Educational

Author Topic: Questions for Lestat: Lestat's Lab  (Read 9507 times)

0 Members and 2 Guests are viewing this topic.

Offline Lestat

  • Pharmaceutical dustbin of the autie elite
  • Elder
  • Obsessive Postwhore
  • *****
  • Posts: 8965
  • Karma: 451
  • Gender: Male
  • Homo stercore veteris, heterodiem
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.
Beyond the pale. Way, way beyond the pale.

Requiescat in pacem, Wolfish, beloved of Pyraxis.

Offline Lestat

  • Pharmaceutical dustbin of the autie elite
  • Elder
  • Obsessive Postwhore
  • *****
  • Posts: 8965
  • Karma: 451
  • Gender: Male
  • Homo stercore veteris, heterodiem
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?
Beyond the pale. Way, way beyond the pale.

Requiescat in pacem, Wolfish, beloved of Pyraxis.

Offline Lestat

  • Pharmaceutical dustbin of the autie elite
  • Elder
  • Obsessive Postwhore
  • *****
  • Posts: 8965
  • Karma: 451
  • Gender: Male
  • Homo stercore veteris, heterodiem
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.
Beyond the pale. Way, way beyond the pale.

Requiescat in pacem, Wolfish, beloved of Pyraxis.

Offline Lestat

  • Pharmaceutical dustbin of the autie elite
  • Elder
  • Obsessive Postwhore
  • *****
  • Posts: 8965
  • Karma: 451
  • Gender: Male
  • Homo stercore veteris, heterodiem
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:
Beyond the pale. Way, way beyond the pale.

Requiescat in pacem, Wolfish, beloved of Pyraxis.

Offline Lestat

  • Pharmaceutical dustbin of the autie elite
  • Elder
  • Obsessive Postwhore
  • *****
  • Posts: 8965
  • Karma: 451
  • Gender: Male
  • Homo stercore veteris, heterodiem
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:
Beyond the pale. Way, way beyond the pale.

Requiescat in pacem, Wolfish, beloved of Pyraxis.

Offline Lestat

  • Pharmaceutical dustbin of the autie elite
  • Elder
  • Obsessive Postwhore
  • *****
  • Posts: 8965
  • Karma: 451
  • Gender: Male
  • Homo stercore veteris, heterodiem
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.
Beyond the pale. Way, way beyond the pale.

Requiescat in pacem, Wolfish, beloved of Pyraxis.

Offline Lestat

  • Pharmaceutical dustbin of the autie elite
  • Elder
  • Obsessive Postwhore
  • *****
  • Posts: 8965
  • Karma: 451
  • Gender: Male
  • Homo stercore veteris, heterodiem
Re: Questions for Lestat: Lestat's Lab
« Reply #111 on: February 19, 2018, 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.

Offline Lestat

  • Pharmaceutical dustbin of the autie elite
  • Elder
  • Obsessive Postwhore
  • *****
  • Posts: 8965
  • Karma: 451
  • Gender: Male
  • Homo stercore veteris, heterodiem
Re: Questions for Lestat: Lestat's Lab
« Reply #112 on: February 28, 2018, 03:54:03 PM »
Oooohhh.....looks like I've just found a particularly powerful vacuum pump within my price range, a diaphragm type, that is capable of getting right the way down to just 10 millibar, digitally controlled, and needs no oil being a diaphragm pump. I like it already. I'll still do some more window shopping on ebay but this might just be it, unless I can find an even more powerful one.

$364 total, inc. shipping, USD

Would be perfect IMO for vacuum distillation of a certain oxime that a colored sample of needs vac distillation to prepare a perfect white crystalline sample, and stop its tendency to oil out, like oximes are so wont to do.

Might buy myself a multistage rotary vane pump whilst I'm at it too as well.

Although I also need to buy some sensitive vacuum gauges in order to be able to control and monitor the vacuum in the systems its being used to evacuate, such as my rotovap, for vacuum distillation etc.

And I should have enough money for 3-4x those tall but narrow fritted buchner w/vacuum takeoff as well as for the pump I want, plus MAYBE also the multiple-stage rotary vane pump, buy some cryogenic traps for it to stop anything nasty getting close to the insides of my pumps.

