Author Topic: different routes starting from nitropropenes  (Read 10315 times)

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armageddon

  • Guest
different routes starting from nitropropenes
« on: April 07, 2004, 05:41:00 PM »
Hi Bees!

I have just tried to remember all possibilities for going from a nitropropene to an aminopropane that explicitly don't use mercury amalgams, lithium aluminium hydride, pressurized hydrogen or other hazardous reagents. I also wanted to exclude reactions using ferromagnetic metal catalysts like iron, nickel or magnesium etc. because they can't be performed without adequate overhead stirring equipment.

But as there are so many methods known to the hive, I got confused. So I decided to write down a "reaction scheme"...  ;D  and ended up with this diagram (made using ChemDraw).
It is only an overview of possible routes using certain easy-to-handle chemicals, for further details on reactions use TFSE, it's all there. If you think something important is missing, please tell me! And I named it "ketones, imines, oximes" because most of the possible ways I remember include these as intermediate products.  :)







[EDIT]
1.

Post 392067 (missing)

(Aurelius: "P2P from Tin (II) and nitropropene", Methods Discourse)

2.

https://www.thevespiary.org/rhodium/Rhodium/chemistry/phenylacetone.html#p2np


   ("Reduction with iron powder")
3.

Post 465461

(Bandil: "Proof of concept!", Novel Discourse)

   

Post 483260

(SpicyBrown: "4-Fluoroamphetamine: A full report.", Methods Discourse)

4.

Post 427794

(Barium: "Nitrostyrenes to oximes with sodium dithionite", Novel Discourse)

5.

https://www.thevespiary.org/rhodium/Rhodium/pdf/nitroalkene-stannite-1.pdf


   

https://www.thevespiary.org/rhodium/Rhodium/pdf/nitroalkene-stannite-2.pdf


6.

https://www.thevespiary.org/rhodium/Rhodium/chemistry/mdaoxime.html


   

Post 319296

(Rhodium: "P2P oxime in quantitative yield", Novel Discourse)

7.

Post 382254

(Barium: "A great CTH method", Novel Discourse)
   
    (although Barium uses potassium formate, the procedure is essentially the same)
8.

Post 460139

(Bandil: "Formic acid reduction - comments", Methods Discourse)

9.

Post 477266 (missing)

(Lego: "Reduction of oximes with zinc/ammonium formate", Novel Discourse)

10.

https://www.thevespiary.org/rhodium/Rhodium/pdf/cth.oximes.formate.pdf


11. + 12.

Post 455901

(Sunlight: "Ammonium salts for imine", Methods Discourse)

   

Post 335851

(Sunlight: "MDA and MDMA from CTH reductive amination", Novel Discourse)

11. + 13.

Post 461926

(cublium: "NaBH4 is just amazing.", Newbee Forum)

[/EDIT]

As I said already, this is only a short overview over the possibilities  starting with phenyl-2-nitropropenes, and if someone knows something that should bee added, go ahead!

Greetz A


Rhodium

  • Guest
Suggestion
« Reply #1 on: April 07, 2004, 07:51:00 PM »
Number the different reactions, and collect links to different procedures to effect that particular transformations, then post those link lists to the various methods as a little lexicon to aid yourself and others to learn about the multitude of routes possible.


armageddon

  • Guest
reaction references
« Reply #2 on: April 07, 2004, 09:19:00 PM »
Ok, (although I wanted to avoid it because of being too lazy  ;) ) it still seems a good idea. So here are links for every of the above reactions (the picture and post have been edited and the reactions were numbered).

(As imine formation from the ketone and following reduction are best perfomed immediately after each other, I have just included routes that involve preparing the imine in situ...)


Hope this will help some bees in getting a better overview of these reactions (including me  :) ).

Greetz A


Nicodem

  • Guest
Nice scheme and links!
« Reply #3 on: April 08, 2004, 02:24:00 AM »
Nice scheme and links!
It is always lovely to see somebee trying to make some order in the chaos, but I miss the reactions from 1-phenyl-2-nitropropenes directly to amphetamines ;) .


armageddon

  • Guest
several nitropropene CTH failures are the reason
« Reply #4 on: April 08, 2004, 03:20:00 AM »
Hi Nicodem!

THX, I like it too (I just like looking at pictures.. ;)  ;D )

But I didn't include nitropropene to amine conversions as they all require pressurized hydrogen and/or ferromagnetic (and for sure pyrophoric, but that's ok) catalysts (raneyNi = ferromagnetic = not mag.stirrer compatible), or if you think of a Pd/C catalysed CTH w/NH4COOH, then I'm sorry to have to tell you but for SWIA this direct reduction didn't work although he tried it several times (w/variations of course), and therefore I didn't include them, too. (SWIA told me he followed instructions found in a document by dreamer,

https://www.thevespiary.org/rhodium/Rhodium/chemistry/nitropropene.cth.txt

) Of course, if you have better knowledge than I do, please post a writeup or a link to one, I would appreciate it. (but remember, NO pressurized H2, NO Fe/Ni/Co/Mg, LiAlH4 and of course no "T+"-style Hg-X things) :)

Greetz A


Lilienthal

  • Guest
LiALH4
« Reply #5 on: April 08, 2004, 05:24:00 AM »
LiALH4 [hint]

nightshade

  • Guest
electrochemical
« Reply #6 on: April 08, 2004, 09:11:00 AM »
electrochemical

armageddon

  • Guest
re: LiALH4 [hint]
« Reply #7 on: April 08, 2004, 10:15:00 AM »
Lilienthal: Sure, metal hydrides are capable of reducing nitropropenes to primary amines, but they also react violently with water if no really anhydrous solvent is used. And the solvents used are ethers and THF... :o

So I didn't include this reducing agent (the goal was to collect routes that don't use Fe/Mg/Ni/Co, pressurized hydrogen, no metal hydrides and no mercury salts, remember)

Nightshade: could you please point out what kind of electrochemical reaction you mean? Perhaps with a link?
That would bee nice!


