Author Topic: Nitroethane  (Read 2059 times)

b6baddawg

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Re: Nitroethane
« Reply #60 on: September 17, 2011, 04:41:50 PM »
Has anyone come up with a simple means for the mono nitration of Acetone? This would be the holy grail of Nitroethane synthesis if it could be accomplished. Reduction of the ketone using amalgumated Zinc could in theory produce gallons of Nitroethane cheep as chips.

"25g 1-nitropropan-2-ol and 37.5g sodium dichromate are mixed in 25mL water. 35mL of 60% sulfuric acid are then slowly and periodically added to the solution over a period of 4 hours, keeping the temperature below 14 degC at all times.
A dark green crystalline substance was then extracted from the solution using ether. Crystals of nitroacetone form after the ether evaporates. The crystals are then recrystallized from methanol (to give a purer product). The resulting nitroacetone from this procedure melts at 46 degC"

nothing simple~economic.  preparation of 1-nitropropan-2-ol involves nitromethane as far as im aware.
mindyou, its a mixed fraction formed during vapour phase nitration, maybe useful one day eh.

andershoveland tried this,  bubbling no2 directly into acetone. he elaborates in scimadness. theres a mention this was tried years ago and an improvement on the bottom link. seems he deviated from the example in urbanski and not for the better.
hXXp://sites.google.com/site/energeticchemical/exeriments.

this link answers a lot of questions on the thread. its 645 pages long though.
hXXp://www.docstoc.com/docs/17302102/Chemistry-and-Technology-of-Explosives-vol-1-by-Urbanski


 i saw this mentioned on scimadness, "mixed Kolbe electrolysis with NaNO2 to provide nitrocarbons (propanoic acid yields nitroethane aside with butane" anyone familiar?


« Last Edit: September 19, 2011, 04:48:49 AM by b6baddawg »

Tsathoggua

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Re: Nitroethane
« Reply #61 on: October 03, 2011, 06:46:28 PM »
Might want to watch it around N2O4. That stuff is a BEAST of an oxidant, and is hypergolic with some organics. IIRC they use a mixture of hydrazine and N2O4 as a hypergolic bipropellant in space rockets. Very, very very poisonous stuff, and extremely reactive. I would expect it to start fires on contact with almost all organics, including lab benches, clothing, lungs, bee wings......vicious stuff to say the least. Oxidising organics with it sounds like a recipe for it to go up in your face.

Only the most unreactive solvents could be used to handle it. Boiling point is listed in wikipedia as 21.1 degrees C, freezing not far below that. Dissociates into nitric oxide when heated or compressed. I'd imagine one needs something like a fluorinated solvent, liquid SO2 perhaps, and I imagine carbon tet, which is again pretty heinous stuff.

I certainly wouldn't want to be around when its mixed with acetone. I imagine that a fully closed-circuit air supply with inert polymer seals is required, breathing any of this stuff will tear your respiratory system to pieces. N2O4 is right up there with fluorine gas, chlorine trifluoride, ClF5, peroxygen difluoride, etc. in terms of 'fucking nasty'

Probably safer to email the DEA and ask if their drug lab has any nitroethane handy they could spare :P
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akcom

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Re: Nitroethane
« Reply #62 on: January 01, 2012, 09:02:58 PM »
You're paying out the ass for AgNO2 (3 equiv to your haloalkane).  You're better off just buying a liter of nitroethane from overseas at that point

Gypsy

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Re: Nitroethane
« Reply #63 on: February 20, 2012, 03:00:22 PM »
haha i dont envy you guys.
Im lucky enough to be able to buy both nitromethane and nitroethane legitimately and locally for only 100USD for 2.5l CP grade. 150 with shipping.

Vesp

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Re: Nitroethane
« Reply #64 on: February 21, 2012, 07:39:47 AM »
It
buying a liter of nitroethane from overseas at that point
Buying List 1 chemical from abroad? Are you ok?
The above paper is a general method of preparation of nitroalkanes from alkyl bromides or iodides with very easy workup and high yields. Maybe I should have uploaded in a different topic.

It really works, and is easy.. with high yield?

Has anyone done this and can vouch? :P
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akcom

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Re: Nitroethane
« Reply #65 on: March 08, 2012, 06:07:25 PM »
If you want to synthesize 30mL's of nitroethane, reckless's synthesis requires the use of over 280 GRAMS of silver nitrate.  Last I checked 250g of AgNO3 is 750 dollars from sigma aldrich.  Go ahead and try that synth.  Please.

