ssdd - 7-5-2007 at 16:22
I'm not sure if this is at all possible or would work at all, but heres what I am thinking:
Some time ago while I was working in my schools chemical store room I spotted a sealed jar of adrenaline. It is in crystal form. I disregarded it at
the time but as I sat and thought this reaction came up in my head.
C9H13NO3 + HNO3 --> C9H10N4O6
I guess this would be called nitroadrenaline. Being adrenaline has 3 OH groups, and OH groups tend to be replaced in nitrating reactions, I would
think that this would work. Would the action of the nitric acid destroy the molecule, and how could this be harvested? Is it water soluble?
Any input would be great... 
Intergalactic_Captain - 7-5-2007 at 18:29
Adrenaline is a phenol, and hence wouldn't nitrate in the way you're thinking - That's only for aliphatic alcohols. Most likely, it would nitrate
once or twice ortho to one of the phenolic groups - I'm guessing it would end up in the 3 position and go no further, but I'm not entirely sure. The
benzyl hydroxyl is a different matter - That position isn't especially reactive, but it might just end up as a nitric ester.
As a general rule to remember, though, aromatic nitrations give the -NO2 nitro group while aliphatic alcohols lead to the -NO3 (-ONO2 structurally)
nitric ester.
[Edited on 5-7-07 by Intergalactic_Captain]
Microtek - 8-5-2007 at 00:43
As far as I can see, all three remaining sites on the ring are activated. Also, the amine group would give a nitrate salt.
ssdd - 8-5-2007 at 02:13
Hmmmmm that's a bit disappointing.
So, Intergalactic_Captain, you are saying that if this were to work at all it would only replace the position 3 OH?
And from what I can gather the amine group would be damaged or destroyed in the reaction, leaving the reaction with very little practicality.
I may run the reaction tomorrow just to see what happens, though I'm thinking all of the products would be water soluble. But at least I would know
what scenario would happen.
Thanks for the input I learned a good deal from researching your answers.
**What would some of the properties of the possible products be?
[Edited on 8-5-2007 by ssdd]
Intergalactic_Captain - 8-5-2007 at 07:01
No, you heard me wrong - It would NOT replace the 3-hydroxyl. Look at the molecule - it has hydroxyls in the 3 and 4 position. When nitrated, the
first substitution would be to the 5-position. I can see where a little bit of confusion could come from, though, as the naming priority would give
3,4-dihydroxy-5-nitro-whatever. As for the amine salt formation, you're probably going to neutralize the resulting product (one would hope) and end
up freebasing it anyway.
And, once again, YOU NEED TO DO SOME RESEARCH! "only replace the 3 position OH" - All I can say is thank god you picked this forum over E&W for
your first post. A little hint - PHENOLIC HYDROXYLS DONT GET REPLACED under standard nitrating conditions. Sure, if you did a little chemical
masturbation you could turn the hydroxyl into a nitro group, but it would take more than one step and probably not be worth the trouble.
And water solubility...Have you ever done any work with aromatic nitration or amines for that matter? Phenethylamines, or amphetamines like
adrenaline (though the benzyl hydroxyl may do something I'm overlooking) are generally in(or very slightly)soluble in water. Nitrated aromatics are
insoluble (generally, though some substitution patterns alter solubility in ways that are hard to understand on paper). The only thing that would
make it soluble is the high acidity protonating the amine and making it soluble - However, you'll end up neutralizing it in the isolation step, giving
(more than likely) insoluble product.
...My info may not be the best, and some of it may even be blatantly wrong, but I don't see anyone else (aside from Microtek, of course) offering up
advice. I'm sure the next thing I say is what everyone else here would - Go to a library, Go to a computer, Talk to a professor, whatever it takes to
actually LEARN something about what you want to do BEFORE you do it. Hell, there's even a copy of COPAE on this site's library if all you want to
make is explosives.
ssdd - 8-5-2007 at 07:52
I think there has been a grand misunderstanding here...
I have not tried this reaction yet, I came here to ask about it before I did it. Do you people really think I would be as dumb to just try something I
have never even researched. I came to these forums to learn not to be an instant expert in everything that is talked about here. Just because I only
have a few posts on the forum doesn't mean I have never worked with anything before, usually you go looking for a forum after you have an intrest and
some work in an area.
If you are just going to sit there and slam me just don't reply to my posts.
mods, feel free to delete this topic...
Axt - 8-5-2007 at 08:18
They may be activated but nitration will deactive it, thus its likely at most 2 nitro groups on the aromatic ring. This will also make it acidic thus
no nitrate salt and not wise to neutralise it as you'd likely end up with a sodium salt. Assuming the molecule isnt destroyed during nitration you'd
end up with a dinitro nitrate which is probably slightly soluble and not much of an explosive. You may be able to turn the secondary amine into a
nitrosamine via NaNO2/H2SO4 prior to nitration hoping to get a dinitro nitrate nitramine.
[Edited on 9-5-2007 by Axt]
Intergalactic_Captain - 8-5-2007 at 08:44
Post count doesn't mean jack...The reason I had a problem with you is that it seemed like you had little understanding of what you are doing. If I
came off harsh, I meant to - If you know what you're doing, you'll disregard me...If not, then it should motivate you to do a little research.