Barium

  • Guest
Nope
« Reply #8 on: April 08, 2004, 10:55:00 AM »
Red-Al can be used to reduce nitrostyrenes directly to amines in decent to good yields. The only solvent needed is toluene and if the toluene at hand is a bit wet, just use some Red-Al as a drying agent.

Nicodem

  • Guest
Zn/HCl,EtOH
« Reply #9 on: April 08, 2004, 01:30:00 PM »
I have never done any but there are alternatives to H2/cat and LiAlH4. Besides the already mentioned electrochemical reduction on a Pb cathode, there are also a few reductions on amalgamated metals (Al/Hg for example, but you said no Hg, right?) and the most surprising one, a simple reduction with Zn in HCl/EtOH (

https://www.thevespiary.org/rhodium/Rhodium/chemistry/leminger.html

). BTW, does anybody know why this one never gained popularity?


Vitus_Verdegast

  • Guest
Zn/HCl route
« Reply #10 on: April 08, 2004, 02:18:00 PM »
It works well, but the workup is horrible, extracting the Zn(OH)2 sludge feels like extracting a can of paint.  ::)


armageddon

  • Guest
"can-of-paint"-route for nitrostyrenes
« Reply #11 on: April 08, 2004, 03:55:00 PM »
Vitus: Besides from the disadvantages you mentioned, the Leminger rxn works only for nitrostyrenes, alpha-methylnitrostyrenes (P2NPs) give mainly the ketone and only minor amine, see also

Post 470515

(GC_MS: "Zn/HCl doesn't work for alfa-methylnitrostyrenes", Chemistry Discourse)

Post 439548

(GC_MS: "Zn/HCl reductions", Newbee Forum)


And Vitride is very hard to get, harder than NaBH4... >:(

Nicodem: could you pleeease give me a link to a electroreduction with a lead electrode? And what is being reduced? P2NP or intermediate (imine?)?

THX A


Rhodium

  • Guest
complex with ammonia?
« Reply #12 on: April 08, 2004, 06:18:00 PM »
It works well, but the workup is horrible, extracting the Zn(OH)2 sludge feels like extracting a can of paint.

Did anyone ever try to complex the Zn2+ with ammonia? It should solubilize the sludge well.


armageddon

  • Guest
sodium hypophosphite as reducing agent
« Reply #13 on: April 08, 2004, 11:22:00 PM »
I just found something I missed previously: nitropropenes (especially the 2,4,6-triMeO from asarone) are reduced to the ketoxime with Pd/C and sodium hypophosphite in high yields (90%+), but piperonal and P2NP give mixtures of the oxime and the ketone, depending on amount of catalyst used and acidity of rxn. here's the link:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/tma-2.oxime.html



What about just hydrolysing the oxime part completely to the ketone, which can then be separated by steam distillation? That would give a nice route to ketones using hypophosphite.

Barium, which reducing agent for getting oximes would you prefer: sodium dithionite or hypophosphite/catalyst? (or what about rhodiums suggestion of using NH3 for basifying tin suspensions? stannite reduction would become alot more attractive - perhaps somebee has xperience with it?)

Thanks!


Nicodem

  • Guest
electroreduction
« Reply #14 on: April 09, 2004, 04:04:00 AM »
Nicodem: could you pleeease give me a link to a electroreduction with a lead electrode? And what is being reduced? P2NP or intermediate (imine?)?

I guess the electrochemical bee would bee Uemura:

Post 47461

(uemura: "Electrochemical Reduction of Nitrostyrenes", Novel Discourse)

There is also

Post 219827 (missing)

(Bandil: "Tin instead of lead as cathode", Methods Discourse)
and probably more threads if you take some more time to UTFSE than I did.

I only have these two papers at home:

Masui and Yijima. Controlled-potential Electrolysis. Part IX. Reduction of two nitro-indolyl-esters in acid solution. ?JACS? (1963) 1101-1105.
(it is about the reduction of ethyl alpha-nitro-beta-indolyl-propionates to DL-tryptophan on Pb or Hg cathode)

Niazimbetova et al. Cathodically promoted addition of nitromethane to aldehydes and exploratory studies of the mechanism of the electrochemical reduction of the nitroolefins so produced. J. Electrochem. Soc. 145 (1998) 2768-2774.
(it is mostly about the electrochemicaly promoted Ph-CHO + MeNO2 => Ph-CH(OH)-CH2NO2, much less on the nitro->amine reduction, there is also a lot on the theory, lots of polarograms and studies of side products)

I can scan them if anybee is interested, but I think there are also better papers out there.

