I was thinking of trying the EtBr and NaNO2 reaction, or the EtNaSO4 reaction and NaNO2.
But using ethyl tosylate, seeing as its such an amazing leaving group ie Ethyl Tosylate, prepared by klutes methanol estification (switch methanol with EtOH and stoich)

Then adjusting one of the reactions to work with tosylate...............
However I have no synthesis design experience, can anyone aid me with this?
The tosylate should work fine in a substituation reaction seeing as thats its primary use....

Radiochemical hey that sounds OTC 
I think if one had the ability to perform a radiochemical reaction, then its likely they would have an Aldrich account and no problem ordering EtNO2.....

This is my plan:

US pat # 4319059

Example 1

To a mixture of magnesium methoxide (0.11 mole) and dimethyl sulfoxide (50 ml) a-bromopropionic acid (0.11 mole) was added at 20°C. with stirring. To this mixture a solution of sodium nitrite (0.145 mole) in dimethyl sulfoxide (65 ml) was added at room temperature. Then, the reaction mixture was stirred at room temperature for 6 hours and was neutralized upon addition of diluted hydrochloric acid. Analysis of the reaction mixture indicated more than 99% conversion of alpha-bromopropionic acid and 94.5% yield of nitroethane.

My plan is as follows;
HBr Bromination of Lactic acid (HBr:Lactic Acid 1:1.1mol) to yeild a-Bromopropionic Acid

Then a stoichiometric amount of Mg(MeO)2 will be made in solution, following klutes work on SM
To this Mg(MeO)2 mix, DMSO will be added and the excess methanol will be distilled off (Mg(MeO)2 is unstable so I figure this will be the easiest method)
Then the reaction will proceed as noted hopefully.

I tested the Mg(MeO)2 synthesis yesterday, which worked with my -200mesh Mg, and somewhat dry MeOH, Klute uses an inert atmosphere and his other ridiculous reagents (I wish  ), I believe I obtained the desired Mg(MeO)2, however, on standing what I believe was Magnesium methoxide (which klute describes as gel like) was left and turned hard almost chalk like, this is probably die to the excess MeOH evaporating and the Mg(MeO)2 drying out.
Ill post pictures of my Mg(MeO)2 endeavours tonight...

Just out of curiosity can anyone find any holes in my plan?, is there an easier Magnesium salt that could be used? (see the following extract), I assume If the mix is left stir for a longer period, Mg(MeO)2 could be substituted

Taken from SM:

This patent shows an easy route from alpha-bromopropionic acid to nitroethane in excellent yield. The patent also say that Magnesium chloride, bromide or sulfate may be used instead of the magnesium methoxide, but it doesn't say if this affects yields.

The reaction proceeds as follows: In the polar aprotic solvent DMSO, the alpha-bromopropionic acid reacts in an SN2 fashion with nitrite ion to give alpha-nitropropionic acid and bromide ion. The role of the Mg2+ ion in the reaction is to facilitate the decarboxylation (removal of CO2) from the intermediate nitro acid, as it forms a chelate between one of the oxygen atoms on the nitro group and the oxygen anion of the carboxylic acid. The electron-withdrawing nature of the nitro group makes the carboxylic acid group labile, and it can easily be given off as carbon dioxide. If magnesium methoxide is used in place of the other magnesium salts, the carboxylic acid is directly deprotonated, probably making the reaction go even faster.

Formula 409

Here's an interesting paper - they use strongly basic exchange resin (trialkylamine-type - same one you buy in fish stores to remove nitrates/nitrites from aquarium water - go figure), alkylate it with ethyl halide (in this case iodoethane) to get the quat.N-ethyl-N-trialkylammonium.Iodide - treat that with sodium nitrite in aqueous solution to replace the iodide with nitrite obviously... then run iodoethane through the dried nitrite resin to get nitroethane and regenerate the quat.Ammonium Iodide resin - ready to be treated again with sodium nitrite.

Preparation of crosslinked poly(N-ethyl-4-vinylpyridinium) nitrite. [P4-Et] NO2

Crosslinked poly(4-vinylpyridine) (20 mmol, 2.12 g) was treated with ethyl iodide (20 mmol, 3.24 g) in acetonitrile (10 mL) and stirred for 24 hr at room temperature. The quaternized polymer [P4-Et] I was filtered and washed with distilled water and acetonitrile. It was then dried under vacuum in the presence of P2O5 at 40C.

To 40mL of a 3 M solution of sodium nitrite was added [P4-Et] I and slowly stirred for 24 hr. The resin [P4-Et] NO2 was filtered off and washed rapidly with distilled water until the filtrate gave a negative test for NO2. It was then washed with ether and dried under vacuum in the presence of P2O5 at 40C (1.6 g).

The activity of these polymers was determined by potentiometric titration with a 0.1N solution of silver nitrate. The activity of polymer (1) was 4.8 mmol/g of the polymer, and the activity of polymer (2) was 3.7 mmol/g of the polymer.

