Well well....its looking rather purtyfull.

The nitrostyrene was first dissolved in MeOH, in which it seems highly soluable, then filtered at the buchner, bright yellow-orange filtrate was evaporated at room temperature and ambient pressure upon which, bright yellow, needle-like flaky crystals deposited, tinted in some cases, on the outside with a little orange. Tituration under dH2O was performed, and the suspension is being permitted to seperate, prior to filtration, then further recrystallization from MeOH.

Color, excluding the traces of orange, was observed by a certain toad-deity to be almost exactly that shade of yellow that matches cadmium sulfide. Orange color appeared to have been removed by tituration under dH2O.

This should be suitable, after dessication over CaCl, should it not, for LAH reduction?

Well the addition of water to a little LAH is planned, in the solid state, and dissolved in a little THF, done outside, to familiarise the experimenter with just how quickly, and violently it will behave.

This will be done, mind you, using a few hundred milligrams of LAH in each case.

The THF available is NOT inhibited, and was supplied in a bottle (its from a reseller who obtains it, along with her other stock in larger quantities then repackages for sale) that has been squeezed and then capped, to exclude all air, and is NOT peroxidation inhibited.

The experimenter's plan is to keep it that way, as much as is possible, and when opening for transfer of the required quantities to a reaction vessel, do so under inert gas, and likewise, perform any and all distillations/transfers/reactions under argon, after destruction of any possible present peroxides prior to distillation under inert gas.

And likewise, it will be purchased in small quantities, sufficient for multiple uses of course, but not so much that prolonged storage will be likely to occur.

Is it safe to distill THF to dryness after making sure it is both completely peroxide free (such as use in a LAH reduction under argon, or distillation under inert gas after dessication first with NaOH then Li or Na) ? Tsathoggua is well aware of the danger of peroxidation, and the fact that it normally must never be distilled to full dryness, thus allowing peroxides to concentrate and in the worst case, solidify then blow the user to kingdom come, but after immediate destruction of peroxides, and taking great care to prevent their formation during the reaction, is it then safe to do so, assuming its done under inert gas?

If not...then what is the reccomended procedure for removing synthetic target from THF? gassing (not titrating with aq. acid, due to  soluability of THF in H2O...) or perhaps addition of a less volatile solvent, preferably one that doesn't azeotrope with THF, then distillation of the THF first?

What I meant, is evaporation of the finished product/THF solution after filtration, by distilling the THF off, post quenching dropwise with dilute NaOH, then with IPA or MeOH, in small portions to the chilled solution until the evolution of H2 ceases to occur to a visible extent.

Final yield is unknown as yet. It was bright yellow in appearance, with, on the edges of small portions here and there of the needle-like, flaky crystalline product. The orange was something tsathoggua was unsatisfied with....so it was triturated under dH2O, and the decanted product dissolved in 50-60ml or so of DCM, in which it appears extremely soluable, plus a few ml more DCM to wash out the pipette used to transfer the crystalline product (yellow) and the residual traces of dH2O remaining on the crystals/as a slurry that it was transferred to the long vial used to clean it in.

DCM fraction was washed repeatedly with dH2O, which turned pale yellow, the DCM fraction being  golden yellow with slight orange tint to it.

DCM was then evaporated at ambient pressure and temperature overnight, leaving a smaller residue behind, which must be the nitrostyrene. This is now, to Tsathoggua's dissatisfaction and slight puzzlement, bright orange and consisting of extremely fine, tiny needles, powdery looking....consistency something like the deposites of elemental sulfur that form around volcanic vents, halfway between fumed deposits of flowers of sulfur, and ground fiberglass/asbestos dust.

While that yellow nitroalkene looked like it should it is evident that the reaction produced considerable H2O soluable byproduct.

Suggested workup from here....perhaps further dissolution in dichlor, and dH2O washes, evaporation and following recrystallization from MeOH, and dessication over NaOH or CaCl2, reduction?

Further experiments using TETA acetate shall bee performed, using the much less precious unsubstituted benzaldehyde...it is evident that at least using the TETA in the form of the commercial epoxy resin hardening compound results in significant byproduct formation. Tsathoggua shall try taking up the TETA freebase in dichlor, then repeated washing with H2O and sat. brine solution, then recrystallising from MeOH, and freebasing  w/ NaOH, extraction into dichlor, and forming the acetate in GAA.

Tsathoggua believes he shall attempt the nitroalkene formation using TETA and the acetate salt both, using PhCHO as the substrate, due of course to price and the comparitive price of the alkoxy substituted aldehydes. More 2,5-dimethoxy-4-methylbenzaldehyde can bee obtained at will, but at present, sitting in toady's lab there is only 7g of unreacted aldehyde available for use.

Not enough to waste testing hithertounexplored amine catalysts. EDDA tetraacetate shall be the catalyst used for further exploration of this aldehyde with nitroethane and MeNO2, and exploration of the resulting nitromethane end product's n-(2-substituted benzyl)-derivatives.

I'm with pyramid, methylamine acetate (generated in situ) being the most consistent and reliable Henry catalyst. My next choice being EDDA, which doesn't always give good results on some substrates. Recently I've been dabbling with ethylenediamine dipropionate (also generated in situ with a molar excess of propionic acid) and it gives comparable results to the diacetate.