Besides from the disadvantages you mentioned, the Leminger rxn works only for nitrostyrenes, alpha-methylnitrostyrenes (P2NPs) give mainly the ketone and only minor amine

I'm kind of convinced that it would work if instead of aq. HCl a solution of HCl gas in ethanol would bee used. It would form an intermediate Ar-CHCl-CHNO2-Me (no double bond!) and this gets reduced on Zn surface. And there would also bee less chances for the intermediate oxime to hydrolyze (no ketone product). Rhodium's idea of using ammonia in the work up instead of NaOH seams pretty good too.


Barium

  • Guest
Both dithionite and hypophosphite-Pd/C are...
« Reply #15 on: April 09, 2004, 03:43:00 PM »
Both dithionite and hypophosphite-Pd/C are good routes. They are about equally cost effective too. it is manly a matter of taste I guess. Some oximes are not hydrolysed by the dithionite route as they are by the hypophosphite route. If one is aiming for complete oxime hydrolysis I would add a good hydroxylamine acceptor. Basically any low molecular weight carbonyl compound which is not sterically hindered is just fine. Acetone is a good example.

Rhodium suggested ammonium complex forming with zinc not tin.

armageddon

  • Guest
re: acetone, tin
« Reply #16 on: April 10, 2004, 02:10:00 PM »
Thanks for your info, Barium. Just read that dithionite reduction gave you ~1% P2P contamination, compared to ~20% P2P resulting from hypophosphite-Pd/C rxn... Dithionite seems to work somewhat cleaner. Hm. Using acetone to affect complete hydrolysis sounds good, but I thought the purpose behind ketone formation was to bee able to separate via steam distillation and to avoid having to solvent xtract (unless the reason is that you NEED ketone, not oxime)? Wouldn't acetone interfer with this?

Oh, and about basifying tin with ammonia: I think tin will normally give a mess upon basification, too (read somewhere that workup of Na2SnO2 reductions to oximes is very hard, and I thought that was the reason why aurelius suggests hydrolyzing w/HCl - to simplify workup?) so I thought Rhodiums idea would perhaps solve the tin problem, too...  :-[
Does tin form complex salts with ammonia? Are they less soluble than hydroxides in nonpolars?

Nicodem:  8)  THX  8)  seems as this method isn't very popular at the hive, I really don't know why!?
And do you have any references for your idea of an anhydrous Zn/HCl reduction? I'm asking because I perhaps may have use for this doublbond-halogenation for some other, eeasy procedure if this really works...(secret) ;)

A


Nicodem

  • Guest
No ref’s, just theoretical bla, bla
« Reply #17 on: April 11, 2004, 04:53:00 AM »
And do you have any references for your idea of an anhydrous Zn/HCl reduction? I'm asking because I perhaps may have use for this doublbond-halogenation for some other, eeasy procedure if this really works...(secret)

Sorry, I don't have any references for the addition of HCl to nitrostyrenes (though I have a faint memory of actually seeing it somewhere). But HCl is known to easily add on the double bonds of Michael acceptors (I know of methyl acrylate as an example, but it is general to similar R-CH=CH-EWG where EWG is an electron withdrawing group). The addition is reversible, shifting completely left in basic conditions. I don’t know what your secret procedure is but if your compound fulfils the above conditions then HCl should add to the double bond. Especially if you have such a good Michael acceptor as a nitrostyrene is, which is perfect as it has a strong EWG (the nitro) and a carbocation stabilizing aryl on the other side.
I even think this could be an explanation for the Leminger’s reduction as well as the hydrogenating reductions that work only in the presence of HCl or H2SO4 (

https://www.thevespiary.org/rhodium/Rhodium/chemistry/mescaline.cathyd.html

,

https://www.thevespiary.org/rhodium/Rhodium/chemistry/catalytic.html

).
It is known that H2/Pd does not easily reduce conjugated double bonds (as C=C-NO2) while it easily reduces benzylhalogenides and similar benzylic compounds. So I guess Ar-CHX-CHR-NO2 is the true intermediate in these reductions (where X = -Cl, -SO3H, -OAc, -OH2+ etc.). To me this is the easiest explanation on why these hydrogenations require HCl or H2SO4/AcOH as well as Zn/EtOH,HCl woks while Zn/AcOH does not.
But these are only guesses, though I hope they are of any use to your “secret” reaction.


armageddon

  • Guest
gosh - how could I forget?
« Reply #18 on: July 07, 2004, 10:07:00 PM »
As Antoncho's "92% yield"-Leuckart-thread became that popular recently (MANY views..), it came into my mind that I forgot this simple route via P2P to make an amph. from a nitropropene...

x-pheny-2-nitropropene __> x-phenyl-2-propanone __> x-formylaphetamine (x-amphetamine through hydrolysis)

..this major stupidity is now fixed!  ;D

A


Erny

  • Guest
One method is missing
« Reply #19 on: July 08, 2004, 04:16:00 AM »

SpicyBrown

  • Guest
Re: https://www.rhodium.ws/chemistry/nitrostyre...
« Reply #20 on: July 08, 2004, 09:03:00 AM »

https://www.thevespiary.org/rhodium/Rhodium/chemistry/nitrostyrene.reduction.alhg.html

Maybee it is too easy?



