Author Topic: Nitroethane (Read 2059 times)

Naf1 · « **Reply #40 on:** December 08, 2009, 01:30:49 AM »

"The obvious issue is that since nitration of 2-chloropropanoic acid would involve a secondary halide, it might prove difficult or impossible to do."

That is fine!

"Method 7: destructive distillation of alpha-bromopropionic acid with sodium nitrite

K2CO3 + NaNO2 + H2O + a-br-propionic acid ? nitroethane 50%yield

Add 20g of the acid to a solution of K2CO3 in the amount of base that causes the solution to be basic to phenolphthalein. The add 20g of NaNO2--there should be approx. 100ml of solution. Place in a 250ml rb flask and distill quickly- the first 100ml will come over before the rxn takes place. Then the nitroethane comes over. Distill until no more product comes over.(don't distill to dryness)

V. Auger. Bull. Soc. Chim. FrancePost no. 3, 23, 333 (1900) by the kolbe method."

"Method 17: Distillation of alpha-bromopropionic acids with NaNO2 in the presence of Magnesium Sulfate in DMSO

US pat # 4319059"

(the alpha-bromo acid can be obtained using propionic acid in the procedure from Org. Synth. CV 1, 115.)

http://www.designer-drugs.com/pte/12.162.180.114/dcd/chemistry/nitroethane.html

Well done!

shroomedalice · « **Reply #41 on:** December 08, 2009, 07:35:35 AM »

I have known a few people who tried this.

you have to be carefull how old your alpha bromo proprionic acid is at it will
convert easily to beta bromo on its own.

I would sujest make it and use it as you need it.

the chloro counterpart does not seem to suffer from this problem
hence the availablity of the chloro acid in industry yet not the bromo.

Vesp · « **Reply #42 on:** December 14, 2009, 01:46:17 AM »

http://www.freepatentsonline.com/5998661.html

Preparations of organic nitro compounds through mixed oxidizing agents

A process for selective, direct oxidation of amine or amine hydrochloride mpounds is described. It uses mixed oxidizing agents of monopersulfate and ozone.

Example:
Preparation of Nitrocubane

A solution of 1,3,5,7-tetraaminocubane hydrochloride was prepared in water, 1000 mg in 200 ml. Ozone was slowly added for 20 minutes and at 0 degrees C. A mixture of potassium monopersulfate and NaHCO 3 was added in portions along with 150 ml of acetone. The ozone was discontinued. The reaction suspension became brown and was stirred for 4 hours. The reaction product was filtered and the filtrate was concentrated on a rotary evaporator. The concentrate was extracted with ethyl acetate washed with aqueous HCl and then with brine. H NMR identified a 1,3,5,7-tetranitrocubane product and the yield was 150 mg.

Rumor Has it That:
Ozone can be produced by the electrolysis of a sulfuric acid solution... monopersulfate can be produced by electrolysis I believe, and is OTC...

Edit: WTF does the NaHCO3 do for this reaction? wouldn't it react with the monopersulfate?
... also consider maybe instead of using the salts, use the acids..
So caro's acid .. which is just produced via H2O2 and H2SO4 + more NaHCO3?

shroomedalice · « **Reply #43 on:** December 14, 2009, 02:23:35 AM »

I wonder if ethylbromide and nitrosylsulfuric acid mixed in a sutable solvent with a sodium acetate buffer would make nitroethane.

I know that nitrosylsulfuric acid and ethanol will produce ethylnitrite though the reaction is probably a little too exothermic for use.

micro · « **Reply #44 on:** December 18, 2009, 01:53:52 PM »

So is that monopersulfate the same stuff as "monoperoxysulphate" oxygen shock treatment for pools.
Faggots are phasing even TCCA in favor of "chlorine free" alternatives. And it fucking sucks.

So finding some real use for that crap would be nice

Wizard X · « **Reply #45 on:** December 18, 2009, 11:53:39 PM »

Quote from: Vesp on December 14, 2009, 01:46:17 AM

http://www.freepatentsonline.com/5998661.html

Preparations of organic nitro compounds through mixed oxidizing agents

A process for selective, direct oxidation of amine or amine hydrochloride mpounds is described. It uses mixed oxidizing agents of monopersulfate and ozone.

Example:
Preparation of Nitrocubane

A solution of 1,3,5,7-tetraaminocubane hydrochloride was prepared in water, 1000 mg in 200 ml. Ozone was slowly added for 20 minutes and at 0 degrees C. A mixture of potassium monopersulfate and NaHCO 3 was added in portions along with 150 ml of acetone. The ozone was discontinued. The reaction suspension became brown and was stirred for 4 hours. The reaction product was filtered and the filtrate was concentrated on a rotary evaporator. The concentrate was extracted with ethyl acetate washed with aqueous HCl and then with brine. H NMR identified a 1,3,5,7-tetranitrocubane product and the yield was 150 mg.