Now I just need to FIND THAT DAMNED CARBON DISULFIDE!!! even if its just ten liters, hell, its a solvent that I only use very very rarely, for specialized purposes, and even a 5 liter can would last me a long time, especially with distilling it off and recycling every last drop I can redistill to recycle for reuse. Which with my solvents, I do wherever possible, its both better for the environment, and also better by far for my bank balance when I can use repeatedly washed, then distilled and re-distilled purified solvent for another reaction, and another, and another and another, for as many times as its practical to recover the used stuff and clean it back up to standard.
« Last Edit: February 28, 2018, 04:12:59 PM by Lestat »
Beyond the pale. Way, way beyond the pale.

Requiescat in pacem, Wolfish, beloved of Pyraxis.

Offline Lestat

  • Pharmaceutical dustbin of the autie elite
  • Elder
  • Obsessive Postwhore
  • *****
  • Posts: 8965
  • Karma: 451
  • Gender: Male
  • Homo stercore veteris, heterodiem
Re: Questions for Lestat: Lestat's Lab
« Reply #113 on: April 16, 2018, 09:56:47 AM »
Just a few pics I took of some new toys and resources :)

First, I'll introduce you to an aborted attempt to produce hydrogen bromide as the anhydrous gas, although it will be recycled, so to speak, in the sense of being used to convert it all to bromine.

(edit-img fixed, this be the brominator)


The funnel shaped like an inverted pear with a ] shaped side-arm connecting itself to itself, is a pressure equalized addition funnel, the sidearm allows the pressure to remain the same so long as the system isn't generating pressure and totally sealed, it was filled with concentrated sulfuric acid, a bit under 100%. Proved too oxidizing for my needs, oxidizing the HBr to bromine, Br2, its a halogen, the element under fluorine, then chlorine on the periodic table, positioned between the gaseous, greenish, sharp and swimming-pool-esque stomach turning chlorine gas, with its sharp biting sensation on contact with mucous membranes with the gas in sub-dangerous concentrationd

The top was plugged, so as to avoid the HBr gas coming out and escaping. Into a 2 neck flask, containing sodium bromide, and I'd jerry-rigged a couple of improv gas taps using the vacuum hose  barbs on a pair of buchner funnels of the fritted type, and duct taping over the top since I couldn't find my gas taps :soapbox:.

This then led to the copper tubing you see, bent into a =U= shape, and stuffed with finely powdered (tens of microns in grain size) copper dust. This, is because sulfuric acid is also oxidizing to a degree, not the most powerfully oxidizing mineral acid but it still is, and in the case of producing hydrobromic acid, a pain in the ass too much so.

HBr is colorless gas in the pure state, whilst Br2, you can see there peeking out. The solid is excess sodium bromide, I'll add more acid and a little bit of hydrogen peroxide later, to make sure its all converted to Br2, salvage the synth by turning the byproduct into the intended product. Works for me.

The mixed bromine and HBr, bromine being the visible one of the two, the, the dark, ruddy brown, foul smelling (the word 'bromine' comes from the ancient greek 'bromos' meaning 'stench', which I find well deserved.)

Kinda rotten eggsy, sharp, pungent and penetrating, not the 'nasty smell, but of cleanliness and sterility' sort of odor of the other two practically speakable, smell-able halogens, chlorine, probably familiar to most, although similar to bleach, its sharper as the element and choking, caustic and irritant to the eyes, mucous membranes etc, fluorine being way, way way too damn dangerous to muck about with for anything but an indispensable reaction, and I have never encountered a good enough reason to have anything to do with fluorine, anything that takes a tiny dilute stream of the stuff to cause a house brick to burst into searing, incandescent flames spontaneously on contact, and that melts your bones and leaches the electrolytes out of your blood and turns the calcium content to insoluble sludge in your cardiovascular system, I find rather a turn-off and a pretty good set of reasons to declare it persona non grata in my lab. Its virulent stuff, elemental fluorine, and so are a lot of its compounds, although as  a substituent group in org chem it does have uses alright, and ones I'm fine with, as a bioisostere for hydrogen and oxygen, but the element, its just vicious, most descriptions make it sound like a fucking nightmare.

