dildoque (Newbee)
04-18-01 19:10
No 185026
      nitroethane  Bookmark   

The Nitroalkane Preparation FAQ describes the synthesis of nitromethane with mono-chloroacetic acid. Would it be possible to get nitroethane from mono-chloropropionic acid ? 
 
 
 
 
    Rhodium
(Chief Bee)
04-19-01 01:16
No 185108
      Re: nitroethane  Bookmark   

No, that reaction will only work with mono-chloroacetic acid. The intermediate 1-nitroacetic acid is decarboxylated because it has only the electron-withdrawing nitro group on the side chain, while 1-nitropropionic acid would also have a methyl group there, making it more stable.


http://rhodium.lycaeum.org
 
 
 
 
    Greensnake
(Stranger)
04-19-01 18:47
No 185290
      Re: nitroethane  Bookmark   

Not quite so. Problem seems to bee not in ease of decarboxylation, but rather in O/N alkylation selectivity,
which in more sterically congested haloacids shifts toward O and gives wrong products. Nevertheless, I have reference to: V. Auger, Bull. Soc. chim. France [3], 23, 333 (1900) ,which claims, that using alpha-bromopropionic acid in Kolbe method gives nitroethan with yield 50% (thats even better than nitromethane yield from chloroacetic acid) No, I don't have original paper and don't know, if the methodics differs from nitromethane one. Alpha-bromopropionic acid one can probably make from lactic acid and hydrobromic acid boiling them together and distilling or something, but don't quote me on that.
 
 
 
 
    Rhodium
(Chief Bee)
04-19-01 20:48
No 185311
      Re: nitroethane  Bookmark   

Alpha-bromopropionic acid can be made from propionic acid, Br2 and PBr3 (or red P). It is also a name reaction, but I have forgotten the name.


http://rhodium.lycaeum.org
 
 
 
 
    dildoque
(Newbee)
04-19-01 21:42
No 185319
      Re: nitroethane  Bookmark   

Rhodium, Greensnake thanks for this information.

BTW: -Bromopropionic acid may be prepared in 8085 per cent yields by bromination of propionic acid, the general procedure given for -bromoisovaleric acid (Org. Syn. 20, 106) being followed and a fraction boiling at 100102 at 15 mm. being collected.
 
 
 
 
    obituary
(Hive Addict)
04-21-01 02:37
No 185566
      Re: nitroethane  Bookmark   

Rhodium, it's the Hell-Volhard-Zelinsky Rxn you were after.
not that it helps a whole lot, but there you go.  maybe it'll bring back some memories of your Orgo I days.
 
 
 
 
    dildoque
(Newbee)
04-26-01 13:14
No 187031
      Re: nitroethane  Bookmark   

Beilstein 1,100: alpha-bromopropionic acid + K2CO3 + NaNO2 + H2O --distillation--> nitroethane (50%) (Auger, Bl.{3}23,333) laugh
 
 
 
 
    Rhodium
(Chief Bee)
04-27-01 04:29
No 187153
      Re: nitroethane  Bookmark   

!!! Could someone get that reference for us?


http://rhodium.lycaeum.org
 
 
 
 
    hest
(Hive Bee)
04-29-01 17:50
No 187888
      Re: nitroethane  Bookmark   

It goes something like this (my frence is not that god)
add 20g acid to a 20% solution of potasiumcarbonate in such amounth that the solution is basic on phenolphtalin. Then add 20g sodiummnitrit you now have app. 100mL solution.
Add the solution to a 250cc round bottom bulp. Mount a claisen and start destilate with good heath. After the first 100cc has distilatet the reaction takes plase and the nitroethane comes ower, distil until no more product comes ower. yeald app 50%

I'll  give it a shot :-)
 
 
 
 
    hest
(Hive Bee)
04-29-01 20:16
No 187908
      Re: nitroethane  Bookmark   

Wonderfull with another astonish sucses, yeald 18% of not so pure nitroethane ho ho ho. I'll gues that the frog is a beather chemist than mee (or full of lie)
 
 
 
 
    Prdy2GO
(Stranger)
05-02-01 07:13
No 188519
      Re: nitroethane  Bookmark   

hum...


Hum did you get that?
 
 
 
 
    Osmium
(Stoni's sexual toy)
05-02-01 13:36
No 188606
      Re: nitroethane  Bookmark   

According to J. Chem. Soc. 109, 701 (1916) ethyl nitrite can be converted to nitroethane at 120-130C with an asbestos catalyst.
 