Rumor Has it That:
Ozone can be produced by the electrolysis of a sulfuric acid solution... monopersulfate can be produced by electrolysis I believe, and is OTC...

Edit: WTF does the NaHCO3 do for this reaction? wouldn't it react with the monopersulfate?
... also consider maybe instead of using the salts, use the acids..
So caro's acid .. which is just produced via H2O2 and H2SO4 + more NaHCO3?

Sulfuric acid can be produced from ozone, starting either from elemental sulfur or from sulfur dioxide:

S + H2O + O3 ? H2SO4
3 SO2 + 3 H2O + O3 ? 3 H2SO4

http://en.wikipedia.org/wiki/Ozone#Chemistry
http://en.wikipedia.org/wiki/Ozone#Production

Vesp · « **Reply #46 on:** December 19, 2009, 02:24:44 AM »

http://www.google.com/search?client=firefox-a&rls=org.mozilla%3Aen-US%3Aofficial&channel=s&hl=en&source=hp&q=Sulfuric+acid+ozone+electrolysis&btnG=Google+Search

Yep?

headstrong · « **Reply #47 on:** April 15, 2010, 05:04:44 AM »

How about Ethyl Phosphate, can it be used as Ethyl Sulphate substitute?

Sedit · « **Reply #48 on:** April 15, 2010, 05:08:51 AM »

Given its ethylating potential im pretty sure it could be but one must ask whats the perks...

What would be the ups and downs of such a substitution?

I still feel that Ammonium ethyl sulfate is the future of this synthesis and wish someone with some balls will prove this correct. It works to methylate NH₃ to form methylamine so I see no reason why it would not work in this synthesis.

headstrong · « **Reply #49 on:** April 15, 2010, 06:56:34 AM »

The reply is so fast, thanks.
Ethyl Phosphate, for safety; this substance can be made in mild rxn compare to ethyl sulphate, less by product like diethyl eter. Less toxic.

I also interest to Ammonium ethyl sulfate route, and i just posted a thread "H2SO4 addition into allylbenzene" that very related with "It works to methylate NH3 to form methylamine so I see no reason why it would not work in this synthesis." Please check that thread.

SOMA · « **Reply #50 on:** April 15, 2010, 10:42:55 AM »

An idea would be making 2-chloropropionic acid from alanine, HCl and a nitrate (as in the known patent) making a solution of the same in DMSO and adding this same solution to a solution of NaNO2 and MgSO4 in DMSO at the boiling point of nitroethane while distilling the formed nitroethane.

coincoin · « **Reply #51 on:** July 28, 2011, 07:23:07 PM »

Has anyone ever been able to actually produce EhNO2 in yield ? ... Seen a lot of post here and there but almost none mentioning success / failures from personal tryouts.

...didn't mean to be rude by the way... just asking

JustDreaming · « **Reply #52 on:** August 05, 2011, 06:03:44 PM »

I was curious about nitroalkanes some time ago. Surprised I haven't seen this reference posted here. It may have been written in 1944, but any chemist working out lab scale preparations via journal should not fall on deaf ears imo. Pretty decent yield(65%), and good information about reaction conditions, lackadaisical synth too.

I suppose my largest question is though, are they using diethyl sulfate? They refer to ethyl sulfate in the text, although in the table they show Et2SO4. I see no reason why they would use the dialkyl, so I'm assuming this is not the case.

Vesp · « **Reply #53 on:** August 05, 2011, 08:29:58 PM »

It looks like it is the diethyl sulfate used.

Made fairly easily...

Quote

Procedure

Ninety grams of sodium sulfate is placed in a dry 1 liter flask connected with a condenser and a receiver arranged for vacuum distillation. The flask is heated by means of an oil bath to 155-165°C. The apparatus is exhausted as nearly as possible by means of a filter pump, and misture of 50 grams of ethanol and 104.5 grams of concentrated sulfuric acid is allowed to drop through a capillary tube on the sodium sulfate at a rate of 120-150 drops per minute. The distillation of the mixture requires about one and one half hours for completion. The distillate, which consists of ethanol and diethyl sulfate is poured into a separatory funnel, the ethanol may be recovered for further use. The diethyl sulfate is washed with a dilute solution of sodium carbonate and then several times with cold water, then dried with anhydrous sodium sulfate, yielding 32.4 grams.

Reference: JACS 46, 999-1001 (1924)

Seems like an over all acceptable process.

JustDreaming · « **Reply #54 on:** August 05, 2011, 11:34:27 PM »

Now that is a bit of a let down. The preparation of diethyl sulfate and even dimethyl sulfate sound reasonable indeed. Although the inherent toxicity and proposed carcinogenicity have both of these reagents off of the ''usable'' list(for myself personally).