It is. Its just worse than its made out to be. Eats glass, sets bricks on fire, sets...well most things, on fire on contact, most reactive of all the elements, most electronegative, which again means it has organic uses in biochem for when one wants a small substituent to mimic hydrogen, but that can't be chewed off, because carbon-fluorine bonds are, well, vicious, it grabs stuff and doesn't let go, personality summed up 'temperamental psychotic fuck with no regard for life or safety whatsoever and an electron klepto, with some serious issues forming attachments, once it does, it has an awful lot of difficulty letting go. Its like the borderline PD member of the periodic table. Even the unstable astatine and synthetic radioisotope superheavy element tennesine, want nothing to do with it so they run to the opposite end of the halogen group, leaving poor old chlorine stuck with the periodic table's biggest bastard as its next door neighbor.

So that, I've never smelled and  don't plan to, because you can't be autistic if you are dead :spazz:, but chlorine smells..well like chlorine..iodine, sort of surgical, sort of like the seaside, its sort of sharp, very fresh smelling if that  makes sense, cleanly and cleansing. Its a solid  and doesn't give off dense vapors  at room temperature, like  Br2 would, or as a gas  like Cl2 and  F2, so its less concentrated typically, and not all horrible and choking. I actually find the  smell of elemental iodine  somewhat pleasant)


This HBr synthesis generating Br2 is now going to be turned into a Br2 synthesis giving off some HBr. Recycle, use for other things. I'm not about to let the valuable bromine content just up and escape, when it can be distilled off, cleaned, dried and bottled for when I actually want some bromine)


Its meant for (the HBr I wanted) cleaving an aryl methyl ether, in a rather nifty tandem demethylation to the phenol and, using anhydrous glacial acetic acid  as the solvent for the reaction, forming the acetyl ester of phenol, which is my target in mind to begin with. And  exploiting the leftover traces yet again, by adding methanol, to strip the otherwise high-boiling glacial acetic acid, using the strong acid  (concentrated acetic acid, aka GAA, is a weak acid as  it doesn't fully dissociate in aq. solution) and HBr a strong one, and a strong acid is needed to catalyze these sorts of esterifications, where one basically refluxes an alcohol with the acid to form the desired ester, its called  a Fischer esterification, that reaction is to be used first to esterify the liberated intermediate phenol in-situ, then the added methanol is  used to form the methyl ester of the reaction solvent, sidestepping a pain in the ass of a high boiling point, even under vacuum. And  I can recycle the methyl acetate and  use it as a solvent or perhaps reactant for something.

The plastic tubing on the far side of the copper =U= tube is when gassing to prepare the solution of HBr in GAA, just stuck in a flask full of  glacial acetic acid, the heat turned on to strip bromine fumes out and a watch kept on the  color of  the GAA, since HBr is colorless and Br2 dark orange brown, plus the flask is placed on a digital weighing scale so I can calculate how  much hydrogen bromide is actually entering and staying in the flask.
« Last Edit: April 16, 2018, 01:30:48 PM by Lestat »
Beyond the pale. Way, way beyond the pale.

Requiescat in pacem, Wolfish, beloved of Pyraxis.

Offline Lestat

  • Pharmaceutical dustbin of the autie elite
  • Elder
  • Obsessive Postwhore
  • *****
  • Posts: 8965
  • Karma: 451
  • Gender: Male
  • Homo stercore veteris, heterodiem
Re: Questions for Lestat: Lestat's Lab
« Reply #114 on: April 16, 2018, 11:10:24 AM »
And a few more random bits and pieces of recent acquisition and projects either done, doing etc.

Some diisopropylaminoethanol, picked it up in order to halogenate it and then rip that halogen off as a hydrogen halide, to get me some diisopropylethylamine, aka Hunig's base, a strong organic amine base, which due to the two bulky, in the way isopropyl groups plus further alkylation to the tertiary amine, as diisopropylethylamine, aka Hunig's base, means that its more or less non-susceptible to alkylation or other substititions, although it remains able to interact with protons so it doesn't end up further substituted itself, during nucleophilic substitutions in which a reagent to serve as a proton acceptor is requisite, as a non-nucleophilic base, due to its great steric hindrance.