 
 
 
    Antoncho
(Newbee)
05-02-01 16:45
No 188626
      Re: nitroethane  Bookmark   

oh my dear friends.
this is not the first time that nitroethane acquisition was discussed here. so like it's been once suggested that one could reduce acetonitrile to ethylamine and then oxidize it. We discussed it with Psyloxy and he told me that dimethyldioxirane would do the job, with excellent yields. i consulted my friends and, can you imagine, it's made really easily. so i decided to put it here. might be useful to someone. that's how it's made.
to conc. H2SO4 there's added an equal volume of 30%H2O2. Slowly and with cooling.  chill to ambient t. then add some acetone slowly, stirring, ice bath. smell it. then add more acetone. when the rxn over it begins to smell of acetone. by that time the soln is filled with white DMDO (insol in water, sol in acetone, ether). wait for 30 min for the rxn to complete. filter. then wash really well, tasting it periodically (not poisonous) - must not be sour. IMPORTANT!!! it will be unstable otherwise. and really easily detonated. will tear your fingers off if you're not careful w/it. in one report 10g of it blew a 3 inch hole in the window sill on which it lay as well as tore apart a 1/4 inch thick screwdriver! with which the uncareful chemist decided to pluck it to see if it's dry. so wash it really well. if pure, it's not that dangerous, as well as in the soln. don't hit it though.
well that's it.
PSYLOXY CAN YOU ELABORATE ON HOW TO DO THE OXIDATION? I am really interested in this 'cause that's how i plan to make nitromethane - lucky you americans, have it OTC - shit i'm so envious :):):)
 
 
 
 
    Osmium
(Stoni's sexual toy)
05-02-01 18:30
No 188642
      Re: nitroethane  Bookmark   

Well, I guess all the Americans are jealous of you because you can get the MeNH2 laugh
 
 
 
 
    hest
(Hive Bee)
05-02-01 20:16
No 188663
      Re: nitroethane  Bookmark   

Antoncho, y'r joking right ?
cyclic peroxides from acetone is not wise to make, they are very unstable and quite explosives, a lot of kids blow off their fingers with this stuff when they try to make a homemade bomb.shocked
 
 
 
 
    foxy2
(Hive Addict)
05-02-01 21:45
No 188681
      Re: nitroethane  Bookmark   

Check out this forum

They have a whole bunch about acetone peroxide, making it safety ect.

The shit sounds dangerous, it would bee easy to get busted/dead if a little of it blew up.


Do Your Part To Win The War
 
 
 
 
    lugh
(Hive Bee)
05-03-01 02:44
No 188750
      Re: nitromethane  Bookmark   

If sodium nitrite can be obtained, there are many safer routes to nitromethane. Perhaps the simplest would be to use the nitration of methanol by means of the method on Rhodium's page. This method hasn't been optimized yet, but IMHO it's worth the effort. Other published approaches are from chloroacetic acid and sodium nitrite (Organic Syntheses, Vol 3 p 83) or from dimethyl sulfate and sodium nitrite (Ber. Deut. Chem. Gesell. 40, 3214, 1907). Direct nitration of propane will produce a mixture of nitromethane, nitroethane and nitropropane, and can be done in electrically heated aluminum tubing using nitrogen dioxide as the nitro source. It's rather likely that methane can be nitrated similarly. If you are experienced in very hazardous synthesis, what you propose may be feasible, but explosives are unforgiving, to say the least.
 
 
 
 
    terbium
(Hive Addict)
05-03-01 03:44
No 188772
      Re: nitroethane  Bookmark   


They have a whole bunch about acetone peroxide, making it safety ect


I spent a year working at a chemical plant that made organic peroxides including methyl ethyl ketone hydroperoxide (MEKP). My opinion is that the term "making acetone peroxide safely" is an oxymoron of the highest degree. Over the years at this plant a number of people had died in explosions and flash fires. I found another job after a year partly because I didn't think I was getting paid enough money for the risks I was taking. One night, shortly after I quit, there was an explosion in the MEKP production building. I heard the explosion at my apartment 20 miles away. The production building had heavily reinforced concrete walls probably 6 inches thick and a lightly attached wooden roof. The intent of the building design was to direct the force of an explosion upwards. It didn't work. The contents of the building and the 6 inch thick reinforced concrete walls were "vaporized" in the explosion.

 
 
 
 
    Antoncho
(Newbee)
05-03-01 14:33
No 188893
      Re: nitroethane  Bookmark   

uhh... i see. But (correct me if i'm wrong) is it not true that DMDO won't explode if in solution or wet (AND handled w/care)? At least, most peroxides i've heard of don't (blush
By the way, methylamine in Russia is, i believe, as available as in the US - it's watched. But one can make it from camping fuel. Chloroacetic costs a fortune (and the yield from it really sucks!).
The nitration of eth/methanol does look promising, though. Unfortunately, no one knows if it works on lower alcohols. Has anyone here had any practical experience with it? I have a strong feel that it might benefit from totally unhydrous conditions and , maybe, microwave irradiation.
 
 
 
 
    Osmium
(Stoni's sexual toy)
05-03-01 15:32
No 188900
      Re: nitroethane  Bookmark   

> The nitration of eth/methanol does look promising, though. Unfortunately, no one knows
> if it works on lower alcohols. Has anyone here had any practical experience with it?

Hold on, what do you mean? The procedure I gave starts with nitrite esters (easily available from alcohols, NaNO2, and some strong acid). And the other procedure mentioned here uses vapour phase nitration of alkanes, which is too difficult for the ghetto chemist, unless you invest LOTS of money and plan to build a continuous production apparatus.
 