20 grams P2NP from 35 grams benzaldehyde using in situ ethylenediamine dipropionate

Conditions were heating at 40°C for 1 hour then standing at RT for 2 days. Solvent was methanol, used 10 drops of ethylenediamine followed by 10 drops propionic acid. Guess that'll teach me for being sloppy.

Also for those that are unaware, P2NP is quite a bitch to crystallize, so always keep some seed crystals handy.

110gr Benzaldehyde + 80gr Nitroethane + 20ml Cyclohexylamine.
After shaking, it turns to light yellow colour. Then i put 30gr of the  mixture on the freezer. And the rest was "refluxed" in water bath at 55ºC for 2 hours.
In the 30gr batch no P2NP was collected, only freezed benzaldehyde.
In the hot batch after freezing, filtering and refreezing the mother liquor 4 times, 110 grams of yellow crystals was obtained.
No traces  orange polymerization was observed and probably no future recrystallization would be necessary.

P.D: Final weight of dry crystals: 92 gr and reduction was succes  .

Correction: ciclohexilamine = Cyclohexylamine http://en.wikipedia.org/wiki/Cyclohexylamine

Oh I forgot to mention some really shitty catalyst (but at this time had nothing else), ammonium acetate and ammonium formate (the latter was never really in use elsewhere, havent seen any reference yet) but as they are both solids and not readily dissolved, i would never recommend them...

I have also done quite a lot of nitroalcohol condensation, hydroxide catalysed (done with the nitronate salt and bisulfite adduct) has it seemed to always fail and never got that oil to precipitate.
BUT! If one is using triethylamine (Et3N) as catalyst, freezer cold run (at least -15° most of the time) for under 3 hours, worked nearly quantitative and always perfectly, and except for the first time the precipitated oil after quenching was almost colourless, indicating good purity. You will only get the much more wanted d,l-norephedrine with an excess of 3 parts l- to 1 part d-norephedrin usually.
Whatever one would wanted to do with it, this is way better to start with for any possible use! Reduction, oxidation, and of course this is also true if one wants to use the aminoalcohol made from the nitro it will also give the wanted 4S,5S methylaminorex, without amide formation if any at all.
It should never be stored for a longer period, then it will change colour over piss-yellow to a nasty red like I had seen not long ago when i had to throw away two dozen grams of phenyl-2-nitropropanol... I have stored it at room temperature for a half year I guess, it was dried dissolved in DCM before.

The problem with that nitroalcohols made with triethylamine catalyst is obvious, as they come in excess of one enantiomer, they tend to racemise even when used in zinc dust reductions, they have to bee done initially by dropping the acid slowly in because too much heat will tend to racemise the nitroalcohol.

Hmmm can you maybe give further details in the conditions used for condensation with hydroxides? Ive done this too, for fun in a gram scale and it worked both times well with pretty high yield?

2 mole benzaldehyde
2.1 mole nitroethane
80ml IPA 99%+
16g n-butylamine* see note

the 2l flask was charged with the above contents and swirled without splashing briefly.
Then placed in an oil bath to 75-80c.

After 6+ hours the solution began to change colour. yellow -going- orange
Coinciding with the colour change was the formation of a water layer.
 
heat was reduced 40-45c until the water layer appeared to have reached theory.
@ 10 hours in theory appeared to have been reached (later it was measured and established to have been exceeded by a few ml ~ perhaps excess catalyst was the reason and reaction wasnt quite 100% complete)

solution allowed to cool to rt. placed in fridge overnight, then freezer 24 hours.
1st yield 224g of very nice yellow crystals,(mp high 50sc) light washed and performed well in subsequent reaction 83-94% yields without recrystallisation.

The carefully filtered mother solution now gave off a scent of benzaldehyde. All was heated gently again 40c ish and separation/crystallisation repeated.
Another 34g of good quality slight orange crystal formed and was processed.

No smell of benzaldehyde remained. a slight burning sharp to the eyes ~ like someone blowing something minty in your eyes.

Dude didnt see the point in repeating a heat then freeze. instead he separated the catalyst/water layer, set it aside.
The now deep orange mother solution he added a capful or two of meoh**, froze then seeded.
a solid formed what didnt look promising, however upon removing and recrystillising twice, another 11g of needle crystals orange was obtained.

total yield 269g believe it or not theres still some p2np crystallised out the mother solution not included in the total.. after leaving for several weeks in the freezer it fell out the solution.

Note*: the 16g n-butylamine was a mistake, 16ml was the intended amount to use.(still a lot i know)
** meoh was added at that point  after reading byproducts was more soluble than the p2np, it made sense to me at that point it may induce more p2np to precipitate out.

Thanks fishinabottle for a informative post on another forum regarding temps of said reaction. It kept this experiment clean and easy to work up producing excellant quality results

pseudo science thought, it appears introducing air into the solution when filtering forms byproducts? i was careful to avoid splashing and covered the funnel when filtering relying on suction pressure rather than airflow.
In the past the filtering point has changed the orange solution too deep red and ive been unable to recover more product, or if so its been a nightmarish scenario for a few more gs.

Theres better more efficient methods on this thread, but in the spirit of things theres nothing like sharing practical experience/results.

look this article