So I managed to pick up those bottles of diisopropylaminoethanol. Just needs the alcohol group removing, to give Hunig's base, which is usually quite expensive, but this was cheaper than I'd expect Hunig's base to be. Got 'em on ebay, on a fairly cheap offer.

https://en.wikipedia.org/wiki/N,N-Diisopropylethylamine


Beyond the pale. Way, way beyond the pale.

Requiescat in pacem, Wolfish, beloved of Pyraxis.

Offline Lestat

  • Pharmaceutical dustbin of the autie elite
  • Elder
  • Obsessive Postwhore
  • *****
  • Posts: 8965
  • Karma: 451
  • Gender: Male
  • Homo stercore veteris, heterodiem
Re: Questions for Lestat: Lestat's Lab
« Reply #115 on: April 16, 2018, 11:20:01 AM »
A set of new fritted buchner funnels of various sizes, as well as some new Erlenmeyer flasks, the Buchners came with that thing with the pistol grip and vacuum gauge mounted on the top underneath the trigger, its not a super-strong one, but its a handheld manual vacuum pump thats meant for suctioning things from Buchner funnels during vacuum filtrations. Came free with that, plus some vacuum tubing bits and pieces and a few keck clips, just plastic ones, but they are free, so I'm not complaining. If I'll use them or not is another matter, I use stainless steel ones, since they aren't assaulted like the plastic ones are, well, not so easily, by some of the things I use in the lab, theres a few things in a few specially resistant bottles that even traces of any of them in vapor form, dilute or not, will rip those clips to shreds in minutes, and with longer exposure, even stainless steel is made to crumble away to dust by some of them.

Beyond the pale. Way, way beyond the pale.

Requiescat in pacem, Wolfish, beloved of Pyraxis.

Offline Lestat

  • Pharmaceutical dustbin of the autie elite
  • Elder
  • Obsessive Postwhore
  • *****
  • Posts: 8965
  • Karma: 451
  • Gender: Male
  • Homo stercore veteris, heterodiem
Re: Questions for Lestat: Lestat's Lab
« Reply #116 on: April 16, 2018, 11:38:04 AM »


These crystals are a result of my experimentation with oxime syntheses. I was practicing, basically, at the techniques themselves, and forming a ketoxime, I just went with the hydroxylamine HCl and sodium acetate to deprotonate it to the freebase, and the cheapest, most easily available bog standard go-to 'generic ketone' that is available to me, acetone.

This is the oxime of propan-2-one, aka acetone, 2-oximinopropane, aka acetone ketoxime, synthesized by reflux in ethanol as solvent,  of the reactants acetone and hydroxylamine hydrochloride in a 1:1 molar ratio, plus sufficient NaOAc to deprotonate the hydroxylamine salt and prepare the needed hydroxylamine base in-situ (hydroxylammonium freebase is not something I keep around as it is, its unstable and can be dangerous) so its made in situ by using a mild base to deprotonate a hydroxylamine salt.

Oximes are often difficult to crystallize, and tend to oil out, although water is ideal for washing, because these oximes are well known as being insoluble in water almost totally.  This acetone ketoxime I happened to look in on, months after it was synthesized on the scale of a few grams in mini-scale.

Very pretty glittering clear crystals, interspersed with a few little lumps or granules of aggregated less pure, yellowish pale colored ketoxime, these were discarded and manually picked out and thrown away, not much just a few grains  and small aggregates. Leaving behind some clear crystals of acetone oxime. Very pretty IMO, coming as aggregates of well-formed much tinier individual crystals of glasslike clarity. Lovely looking, like tiny little diamonds fused together in bigger chunks of tiny diamonds if they were to be stuck together. Pretty, aren't they?
« Last Edit: April 16, 2018, 11:40:04 AM by Lestat »
Beyond the pale. Way, way beyond the pale.