 
 
 
    Chromic
(Hive Addict)
05-03-01 21:37
No 188946
      Re: nitroethane  Bookmark   

Last I checked, acetone peroxide is not dimethyldioxirane (DMDO). DMDO is like acetone, but instead of (CH3)2C=O you have (CH3)2C=(O-O).

Acetone peroxide is a cyclic species that likes to explode.
 
 
 
 
    lugh
(Hive Bee)
05-04-01 02:32
No 189039
      Re: nitromethane  Bookmark   

The alcohol nitration procedure referred to is on Rhodium's page at: http://rhodium.lycaeum.org/chemistry/alcohol2nitro.html  it's much superior to the ester route, since it starts directly with the alcohol. Yields are low so far, but only one bee has attempted it and reported results. As far as the vapor phase nitration process, it was done in a lab, it's not only industrial scale, basically it would involve two tanks of gas (propane/methane and nitrogen dioxide), suitable valves, and a reactor made from small diameter conduit of sufficient length heated with electrical heating tape (they used molten salt) and then insulated. A condenser and reciever would also be required. Obviously, this is suitable only for those with the McGyver impetus. I can post a reference if anyone has serious interest. Also, chloroacetic acid is generally produced by chlorinating acetic acid in the presence of acetic anhydride, phosphorus or sulfur.
 
 
 
 
    terbium
(Hive Addict)
05-04-01 03:43
No 189058
      Re: nitroethane  Bookmark   


Last I checked, acetone peroxide is not dimethyldioxirane (DMDO). DMDO is like acetone, but instead of (CH3)2C=O you have (CH3)2C=(O-O).

Acetone peroxide is a cyclic species that likes to explode.


True that DMDO is different from cyclic acteone peroxide. DMDO is cyclic though - one carbon and two oxygens for a ring isn't it? In any event, I thought that DMDO also liked to explode too. Acetone and methyl ethyl ketone hydroperoxides will certainly explode, they just aren't quite as shock sensitive as the cyclic forms.

 
 
 
 
    blue
(Delicioso!)
05-09-01 17:41
No 192966
      Re: nitromethane  Bookmark   

for what it is worth the synth from sodium ethyl sulfate and NaNO2 runs fine, it uses a fair bit of NaNO2 for the amount nitroethane produced

100g NaNO2 + 160g NaHEtSO4 + (catalytic amount)KHCO3 + heat =yeilded 25g nitroethane and a similar amount of what is assumed to be ethyl nitrite, that disappears in the water wash.
yeild ca 30% (yeilds could be improved by mixing reagents better than was done for this experiment)
rxn goes quik, 1/2 hour. its making the sodium ethyl sulfate that is tedious.

i'll warn ya though you need a shitload of headroom cuz the rxn foams ALOT! like a 2l flask for the above size rxn.

that other route via ethanol and NaNO2 also runs (triied nanonscale), but uses HUGE amounts of DCM that has to be stripped off, so it is volumetrically problematic. if i remember its like 250mls DCM to get a couple mls nitroproduct.

methods that scales better would sure be nice.

btw - how were they planning on oxidizing the ethylamine?



as in cobalt
 
 
 
 
    Osmium
(Stoni's sexual toy)
05-09-01 20:17
No 192991
      Re: nitromethane  Bookmark   

Nobody interested in the ethyl nitrite conversion?
Pfffffft. mad
 
 
 
 
    blue
(Delicioso!)
05-09-01 20:50
No 192997
      Re: nitromethane  Bookmark   

I'm all ears Os, just have to take a day off work to get to the library before i'm in any position to comment.crazy

it's similar to whats going on the sodium ethyl sulfate synth as well isn't it (minus the nitration)?


as in cobalt
 
 
 
 
    obituary
(Hive Addict)
05-09-01 23:17
No 193036
      Re: nitromethane  Bookmark   

can't remember exactly , but the sodium nitrite and ethanol does work at the either 50 or 500x scale to what's on Rhodium's site.  (try without the DCM- didn't want to mess with the solvent volume, so left it out-worked just fine)  just filter, wash, distill- however you want to purify. 
 
 
 
 
    Rhodium
(Chief Bee)
05-10-01 00:24
No 193054
      Re: nitromethane  Bookmark   

Obit: I am very interested in a detailed writeup on that scale-up, including yields and stuff like that.


http://rhodium.lycaeum.org
 
 
 
 
    halfapint
(Hive Bee)
05-13-01 13:51
No 194007
      Re: nitromethane  Bookmark   

Yes, Obit: please clarify. Are you implying that you put sodium nitrite in ethanol, added acetic acid then hydrochloric acid, and casually distilled off a whole bunch of nitroethane? Because that would bee big news around here! TIA...


Half a pint's a half a pound, a half the world around, around.
 
 
 
 
    obituary
(Hive Addict)
05-14-01 23:05
No 194378
      Re: nitromethane  Bookmark   

sorry for the long wait but obit has been out of town for a while and will re-run the rxn and post the results, it's been to long for this short-memory bee to remember the details.  get back with ya- hopefully with good news.