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goldberg
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Catalytic hydrogenation - preparation of hydrogen in situ
I tried to search for this topic but failed, if i missed similar thread sorry for that.
Generally in hydrogenation reactions there is pressure vessel filled with compound to be hydrogenated and catalyst, then external hydrogen is added.
I'm curious if it would be possible to use hydrogen generated in situ?
Let's say i have open flask with dissolved compound (let's assume that everything happens in aqueous medium) and catalyst (let's say raney or
urushibara nickel).
Then add metal like zinc or alumina and acid or base to digest it.
Assuming that compound to be hydrogenated will not react with given acid or base would it make sense?
There is classical way of reducing nitro compounds with Zn or Fe and HCl.
The only similar thing that i have found is strange looking procedure of preparing amphetamine (that i am NOT intrested in in any way) found on
rhodium archive. This procedure tells that it uses urushibara nickel but procedure for preparation of this 'catalyst' looks very different than proper
preparation of urushibara nickel. Like mix NiCl2 and hydrochloric acid then add aluminium foil. This article has no references so i do not count it as
realiable resource of information.
I am intrested in this way becouse i would avoid complex apparatus for handling hydrogen under pressure. Moreover i hope that hydrogen in statu
nascendi will be more reactive.
Has anybody experience with this topic? Does my reasoning make sense?
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Chemi Pharma
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See this topic about nitrocompounds reduction with many reagents couple:
http://www.sciencemadness.org/talk/viewthread.php?tid=84372&...
and this one about generation of nascent hydrogen from borohydrides and nickel salts or nickel raney, using nickel boride generated in situ as a
hydrogenating source agent:
http://www.sciencemadness.org/talk/viewthread.php?tid=80555&...
and a sucessful experience about this last kind of hydrogenation in the sequence of the thread:
http://www.sciencemadness.org/talk/viewthread.php?tid=80555&...
[Edited on 28-7-2018 by Chemi Pharma]
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alking
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Yes, that is very common. The metal hydrides are the most common commercially but generally more difficult to obtain for home chemists. You can use
various combinations of metals and acids for a transfer hydrogenation, amalgums, or if you get something like Pd or Pt on carbon you can keep reusing
it via catalytic transfer hydrogenation. Do some research on the group you're trying to reduce and you should come across various methods, some work
better than others, some are not strong enough/too strong, etc.
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goldberg
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Thanks for links i am reading them.
Unfortunately i have no access to metal hydrides and making them myself looks extremely labour intensive. Like lithium and hydrogen and high
temperature. Making elaborate apparatus does not look feasible. Or maybe i am not aware of some route.
Second i'm curious about using freshly prepared hydrogen. One thing is that hydrogen bottles are dangerous and expensive. Second is that freshly
prepared hydrogen is much more active that one that will stand in bottle for a while(at least i was taught this). So maybe it would make sense to use
freshly prepared hydrogen instead of one from bottle?
BTW. can You recommend me some source of Pd and/or Pt for preparation of catalyst? This metals are very expensive and i did not noticed any places
where i can buy them in pure form other than even more expensive jewellery.
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Chemi Pharma
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Oh Man, in what country do you live that you don't have acess to metal hydrides?
Pd/C or Pt/C is very, very expensive and difficult to recover from the reaction. At maximum you will spend a lot of money and will use the catalyst
just twice. They are generally sold as one gram everywhere you watch for it. Just to you think about.
Urushibara nickel it's not feasible cause the low yields you achieve and cause the difficult work up to make it. Any mistake you did, you will stay
with a unuseful reagent to hydrogenate anything.
Aluminium amalgam is extremely toxic and dificult to take off all the mercury dissolved in the work up.
The modern chemistry, applied by the pharmaceutical industry uses borohydrides to do professional hydrogenations. More over, hydrogenations done with
hydrogen reactors under pressure it's a surpassed thing. Nowadays are used LiALH4, NaBH4 and metal couple, like nickel, cooper, cobalt or other exotic
reagents, DIBAL, Red, Silanes, etc.
If you can't buy NaBH4 I can sell it to you. 100 grs is enough? What do you say about 30 (thirty) dollars + shipping cost? Very cheap huh? Too much
cheapper than Mario840 will charge you if you try to buy with him. I'm really just thinking about start selling chemicals here at SM. May be I could
start with you!
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alking
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Pd/c is difficult to recover and only reusable once or twice? So long as what you're hydrogenating is dissolved you literally just need to filter the
Pd/C off, wash it, and it's good to go again. You'll lose maybe a few percent each time, but not much. You should easily be able to reuse it in the
10's of times, not two. If you could only use it twice no one would use it.