Requiescat in pacem, Wolfish, beloved of Pyraxis.

Offline Lestat

  • Pharmaceutical dustbin of the autie elite
  • Elder
  • Obsessive Postwhore
  • *****
  • Posts: 8965
  • Karma: 451
  • Gender: Male
  • Homo stercore veteris, heterodiem
Re: Questions for Lestat: Lestat's Lab
« Reply #117 on: April 16, 2018, 11:54:17 AM »


Bromine souffle' The solids are unreacted, excess sodium bromide, reacted with H2SO4 whilst seeking hydrogen bromide with the apparatus I meant to post and will edit, that I put up first in this series, needs some more H2SO4 and an oxidizer, to ensure all HBr is oxidized to elemental bromine, the dark liquid is elemental bromine, the liquid member of the halogens, below green, pongy, acrid  chlorine gas and solid, silvery, metallic looking, beautiful iodine. (I have to admit, that the sight of big homogenous lumps of elemental iodine, looking for all the world, like little asteroids, metallic appearing, glittering, yet pitted and volatile, staining all it touches  dark brown, yet when a little iodine be heated in fr.ex a closed test tube, the vapor is not brown at all, rather its a gorgeous shade of deep violet.

I'll need to react this excess NaBr with some more sulfuric  acid and some hydrogen peroxide.
and then distill the result, under vacuum and  wash and dry the resultant bromine, before consigning it to one of my special super-resistant bottles that I know can take the kinds of punches that get thrown at them, with the threads wrapped in teflon tape to ensure that nothing noxious gets out, considering the things I use those special reagent bottles for containing)
Beyond the pale. Way, way beyond the pale.

Requiescat in pacem, Wolfish, beloved of Pyraxis.

Offline Lestat

  • Pharmaceutical dustbin of the autie elite
  • Elder
  • Obsessive Postwhore
  • *****
  • Posts: 8965
  • Karma: 451
  • Gender: Male
  • Homo stercore veteris, heterodiem
Re: Questions for Lestat: Lestat's Lab
« Reply #118 on: April 30, 2018, 04:52:21 AM »
Experimenting with another variation on producing Br2, this time, by passing a stream of chlorine gas, generated in the bottle with the white cap that you see to the left side of the flask, which has a filling of potassium permanganate, into which, via a length of plastic tubing grafted into the cap, a glass syringe is fitted, containing concentrated hydrochloric acid, dripped onto the permanganate, which oxidizes the HCl, giving off chlorine gas.

The Cl2 is then piped into the 2-necked RBF clamped to one of my clamp  stands via a length of plastic tubing fitted to the end of a pipette (to avoid the plastic being in contact with the bromine and both turning it to goo, dirtying my flasks with something really nasty to have to get off again, and to avoid contamination of my bromine.)

Currently, its been successful in discharging a steady stream of chlorine gas into the solution of sodium bromide in the RBF, which rapidly turned the deep red you can see in this picture, I'm hoping that once I've passed enough chlorine through, the bromine, which has a limited solubility in water will start falling out and collecting on the bottom of the RBF. The process works by virtue of the more electronegative of the two halogens, chlorine, competes with the less electronegative bromine in the sodium bromide to get that extra electron it so hungers for, by snatching the sodium cation out from under the bromide anion's nose and becoming sodium chloride in the process, displacing poor little bromine from it's comfortable anionic sofa, since it was too weakly electrophilic to avoid that big ol' bully chlorine pulling the rug out from under it :autism:


https://s7.postimg.cc/vlyezrvgb/Bromine_water.jpg

It already stinks something pretty foul, a mixture of noxious fumes, chlorine and bromine vapor, Br2 smells IMO worse than chlorine, and I really don't like the odor of chlorine. Both are sharp, irritating, choking and acrid, penetrating sort of smells, that irritate or burn the mucous membranes and definitely are most unhealthy if inhaled. But where chlorine can have a sort of sanitary, disinfectant sort of smell, nasty as it is, Br2 is similar in that its sharp, penetrating, acrid/burning and irritant, but IMO it has a distinctly musty, dirty, soil or decay and rotten sort of note to it. Quite offensive to the nose.