General procedure for conversion of alkylhalides to corresponding nitroalkanes

To a mixture of alkylhalide (1 mmol) and n-hexane (10 mL) in a round-bottomed flask (50 mL), 2 mmol of polymer (1) or (2) was added, and the mixture stirred at room temperature for 17-72 hr (Table 1). The formation of nitro compounds was monitored by TLC (eluent: chloroform) or GLC. On completion of reaction, the mixture was filtered and washed with n-hexane and ether. The combined filtrate was evaporated to obtain nitroalkanes in 11-99% yield. The spent polymeric reagent was regenerated by treatment with sodium nitrite solution. The regenerated reagent has the same capacity as the original form.

Preparation of nitroethane from iodoethane by using polymer (2):

A typical procedure: To a mixture of iodoethane (0.4 mL, 5 mmol) and n-hexane (10 mL) in a round-bottomed flask (50 mL), 10 mmol of polymer (2) (2.7 gr) was added, and the mixture stirred at room temperature for 33 hr. The formation of product was monitored by GLC. On completion of reaction, the mixture was filtered and washed with n-hexane and ether. The combined
filtrate was evaporated to obtain nitroethane. b.p = 110-114C, 1H NMR, (ppm): 4.3 (q, 2H), 1.38 (t, 3H).

Kind of supports the idea that the reagents need not be in solution doesn't it? I wouldn't cite it, but there are numerous, quite difficult to acquire references to similar outcomes... I'm not exactly going to be the world's biggest believer in this due to what is in "Journal of the Chinese Chemical Society", but the fact it is in a peer-reviewed (or supposedly at least) journal, makes me wonder...

PS I threw a copy of Kornblum's Nitroparraffins on as well, always a good read

Sorry for the cross-posting - but this is an exciting paper

This is from page 127/167 of a VERY interesting thesis I found online - a whole bunch of safrole derivatives - MDP2P (via Wacker), Nitropropanes (including the Nitrosafrole), etc. with Shulgin as the external examiner... Notwithstanding all of that, here is the preparation of Nitroethane:

Nitroethane

Ethyl iodide (3.12g, .02 mole) freshly distilled was stirred in an ice bath at 0'C. Small portions of dry AgNO2 (3.08g., .02 mole) prepared as described (579) were dropped in. The internal temperature rose to 16'C. The reaction mixture was left overnight (12 hr.) in a cold water bath at 15'C and distilled at atmospheric pressure (739 mm). First fraction (70-75'C) (ethyl iodide 1.84g) and second fraction (108-115'C), (nitroethane, 570mg) were collected.

Yield: 38% (95% conversion).

What about if excess Ethyl Halide were used, in anhydrous EtOH, and the Sodium Nitrite were supported/thinly distributed on silica? Quite simply, I see now way (given the known solubility issues of Nitrite salts) that 1:1 molar ratios (and almost 1:1 weight/mass ratios too) of AgNO2 would be soluble in EtI. It would be, at best, a paste

Just have to wait until we get some action on the ref request thread - one is the long-lost DMSO/sodium nitrite paper and another goes into how and why the different reagents give the products they do... Sure seems like it might be worthwhile reading, especially given the price of silver and the headfuck involved in reclaiming it from AgI.

Here is a bunch, the one Java uploaded for me over @WD is accessible still (I didn't realise that Java, sorry mate) and I have attached it here, it deals with the use of a column with silver nitrite (also 1 reported trial with sodium nitrite) where they run the gaseous (at that temp) ethyl halide through a column of the nitrite/silica to get the nitroethane... IIRC they claim they managed a 20% yield of EtNO2 from sodium nitrite @100C which sounds like shit, but the absence of solvent, the ease of separation and the fact that it actually works (well claimed to at least), makes me interested... I mean, whatever doesn't react could surely be used again, right? Just run a massive excess of Ethyl Halide (sufficient to ensure all of the nitrite reacts) through a column @ 100C (pass said column through a jacket filled with steam) through a column packed with sodium nitrite and sand, separate the ethyl halide and nitroethane (distillation should do it, iodoethane, BP.72.4C & Nitroethane, BP.112-116C, that is what 40-odd degrees celcius?)...

Otherwise, there is a bunch of fun reading....

Acetonitrile found in a few Non acetone nail polish removes and can be synthesized from Acetamide can undergo reduction to yeild Ethylamine followed by a few various oxidations with various over the counter oxidising agents yeilds Nitroethane. This could prove to be a simple and high yeilding process able to make Nitroethane in bulk for once but... does anyone know how to form a Nitro compound directly from a Nitrile.

Isocyanates are the main product of oxidation.

Im not sure I understand. The paper seems to suggest the need for an aprotic solvent in order for the reaction to proceed as planed. Else without atlest .5% solvent and 100C the reaction produces little but your starting halide as a result.

I do like the idea that Nitroethane is favored at lower temperatures, aside of Ethylnitrite, at and below 100C so perhaps a longer reaction time at lower temperatures could lead to a quantative yeild of the given Nitro compound.

For all else I honestly feel you may just need that solvent inorder for the reaction to progress.


PS: you want to hear somethng sickly funny??? In the time it took me to write and review this I forgot almost everything in the paper I JUST read.... .... I need to see a doctor I think :'(

At the "GAYLORD" factory?  OK, y'all must be in California then