It's pretty easy alright. The workup isn't even that bad - the secret is in using the isopropyl alcohol which will carry your product out of the sludge once it becomes saturated enough with ions.

Be careful though - Don't go adding all the Al at once like some suggest in there, no matter how potent you think your condensor really is... Recently scrubbed Al/Hg SHIT off the ceiling...

-SpicyBrown


armageddon

  • Guest
not too easy - too dangerous for the environment
« Reply #21 on: July 08, 2004, 02:51:00 PM »
Erny: it is not too easy, but too poisonous. (I'm still wondering why you all like Hg that much: it is an insidious, deadly poison which accumulates in your body and makes you slowly become insane after months - and I started the thread with the words "I was trying to remember all routes from a nitropropene to an amphetamine that explicitly don't use mercury, metal hydrides, pressurized hydrogen and/or other hazardous/toxic reagents", so Al/Hg doesn't belong here..)

In case you still want tu use mercury amalgam for reducing: how about adding a bent drying tube on top of your condensor? You could direct possible spillovers into a plastic dish (instead of your ceiling). Think it is easier to dispose off mercury sludge this way... ;)

A


armageddon

  • Guest
another one
« Reply #22 on: July 08, 2004, 03:11:00 PM »
Well, nitropropenes can be reduced to ketones via different routes, which easily form oximes (see picture in 1st post). These can also be reduced using elemental sodium/alcohol (see rhods page). (nice advantage: oxime reductions result usually in more potent product, as the syn/anti ratio of the intermediate oxime is 9:1 or something like that. In most cases, this means a more potent phenylisopropylamine - not with 3,4-methylenedioxy compounds, but in most other cases)

Greetz A


Vitus_Verdegast

  • Guest
well
« Reply #23 on: July 08, 2004, 03:27:00 PM »
I'm still wondering why you all like Hg that much: it is an insidious, deadly poison which accumulates in your body and makes you slowly become insane after months

You don't have to eat it...

Take the necessary precautions, and dispose of your waste properly.


Captain_America

  • Guest
In case you still want tu use mercury amalgam...
« Reply #24 on: July 08, 2004, 03:44:00 PM »
In case you still want tu use mercury amalgam for reducing: how about adding a bent drying tube on top of your condensor?

They are Russians, not pussies, these guys are real chemists. They take a kitchen jar and shake it so violently that the bottom falls off, but hey - they still reduce nitropropene to amine, so save your advices.

hypo

  • Guest
why i like mercury
« Reply #25 on: July 08, 2004, 03:54:00 PM »
> I'm still wondering why you all like Hg that much

1) the name
2) the only liquid metal at RT (alright, gallium is cool too)
3) perfectly OTC (hint: mercury switch)
4) a flask full of mercury is surprisingly heavy
5) salts are surprsingly heavy too
6) salts have all kinds of colors
7) gives funny bubbles when spilt
8) scares the shit out of chemophobics
9) unique chemistry (amalgams/overvoltage)
last but not least:
10) it just works.


armageddon

  • Guest
mercury fanatics all over the place?
« Reply #26 on: July 08, 2004, 04:56:00 PM »
To Vitus: Indeed, you don't have to eat it, inhaling Hg vapors over extended time periods is very unhealthy as well! And disposing properly of something covering your laboratory ceiling? Have fun with that - without me... ;)

To Capn_America: well, where I live, we usually make jokes about "the russian method" and so on whenever something involves old-fashioned BIG-scale equipment, huge amounts of tech-grade solvents, heating pressurized pipe bombs, reacting huge amounts of toxic/hazardous compounds without proper safety precautions etc. - so to say whenever something DANGEROUS is attempted at big scale, but without good equipment/good resources (which surely is related to the bad, bad infrastructure in russia, forcing the poor, but indeed often ingenious chemists to use outdated, tedious procedures rather than the state-of-the-art high-tech thingys they surely would like to do instead).
But since I don't live in russia: no mercury for me please - at least not in this thread *lol*...

To Hypo: Wait, lemme guess: H2S is another favorite chemical for you, as it stinks, is a gas, forms funny coloured sulfides... - I'm lucky I don't have to work in your lab!

(two reasons against using Hg: 1. It's toxic 2. Other non-toxic chemicals do the same job better - now you again!)


C'mon guys, I don't question your credibility or anything else by not mentioning your preferred reducing agent - it is just that I personally dislike Hg and therefore I decided time ago to start a thread dealing with other, not-so-dangerous reagents suitable for arriving at subst. amphs - so why this "Mercury over all"-movement?  ;D

Greetz A


Captain_America

  • Guest
well, where I live, we usually make jokes...
« Reply #27 on: July 08, 2004, 05:27:00 PM »
well, where I live, we usually make jokes about "the russian method" and so on whenever something involves old-fashioned BIG-scale equipment, huge amounts of tech-grade solvents, heating pressurized pipe bombs, reacting huge amounts of toxic/hazardous compounds without proper safety precautions etc. - so to say whenever something DANGEROUS is attempted at big scale, but without good equipment/good resources (which surely is related to the bad, bad infrastructure in russia, forcing the poor, but indeed often ingenious chemists to use outdated, tedious procedures rather than the state-of-the-art high-tech thingys they surely would like to do instead).
But since I don't live in russia: no mercury for me please - at least not in this thread *lol*...