It is expensive but when you consider the ease of use and that you can reuse it numerous times it becomes much more cost effective. If you're only
getting 2-3 uses out of yours I'd suspect you're not storing it properly or something, that's not right. You can get it on ebay I know, I'd also check
with mario on here (he has a thread in the acquisition subforum).
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Loptr
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Quote: Originally posted by alking  | Pd/c is difficult to recover and only reusable once or twice? So long as what you're hydrogenating is dissolved you literally just need to filter the
Pd/C off, wash it, and it's good to go again. You'll lose maybe a few percent each time, but not much. You should easily be able to reuse it in the
10's of times, not two. If you could only use it twice no one would use it.
It is expensive but when you consider the ease of use and that you can reuse it numerous times it becomes much more cost effective. If you're only
getting 2-3 uses out of yours I'd suspect you're not storing it properly or something, that's not right. You can get it on ebay I know, I'd also check
with mario on here (he has a thread in the acquisition subforum). |
I have been contemplating acquiring some Pd/C and was wondering what storage guidelines should be followed to insure it doesn't degrade between uses.
Also, do you have to use Celite to recover it? It seems that it would be difficult to separate from the Celite while keeping it wet.
Any experiences you guys would like to share?
On a different note, the last couple of days I have been working to try and prepare an activated carbon supported nickel catalyst. I started with an
NiCl2 solution that I soaked into some activated carbon and then dried in a dish on a hot plate. I then dumped the activated carbon into an oxalic
acid solution with stirring and left it over night. This morning I filtered the solution through a fritted funnel, and plan to continue work up
tonight.
The plan is to dry the impregnated activated carbon using the same drying method as before keeping the heat low enough to keep it from decomposing,
and then place the impregnated carbon into a two-neck round bottom flask fitted with a dropping funnel filled with water and vacuum adapter. I will
apply a vacuum and evacuate the flask and then heat it strongly to decompose the nickel (ii) oxalate to deposit nano nickel powder within the
activated carbon. Once I feel that enough heat has been applied, the flask will be cooled down to RT and then flooded with distilled water.
I have no idea what will come out of that flask tonight, but I plan to try this again with more care taken to measuring and weighing, with an attempt
to calculate how much nickel is deposited on the activated carbon.
I have some ideas regarding activating it, such as putting it into a beaker with aluminum powder and then pouring in a sat. NaOH solution to generate
H2 in-situ, and hopefully "activating" the fine nickel particles in the process. I am hoping to see some activity, and that it isn't too pyrophoric.
I want to try and use this catalyst to hydrogenate cinnamaldehyde with ammonium formate, or something along those lines. Not sure yet. I am hoping to
see selective reduction of the double bond, but if reduction does take place, it will likely be both the double bond and the aldehyde to the alcohol,
since I have read that happens with other nickel catalysts. Apparently, pyridine can be added to modify the activity of nickel catalysts to
selectively reduce the double bond in cinnamaldehyde without reduction to the alcohol.
Any thoughts?
[Edited on 30-7-2018 by Loptr]
One of the other reasons that I am impregnating it on carbon is to be able to easily be able to recover it post-reaction for reuse. The activated
carbon that I am using is a little bigger than beach sand at this time, but I plan to vary the mesh size as I go forward. This attempt has been very
unscientific, but that will change as I now have very specific questions that I would like to get answered. For one, I have no idea how much nickel
oxalate is actually in the activated carbon. There is some on the outside of it for sure, but how much as actually absorbed. Knowing the nickel
content of the catalyst is important.
Pretty much expecting a failure this time, but that's how this goes.
[Edited on 30-7-2018 by Loptr]
"Question everything generally thought to be obvious." - Dieter Rams
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Chemi Pharma
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@alking, oh, ok! and may be you think 1 gram is too much powder, huh? The physical loss in the filter paper is around 1/4 of your Platinum or
Paladium, mixed with activated charcoal. Losses in the total process plus another 1/4. I just have used Pt/C in the University Lab, never more at my
Lab, and I can tell you it's a pain in the ass to recover the catalyst. If you are lucky, you can get to use this 1 gram three times.
By the way, don't spend your time asking Mario about prices. I know him. Even have bought twice with him, but now he is not accepting pay pal no more,
just cash by Western Union transfer or bit coins. And his prices? oh, his prices are now more expensive than Sigma Aldrich can charge you.