Suppose it's one of those cases in the literature where the naming is nearly misleading. Something about di-esters and naming has always troubled me. "methyl oxalate" implies di-methyl oxalate, which of course is somewhat obvious knowing the structure of the compound, though is frustrating imo. Especially considering there is ethyl sulfate and diethyl sulfate, both with very different applications.

Sorry for running off on a tangent. Hmm...

b6baddawg · « **Reply #55 on:** September 16, 2011, 07:40:52 PM »

someone said msds is your friend. not always the nitroE gets replaced and the label doesnt always reflect this, them kinda "legit" sources arnt forever either.
i had two not no more..

theres a few synths on here what arnt really cost/economically effective for the time n effort $:-\$

vapour phase nitration looks ok but the conversion takes place over multiple feedback loops i dont have a fucking clue how to build that into a system? without it its like 3-6% yields of mixed fractions. i seen 5 feedback loops in a patent mentioned giving good conversion rates when you consider cost

a salt reactor to stabilise temps looks promising. flow rate can be controlled and contact times are all doable with a bit of math and patent examples, the fractions can be manipulated a little to give more nitroE and nitroM but it needs feedback loops built in to recycle whats going in what hasnt been converted to be cost effective.

seems once feedback loops are incorporated it involves a pressured reactor. sounds scary to me, blow outs from incorrect mix etc without pressure arnt a worry, under pressure.. hmmm

how about ideas for the feedback loop system anyone? solve that safely and its a winner. once the sytem built 100 bucks of material will give gallons of nitroE and M

Tsathoggua · « **Reply #56 on:** September 16, 2011, 09:23:40 PM »

Are you saying, without naming sources (don't do it, not appropriate here at all!) that some unscrupulous fuckwits have been supplying fake nitroethane? Toady always has got his from reputable businesses that would neither do such a thing, nor ever dare to, as they would be ruined. Or from individuals who are just out to do good business, and earn an honest wage doing so, so is unlikely to face that issue.

But what happened? Ye Olde One cannot think of many things that would be able to replace EtNO2 and successfully pose as it. It smells quite distinctive. Maybe a mixture of acetone and benzaldehyde would smell similar, he thinks so...MeNO2 smells very similar to identical of course. A mixture of acetone an BnCHO would be easily detected however by attempting reaction of a small amount with bisulfite, forming a crystalline adduct. (quick question btw....do ketones form bisulfite adducts just as aldehydes do? one would think so, but it never hurts to enquire and learn)

b6baddawg · « **Reply #57 on:** September 16, 2011, 10:29:01 PM »

Tsathoggua

well its not so much unscrupulous fuckwits, its companies changing to alternative solvents/degreasers which doesnt affect the product, theyre maybe using a lesser nitro compound instead. i mean as an example if you look at a tin of paint the contents can vary in % massively it may say <25% nitroE and 5>-<30% nitroX(which ever lesser one i dont remember offhand) ok theyre using mixed fractions but nitroE may be getting removed as its economically viable to do so. they might not have used nitroE in the fraction for years but theyre under no obligation to remove it from the possible contents. besides it costs money to change a label.
my example is fictional, but look at products and youll get what i mean.
so will the bees whose distilled a product and found.. nothing.

itll get phased out one day better to be one step ahead and like this thread discuss alternatives -OTC etc.

Sedit · « **Reply #58 on:** September 17, 2011, 08:31:45 AM »

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.

Sedit · « **Reply #59 on:** September 17, 2011, 12:03:45 PM »

Oxidation from what the HNO₃? I don't even think standard nitrating reagents work on acetone but I could be wrong.

Please explain your logic and mechanism for the formation of Nitromethane. If this is case it would be even better because MEK should cleave to form Nitroethane directly. When dealing with such available and cheep reagents even low yields would be highly acceptable.

I however really need to see a reference for the claims your making because I just can't envision how this would proceed to form the products you mention.

Author Topic: Nitroethane (Read 2059 times)

Naf1

Re: Nitroethane

shroomedalice

Re: Nitroethane

Vesp

Re: Nitroethane

shroomedalice

Re: Nitroethane

micro

Re: Nitroethane

Wizard X

Re: Nitroethane

Vesp

Re: Nitroethane

headstrong

Re: Nitroethane

Sedit

Re: Nitroethane

headstrong

Re: Nitroethane

SOMA

Re: Nitroethane

coincoin

Re: Nitroethane

JustDreaming

Re: Nitroethane

Vesp

Re: Nitroethane

JustDreaming

Re: Nitroethane

b6baddawg

Re: Nitroethane

Tsathoggua

Re: Nitroethane

b6baddawg

Re: Nitroethane

Sedit

Re: Nitroethane

Sedit

Re: Nitroethane