Which means the other lot, that is up in the lab in a stoppered flask, of bromine, mixed with concentrated sulfuric acid, is going to have to be distilled to purify it. And I can't say as I'm looking forward to having to do the distillation. I think I'm going to go on ebay now and buy myself a couple of things-A-a new gas mask of the full face visor type, either cartridge based or with a direct hookup to a tank of compressed air and a regulator, operating in a pressure supplied or demand valve based mode,

B-a couple of tubes of a perfluorocarbon grease, resistant to attack from near anything and everything, because many greases are attacked and degraded by bromine fumes, chlorine gas, or any bromine monochloride that might form transiently, which if iodine monochloride is anything to go by, following general reactivity trends, its probably even worse. And I consider iodine trichloride to quite possibly be one of the most dangerous substances in my lab, its extremely aggressive, highly toxic stuff. ]

And its not going to get more pleasant when iodine is replaced by the far less tame, more oxidizing bromine. The trend is more or less the more electronegative the halogens in an interhalogen compound, the more virulent its going to be. And iodine monochloride is, IIRC the very mildest, politest little church mouse of the interhalogen compounds, and it still disintegrates plastics within a few minutes even in very diluted vapor form, as well as severely attacking and corroding stainless steel in similar conditions, being exposed to diffuse, dilute ICl fumes and just turning into an organized, shaped piece of rust flakes, in a form corresponding to that of the original steel article before it got chewed to little pieces and spat back out screaming.

Aside from the Br2 itself, the portion that remains in solution, will be useful as well, after determining concentration and if needs be making a few tweaks and adjustments to molarity/percentage, as a dilute aqueous solution of Br2, known as bromine water is very useful for chemical analysis, because it is both strongly colored, and highly reactive, able to add across double or triple bonds, phenols, acetylated compounds and others, and also, given the reactivity with alkene double bonds, it can be used to determine the degree of unsaturation in a substance of known molecular formula and known sample size, by virtue of the fact that on addition of an alkene, bromine in the bromine water adds across the double bond to form an alkyl bromide, and the color disappears, so bromine water can be used for colorimetric titrations for determining things like concentration, degrees of unsaturation, and besides, another use for it, is that it doesn't take much bromine to make, its only a dilute solution. So I can make it up on the cheap (nothing wrong with it, not on the cheap as in cutting corners, it just doesn't cost me much to make) but then go and sell it on on ebay for a profit.

And of course, sell bromine itself, that is the sort of chemical all sorts of people would jump at the chance to buy themselves a bottle of dried, double-distilled elemental bromine in an amber glass bottle and resistant cap/seal.

Obviously I'd be keeping a lot of it for my own use, but if I do end up with a fair lot of surplus bromine, I bet I could make something like £500-600 a liter, and smaller quantities could still fetch a fair whack.



Beyond the pale. Way, way beyond the pale.

Requiescat in pacem, Wolfish, beloved of Pyraxis.

Offline Lestat

  • Pharmaceutical dustbin of the autie elite
  • Elder
  • Obsessive Postwhore
  • *****
  • Posts: 8965
  • Karma: 451
  • Gender: Male
  • Homo stercore veteris, heterodiem
Re: Questions for Lestat: Lestat's Lab
« Reply #119 on: May 20, 2018, 07:47:46 AM »
After finally freeing a stuck teflon-coated joint in a glass setup, I managed to pour out the liquid that came from hydrolyzed residues of iodine monochloride to form a funky hydrohalic acid that is, I believe, HCl2I. Most unusual.

AFAIK HCl2I, fucked up or what! TWO halogen species in a non-oxyacid hydrogen halide acid, and not just binary, but a trinary system! I am really quite surprised to find such a thing exists, although the interactions holding it together, I'm really not sure about....intermolecular hydrogen bonding to form higher-order polyanionic species, or intramolecular halogen bonding between chlorine and iodine..what in the name of fuck!

