Haven't tried this yet, but I just by chance found this publication by a member of sciencemadness.org, an unusually facile synthesis of the versatile reagent, sulfur trioxide, the acid anhydride of sulfuric acid, SO3. Usually a rather difficult reagent to synthesize, and definitely dangerous to handle, being an extraordinarily powerful dehydrating agent, violently, explosively reactive with even small quantities of water. Useful for making dimethyl sulfate, diethyl sulfate and similar dialkyl sulfates, potent alkylating agents, via reaction of dialkyl ethers with sulfur trioxide. And by reacting SO3 with sulfur dichloride, SCl2, the extremely valuable reagent, thionyl chloride, which is watched by three letter agencies, if you get what I mean, to some degree, too much for my liking. Oh boy, SOCl2 is JUST the sort of reagent I'd absolutely love to be able to make myself, thats making it look accessible for DIYing with the sulfur trioxide synthesis. Oh this is NIIICE.
And I can make the SCl2 at home I should think, without too much difficulty by chlorinating sulfur powder with Cl2 gas, and fractionally distilling the product to separate out the disulfur dichloride, any sulfur monochloride etc. and saving those for other uses. Still useful, for chlorinating things amongst other things. Plenty of delightful sulfur halide chemistry to be had there. But SOCl2 is the REAL prize amongst sulfur/halogen chemistry. And thionyl bromide would be even MORE useful to have as well, because the bromide anion is a better leaving group than chloride, so could perhaps improve the yields where the halide is just being used as a leaving group to stick some nucleophile on there in it's place. As well as making acyl halides, alkyl halides (the alkyl bromides would give a higher yield generally than the corresponding alkyl chlorides, probably not matter too much with acyl halides, carboxylic acid chlorides are reactive enough as they are, reacting really rapidly).
http://www.sciencemadness.org/member_publications/SO3_and_oleum.pdfReading this atm. Found a finished writeup for hydrazine synthesisl synthesizing it from urea via a ketazine. Urea is cheap as shit, and generally speaking not the most exciting chemical in the world. But, hydrazine on the other hand, N2H4, a relative of ammonia, although much more 'excitable' so to speak, very useful reducing agent amongst other things. The freebase of hydrazine is volatile, and highly dangerous, but this route furnishes the sulfate salt, which can be stored far more safely, and hydrazine freebase generated in-situ and distilled into a reaction mixture or solvent for addition to a reaction mixture, outside and wearing a gas mask and full protective gear due to its severely toxic nature Urea.....made exciting. Damn. But nicely stored as the sulfate salt, a crystalline solid, which can be deprotonated with KOH or NaOH and the hydrazine driven off and dissolved in a solvent, carefully.
Since, hey, who wouldn't want to have hydrazine on tap
Just starting from high-purity urea, a little gelatine to bind trace transition metal ions and trap them, safely sequestering them away from the reaction where they would foul up the reaction and potentially completely fuck it up, MEK (methyl ethyl ketone, a common solvent similar in nature to acetone, often use for cellulose thinners), sulfuric acid and sodium hydroxide, as well as strong sodium hypochlorite, which I happen to have a huge glut of, more than I'll use in a bloody looooooong time, after going on a late night/early morning random walk one sleepless night and just happening to chance upon a rather large drum of industrial strength hypochlorite, of just about the strength demanded for the hydrazine synthesis.
http://www.sciencemadness.org/member_publications/hydrazine_sulfate_ketazine.pdfI think I just found a couple of new projects that should provide me with a good challenge, and endless fun and especially in the case of the sulfur trioxide synthesis, finally, the access to SO3 needed to produce my OWN thionyl chloride and thionyl bromide. Fuck....Ing...SWEEEET
Although I do have another project that takes precedence, or shall do once I can obtain some nitromethane. I need both nitromethane and nitroethane for it, for something special, and very, very rare, that as far as I can tell has possibly never even been synthesized, that will tax my skills in microscale chemistry, for I need to get definitely two, and possibly as many as four end compounds starting from just 5g of a rare, precious, DAMN difficult to obtain and most unusual starting compound. I have that, although at considerable expense, nearly £100 for the 5g I have to work with. I have the nitroethane, but no nitromethane left. I'll only need a few milliliters, but I do have plenty other uses for nitromethane, so I'll probably grab a 5 or 10 liter can of the stuff. Will need some specialist, very mild and selective hydride type reducing agents, something that won't abstract the bromine atom from an phenyl bromide, whilst reducing an aliphatic nitro paraffin group and an aliphatic double bond, both at the same time. Considering looking into Red-Al, aka vitride, as the reagent I'd otherwise use for the nitroalkene reduction to the aminoalkane, Lithium aluminium hydride, has considerable potential to rip that bromine atom right off the aromatic ring, which considering the tiny quantity of the starting compound available to me, its huge cost, and the fact I need to stretch it into at least two, more likely four different products, maybe ending up with just half a gram of end product, a gram of each if I am both fortunate, work with a light touch, and great care, just enough for the tests I need to perform plus characterization of the melting point, and thin-layer chromatography analysis to determine RF values, although for the TLC and melting point analysis that won't take anything worth note, even for such delicate work, as I'll only need a few milligrams for each test, although running the MP tests still needs to be done for each target compound in triplicate, it takes only a few tiny little crystals sealed in a glass microcapillary tube, and slowly heated in the oil bath of a Thiele tube.
