Author Topic: Questions for Lestat: Lestat's Lab  (Read 2387 times)

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Offline Lestat

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Re: Questions for Lestat: Lestat's Lab
« Reply #105 on: January 15, 2018, 01:09:47 PM »
Just spent near $500 on new glassware, and I'm not even close to done yet, still got chemicals to buy too. The 'what have you bought' thread shows the list of what I've gotten myself, as my to-self xmas gift so far.

Still want some chemical supplies too, and a few more bits of glass, mostly flasks, 2 and 3 neck round bottom type, still want the following:

1l pyridine
some triethylamine
more diethyl ether
I've got my eyes on a rather nice deal (about $20 for 100g) on lithium metal, sold as pellets stored under argon in a sealed container. Quite a nice price. I do have some lab-grade Li metal already, but only about 25g, and mine is in the form of flat squarish strips, 25g, minus what I have already used, again came stored in a hermetically sealed inert gas filled dry-bag, inside another inert gas filled dry-bag, again hermetically sealed. Once I opened it, I store the inner container, again re-purged with dry argon welding gas, of which I have many tanks since I use quite a lot of inert gas and argon does the trick perfectly, there are very, very, VERY few things which can react with argon, although  IIRC a few fluorine-containing compounds, prepared under extreme conditions can exist, as can non-bonding 'compounds' where argon atoms are trapped in molecular cages, and clathrates can exist containing argon although those are not true compounds of argon)

Could do with some sodium nitrite (not nitrate, I've a couple of kg of NaNO3, its NaNO2 I want.
Some 4-dimethylaminopyridine, for its ability to catalyze esterifications within minutes at room temperatures under the mildest of conditions and giving extremely high yields. Although it is extremely toxic, potentially lethal upon skin contact, so of course one must be rather scrupulous in removing the para-DMAP from one's rxn mixture once the esterification is completed, and in recycling and regenerating the 4-DMAP.

And both ammonium formate, 99% formic acid, and formamide, plus a couple of liters of DMF (dimethylformamide, a polar, aprotic solvent, although extremely high boiling point)

Could do with some conc. aq. hydrobromic acid although I can make that myself from some of my sodium bromide.

And from then on....oohhh...I've seen a nice looking ampouled sample of dendritic crystalline calcium metal at a reasonable price, as well as one of barium metal for a little over a tenner in the latter case.

Want some phosphorus pentoxide too, a few kg. I COULD make the P2O5 (actually phosphorus pentoxide [Phosphorus (V) oxide] is dimeric, P4O10), myself, by burning red or white phosphorus, but, whilst I do have 2kg of red, and as such, I can prepare as much white as I desire, via distillation of red phosphorus under inert atmosphere, sufficient heat causes red phosphorus to convert to the white allotrope (the red form is flammable if lit, whilst white phosphorus ignites spontaneously upon contact with air, burning, in either form to give phosphorus (V) oxide fumes, but just setting elemental phosphorus on fire in a dry-box and collecting the fumes on the inside of a cold flask then transferring them to a tightly sealed, dry container, would be a hideous waste of elemental phosphorus, since the pentoxide is a LOT easier to purchase than the elemental red OR white allotropic forms of phosphorus. Elemental phosphorus is watched like a hawk, because red phosphorus and iodine, is a common combination for reduction of pseudoephedrine or ephedrine to methamphetamine, but, given my connections I can get red phosphorus, from which to make other, very useful phosphorus compounds such as the tri- and pentachloride and pentabromide/tribromides, prepare white phosphorus, and to serve as a start point to make the different elemental forms of phosphorus for the element collection I want to build, basically a wooden periodic table shaped set of chambers, each containing the relevant element, as a sample sealed under inert gas (excluding of course the gases which do not require inert gas, and the inert gases themselves. The gaseous elements will be put in electrically excitable plasma discharge tubes to display on demand the different excitation spectra, at least those parts within the visible range, also including a mercury vapor discharge tube as well as a sample of mercury metal)

And containing, in the cells, the relevant allotropes of the elements too, as many as I can prepare, all the elements from hydrogen (inc. separate plasma discharge tubes containing deuterium and tritium) to uranium (the barely radioactive, 'depleted' form, 238U, quite safe to handle, its toxic, but only in a typical heavy metal kind of way, like say, lead), the really  unstable radioactive elements that have such a short half life as to barely exist in nature or if artificially made, that just disintegrate by spontaneous fission within fractions of a second to a few hours, those will be represented by a radioisotope of another element which can be stored and which includes the super-unstable (thinking astatine and francium here) elements that can't be stored due to the incredibly short half life, serving as a placeholder of sorts, since during the decay, these elements will exist as at least a handful of atoms at any given time, with an explanation of the decay chain carved  into the display case cell for that element.

Have found though some rather rare stuff that I really want and intend, now I have the money, to buy. I've spotted somewhere which has a glass tube containing a strip of pure gold, given a plating of polonium, covering the piece of gold, in the form of real, genuine 210Po metal in the elemental form. Beautiful, can't see the gold substrate at all, just a silver layer, a perfectly visible to the naked eye piece of 210Po. Radioactive in the extreme, although an alpha particle emitter, and alpha radiation is blocked even by a thin sheet of paper, unless it is for example, in the form of an extremely energetic particle beam from a particle accelerator), and there ought to be no bremmstrahlung from the 210Po in a light element based container such as borosilicate glass. The sample costs at least £400 for one piece, although one is all I will need, since it is for a display piece for the element collection only and I do not intend on ever, ever opening the tube. That, I think, must be the heart of my to-self xmas treat, the really special treat out of all my xmas to self buying to pimp out the lab. That polonium metal sample, is to be 'It', it is beautiful, and I must, MUST own it. Sheer beauty and such a piece as this is of incredible rarity on the market for private individuals.