I'm not well up on halogen bonding either, its not widely known.From observation though it appears to be quite a strong acid, immediately attacking magnesium powder liberating hydrogen gas when a few drops of this hydrohalic acid mutant freak are added to a test tube containing perhaps 20-30mg or so of finely powdered magnesium metal. It tests as acidic as  the PH paper I tested it will actually read. Certainly PH1, perhaps below. Oddly it appears to bleach the coloration of the PH paper. The stuff I used was orange, it instantly went pinkish when a drop of the presumed HCl2I was placed upon it, and in an expanding zone, it went the bright pink-red of a PH-1 strongly acidic substance, but with the color of the paper itself returning after a moment, resulting in a spheroid with a center coloured the same as  the PH paper usually is meant to be, unused that is, almost as if without destroying the paper itself, it first caused the PH-sensitive indicator to give an acid-positive reaction and then destroyed the chromophore, nuking the dye whilst sparing the paper, although the physical observation has to be taken immediately, because the acid won't waste any time whatsoever in, it seems, attacking the PH-sensitive indicator dye or its protonated form.

Currently preparing the magnesium salt for further characterization of the acid. Might also some tetraammoniumcopper (II) complexes and use this oddball hydrohalic acid as the anionic portion of the metal complex. Should be able to crystallize a salt of tetraaminecopper (II) (itself prepared by adding a divalent copper salt to ammonia, upon which it goes bright, vivid, deep  ultramarine blue, very pretty in concentrated solution)

Plenty other things on my plate today. For some reason they mostly seem to involve halogens. All of them except fluorine and of course both astatine (extremely radioactive, longest lived isotope has a half life of about 8 hours, just over 8 hours) and tennesine (created artificially, a superheavy transactinide element first made a couple of years ago IIRC, created a few atoms at a time and detected via its decay chaining)

(astatine isn't THAT ultra-radioactive as to disintegrate within microseconds to milliseconds, but tennesine is about as stable as donald trump with a crack pipe in hos mouth.) Although even so, without external freezing, a sample of astatine of visible size would vaporize it in it's own heat of radiolysis, its own radiation cooking it extra crispy basically,nobody has ever seen astatine, its only ever been detected, never brought about so that a pair of human eyes could look at it through lead-glass windows could have a look at some astatine before it vanishes due to its decaying  to other elements)

Would fucking love to see it though, if a target were ever to be made in a cyclotron, and then neutron bombardment of bismuth to transmute it to astatine, using the correct isotope of bismuth, and cooled with say, liquid nitrogen or liquid helium, to be able to actually SEE some elemental astatine, because its right on the border, it seems between semimetal (metalloid) and a metal, on one half, and a nonmetal on the other.

Theory predicts it to behave as with iodine, similar oxidation states etc., a hydrogen halide, HAt formed, but with a more metallic character than iodine. And indeed astatine MIGHT even BE a metal or a semimetal.

(semimetals are usually the elements used for semiconductors, silicon, germanium, one of the allotropes of arsenic, tellurium and selenium, are good examples. Look like metals, yet quite different. If I were to take a hammer in my hand and strike a piece of tellurium or selenium 'metal' it would shatter like glass even though it looks like a metal.  Its electrically conductive in this state, and yet unlike a metal, if it were lit, it would melt with a cigarette lighter flame and produce a small and nonviolent flame, not superhot like metal fires, although the vapor I REALLY wouldn't want to be anywhere near, in the case of tellurium.

https://en.wikipedia.org/wiki/Tellurium The pic just a bit down, it REALLY looks like a metal doesn't it? but it isn't. It's fragile like sulfur, of which it is a heavier relative, and it burns and melts like sulfur afaik.  Although I haven't personally picked up a stick of Te 'metal' and lit the end to see how it burns. Especially because of the notorious 'tellurium breath'.

Which put it this way....people have apparently, committed suicide after being exposed to Te
and absorbing traces of the element, subsequently excreting them in shit, piss, sweat, saliva, anything coming from a mucus membrane with fluid there..its apparently so foul that chemists even use 'tellurium breath' as an insult hahaha/
Beyond the pale. Way, way beyond the pale.

Requiescat in pacem, Wolfish, beloved of Pyraxis.