You really like to talk a lot. What does the state-of-the-art equipment has to do with chemistry? I suggest you to read some old chemistry books;

http://bcis.pacificu.edu/~polverone/

. Too bad the soul of the organic chemistry is slowly dying with the introduction of these computerized robots where you push buttons. Back to the topic, the most simple way for a basement shaman to reduce a nitropropene to amine in one good-yielding step is by using the kvicksilver aluminium amalgam. I would vote for it any day. Once you've obtained couple of grams of Hg (II) salt, you never again have to worry about reductions. It simply lasts forever. How about that? Only downside is Al(OH)3.

hypo

  • Guest
ok
« Reply #28 on: July 08, 2004, 11:52:00 PM »
> two reasons against using Hg: 1. It's toxic 2. Other non-toxic chemicals do
> the same job better - now you again!

1) mercury isn't dangerous when handled correctly (where i live we
store chemicals in closed flasks) and every chemist should be able
of handling 100mg of HgCl2 without poisoning himself/others
2) you failed to provide any alternative which matches mercury in
OTCness/easiness:
Zn: not as OTC/from what i've heard equally annoying workup
Pd/C: not nearly as OTC/much harder to make than HgCl2
NaBH2: not nearly as OTC/much harder to make than HgCl2

sure, if someone had free access to chemicals, then nobody would use Al/Hg
reductions (not because of it's toxicity but rather because of the annoying workup),
but the interesting thing about clandestine chemistry is that people have other
constraints like OTCness.


GC_MS

  • Guest
Hg
« Reply #29 on: July 08, 2004, 11:59:00 PM »
why i like mercury

hypo, you forgot to mention it is a very useful substance to eliminate idiots from our Planet.


armageddon

  • Guest
ok I see
« Reply #30 on: July 09, 2004, 04:34:00 AM »
I see, mercury has its place in your chemical education, you love it, can't get other reducing agents, are simply charmed by the alchimist attitude arising from Al/Hg containing bubbling glass bulbs with huge condensers - might I again mention for my defense that I started this thread with the intention of simply gaining a quick overview of reduction methods besides mercury/"kvicksilver" (and other dangerous..)? That it is part of my chemical education to avoid the use of toxic compounds wherever possible (not only because of health concerns - but environmental/ecological reasons too)? And finally, that the leuckart (or dithionite reduction of P2Ps to their oximes and then to amines with Zn/NH4Cl) are at least as OTC and "old-fashioned" (keeping the spirit of oldschool organic chemistry alive, although partly adapted from newer scient. papers) as the Hg mess you seem to celebrate with joy/pride?  ;D

(don't take it personally, just think about the fishes - or about all the money you have to spend when regularly disposing of Hg waste. Not that I have never touched mercury - I have some 100g of HgCl2 lying around - but it is simply not necessary to dissolve tiny amounts of a deadly poisonous (even if handled correctly!) substance in huge amounts of liquid again and again)

A


GC_MS

  • Guest
Toxic
« Reply #31 on: July 09, 2004, 04:36:00 AM »
That it is part of my chemical education to avoid the use of toxic compounds wherever possible (not only because of health concerns - but environmental/ecological reasons too)?

Everything is toxic. How often do I have to paraphrase Paracelsus...


armageddon

  • Guest
don't think
« Reply #32 on: July 09, 2004, 04:42:00 AM »
I don't think that "a bit of poison now and then" matches with the toxic properties of mercury..

many things are toxic in larger amounts (borohydride for example) - mercury is very toxic even in trace amounts, it accumulates in your body, no matter how small the amount you ingest/inhale is, and pure mercury is the worsest of all: spillages require thorough decontamination of affected areas as it splatters everywhere, forming the nice little droplets hypo loves so much...

(have fun with it! You will surely remember me if you have to wipe up said mess - and it will happen sooner or later to everybee of you)

Hypo: "where I live.." - I dunno where you come from, but most contries consider mercury as poisonous, whereas zinc is only considered "irritating" (if anything at all), and so does mine. Here obtaining zinc granules, powder etc. is NO problem, but even the mercury switches contain very tiny Hg amounts (if any - gallium/indium is used more often nowadays as it is not as toxic as mercury, and same thing with thermometers...). But if you like, just use Hg amalgam as you are used to. I'm not trying to convince anyone - only to justify why I decided to exclude your favourite heavy metal from my reducing agent overview..

A


armageddon

  • Guest
real russian style harcore chemistry
« Reply #33 on: July 09, 2004, 05:24:00 AM »
Dear Captain "shaman" America: I think if I meant high-tech chemical laboratory eqipment, you can say that high-tech is well related to chemistry. And I meant chemistry related equipment. (BTW I know several old organic chemistry textbooks)

Are you proud about the poor infrastructure russia has to offer? Or proud about being able to shake a kitchen jar until it explodes?  :(

Or did you simply want to show the friendliness of a russian chemist when telling me to keep my advice for me??
(do you want to encourage others to stop posting useful tips? then go ahead.. I don't remember who asked YOU about your opinion??)

>:(  A  >:(


Organikum

  • Guest
Look here armageddon:
« Reply #34 on: July 09, 2004, 06:32:00 AM »
Krause: Chem. Ztg. 40, 810, (1916)

Post 474887

(lugh: "Requested Article", Chemistry Discourse)

This might answer some questions and show better ways. With iron filings and HCl to amphetamine directly from the nitrocompound. In almost quantitative yields.