They have thorium metal and uranium metal too. I might just grab myself one of the thorium samples (somewhat less common as metallic thorium than is 238U) if I have enough money left after I buy that super-rare and absolutely fucking gorgeous polonium-plated gold slice. Even at £400, I reckon it is worth every single penny. And...well, lets just say that it has had me slavering and drooling over it for months, spending only what I absolutely must, and building up a sizeable pile of cash in the bank. Of which, that polonium slice is being bought up first, and then I go reagent shopping, with whatever is left. I spent a fair bit, nearly 500 dollars, although that'll be equal to less in GBP, and I'd over a thousand pounds in the bank.

Already bought up a lot of glassware, a good many pieces and items I've wanted for a while. The 4-neck round-bottom flask of 5-liter capacity is especially sweet.

But if its still available, that polonium 210 sample in its borosilicate glass vial, an actual visible sample of elemental polonium metal that will be sweetest of all. And I want it....I MUST have it if it is still possible to grab it.
 

And a new, powerful vac pump.
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Offline Lestat

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Re: Questions for Lestat: Lestat's Lab
« Reply #106 on: February 05, 2018, 01:54:36 PM »
Whats that damnable stench......ugh. I KNOW I smell something of the  mercaptan (thiol, R-SH, the analog of an alcohol where sulfur replaces oxygen) breed. I just don't get where from because I sure as hell haven't made any, and there obviously hasn't been a gas leak for days on end. Had to move, of all things a pillow (well sofa cushion but I sleep on the sofa so it was a pillow for me...and I KNOW its not me. I KNOW what its like to accidentally cause something to form a mercaptan in-vivo and its definitely, definitely not me. I'd be able to smell me from several hundred meters away easily if there were any significant amounts coming out of ME. And people would start running from an equally long distance down the street in the open air.)


(Oh, and correction.....I meant, in the other post with reference to the radioactive metal plated onto gold, as a display piece..its not 210Po, its technetium metal, as 99Tc, although still plated onto a gold strip. I done gone derped for a moment there before)...I do mean 99Tc though, the transition metal, not polonium, the metalloid heavier, radioactive alpha-emitter answer to sulfur, selenium, tellurium, and then Po.) My bad. Mea Maxima Culpa.

Still got to have it for my collection though. I think that'd be the piece around which I actually build the frame and display case for wall-mounting, since its such a rare and well-made real beaut of a piece.

Bought some pipettes (1-2ml or so, with removable bulbs so they can be used on larger (longer) ones too),  those came, as well as some graduated measuring cylinders, that unlike the one I had (currently occupied, mostly by a protective filling of degassed water, but at the bottom, with a small sample of the white allotrope of phosphorus, prepared by my good self, by means of a means similar in practice to what they call 'destructive distillation', which is pyrolysis of a substance to be subjected to the technique using a container to hold the substance to be destructively distilled, and exclusion or depletion of oxygen from the container, in this case, the vessel was filled with argon, and more argon used to sweep the white phosphorus vapors liberated from a sample of red phosphorus heated in the absence of air, through the long, deep graduated cylinder filled with ice cold water to solidify the vapor as a chunk of white, waxy, pyrophoric solid, traces taken from which glow in the dark if applied to a substrate, like a piece of brick or glass in the dark) Done outside of course, and just as well for I need a new alembic as a result, as my last one got too hot and broke, resulting in an instantaneous whomping great fireball of glowing white flaring flame with a greenish under-tint to it, like white phosphorus has when you see small quantities, or else its too cold for it to autoignite straight away.

That though, wasn't, and I lost several hundred grams of red phos, or rather, red turned to white phosphorus, forming an orangey yellow liquid, that was boiling and refluxing fairly vigorously in the alembic. And the tiny traces of oxygen not removed by the repeated argon purge were causing it to glow with that spectacular and really quite pretty,  even if somewhat eerie green phosphorescent acid-green glow.

Needless to say, I am very glad indeed, not that I'd ever have even attempted such a preparation without it, and lots of it, that I was wearing overkill with regards to protective gear, to prevent any skin contact (if one is burned by white phosphorus, and doesn't immediately dig it out of you, under-water and there is enough it can easily literally burn right through you until it comes out of the other side, leaving concentrated strong acid (orthophosphoric acid, H3PO4) in its way, from the violently exothermic reaction with water of the anhydride, phosphorus pentoxide, which one sees as huge billowing clouds of corrosive, dense, white acidic smoke when white phosphorus burns, and which is both strongly acidic itself, and a real bastard of a heavy duty dessicant, that for acid-tolerant substrates, if it CAN be dessicated, phosphorus pentoxide is the way to do it and be bloody thorough about it, stuff makes no bones about that, its even strong enough to dehydrate concentrated sulfuric acid, all the way to sulfur trioxide, the anhydride of H2SO4 IIRC, although I've never actually attempted to do so, because I've never needed to, and I don't really want SO3 around  if I can help it without having a good reason to. Conc. sulfuric acid is itself one of the most powerful acidic dessicants going that one might encounter in a lab, and pouring it onto sugar will suck the water right out of the hydroxyl groups and after a lot of stinking and smoking, the sugar expands in its container, with the release of a LOT of heat, to form a lump of foamy carbon as the H2SO4 hydrates. To DO that, to dehydrate H2SO4 to sulfur trioxide...that takes the drying agent equivalent of an anti-ship missile scoring a direct hit. Against a canoe :autism:

And a big anti-ship rocket at that! Although it produces a fucking ton of heat (phosphorus (V) oxide) when it hydrates irreversibly to form H3PO4, easily enough to char organics to carbon ash, and start fires while doing it too. Not the cheapest dessicant for sale, but if the substrate will tolerate acid, then, used carefully after pre-drying via distillation, more conventional and less violent and brutal dessicants then it will get the job DONE. Its the mike tyson (that psychotic fuck ear-biting-off-er black boxer) of drying agents. Pricy, and you need to be careful with the glassware too, because hot, concentrated phosphoric acid etches glass. So it has to be added slowly and carefully bit by bit and handled in a dry-box while measuring/weighing or having a container of phosphorus (V) oxide open, and it can't be recycled by means of using  heating the bejeesis out of phosphoric acid either, so its one-shot-only, unlike many drying agents, including conc. H2SO4 that can be redried thermally, at least not unless a phosphate salt is prepared with the acid, dried thoroughly and mixed with charcoal dust and fine silica powder, then heated to over a thousand degrees 'C, and the vapors condensed under inert atmosphere to give (white) elemental phosphorus, a process which is a modernization of the first discovery of the element phosphorus by Hennig Brandt, the alchemist who first prepared elemental phosphorus in any of its allotropes (white), by a laborious and frankly quite unpleasant sounding task of boiling down vats of putrefying human urine 'until it breedeth worms' and roasting the resultant carbonized, phosphate-rich ashed solid residue from the putrescent maggoty piss (which isn't necessary, the putrefaction or the maggots, bet ol' Brandt would have had a much happier time if he knew he could phosphate from rocks rather than boiling down hundreds of liters of rotting piss) in a furnace, with a specially sealed retort and distilling off the white phosphorus fumes and condensing them into solid WP.

Generally nasty stuff to handle, but useful synthetically for preparing other reagents like phosphorus halides, about as toxic as cyanide (as KCN, lethal dosage is about 40-50mg, so perhaps slightly more toxic than potassium cyanide), bursts into flame, leaves VERY painful wounds that heal slowly and in case of a sub-lethal exposure, leave the affected part very weak in terms of a kind of shaky palsied partial paralysis for some time (a little speck, the size of a match-head inflicting a burn is enough to do so. At least it is to a child, not sure about an adult, I've never been burned by the stuff as an adult, and I don't want to either. It hurt enough and left nasty enough effects for long enough for once to be twice too many. I got off lightly with a lot of pain, followed by shaking and near paralysis, and complete inability to grip even a pencil in the hand attached to the affected arm, which was afflicted thus all the way up to past the elbow, the burn itself being sited just past the wrist joint, on the upper side, closest end towards the elbow) and it lasted for weeks, and my having to avoid some rather hard to answer questions at school as to why I was persistently writing with my left hand..I think they thought I was taking the piss (historical pun intended), if not the rotting, maggoty fermented piss...but in a LFA school I could hardly very well answer the teachers 'I was up past my bed time, roasting red phosphorus and distilling the white allotrope. Don't mind me, accident with something about as nasty as cyanide give or take 5-10mg, its just paralyzed my arm, temporarily, I think...

Because chances are, they'd have fucking freaked if they even had so much as an idea that I had as much as the ability to prepare phosphorus or cyanides :P The little kid that rocked and flapped and was DX LFA....up all night long, never mind past 'bed time' (at least the time I was ordered by parental units to retreat to my lab...err...bedroom, at the time...well...both...had to piss with the dick I had, so to speak at that age. One end of the room held a bed, plus a crop of weed plants under lights and reflectors made of tin-foil to increase efficiency underneath, whilst the other had a bench from wall to wall, along with a wide range of wood and metalworking equipment, a closet full of chemical reagents, and various bits of glassware and home-made metal, ceramic etc. retorts, crucibles and the like, bottles of acid underneath the bench...HCl, phosphoric, formic acids, concentrated (as strong as 98%) sulfuric acid, perchloric acid (!) (HClO4 doesn't fuck about, its one of the strongest inorganic acids encountered in most labs, and has a nasty tendency, over a certain concentration to explode, or if spilled, react with things like bench tops, or the fumes to react with the insides of ducting in fume hoods to form explosive perchlorate derivatives. And its stronger, in terms of proton donating capacity, and hence acidity, than pure, 100% sulfuric acid)

Lets just say that I had....how should I put it...a somewhat unusual nocturnal life, as (and for) a kid. By day, a LFA spazz kid. By night, a beginning chemist LFA spazz kid. Like spider-man, only with stereotypy and a bent for some weird and wonderful (and occasionally accompanied by the odd  detonation, one or two house-wide power cuts over the years, one of those accompanied by a rather loud bang and a shower of caustic, plus one of mom's vases blasted to smithereens and accompanied by a heavily modified mains plug, with the wires melted in a fraction of a second, although the noise of the explosion was probably covered up by the exploding vase...didn't know at the time I couldn't use AC current, and that I needed a step-down transformer and DC rectifier for molten caustic soda electrolysis, aimed at producing sodium metal She never did see that vase again. Neither did I, at least, not in any chunk wider than a couple of inches, although it started at about a foot and a bit tall and maybe 6-7 inch wide) experimenting.