Mario no more, thanks. I'm thinking seriously start to sell chemicals here at SM to make a competition and force him to put down his prices. I have a
legalized Chemical Lab and lmportation/exportation licences and can get whatever chemical you want that has a CAS number, like him. Making profits has
a limit. What he's doing have other name: greed!
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clearly_not_atara
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Al/NiCl2 usually converts nitroalkenes to ketones. There's a Japanese paper about it somewhere if you're interested. I don't think that this rxn
counts as "hydrogenation", I think it's just a reduction with metallic nickel generated in situ. According to the mechanism proposed by the authors
the nitroalkene is reduced to a nitronate which hydrolyses to the ketone.
[Edited on 04-20-1969 by clearly_not_atara]
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Loptr
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I don't know why I didn't say this earlier, but I do have some papers that use the Raney Nickel activation process to provide the necessary H2 for
reductions. Essentially in-situ H2 production.
I will find the paper when I get home.
Al:Ni + H2O + NaOH + substrate --> Raney Nickel + Reduced substrate
[Edited on 31-7-2018 by Loptr]
A simple search yielded an example: http://pubs.ub.ro/dwnl.php?id=CSCC6201504V04S01A0001
[Edited on 31-7-2018 by Loptr]
"Question everything generally thought to be obvious." - Dieter Rams
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goldberg
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Thanks for replies. I'm reading literature and did not found other mentions about problems with activity of Urushibara nickel. Both original papers
by Urushibara and books about hydrogenation says that it is comparable to Raney nickel.
I read article about hydrogentaion at atmospheric pressure by Brown and it looks very friendly.
I'm starting to look for materials that i could use if i decide to build apparatus for high pressure hydrogenation.
Typical steel and aluminium alloys will break under influence of hydrogen after enough long time.
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Corrosive Joeseph
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You NEED access to References Forum................ 
/CJ
Being well adjusted to a sick society is no measure of one's mental health
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Loptr
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| Quote: Originally posted by goldberg | Thanks for replies. I'm reading literature and did not found other mentions about problems with activity of Urushibara nickel. Both original papers
by Urushibara and books about hydrogenation says that it is comparable to Raney nickel.
I read article about hydrogentaion at atmospheric pressure by Brown and it looks very friendly.
I'm starting to look for materials that i could use if i decide to build apparatus for high pressure hydrogenation.
Typical steel and aluminium alloys will break under influence of hydrogen after enough long time. |
I think most of the time people are not properly preparing Urushibara Nickel, and then turn around and claim that it sucks or doesn't work. Follow the
literature to the letter and document your attempts, and then do it several times, and compare your experiences. There is no one shot silver bullet.
You have to experiment.
[Edited on 31-7-2018 by Loptr]
"Question everything generally thought to be obvious." - Dieter Rams
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Chemi Pharma
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I really don't know what happen with you, guys.
Even someone showing you the better way to do a decent hydrogenation you insist to follow the bad way. Tell me really why should I spend my time, my
efforts and my money with Urushibara nickel or hydrogenation bomb apparatus if I have modern materials like borohydrides complexes, DIBAL, LiAlH4,
Silanes, Red and alkyl lithium?
If the goal is to experiment amateur chemistry, and cry over your failures, ok, I appologize, but I think the goal of every amateur chemical is to
professionalise himself and do the things better and better. Why insist with old and precarious techniques? To see a big failure? to explode your face
with a homemade hydrogen bomb apparatus? I can't believe I'm reading some kind of things.
Oh, come on! no excuses to anyone that claims "oh! I can't get this chemical," Even as an individual person everyone worldwide can get chemicals. At
the NET, E-bay, Alibaba, here in SM, with companies, etc. I beg your pardon but no excuses you have to still saying: oh no! This chemical is very hard
to purchase.
Let's evolve ourselves and pratice the better chemistry guys. stubbornness will get you nowhere. It's a joke of mine.
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Loptr
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| Quote: Originally posted by Chemi Pharma | I really don't know what happen with you, guys.
Even someone showing you the better way to do a decent hydrogenation you insist to follow the bad way. Tell me really why should I spend my time, my
efforts and my money with Urushibara nickel or hydrogenation bomb apparatus if I have modern materials like borohydrides complexes, DIBAL, LiAlH4,
Silanes, Red and alkyl lithium?
