eine neue Synthese von Mezcalin, N-Methyl- und N,N-Dimethylmezcalin
K. Banholzer, T.W. Campbell, H. Schmid
Helv. Chim. Acta. 35, 1577-1581 (1952) (https://www.rhodium.ws/pdf/mescaline.diazoketone.pdf)

^{The Hive - Clandestine Chemists Without Borders}

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