And please do us the favor and stop this mercury hysteria. CHEMOPANIC! If you dont like it, dont use it but dont start a crusade.
btw. H2S, Cl2 and Hg are very useful (and chloroacetone, BzCl, benzene, chloroform ....) and no big deal when basic lab-safety is applied.

Stop telling whats allowed and whats not - there is to many forbidden already on this world and actually we all are here at the-hive because we dont listen when somebody says "nono!"  :)

ORG


hypo

  • Guest
sheeesh....
« Reply #35 on: July 09, 2004, 07:32:00 AM »
what reaction are you talking about?

> are simply charmed by the alchimist attitude arising from Al/Hg
> containing bubbling glass bulbs with huge condensers

you can do up to 100g batches without problems in standard glassware.
just because you messed up one certain Al/Hg doesn't mean that all suck.

> And finally, that the leuckart (or dithionite reduction of P2Ps to
> their oximes and then to amines with Zn/NH4Cl) are at least as OTC

err... no. formic acid or dithionite are not as OTC as mercury switches.

> but even the mercury switches contain very tiny Hg amounts

hogwash.
the big mercury switches (about $10) contain 15-20g mercury. that should
last a lifetime for a smallscale cook. as opposed to Zn, the Hg is not
the reducer.

> I'm not trying to convince anyone

doesn't sound that way.

ps: i don't like H2S, but sulfur is one of my favorite elements, that's true.
very rich chemistry  :) . and it's cool for neutralising mercury spills too.


_mu_

  • Guest
, and pure mercury is the worsest of all:...
« Reply #36 on: July 09, 2004, 09:17:00 AM »

, and pure mercury is the worsest of all:


Then, maybe you shouldn't do chemistry.  If you can't stand the heat, don't get even close to the kitchen.

armageddon

  • Guest
Hg thread opened!
« Reply #37 on: July 09, 2004, 10:24:00 AM »
OK there we go, I declare this the official MERCURY-THREAD!  ;D

Come on, you are invited to post! (obviously you need some place to talk about Hg..)

BTW I did in no way try to tell anyone what to do or not, did I?? Nor am I a "chemopanic" - just not "chemophile"!!

(OK some nasty compounds are pretty useful, and even Hg might be: but WHY DO YOU GUYS WANT TO DISCUSS THIS REDUCING AGENT IN THIS THREAD??)  ;D  ;D

Anyway, go ahead: I think I expressed clearly enough what I think about your BELOVED mercury and therefore I think I won't participate any longer in this discussion..  ;)

Greetz A


armageddon

  • Guest
did I mention
« Reply #38 on: July 09, 2004, 11:11:00 AM »
Did I mention how FUNNY it is being flamed for saying "mercury amalgam reductions don't belong here" in a thread starting with the words

I have just tried to remember all possibilities for going from a nitropropene to an aminopropane that explicitly don't use mercury amalgams, lithium aluminium hydride, pressurized hydrogen or other hazardous reagents.


 - and being further flamed for saying "mercury is toxic"...

but that's OK. I have bad days too.

(Organikum: let me know if you happen to successfully reduce P2NP to amphetamine with iron filings/HCl - I'm looking forward to read about this revolutionary, simple, totally unknown method - noone ever heard of it during the last >80 years, hm?..)


Rhodium

  • Guest
Everybody is entitled to have incorrect opinions
« Reply #39 on: July 09, 2004, 12:11:00 PM »
I don't want to see any more comments from either side of the camp regarding their opinions on either mercury or their rhetoric opponents - consider anything in that direction as a request for the thread to be closed.


armageddon

  • Guest
really!?
« Reply #40 on: August 11, 2004, 07:59:00 PM »
"Everybody is entitled to have incorrect opinions"

I don't think so.
The following text passage is simply copied from the "HIVE laboratory and safety data sheets", found here

Post 440024 (missing)

(LaBTop: "©HIVE® Laboratory Safety & Data Sheets", Newbee Forum)
....




M

MERCURY , MERCURY SALTS SAFETY

Practical considerations when working with elemental mercury in the laboratory.

SEARCH keywords : mercury , Hg , Hg salt , toxic , practical , spill , clean up , thermometer , liquid , metal , reuse , recycling ,  dimethylmercury , lab , laboratory , environmental , precaution , procedure , element , poison , poisoning , health , safety .

Is there a medical test to show whether I've been exposed to mercury?
Tests are available to measure mercury levels in the body. Blood or urine samples are used to test for exposure to metallic mercury and to inorganic forms of mercury. Mercury in whole blood or in scalp hair is measured to determine exposure to methylmercury. Your doctor can take samples and send them to a testing laboratory.

INDEX:
Introduction and Background
Working With Mercury in the Laboratory
Recycling Mercury in the Laboratory
Risks and Environmental Impact
Further Resources

Introduction and Background

With proper controls and training, elemental mercury , Hg , can be safely used in a laboratory setting.  However, when spilled or misused it can present a significant hazard; see Cleaning Up The Quicksilver Mess
(

http://www.msta-mich.org/publications/newsletter/newsletter.september00/mercury.html

) for a chilling example.  Therefore, minimize your use of mercury and mercury compounds whenever possible.