Beginner's mistake, and one of a few on the road to becoming a lot more cautious, more talented and well-studied, and far, far far better equipped chemist. One has to start somewhere, no?
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Offline Lestat

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Re: Questions for Lestat: Lestat's Lab
« Reply #107 on: February 05, 2018, 01:58:28 PM »
And thats saying nothing about the odd (at times, VERY...errrmm...'odd') stench that I had no explanation for that I could give anybody and that'd fair turn your  toenails curly in horror. At times worse than odd. Like the abyss just farted, followed through and  shat its pants after a bad prawn curry.
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Offline Lestat

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Re: Questions for Lestat: Lestat's Lab
« Reply #108 on: February 05, 2018, 04:14:47 PM »
Hmm...nice. That IS interesting....

I just stumbled upon, by chance really, during reading up on phosphorus halides, an interesting reducing agent, namely diphosphorus tetraiodide, which seemingly will under very mild conditions, and forming phosphorus based byproducts insoluble in the reaction solvent, (ethers) induce beckmann rearangement of ketoximes, and as it happens, formation of nitriles (organic cyanides, which generally, although not exclusively, are MUCH less toxic than ionic cyanides that easily liberate free cyanide anion), from aldoximes. And THAT, was precisely the sort of thing that falling into my lap, metaphorically speaking, is just the thing I wanted to hear. Means I might have a shot at a certain reaction I very much want to try for synthesis of a couple of intriguing end products, the intermediate I had planned involved an inorganic cyanide, such as sodium or potassium cyanide, which are toxic as hell, as is well known, and capable of a very quick kill, long before an ambulance gets to the scene, for production of a desired nitrile intermediate followed by reduction of the nitrile to the amine and an alkylation.

Now I think I've found just what I want. Would mean I have to reduce a carboxylic acid to an aldehyde, which might be a bit tricky; but its the sort of synthetic transformation that every chemist and his dog would like to have in their book of tricks, and under the mildest possible conditions too, so people will have tried. I have the terminal carboxylic acid in question that I want the corresponding acetonitrile derivative of (a substituted, in this case, derivative of acetonitrile, aka methyl cyanide) to then reduce to the amine. That I know I can do easily enough (the nitrile to amine reduction), haven't looked yet, but if I can find a reductive monoalkylation or even dialkylation of the substituted methyl cyanide in question...then I'm in business and smiling all the way, because at no step will I have to ever produce, buy, store, handle or use ionic cyanides.

And compared to say, NaCN or KCN or hydrogen cyanide gas, which takes maybe 40-50mg to probably kill somebody within as little as a minute or two, acetonitrile itself, you just wear gloves and a gas mask and avoid drinking it or bathing in it and your golden.

It IS capable of delayed slower releasing of cyanide anion if ingested but acetonitrile isn't particularly nasty, I've got IIRC a liter of acetonitrile itself/methyl cyanide (which is giving me more ideas just thinking about the MeCN for going about it an altogether different way, essentially in reverse, and potentially, if I were to use isopropyl cyanide, although I haven't got any iPrCN in the fridge as I do acetonitrile/methyl cyanide, I could doubtless either buy it or make it. ) and its not scary, in fact I've about as much nervousness about use of acetonitrile as a solvent by the flask full as I do about ether. Although I wouldn't drink acetonitrile, whilst diethyl ether makes for a viable cocktail ingredient and alcohol substitute, thats actually preferable to alcohol IMO.

Actually, ether scares me more, although not much. Ether, THF etc. can peroxidize in storage once allowed access to oxygen, although they can be tested and treated to destroy peroxides easily enough and regular testing ensures your ethers don't form nasty alkylidene peroxides or hydroperoxides that have a nasty property of being both explosive and coming with, as things that go 'boom' and convert fridges, lab benches, fume hoods etc. and glassware into new ceiling ornamentally arranged shrapnel-hailstorms. (never happened to me, but I've heard many tales of crusty antique bottles of ether and the like, forgotten about in the back of a uni lab etc. and tearing a room to pieces, blasting the windows out and starting a fire in the process)...I'm more careful about that.

In fact just thinking about it makes me want to go and buy a potato and a bottle of cheapo dilute 3-12% etc. hydrogen peroxide or some sodium peroxide etc. for safe calibration and test my ether, my DIPE and my THF. Too late to go out and buy a potato now (the test strips work by the characteristic color change induced by iodine in the elemental state with starch. One soaks the paper in starch, such as solution made from boiling down potatoes, which are rich in starch, or I could just get some laundry starch spray etc. and also in potassium or sodium iodide. I have some KI, and it doesn't take much.

The oxidizing nature of the peroxide oxidizes the iodide anion to free iodine which reacts with the starch to form a blue-black color, the deeper the color the more oxidizing the conditions, and ergo, in a situation where the known oxidant is a peroxide, the relative contamination can be deduced by the intensity of the color change by application of a drop of the ether/s to be tested to a strip of the prepared KI or NaI+starch paper. Like a litmus paper test, only for making sure your ethers are nice and friendly like they ought to be (albeit flammable as the day is long, but thats just ethers for you, they are flammable, end of and no treatment will prevent that, its like asking for petrol that doesn't burn and fuel cars, or water that isn't wet and containing two hydrogen/hydrogen isotope atoms and one of oxygen per molecule. Flammable is something I can live with, unstable boom bye bye lab and a fridge through the roof on the other hand, is much less desirable.)