At that point, I would rather pay some shoddy chinese company to mislabel me some nitroethane.

akcom

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Re: Nitroethane
« Reply #66 on: March 08, 2012, 09:07:32 PM »
I was trying to give some casual examples, but lets go for a more concrete one.  Let's say you want 10g of phenyl-2-nitropropene.  Lets assume the henry condensation yields 80% (less is probably likely, but lets be optimistic).  Lets also assume the nitroethane synthesis yields 90% (very unlikely, but lets be optimistic).  That means you're going to need ~58 grams of silver nitrate (~90 dollars) to yield ~6.3mL of nitroethane.  That's assume no mechanical loss and ignoring the solubility of nitroethane in water.

This is an interesting synthesis for sure, but when you can buy a liter of nitroethane for not much more than the cost of the silver nitrate, it doesn't make any sense.  not to mention the work (regenerating your silver nitrate, etc).  There are much more practical uses for silver in the world of underground chemistry.

nk40ouvm

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Re: Nitroethane
« Reply #67 on: March 16, 2012, 12:11:49 AM »
It only makes sense if you recycle your silver nitrate. And if you recycle your silver nitrate there's no reason to buy it from a lab supplier in the first place. You can buy two one-ounce bars or rounds of silver (~62 grams) for about $75 retail. 62 grams of silver will make 98 grams of silver nitrate. The cost of nitric acid is negligible if you already have the glassware; drain cleaner sulfuric acid and fertilizer nitrates are dirt cheap and perfectly acceptable. Silver recycling is easy to do with high recovery rates.

Unlike nitroethane, silver, sulfuric acid, and nitrate salts are unwatched and available OTC in some places. If you have to buy nitric acid through a lab supplier it's uneconomic. I wouldn't import nitroethane where I live, no matter the price; if I want to screw myself to save a buck I could just go straight for imported ephedrine.

Tsathoggua

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Re: Nitroethane
« Reply #68 on: March 16, 2012, 04:43:08 PM »
Buying a bunch of nitrates could raise eyebrows for other reasons than as a drug precursor, bear that in mind. I.e terrorist types spoiling it for the rest of us with ANFO bombs and the like.

For small quantities, some instant cold packs use the endothermic reaction between ammonium nitrate and an inner sachet of water..or outer, I forget. Inner I think. And buying cold packs is not likely to yield any suspicious reactions from busybodying jobsworths, who probably don't know how they work.
« Last Edit: March 16, 2012, 04:44:41 PM by Tsathoggua »
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I'm hyperbolic, hypergolic, viral, chiral. So motherfucking twisted my laevo is on the right side.

java

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Re: Nitroethane
« Reply #69 on: December 01, 2012, 07:08:08 PM »
 oxidation of ethyl amine to nitroethane with dimethyldioxirane

A new synthesis of nitro compounds using dimethyldioxirane(DMDO)
Tetrahedron Letters,Vol.27,No.21,pp 2335-2336,1986

Abstract: Dimethyldioxirane oxidizes primary amines to nitro compounds in a facile, mild, high yield process.


DMDO is not commercially available because of its instability. DMDO can be prepared by the reaction of acetone with oxone, where the potassium peroxymonosulfate is the active ingredient:[1]

.....source,

http://www.erowid.org/archive/rhodium/chemistry/nitroethane.html

Note.

Preparation of DMDO

The preparation of DMDO is rather inefficient (typical yields < 3%) and typically only yields a relatively dilute solution in acetone (only up to approximately 0.1 M).



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 However, this is of no consequence, since DMDO is prepared from extremely cheap starting materials: acetone, sodium bicarbonate, and potassium peroxymonosulfate (commercially known as "oxone"). The solution can be stored at low temperatures and assayed immediately prior to use to determine its actual concentration.
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atara

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Re: Nitroethane
« Reply #70 on: December 01, 2012, 08:53:10 PM »
You guys need to be careful about mixing up silver nitrite and silver nitrate. The former will produce nitroethane, the latter, ethyl nitrate -- a high explosive.

Silver bromide can be reduced by ammonia and a sacrificial aldehyde e.g. glucose. The resulting elemental silver dissolves violently in nitric acid.

phaseolus

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Re: Nitroethane
« Reply #71 on: February 05, 2013, 03:47:40 AM »
The industrial route to nitroalkanes is vapor phase nitration (with nitric acid) of propane at high pressure/high temperature. From there take the nitroethane fraction from nitropropane and nitromethane (just hydrogenate it and you've killed two birds with one stone) among others. The only problem of course is the insane pressures. Fuck that. I read an old paper from around the 50s that described doing the same at atmospheric pressure, but it yields mostly nitropropane. The former industrial technique is a free radical reaction, leading to the cleavage of propane. I wonder if doing the same with ethane will make nitroethane in high purity.