If the goal is to experiment amateur chemistry, and cry over your failures, ok, I appologize, but I think the goal of every amateur chemical is to
professionalise himself and do the things better and better. Why insist with old and precarious techniques? To see a big failure? to explode your face
with a homemade hydrogen bomb apparatus? I can't believe I'm reading some kind of things.
Oh, come on! no excuses to anyone that claims "oh! I can't get this chemical," Even as an individual person everyone worldwide can get chemicals. At
the NET, E-bay, Alibaba, here in SM, with companies, etc. I beg your pardon but no excuses you have to still saying: oh no! This chemical is very hard
to purchase.
Let's evolve ourselves and pratice the better chemistry guys. stubbornness will get you nowhere. It's a joke of mine. |
Yes, I have most of those as well, but I also don't like the idea of being limited to a harder to get reagent. It is my goal to be able to have a
number of options at my disposal. What happens if I can't get the more difficult to obtain reagents in the future?
I might also not want to use my "reserved stock" for some reactions. Why are you being such a blow hard about this?
"Question everything generally thought to be obvious." - Dieter Rams
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Chemi Pharma
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I give up to argue with someone thinking like you.
You have all rights to think like that, but don't ask me to think like you.
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Loptr
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| Quote: Originally posted by Chemi Pharma | I give up to argue with someone thinking like you.
You have all rights to think like that, but don't ask me to think like you. |
It's obviously a mindset difference considering the topics of your other posts. You come to an amateur chemistry forum and complain about the amateurs
still discussing older chemistry, which is generally more accessible.
You are the only one trying to make anyone think differently.
I honestly don't give a f**k what you use or think. If you have something useful to offer, then I will gladly part with that. I take what I need, and
leave the rest behind.
[Edited on 31-7-2018 by Loptr]
Also, it's not a matter of not wanting to use the latest and greatest. That stuff is usually EXPENSIVE if you chose to purchase some. I have majority
of what you have listed, so I know how much they cost the amateur. I have a lot of NaBH4. It's up for sale right now. I like using it a lot. Very
clean reactions. It's also not the end all, be all. I might want more selectivity depending on a functional group present in the molecule. It's not
all about reducing imines, nitro groups to amines, or amides to N-alkylamines.
For me, it's more about the journey than the destination.
[Edited on 31-7-2018 by Loptr]
[Edited on 31-7-2018 by Loptr]
"Question everything generally thought to be obvious." - Dieter Rams
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Chemi Pharma
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I'm not complaining about anyone, except of you, a guy that's understand nothing about what I'm defending here. I "didn't come to an amateur chemistry
forum". I still here for more than two years and all of your five stars and the time you ingressed in this forum doesn't say nothing to me, cause the
time I've been here I met people with much more knowledge in chemistry than me, and I look to learn with them. But, on the other hand, I had an
unpleasure to know people like you, arrogant, that think your five stars covers you with a mantle of wisdom, incapable of say bullshits like you say,
and make mistakes like any human beeing.
Grow up and turn yourself in a better person. May be I excuse your rudeness and learn to respect your five stars, ok?
Oh, and I'm not the only one trying to make people here think different, ok? Exists more people intelligent here that you think. And for sure they are
laughing of you.
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Loptr
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At this point, I honestly have lost any semblance of a clue I might have had as to what you have been babbling on about or "defending". Defending
what? Your right to party? I don't know what I am missing in your posts within this thread, but I am respectfully bowing out as your hubris is too
much for me.
[Edited on 31-7-2018 by Loptr]
"Question everything generally thought to be obvious." - Dieter Rams
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alking
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| Quote: Originally posted by Chemi Pharma | @alking, oh, ok! and may be you think 1 gram is too much powder, huh? The physical loss in the filter paper is around 1/4 of your Platinum or
Paladium, mixed with activated charcoal. Losses in the total process plus another 1/4. I just have used Pt/C in the University Lab, never more at my
Lab, and I can tell you it's a pain in the ass to recover the catalyst. If you are lucky, you can get to use this 1 gram three times.
By the way, don't spend your time asking Mario about prices. I know him. Even have bought twice with him, but now he is not accepting pay pal no more,
just cash by Western Union transfer or bit coins. And his prices? oh, his prices are now more expensive than Sigma Aldrich can charge you.
Mario no more, thanks. I'm thinking seriously start to sell chemicals here at SM to make a competition and force him to put down his prices. I have a
legalized Chemical Lab and lmportation/exportation licences and can get whatever chemical you want that has a CAS number, like him. Making profits has
a limit. What he's doing have other name: greed! |
I see what you mean with mechanical losses, it depends upon your scale and equipment. With 1g or less you're of course going to lose a lot more than
say with 10g. With 10g you should be able to use the same filter and tools so if you lose even half a gram that's not such a big deal, 5% loss
compared to 50%(!). If mechanical losses are a concern and/or you're working with smaller amounts it may be better to get a lesser loaded substrate to
mitigate it.