So, although I've not opened it, that 5l of tetrahydrofuran should be tested on principle, although its not old, and is kept in a fridge when not in use, and also the empty headspace of a container of THF or any other ether is topped off, and the liquid portion sparged with argon as an inert gas to drive out oxygen wherever it makes sense to do so, so properly treated there is no more problem with them than there is other solvents of equal or lesser toxicity.

And as for that nitrile...(not the acetonitrile I use as a solvent, the substituted one I have in mind as an intermediate. That, that can definitely make for some looking into now, much more encouraging to use diphosphorus tetraiodide, than cyanide salts or worse, HCN (at least the inorganic metal cyanides are just toxic, and liberate hydrogen cyanide on treatment with acids, they aren't highly volatile like cyanide gas (HCN) is), and if I can I'd far sooner prepare and use the diphosphorus tetraiodide, especially if the conditions are as mild as the abstract of the article I've seen so far (just need to pull the full article) claims and the yields as high as they make out (up to 95% in some cases) which would be very good, and better most likely yield wise, plus involving no inorganic cyanide salts...if the nitrile I have in mind gives as good a yield as that, or reasonable even, within the scope (45-90-95% depending on substrate) then this is looking better by the moment. Might even be able to use acetonitrile for something a little different than I had planned as a test case, say, formaldoxime to acetonitrile, and acetone oxime to test the beckmann rearrangement. I already have some acetone ketoxime prepared as a test case study actually, as simple practice in forming oximes themselves (via reaction with hydroxylamine hydrochloride, or the re-calculated for higher molar wt. of the sulfate ion compared to the HCl counterion if NH2OH sulfate is used in lieu of NH2OH.HCl, although I don't have to stress myself out with the math since my hydroxylamine is the hydrochloride, and use of a very mild base such as sodium carbonate or sodium acetate to deprotonate the hydroxylammonium salt to the base in-situ (the base isn't stable especially when heated, but thats avoided by in-situ formation, where its produced as fast as its consumed in the reaction itself rather than preparing and isolating the base separately)

Would be super-sweet if I can work out a one-pot for the nitrile>amine>secondary or tertiary amine and if I can find a way to go from carboxylic acid>nitrile in a one-pot, then oh so much the better.  Smiling all the way to the bank, as the expression goes. Especially at the no-cyanide-anion part. That I like very much, and oximes are not vicious evil bastards like cyanides, they can be difficult to crystallize, but the oxime functional group itself isn't virulent. Actually some oximes such as pralidoxime, obidoxime and others are used as part of the 3-component injector kits used by the military in counter-chemical warfare, to reactivate poisoned acetylcholinesterase enzyme if soldiers are poisoned by nerve agents.  And the aldoxime I have in mind shouldn't be evil stuff, and in any case, I'm not about to start rubbing it into my eyes, snorting lines of it, sticking it up my ass or any other method of delivery :autism:

this P2I4 compound is stable too, unlike the other phosphorus iodides known, and I have both red phosphorus and iodine (no, not for making meth). A little white phosphorus too. And if white phosphorus is needed for preparation of diphosphorus tetraiodide then so be it, I can prepare white from red easily enough, done that several times, even a kid could do it (albeit one got burned accidentally by the WP once, but he WAS a nipper just starting out in chemistry at the time)

Not difficult though, especially not on the scale of a a bit more or less than 10g of phosphorus, if I need the white, and as for the red, I've 2kg of that, minus any I've used already, and that just sits there until its called upon to react with something, or somebody does something like apply a flame, in which case it will catch fire and cause a massive smoke cloud of acid-smog, but as far as handling goes, red phosphorus, unlike white P, it isn't pyrophoric (I.e doesn't spontaneously catch fire of its own accord if left to its own devices), it isn't highly toxic (its used in fact in small amounts on the striker pads of safety match boxes, where meth cooks apparently spend time buying loads of those and scraping the red phosphorus off, and when I was just a little kid, got my first gram or two of red P for experimenting on preparing and using white phosphorus)

But no need to do that for me, since that 2kg certainly didn't come a few tens of mg at a time from matchboxes. All nice clean crud and additive-free lab-grade fine quality red P courtesy, originally of sigma-aldrich, one of the biggest chem companies out there, albeit one that won't so much as wipe their arses with citizen scientist's orders, they wouldn't even answer them to say 'no, piss off' afaik. But, as they say, 'where there is a will, there is a way. Or a dead relative'

And in my case, I didn't inherit my phosphorus from a dead grandparent etc. Just sitting there waiting for me to find that interesting looking diphosphorus tetraiodide article and to pull the full paper with sci-hub :) yay! no cyanide!  not something any chemist is likely to bitch about not having to use :LOL1:
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Offline Lestat

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Re: Questions for Lestat: Lestat's Lab
« Reply #109 on: February 06, 2018, 09:21:21 AM »
And, although I need either a pair of adapters to use the cows I have already with it to mount a short length of glass tubing leading to a pair of 24/40 or 24/29 male joints, my forkhead adapter arrived today.