It's also possible to catalytically nitrate methanol using nitric acid at pressures of 6-50 psig/600°C to produce nitromethane. See US patent 4431842 "Catalytic Preparation of Nitroalkanes." Could be bogus. The catalyst can be calcium chloride or barium chloride. You can swap methanol for ethanol. Interestingly it says you can substitute nitrogen dioxide for nitric acid. Nitrogen dioxide can be produced (very inefficiently) from air passing through an electric arc. Think about it. Nitroethane from booze and thin air.

Sydenhams chorea

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Re: Nitroethane
« Reply #72 on: March 09, 2013, 06:38:53 PM »
Quote
andershoveland tried this,  bubbling no2 directly into acetone. he elaborates in scimadness

That guy is well known at scimad for deliberately spreading false information. Don't trust anything he says or claims to have done.
It is perhaps the narcotic. Hyoscine affects certain people very oddly. One cannot be sure. Sometimes, these cases take strange forms. The victim becomes in a sense, 'mediumistic', a vehicle for all the intangible forces in operation around her.

Sydenhams chorea

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Re: Nitroethane
« Reply #73 on: March 09, 2013, 06:44:13 PM »
Nicodem suggested this in the past, it's very straightforward, and I believe nobody has reported result as of yet:
http://www.sciencemadness.org/talk/viewthread.php?tid=909
Quote
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  • posted on 8-3-2005 at 02:46    


As already briefly mentioned by Kinetic, there is also another efficient OTC oxime-to-nitro oxidant, for those of us who can't get Oxone. Sodium perborate in acetic acid oxidizes oximes of many types into their nitro counterparts. Like usually happens when I search for something in the mess of my files I couldn’t find the paper but I think the reference (found in another paper) is Synlett (1992) 337. I remember that the method worked on aliphatic oximes as well.

Anyway, what’s maybe new and more important, pyruvic acid oxime should be as useful (or even more) as a substrate to be oxidized to nitroethane. Pyruvic acid is much more accessible than acetaldehyde or its trimer. It can be made by pyrolisis of tartaric acid in the presence of H2SO4 (a glycol rearrangement to HOOC-CH2-CO-COOH, followed by decarboxylation to Me-CO-COOH). I see no special reason why the perborate oxidation would not work on Me-C(=NOH)-COOH just as it works on other oximes. The beauty is that both the oxime formation and its oxidation can probably be made in one pot. The intermediate 2-nitropropionic acid easily decarboxylates to nitroethane. So you already get your favorite product at the end. Off course, pyruvic acid must be used as an alkali salt in order to form hydroxylamine from H2NOH hydrochloride or sulphate. Alternatively sodium acetate can be used as a base. Luckily calcium pyruvate can be bought online if you look hard enough on the net, so for some there is even no need to make pyruvic acid at all. The reactions involved would be:

Ca(MeCOCOO)2 + 2NH2OH×HCl =[AcOH]=> CaCl2 + 2H2O + 2Me-C(=NOH)-COOH
Me-C(=NOH)-COOH + NaBO3×4H2O =[AcOH]=> Me-CH(NO2)-COONa + H3BO3 + 3H2O
Me-CH(NO2)-COONa + HCl =[AcOH]=> Et-NO2 + CO2

Unfortunately I never was so desperate to try the reaction myself (who needs nitroethane anyway ;) ), but if I would I would do it like this:
I would dissolve the calcium pyruvate in acetic acid solvent and add two equivalents of hydroxylamine hydrochloride. I would then let it reflux for a few hours in order to assure the conversion to the oxime, then add the sodium perborate and continue the reaction by the instructions from the paper (which I can’t find at the moment). At the end I would however add as much of conc. HCl as it is needed to acidify the reaction and continue the reflux for one hour more (a 20% excess in relation to sodium perborate should do). This is because 2-nitro-propionic acid is a considerably stronger acid than acetic acid and is therefore mostly deprotonated due to the formed borate being basic. Its deprotonation would inhibit the decarboxylation step, so the addition of HCl is in order to assure all of the acid decarboxylate to the nitroethane. The work up should be a simple dilution with cold water, separation of the EtNO2 layer (extraction with CH2Cl2 or ether is also advisable), washing with water, NaHCO3, brine and distillation
It is perhaps the narcotic. Hyoscine affects certain people very oddly. One cannot be sure. Sometimes, these cases take strange forms. The victim becomes in a sense, 'mediumistic', a vehicle for all the intangible forces in operation around her.