Small amounts of mercury residues left behind on contaminated glassware can be removed (dissolved) with a dilute nitric acid solution, HNO3. Be sure not to pour the acid waste down the sink. Collect the used acid solution in a waste container that is used only for mercury-contaminated nitric acid waste and dispose of it properly.

The element mercury is a liquid metal with a vapor pressure of 0.00185 mm at 25 degrees C. This corresponds to a saturation concentration in air of 20 milligrams of mercury per cubic meter of air or 2.4 ppm . The American Conference of Governmental Industrial Hygienists has established a threshold limit for mercury vapor of 0.05 milligrams of Hg per cubic meter of air for continuous 40 hour per week exposure. Long term chronic exposure to mercury vapor in excess of 0.05 mg Hg per cubic meter of air may result in cumulative poisoning. The use of mercury in laboratory amounts in well-ventilated areas is fairly safe; however, mercury can present a health hazard under the following circumstances:

. . . When a mercury spill is not cleaned up promptly it may be ground into the floor, fracturing into extremely small particles with a large total surface area (6.4 ft for 1 ml as 10 micron spheres). From such large areas mercury may vaporize at a rate faster than the room's ventilation can safely dilute it.

. . . The rate of mercury volatilization is directly related to temperature. Whenever elevated temperatures are involved special care must be exercised to provide adequate ventilation. A common occurrence is the breaking of thermometers in ovens due to bumping or raising the oven above the thermometer's capacity.

. . . The impact of mercury at high velocities or its release into high air velocity systems will atomize mercury into extremely small particle sizes and large surface area. This generally results from inadequate connections in pressure systems.

. . . Mercury is often dumped into drains. These drains may eventually leak and a workman using a torch to free the joints may, as the result of another's carelessness, receive an overexposure. [Such releases are also a violation of EPA regulations].
 
Mercury compounds can be quite dangerous. A professor at Dartmouth University (an experienced researcher and expert on the toxicology of heavy metal poisoning) died in 1997 after spilling just a few drops of dimethylmercury on her latex gloves (

http://www.denison.edu/naosmm/topics/dartmouth.html

).
In case of underground chemists, the chance to ever work with methyl or dimethylmercury is neglectible small.

Working With Mercury in the Laboratory
Whenever you perform any action with mercury it will spill and splash. It inevitably forms tiny beads that cling to many surfaces and roll several feet away. Large drops quickly break up into thousands of small ones as described above.
Mercury can be handled safely by a professional chemist, although you should minimize or eliminate its use whenever possible. Here are some prudent practices when using mercury:

1. Find an alternative to using mercury in the first place:

   a. Use alcohol thermometers instead of mercury ones.

   b. Use oil bubblers instead of mercury bubblers when possible.

   c. Consider using reducing agents other than mercury amalgams in your laboratory procedures.

2. NEVER use a mercury thermometer in a laboratory oven. If it breaks in a hot oven, you have not only the obvious health concern, but also a possible unavoidable HazMat response situation. You'll have to shut down your lab completely, probably for several days, for cleaning and testing. The oven will have to be disposed of as hazardous waste. A break in a cold oven is an equally serious situation.
   The cost of cleaning up a thermometer break in a laboratory oven far exceeds that of a new laboratory oven with a built-in digital temperature display and fail-safe mechanism.

3. Do not leave open containers of mercury in the laboratory. If used in a bubbler, the exhaust should go up a vertical tube to eliminate splashing and should be vented to a fume hood.

4. Do not keep excess mercury around if you do not need it.

5. Clean up spills promptly. When handling mercury use a glass, plastic or steel tray to contain any spills that might occur. Caution: mercury amalgamates with many common metals such as aluminum, so choose your container carefully.

6. Glass or plastic vessels should have a secondary steel or plastic container around them in case the vessel fails.

7. Do not use mercury where it could contact a hot surface and vaporize.

8. Avoid inhaling mercury vapor and use suitable gloves when working with it.

9. Put mercury waste in a special waste container. Do not combine it with "regular" organic or inorganic wastes. NEVER dispose of it down the sink!

10. Do not wear gold or silver jewelry when working with mercury; it will amalgamate and irreversibly damage your jewelry!

11. Although not a safety issue, mercury is very expensive to dispose of as waste.

12. Take appropriate measures in the event of a spill. Sprinkling elemental sulfur on spilled mercury is virtually ineffective; the reaction between Hg and S is not appreciable at room temperature. Amalgamation with fresh zinc dust works fairly well for "soaking up" those noisome tiny beads of mercury once the bulk of the spill has been collected manually.

13. Read the Material Safety Data Sheet (MSDS) for mercury before using it. As indicated on the MSDS, mercury is dangerously incompatible with aluminum, ammonia, chlorates, copper, copper alloys, ethylene oxide, halogens, iron, nitrates, sulfur, sulfuric acid, oxygen, acetylene, lithium, rubidium, sodium carbide, lead, nitromethane, peroxyformic acid, calcium, chlorine dioxide, metal oxides, azides, 3-bromopropyne, alkynes + silver perchlorate, methylsilane + oxygen, tetracarbonylnickel + oxygen and boron diiodophosphide.