I've even had to buy some glassware specially for these syntheses, such as a Buchner funnel of the type with a glass frit, in this case of small capacity, just 30ml, and with a tall, narrow profile rather than squat and wide, and in this case, having a frit with an upper porosity size of just 5 microns. Which of course means gravity filtration is out the window completely, and I'll be filtering it under vacuum, the Buchner having a 24/40 ground glass joint with a vacuum hose barb on the side to hook it up to a vacuum line, the frit is tiny, meaning my precious products will be nicely confined on a frit a little less than just 30mm wide, and of such fine porosity that the tiniest crystals will be collected and retained. So fine, in fact that even bacteria will be stopped from passing through the pores of the frit.
Had to buy it specially, and at not inconsiderable price, cost me over £50 for the one piece of glassware. And I have a small (100ml or so) 3-neck flask just for the purpose. Actually I may even work with my 10ml micro-scale round bottom 24/40 flasks, or something like a 50ml RBF for the filtration, and will be using the absolute latest bleeding-edge technology for synthesis of the intermediate between starting material and the nitroalkanes (plus catalytic base, in this case something rather special, an ionic liquid catalytic base, that has been known to give almost stoichiometric yields for other, much more commonplace instances
of the same overall field of chemistry, which I'm not altogether inexperienced with, although the ionic liquid base catalyst will be entirely new to me, so I'll test it with both completely non-precious intermediates of the same overall chemical type, and reactions first, as well as some more precious by far, but obtainable
materials, more exotic, but I want to build up a library of tested intermediates of the same overall structural patterns, just with different substitutions on the phenyl ring than the bromine atom in the unusual position it is located in, one nigh totally unexplored in scope for electron-withdrawing substituents such as halogens, cyanide groups, nitro or trifluoromethyl groups, and also another oddball, a difluoromethyl ether. Going to be quite some fascinating and very novel research indeed, quite possibly a first, and almost certainly a first-in-man trial of the end products, two of them certainly, although whether I can squeeze all four desired compounds out of that 5g of intermediate....oh boy, it'll be taxing work on such a delicate material on such a tiny scale, but I'm going to thoroughly enjoy myself doing it
Can't WAIT to grab some nitromethane so I can proceed. Tempted to do the half of the work with nitroethane first as I have it, but no nitromethane. But, the starting material is air-sensitive too, just to make things more challenging and difficult, although perhaps even if oxidation does take place can salvage it, by reacting the resultant substituted benzoic acid with thionyl chloride and then reacting the resultant benzylic acyl halide with sodium azide followed by reduction of the arylalkyl azide in mild conditions to afford the desired amines. In fact I might even use that route, but first, I'll stick to what I know, albeit at the cutting edge
of synthetic procedures, where I'll have the added bonus of broadening my knowledge and capabilities. Because hopefully this, the ionic liquid catalytic base will be an improvement over even the microwave irradiation-based route that I've been using for this particular type of synthesis with other starting materials, which is very, very fast, and gives a quite pure product in better yields by far than the old route using conventional heating, this I should be able to run at room temperature, under inert atmosphere and with degassed, then argon-sparged solvents.
Then, after that, maybe I'll let my hair down a bit and work on sulfuric anhydride (sulfur trioxide) synthesis, production of oleum (concentrated H2SO4 with additional dissolved sulfur trioxide, known as oleum, fuming sulfuric acid, or to use the archaic nomenclature, fuming oil of white vitriol) and on hydrazine synthesis via the ketazine process, using gelatin to bind trace levels of transition metal ions which otherwise would throw a spanner in the works and lead to my getting back dick all. Still, caustic soda, sulfuric acid, urea, methyl ethyl ketone, hypochlorite, nothing there is precious or super rare or hard to get, all commonplace starting materials. I'll treat myself to a brand new flask for it though, one I know has never, ever been treated with sulfochromic acid etch to strip out crap, as the Cr (VI) used, even in traces, would probably result in it's interference with the hydrazine synthesis using the ketazine route. And the urea I'll use, I'll have to buy some near analytical grade urea, of super-high purity and specifically trace metal ion free.