I like Mario, he has helped me out a few times now but some of the things are not worth getting from him, certainly more common things. I assume he is
buying from sigma or the like so of course he will have to mark it up a reasonable amount to make it worthwhile for him to sell. Most of us as
amateurs cannot buy directly from the big suppliers so that's the price we pay to be able to. With that said I'm sure some competition would be more
than welcome, I hope you decide to do so.
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Chemi Pharma
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Thanks @Alking, I will try to make a competition to benefit all SM users until the rest of the year. Do you know? I have quoted some reagents from
Mario and got the price from China Chemical suppliers. Mario is charging more than 30 X (yes. You read well. More than thirty times the chinese value)
and more than 03 times the price charged from Sigma Aldrich. I have bought goods with Mario. I know how he mislead the country customs. The label
withdrawal and etc. For me, as a company, would be very easy export the goods to every SM users with a low price, in dollars and with credit card by
Pay Pal. I can withdrawal the labels the same way, repack the goods imported, like I do in my Lab and send like a cleaning product, declaring the
value as a few dollars to escape the custom taxes and send it all over the world.
About Pt/C, yes, I had a bad experience with it at the university lab, cause the packs were sent as 1 gram. 1 gram of Platinum is almost nothing. If
you breath in front this all the powder will be lost. May be with 10 grams it's better to work with. I never tried with this ammount and I desire to
who want to try the best luck as possible. I'd rather the borohydride complexes.
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clearly_not_atara
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| Quote: Originally posted by Chemi Pharma | | Oh, come on! no excuses to anyone that claims "oh! I can't get this chemical," Even as an individual person everyone worldwide can get chemicals. At
the NET, E-bay, Alibaba, here in SM, with companies, etc. I beg your pardon but no excuses you have to still saying: oh no! This chemical is very hard
to purchase. |
Interesting logic: because you don't have a problem, nobody has the problem. Suppliers won't
sell to individuals in many jurisdictions. Most places won't allow you to set up a lab. And the licensing fees cost way more than Pd/C. Plus,
complexes are expensive: if you lose 0.25 grams of palladium per run, is it worth paying for 50 grams of Red-Al? Possibly no.
Also, you may be interested in recovery of palladium via dimethylglyoxime:
https://link.springer.com/article/10.1134%2FS002016851314007...
Dimethylglyoxime is made from methyl ethyl ketone, which itself can be made from levulinic acid if it's restricted for some reason.
[Edited on 31-7-2018 by clearly_not_atara]
[Edited on 04-20-1969 by clearly_not_atara]
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Chemi Pharma
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Funny @clearly_not_atara, The discussion I had with @Loptr make me remember an old discussion the two of us had at a thread dealing with Ni/Al and
Urushibara nickel reductions. Do you remember? I think you were so rude as Loptr went with me now, in that occasion.
I'm just saying getting chemicals is not a problem anymore to SM members. If you can't get it on the Internet or with a supplier as an individual,
SOON, YOU CAN GET WITH ME! Like Mario does in the "Reagents and Apparatus Acquisition" section. With a too much better price! Is it ok for you? Do
you want to be my first client?
So, in your oppinion I'm should feel lucky, cause I got a licence to my Chemical Lab, a TAX ID, a custom licence to import and export
U$100.000,00/year. No my dear, I tried hard myself to get this licences, paid a high value and invested in my business, although I feel like an
amateur yet and have a lot of things to learn with SM Members here, cause here in Brazil happens the same of the rest of the world.
Thanks for the tip on how to recover the catalyst with DMG.
Greetings!
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goldberg
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I am curious of Urushibara nickel because it looks very safe to handle (does not ignite on air etc).
All literature that i have read states that it is comparable to W-7 Raney nickel (Handbook of heterogenous catalysis and
another similar book).
I am looking for material for vessels for slightly higher pressures than atmospheric. Typical stainless steel is not an option
because it will break under influence of hydrogen, aluminium alloys too.
I will first experiment with atmospheric pressure but i'm curious about slightly elevating it.
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Herr Haber
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Would I buy from someone that I dont know, who picks up a fight with 2 SM members in this topic and badmouthes Mario several times just to push his
own business ?
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