It seems like there is more and more glassware arriving every day, every time I see a crate arrive or a styrofoam box wrapped in yellow packing tape, or the occasional rather distinctive blue dense styrofoam-like material crate-boxes for mediumweight loads of multiple lighter glass items (along with more fucking packing peanuts than I know what to do with, unless I decide to save it all up and after melting it down, subject it to a thermal depolymerization and Willgerodt reaction and make some phenylacetic acid, which is worth selling off, as stinky and toxic-gas-evolving as the Willgerodt-Kindler is, using styrene as a feedstock from pyrolysis of polystyrene back to styrene monomer, or valuable intermediates like styrene epoxide etc. or its epichlorhydrin and the like could be a way to, using sulfur and a few basic chemicals, perform the Willgerodt and flog off the resulting styrene derivatives after purification and distillation from glassware once pyrolyzed and all the accompanying likely tars and polymeric glorp (technical term that, highly technical, is 'polymeric glorp'. Its the technical scientific term for, well, glorpy shite thats polymerized and needs nasty treatment of glassware with pricier reagents, and better dealt with by using disposable stuff made of cast iron, tin cans and shite of that kind, in a 'fuck 'em , burn 'em and chuck 'em' kind of way. Sort of what you'd do with a really ugly drunken one night stand if you were that type, only with more blowtorching involved :autism:
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Offline Lestat

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Re: Questions for Lestat: Lestat's Lab
« Reply #110 on: February 07, 2018, 05:05:17 PM »
Heh as it happens, based on some reading I've been doing, I might just have use for a pyrolytic tube furnace, for a vapor-phase pyrolytic oxidative decarboxylation of a certain diphenylcarboxylic acid, using either a thorium dioxide based catalytic system, or perhaps a manganese salt-doped magnesium oxide impregnated onto activated charcoal, or onto porous ceramic like zeolites..wonder if my molecular sieves, if I got some with a pore size bigger than 3A (3 angstrom, a unit of atomic width), not sure how a manganese-dopant impregnated thorium dioxide catalytic furnace tube would perform. Although thorium is radioactive, although manageably so. And its looking like the magnesium oxide, spiked with IIRC trivalent manganese will be the better catalyst. Or alternatively I could go via pyrolysis of the lead salt of the acid itself, or possibly of its calcium salt. Not sure which works best though, calcium or lead.

Either way would provide my desired ketone. Or else I can look into amination routes via either cyanide-based or diphosphorus tetraiodide based synthesis and reduction of the nitrile to an amine.

I've heard whisper, of in the case of a different arylcarboxylic acid, phenylacetic acid, that yields with one of the nitrile routes to an amine, although it is a secondary amine that I need rather than directly a primary amine, and need to avoid reductive decyanation of course going via the diphenylalkylcyanide that is in mind. Reduction, yes but not the decyanation part, since it'd be the alkyl cyanide that provides the amine moiety upon reduction.

Got me a neat little biology project in the pipelines too. Something that targets not one, not two but three most sought after targets. And in combination too with two of either as a pair, but three? that'll be the ideal perfect storm in a single molecule.
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Offline Lestat

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Re: Questions for Lestat: Lestat's Lab
« Reply #111 on: Yesterday at 09:09:56 AM »
Now theres a bugger. Looks like the synthesis of that diphosphorus tetraiodide is quite easy, by a spontaneous disproportionation reaction of the unstable phosphorus triiodide in dry diethyl ether, to afford a solid, albeit water-sensitive, tractable solid crystalline reagent.

The phosphorus triiodide is easy enough, starting from red phosphorus and iodine. I am a BIT short on iodine, but only in the sense of its getting to be time to buy another couple of kg and bung it in the chemicals fridge, and use up what I have from my last tub full of I2. It isn't stable in the sense of being suitable for preparation of PI3 and keeping it in a bottle on the shelf, rather, its typically made in-situ due to its not being too stable, but its synthesis itself is easy, and in the case of P2I4, we WANT it to be unstable, otherwise it wouldn't disproportionate now, would it :autism:

But making it isn't difficult. Its the reagent formed in-situ by meth cooks reducing pseudoephedrine with elemental (red) phosphorus and iodine, kicked off by just a trace of water to allow the reaction to  first begin. And preparing it (although I've never done so in an ethereal solvent mind you) is very easy, by simply mixing together elemental iodine and the red allotrope of phosphorus. I've still got most of 2kg of red P, bought at a discount since I took advantage of the opportunity to grab some in bulk and took more than their 1kg minimum quantity order; that I picked up for two reasons, mostly for making other phosphorus-based reagents such as phosphorus trichloride, phosphorus pentachloride and the other halides of that sort and other less well known but still potentially very useful phosphorus-requiring reagents (its probably my favourite chemical element too, due to its A-having such a huge variety of interesting allotropic forms of the element with such widely differing physical and chemical properties, from the flammable, but not acutely particularly toxic red phosphorus, to the deadly-poisonous [about as toxic on a weight basis as potassium cyanide] white phosphorus, a waxy, soft solid which can be cut with a knife like a piece of cheese, and which if not stored under water, or other suitable containment, spontaneously bursts into a blinding white flaring flame with a lurid greenish tinge, due to the fact that it is the source of the word 'phosphorescence' and glows in the dark, in either small quantities too small to, or if in larger amounts, before it has had time to burst into flames, with a green glow that in the dark, one can write on paper with a stick with a blob of white phosphorus on the end and watch the writing appear, before finally igniting and burning the letters through the paper, to the black allotropes, nontoxic, not a flame hazard, difficult and demanding to make, and black, and taking on a layer-structure in sheets of phosphorus atoms, akin to graphite, and like graphite, possessed of electrical conductivity, to violet phosphorus, which isn't very well known, and takes quite some effort from what I've read, to make it, the easiest way, apparently being to sandwich red phosphorus between layers of lead metal, under inert gas, potentially with trace levels of doping chemicals as a catalyst in the phosphorus, hold it for at least 24 hours under molten lead, and then slowly, slowly, a few degrees at a time, recrystallize it from the molten lead before finally dissolving away the lead once cooled using nitric acid..been planning to prepare samples of them all, as display pieces for a periodic table showcase, red phosphorus obviously being first, since that takes no more preparation of a sample than putting some in a vial, under some inert gas then sealing the ampoule. Then white, in its various cubic, monoclinic etc. forms, that I can begin with as the first needing any effort more than pouring some out of a tub of something I already have, by heating red phosphorus under dry inert gas in a retort, using a blowtorch, and distilling it out into a long, deep column filled with ice-cold water topped off with a slurry of salted ice to condense the phosphorus vapors, then finally, cleaning off the oxides that make it white, which, I have read of someone doing, using a dichromate-concentrated sulfuric acid bath, then cleaning away the acid carefully by remelting under water, removing oxidizing agents..I want to see if I can prepare a crystal-clear sample like that and actually have it STAY that way, by doing the whole cleanup in boiled then vacuum-degassed, vacuum-distilled and argon-sparged ultrapure water, then ampouling it, after dessication, by carefully remelting it as many times as needed whilst standing over phosphorus pentoxide, a truly nutty-strong dehydrating agent, capable even of intramolecular dehydration of anhydrous sulfuric acid to form SO3, but without oxidizing properties, and finally sealing the amp under inert gas after repeatedly vacuum-purging a chamber built for the purpose, possibly using electrical heating to melt the glass of the amp neck....it would just be really neat if its possible to have a sample of ultra-pure WP that has been cleaned so thoroughly that the white color disappears and instead what is left, is clear, and have it storable. Using glass with additives to block ultraviolet light if needs be, which contributes seemingly to the normal discoloration of regular-purity white P.

