I need to find a source of DIBAL-H (diisobutylaluminium hydride), a powerful hydride reducing agent, for reducing a matching 'set' of ring-substituted phenylnitropropene and nitrostyrenes. I WAS going to use lithium aluminium hydride, or possibly Red-Al, but then I happened to read a journal article which specifically mentioned use of LAH to dehalogenate aromatic rings, and they did it to, specifically, a bromophenyl group, removing the bromide, Which is something I HAVE to avoid in this case, I can't take the slightest chance of it happening. Then people said they didn't THINK that Red-Al would dehalogenate a phenyl ring, except under forcing conditions, but again, if they are wrong, then I'm royally bloody well buggered. I've a certain brominated benzaldehyde, that needs to be made into two, possibly as many as four compounds, depending on how tightly I can squeeze it until it screams, so to speak. Everything in the way of the very latest technology will be used to ensure maximal yields of the intermediate, a most unusual benzaldehyde, that I happened to be able to obtain by dint of sheer luck, its rare, very rare to see anything like it on the market, and rarer still for it to be available to even a well connected private individual like myself.
Then someone mentioned an alternative hydride reducing agent which will reduce the nitroalkenes to the aminoalkanes whilst quite certainly not touching that bromo substitution. I can't tolerate the slightest loss, I've even bought more microscale glassware and a really tiny Buchner vacuum filtration funnel, with a frit so fine that it won't just catch the crystals of the intermediate, even in the form of the finest fluff, but at 3 to 5 microns in pore size of the frit, that'll even partially sterilize it, it'll even catch most bacteria! not viruses, bar perhaps a few unusual giant viruses which prey on amoeba, which are so large they can even be seen under a high-powered optical microscope!. Not that they will be turning up in what I'm making. But damn, that is one FINE frit!, just 30mm to just under 30mm in diameter, a couple of millimeters thick, and the funnel itself is barely wider than that inside, tall, rather than short and squat, so the crystals when I produce the intermediates won't be distributed as fine fluff or tiny needle like crystals that are hair-thin, when the stuff is filtered after synthesis, under vacuum, then washed with ice cold water, then freezing cold sodium bisulfite solution, to remove any traces of unreacted aldehyde to prevent them, if present, from interfering with the reduction process.
I might even take a bit of a risk, and convert the aldehyde to a carboxylic acid first, then to the acid chloride using thionyl chloride, and react with the corresponding aminoalkyl azide. Would need sodium azide to make it though, which is highly toxic, interfering with the electron transport chain, like hydrogen sulfide or hydrogen cyanide do, and capable of a similar rapid kill as cyanide, only unlike cyanide there is no antidote. It also is somewhat physically sensitive. Sodium azide being, along with chemicals to remove the sodium left behind as the azide decomposes to nitrogen gas, the stuff used in car air-bags, because it goes off like gunpowder if ignited or subjected to friction. Although unlike heavy metal azide salts, which are very sensitive, and violently high-explosive, NaN3 and other alkali metal azides just deflagrate violently, along with giving off deadly, and very, very unstable and explosive hydrazoic acid, which can more or less be thought of, in terms not of chemical reactivity, but physical and toxicological properties as schizophrenically explosive cyanide gas. So if I go that route, via the carboxyl azide extreme care is going to be needed. Not that it isn't for DIBAL-H, which needs to be handled entirely under inert atmosphere, in flame-dried glassware, and transferred from it's container to the reaction vessel by means of glass syringes, that have been freshly flame-dried and repeatedly purged with argon, and the same goes for the double-pointed steel cannula needles used to transfer it between flasks in a Schlenk line, which I'll need the glassware to set up, a few more specialist items, although I've been paid today plus have some savings. Annoyingly, my rent is due too. But still, the savings will help mop up some of the cost so I can get as much of the setup for the Schlenk setup, and as many of the reagents as possible. Plus I could do with a couple more clamp stands, and more flask clamps, as I've got most of mine in use, and all of the stands. Might have to order some dry ice a day or so before actually doing the reactions, to keep the intermediate in solution very, very cold, with a dry ice-acetone bath to minimize any losses due to heating when adding the DIBAL-H in THF or 1,4-dioxane.
(it bursts into flames if it gets wet, even slightly, or on exposure to air.) And it'll be DAMN difficult to obtain any, although there is a chance I might be able to make it myself. Which would be hairy as fuck doing it to say the very least. But I do have one source, which might well be able to get me some. For a price. Although I won't need huge amounts, as I've only 5g of the aldehyde to work with. But no chance of getting any more. So I've really, REALLY got to make the best of what I have, using every scrap of knowhow, artifice, tricks and the bleeding edge of the state of the art in nitrostyrene and nitropropene chemistry to do it. At least to get good yields. Which still won't be more than a couple of grams at most. Although I've high hopes for DIBAL-H, that it won't be too harsh and cause any losses in yield, or at least, as little as possible. This little project of mine is something special I've had in the pipeline for a couple of years now, but only just recently found the benzaldehyde I'll need to make the two intermediates for the 'matching set' of compounds, sealed up in a glass bottle stoppered tightly and the container purged with inert gas, and the actual aldehyde in a sealed ziplock bag, that will only even be opened to weigh it under inert atmosphere itself, to prevent any oxidation, as benzaldehydes easily oxidize to the corresponding benzoic acids.
So it'll be handling everything, right from the start with silk-lined tweezers, so to speak, and kid gloves on. I'll skin the kids myself just to make sure they are fresh. Pick a nice juicy tender premature baby
Won't let the rest go to waste though, I bet it'll be really tender and juicy once marinated, spiced and lightly fried or grilled.