Like I said, what got me the most is your misunderstanding of aromatic substitution - What's worse, I highly doubt nitrated adrenaline exists in the
literature...When working with something unknown, there is always a very real chance of catastrophic failure. What would happen if you ended up with
some something hellishly sensitive? Would you expect it? Would you prepare for it? What if it was highly toxic? Perhaps what I define as failure
is exactly what you're after...Pherhaps not. Either way, the message is to exhaust your abilities to research something before you even consider
doing it.
As for the nitro-nitrosamine-nitrate, that sounds kind of cool...Now if only we could do that to pseudoephedrine and get 2,4,6-trinitro-(don't have
time to think of rest of name, but a nitrosamine-nitrate)-ephedrine...It'd be illegal by the ATF and the DEA.
ssdd - 8-5-2007 at 11:59
Alright then can someone give a suggested text I should go out and buy? Anything on general organic chemistry would be great. I'm in high school and
haven't had much exposure to these type of things yet.
Again thank you for an input you can offer.
Just a note: I'm not here because I want the explosive, I just thought it would be an interesting reaction to try, and being most nitrations result in
something energetic I simply thought this would be the place to post it, sorry for the flame war it wasn't intended.
Nicodem - 8-5-2007 at 12:31
Adrenaline is a substituted catechol and as such can not be nitrated without oxidation. Actually adrenaline is a terribly sensitive compound toward
oxidation, its solutions gets oxidized with O2 from air in matter of hours unless well protected. Its aliphatic OH group is a secondary benzylic
alcohol and thus very hard to esterify with nitric acid or HNO3/H2SO4 mixture without elimination being the main reaction.
Anyway, attempts in nitration of adrenaline would yield crap. There are many other starting material that can be used for making crap so it would be
quite stupid to make crap from something that costs 10 to 20EUR per gram. (Not to mention the extreme irrationality of attempting to make a weak
explosive from an expensive, enantiomericaly pure and toxic medicine.)
[Edited on by Nicodem]
Intergalactic_Captain - 8-5-2007 at 12:49
Now how hard was it to come clean? You'll find here that people are more willing to help someone with an interest and willing to learn than someone
who just wants an answer. Especially in this forum - Theoretical discussions of explosives are fine, but don't come here wanting info on a known
procedure...I'm no experet, but some of the people here - Notably Axt, and a couple of others who's names escape me.
As for books, check out the library on this site first - In case you didn't realize, this site is more than just a forum. In the site library, you'll
find "Vogel's (something) Organic Chemistry"...Read it, then read it again. After that, read "Principles of Dye Chemistry," also found in this
library. Finally, thumb through COPAE and find something relatively inert that'll hone your skills in chemistry while still giving an explosive (I
know this isn't quite where you should start, but I found at your age that explosives will keep your attention longer than anything else, if that's
what you're interested in) as a product.
As for buying books, I'm not a particular fan of it...You can find older editions of most texts online, along with quite a few old journal articles.
Personally, I only buy books on eBay, a few other used book sites, and of course garage sales and flea markets. I find it very hard to justify
spending $200+ on a book when I know it'll be worth less than $50 in a year when the new edition comes out.
If you can, hang out around a university library...I know that at UB at least, anyone (student or not) can walk in and browse the book and microfilm
collections at ANY of the libraries...You just can't log in to the computers. This may not be the case (at least I hope its not, simply for security
reasons...You should at least have to sign your name somewhere or show ID if you're not a student) at other schools, but it is here.
Once you get into college, you'll be amazed at the access to scientific journals (and just about every other field) that you'll have...I think I have
free access to 10,000 (probably more, that's just the number they advertise) different titles from just about every country.
The best piece of advice I have found, though, is not to research what you are looking to do - Rather, research the type of reaction or class of
compounds or whatever...You'll do a lot better learning mechanisms and general properties than you will knowing specific things - Memorization may
work for a little while, but when you find out that your "basic" organic chemistry book weighs 25lbs and is over 2000 pages long you'll wish you
learned HOW and WHY things work rather than that they just do.
In short, welcome to the world of chemistry - Read, Learn, Conceptualize, Do...In that order...Ask intelligent questions, and have a good
understanding of what you want to do before you do it. You'll soon see (in case you don't already) that the chemists are at the top of the food chain
- The modern world simply wouldn't exist without us, and we get to profit massively off of all those little "conveniences" that peope take for granted
as part of daily life.
ssdd - 8-5-2007 at 13:07
Thanks, thats probably some of the best advice I've had in awhile. Ironicly I have the Vogel pdf on my desktop right now. I'm gona see if I can get a
printed copy of that somewhere. (I hate reading long things off a computer screen to easy to get distracted.) 
Sadly I don't have access to a very big library, so I do most of my hunting for material online, which I'm starting to find limiting. (There isn't
much here in south jersey)
I wont be bothering with this reaction, or adrenaline anymore. Other than its medical applications it seems to have very limited uses. I have access
to a decent chemical room, I'm sure I can find something else that interests me. 
JohnWW - 8-5-2007 at 18:10
It is about time that access to scientific journals was made available to everyone, for free! But the only way that could happen would be for them to
be 100% subsidized by governments, by turning the publishers into public servants and putting them on state salaries.
As for nitration of adrenaline (or possibly formation of covalent nitrate esters of it by replacing the phenolic -OH groups), which has a biochemical
energy-releasing effect, what do you hope to achieve? Of course, the nitro-group and nitrates are also "energetic", but adding such groups would
probably not increase its biochemical energy-releasing activity, which depends on highly stereospecific biochemical reactions.