As for my P2I4 synthesis, for dehydration-cyanidation of a carboxylic acid to a nitrile (nitriles are organic cyanides), which is a rather unusual type of reaction, but definitely a very neat one, and all the more so if I need no ionic cyanides at any point, for obvious reasons)....very slick. The one downside...looks like I need to run it in anhydrous carbon disulfide. I should be able to get some, and dry it. BUT...its not easy to obtain, even for me, via buying it. It doesn't seem to come up on ebay either, not for want of looking. Its toxic, it smells foul unless very, very pure due to thiophene impurities, when extremely pure it is said to smell ether-like, although I've no desire to inhale any to find out. And it is the mother of satan when it comes to flammability. Never worked with it, but from what I have read, dipping a glass rod in hot water, and touching the warmed glass rod to some CS2 is sufficient to ignite it. It isn't actually pyrophoric, per se, just has a ludicrously low temperature at which it will catch fire, needing only to be warm, no flames or sparks or static discharge needed, just a warm glass rod, at a temperature which wouldn't even burn human skin and enough oxygen to allow combustion to take place.

Although the dehydration-cyanidation reaction of the diarylalkyl carboxylic acid to form the corresponding nitrile intermediate I have in mind can be run in certain other solvents, most notably carbon tetrachloride (which I'd either have to put some significant effort into making from scratch, probably via chlorinating chloroform, which if I didn't buy or have someone wishing to trade me reagents for some chloroform, benzene and a couple of other things, I'd make by means of the haloform reaction, using sodium hypochlorite and caustic alkali such as lye or caustic potash [NaOH/KOH respectively] on acetone as the substrate. Yields aren't wunderbar, and it takes a large volume of liquid to prepare a decent volume of chloroform that way, and it is quite an exothermic reaction, gets pretty hot whilst its cooking up one's chloroform from scratch, but it could be the ideal baptism for my new 4-neck 5 liter flask :)

And it isn't like bleach and caustic are expensive, or acetone for that matter. And I already have some acetone, and can easily buy more if I want, got plenty of caustic soda and a kg of caustic potash [I use NaOH a LOT, but relatively little KOH, primarily I keep it around for either occasional use when NaOH isn't quite strong enough to deprotonate something in need of deprotonation but KOH will do so, without having to resort to alkoxides, sodamide, potassium hydride  [from weaker to stronger and increasingly dangerously reactive in > order, to say nothing of increasing stepwise in the same order in terms of being difficult to make or buy and more expensive to do either. Generally effort goes up in every sense there*

*actually I have a theory. That there is actually a linear relationship between how useful a chemical is and how expensive, difficult to find or make, and dangerous it is likely to be. The how low-use a given chemical is, being inversely proportional to the summed modalities of difficulty x cost+rarity.

I don't think it'd make for a uni thesis, but I've a distinct hunch that I am in fact, correct there. The more useful it is, the more its going to cost you and the bigger the ache in the bollocks it will be to make any, the lower your yields and the more dangerous the process is going to be, and the more flammable, poisonous, corrosive, difficult to contain, foul-smelling, foul tempered and the greater the likelihood of it being pyrophoric the end product will be.

In the case of CS2..the production process involves passing sulfur in vaporized, gaseous form through a tube furnace packed with coke as a carbon source and heating it to several hundred degrees, accompanied by an input of inert gas to prevent its just igniting, then carefully, meticulously condensing the searing hot carbon disulfide vapor down from red-hot coke temperature to room temperature or preferably below it as much as possible, before distilling it under inert atmosphere with a warm-water bath. Sulfur is a total pain in the arse if you need it in gaseous form, because whilst melting, it gets thick and viscous, like thickened motor oil, and there is bugger all way I'm using any of my lab glass to vaporise it from.