14. As with most other chemicals in your laboratory, access to mercury should be restricted to a locked cabinet or room. Do not leave mercury where a passerby or unauthorized person can swipe it (see the Quicksilver Mess article above).

Recycling Mercury in the Laboratory
Those who use mercury know that clean mercury has a wonderfully shiny surface. But over time, the mercury in your bubbler or diffusion pump tends to get dirty and contaminated, usually with a floating film of gray/black sludge. While you certainly need to clean your apparatus, you can easily recover most of the mercury for reuse rather than replacing it. This saves on disposal costs and reduces the amount of mercury you need to use.
The "best" cleanup method in a chemical sense would be distillation However, boiling mercury and then cleaning up the distillation apparatus afterward is not appealing for a number of obvious reasons. Luckily, there are two easier methods that work quite well for most needs. Before using either of these, set up a large steel or plastic spill tray in a fume hood! Do not try this on the bench because you will spill some mercury :

  1. The syringe technique. Get a 10 mL syringe with needle. Stick the needle below the surface of the contaminated mercury and withdraw clean mercury. Hold onto the syringe with both hands when you withdraw it, keeping the syringe vertical and holding the plunger to prevent/reduce mercury from dribbling back out. Transfer the mercury to your recovery vessel (which should be only an inch or two away).

  2. The filter paper technique. Fold a filter paper into quarters and then rip a tiny hole in the bottom of the cone. Place the paper in a glass or plastic funnel with the stem of the funnel as close to the bottom of your collection vessel as possible (to minimize splashing). Slowly pour your contaminated mercury into the filter. Most of the sludge will remain behind on the filter paper. You may need to refilter one or more times.
 
Clean mercury has a mirror-like surface. These cleanup methods work because the sludge is insoluble and less dense than mercury. If your mercury is contaminated with a metal that has amalgamated such as sodium, you may be able to remove the metal chemically, for example, by quenching the sodium metal using established procedures. If the metal is not easily or safely removable through such chemical means, then proper disposal (rather than dealing with distillation) is your best option.

Small amounts of mercury residues left behind on contaminated glassware can be removed (dissolved) with a dilute nitric acid solution. Be sure not to pour the acid waste down the sink. Collect the used acid solution a waste container that is used only for mercury-contaminated nitric acid waste and dispose of it properly.

Risks and Environmental Impact
Remember, inhalation is the primary danger from mercury, especially if there is no good ventilation.
Brief, one-time exposures on the skin (from handling mercury) or even ingestion (it has been used as a laxative) are not likely to produce significant health effects in most cases, but don't test your luck. Chronic (long-term) exposure of any sort can lead to all sorts of nasty effects including permanent central nervous system damage, fatigue, weight loss, tremors, personality changes and death.
Because of the ease with which mercury is spilled, the difficulty of ensuring complete cleanup, the curiousity factor of a room temperature liquid metal, and the known health risks, it is recommended that mercury use for fresh Newbees be discontinued entirely. This includes both mercury-containing compounds as well as equipment such as thermometers.

Further Resources
ATSDR has a Public Health Statement (

http://atsdr1.atsdr.cdc.gov/ToxProfiles/phs8916.html

THE MOST EXTENSIVE MERCURY FACTS SOURCE THERE IS !!!) as well as a Toxin FAQ (

http://atsdr1.atsdr.cdc.gov/tfacts46.html

) on mercury.
Mercury In Schools (

http://www.mercuryinschools.uwex.edu/

) is an excellent site with lots of additional information.
UNL has a page briefly detailing how to handle mercury spills in the laboratory (

http://bifrost.unl.edu/ehs/FactSheets/mercmetl.html

).

MSDS DATABASE

Search the SIRI MSDS database or check for an MSDS direct from the manufacturers lists, or, if you need chemical toxicity data , you can search Toxicology Reports here as well (These are NOT MSDSs), you can also search via CAS numbers you can find in chemicals catalogues :

SIRI MSDS Index :

http://hazard.com/msds/



MSDS Translation and MSDSs in languages other than English :

http://hazard.com/msds/language.html

  :

3DWord ,

http://www.3dword.com/msds.htm

MSDS translation to all major languages
Racco Safety ,

http://www.raccosafety.com.br/

  (Brazil) MSDS in Spanish and Portugese
Dell Tech- MSDS Authoring in English, French and Spanish ,

http://www.delltech.com/


Pro-Active Translations ,

http://hazard.com/msds/www.biomedtranslation.com


MSDS-Mexico ,

http://www.msds-mexico.com/

Automatic or manual creation of MSDS in Spanish
Harris ,

http://www.harrisind.com/spcat.htm

  Safety warnings and signs in Spanish
MSDS and Safety information in Italian ,

http://www.eidos.it/



Internet Resources for MSDS :

http://www.ilpi.com/msds/


Scroll down !!!






Remember there are lots of other reducing agents besides mercury amalgams, and then remember those words:

"Mercury can be handled safely by a professional chemist, although you should minimize or eliminate its use whenever possible. Here are some prudent practices when using mercury:

1. Find an alternative to using mercury in the first place:

   a. Use alcohol thermometers instead of mercury ones.

   b. Use oil bubblers instead of mercury bubblers when possible.

   c. Consider using reducing agents other than mercury amalgams in your laboratory procedures."
...

...and think about it... ;)

Greetz, A