Instead if I have to make some for the solvent in my P2I4 R-COOH>R-C=-N inorganic cyanide free cyanidation reaction. I'll weld up a disposable metal still that I can fill up, torch from the outside or electrically heat, with a thin pipe connection with a one-way valve away from the heat to avoid melting it, that I can hook up to a cylinder of argon and a regulator, since the CS2 is hard to buy (not sure about price, I've never bought carbon disulfide before, or made it, or worked with it.

Only experience of it is reading of its properties and  character, it'll be a new one on me, short of having my nose in a chemistry textbook or journal reference. Not a first date I entirely look forward to. But, all the same, it does have its niche, specialist uses, and also it acts as an excellent solvent for sulfur, or for white phosphorus

[although a solution of WP in such a volatile and flammable, rapidly evaporating solvent is also a pretty incendiary kettle of fish to deal with and require the utmost care to be taken in preparation, use and handling of it, not something I'd even make up and keep, but rather, prepare, if ever I need WP in CS2, just the quantity that I am going to require then and there for a specific task at hand, make it and use it, so as to have no leftovers of such a volatile and dangerous mixture of toxic, pyrophoric WP in a toxic solvent with a hell of a low boiling point and that needs very little encouragement whatsoever to catch fire without anything else in it]

After that though it looks alright. Once the CS2 is in hand, and the organocyanide is formed, reportedly within a couple of hours, at room temperature when conducted in carbon disulfide, with yields up to 90% for some substrates and typically at least 80something percent, then distillation and recycling of the carbon disulfide will be a piece of piss, given the insanely low boiling point, and that distillations under inert gas (or vacuum distillation, but I'll do it under inert gas because vac distillation lowers the boiling point of whatever it is thats being distilled, which is often as not, the entire point of doing it under vacuum in the first place) are nothing new to me.

Followed by one of the reductions of nitriles to primary amines in the literature, whichever after some research and digging around seems to be likely to provide the highest yield of the primary amine intermediate. First potential candidate being in-situ formation of STAB (Na triacetoxyborohydride) from sodium borohydride (got plenty NaBH4 so no need to buy any more yet, got it stored under argon, in solid 1g-unit tablet form so less surface area to react with oxygen, the bottle of NaBH4 tablets itself, stored in the same metal outer can it came in from the factory, with the top cut out, and replaced by an improvised air shield consisting of the bubble-wrap pouch that a piece of my glassware came in stretched over the outer rim of the end of the metal can, the can itself, like the bottle, being purged with dry argon) NaBH4 already has a good shelf life too, its a lot more tractable and stable than most hydride reducing agents, to the point that it isn't even pyrophoric, and can even in some cases be used in aqueous or partially aqueous solvent systems! whereas say, sodium hydride, if a spatula-full be thrown at arm's length, whilst wearing a blast shield and goggles etc., into a bucket of water, then the result is an instantaneous decomposition, a sodding great plume of hydrogen and potentially catching fire, taking the hydrogen with it. The 'potentially' being a matter of only a spatula tip being thrown into the water. Larger amounts in contact with water, or atmospheric moisture are going to violently burst into flames and a large evolution of flammable hydrogen gas. Needless to say it needs very cautious storage and handling. Borohydride is pretty damn tame, compared. Although it bucks the trend of my little hypothesis about the linear relationship between price+propensity to bite your face off and crap on your skinless screaming skull afterwards, since its still really, really useful stuff for a large variety of uses. Not the easiest of reagents to buy but easy enough that ebay can often be a viable source :autism:

Once the nitrile is reduced to the corresponding primary amine via whatever route is eventually chosen as seeming best after research, the final step is, for the main end target (I've two, possibly three that I consider worth directing research time and resources at), reductive di-methylation to a tertiary amine. Not usually the easiest reaction, to react a primary amine and end up with either secondary or tertiary amines, sec.amines being particularly hard; because they become progressively more nucleophilic as they go from primary through secondary and most of all, tertiary amines, and its really easy, and in most reactions the result is peralkylation all the way to the quaternary ammonium salt. It is possible to effect dequaternization reactions, in some cases at least but thats one more step and ergo, less yield and more cleaning up to do.

But since this is a methylation, for the main target of interest, I plan to form an imine using excess formaldehyde and HCOOH as a hydrogen donor to go direct to the tertiary amine forming an intermediate secondary amine in the process via a subsequent imine or iminium ion, but its transient as the reaction goes on without isolating the 2' amine to afford the methylated tertiary desired. That is known as Eschweiler-Clarke methylation, and ends without quaternization since it relies on the formation of an imine or iminium species and the tertiary amine cannot form one, unlike a primary or secondary amine, so thusly that undesired, and usually significant or complete quaternization of the starting amine. And from then, after the Eschweiler-Clarke, its a matter of cleaning and recrystallizing to the desired standard of purity, and performing the usual analytical tests such as either TLC or paper chromatography and melting point tests of various salts, the freebase etc. on samples of a few milligrams a piece, packed into a microcapillary tube, strapped to a thermometer at the top with a rubber band and immersed in the oil filling of my Thiele tube. Once it passes my tests for purity, then my labors will be complete, and my target compound will be there, finished and sparkling clean as a pretty pile of crystals :)

And as far as the overall scheme goes, the end compound is known, and data like melting point, TLC RF values etc. are known, but the actual reaction I designed myself.

(https://en.wikipedia.org/wiki/Thiele_tube)
Beyond the pale. Way, way beyond the pale.

Requiescat in pacem, Wolfish, beloved of Pyraxis.