Ether is cheap to make using denatured (methanol only) ethanol. One simply needs boiling hot concentrated sulfuric acid, and to drip in the alcohol from a sep or addition funnel. Too hot and you get mainly ethylene (ethene), IIRC right temp is about 120'C, just keep the boiling sulfuric lower than 150 and you're golden mate, slow addition of EtOH drip by dribble and distill out the diethyl ether as it forms. Its an old fashioned method but far cheaper than the william synthesis, where an alkoxide is reacted with an alkyl halide. Or tosylate, brosylate, nosylate etc. but not essential. And really, ethanol and concentrated sulfuric is as cheap as your gonna get. 60 quid for a liter of ether is a fucking rip IMO. I wouldn't pay that for one liter of ether, buggering bollocks to that for a lark.
Also with regards to ether(s), they should not be feared, but are often highly flammable and very volatile. Also, they have a tendency towards forming extremely heat, shock and friction-sensitive primary high explosive peroxides and some less hideously unstable but still unstable and nasty shit hydroperoxides.
These can, in the case of old bottles of ethers, accumulate in the screw thread of the bottle, from the ether in the vapor phase passing through the threads.
Needless to say, this is a bad thing, and it turns from a bottle of old solvent, into a bomb. No two ways about it. A bomb. Courtesy of the highly brisant, powerful and unstable HEs in crusty old ether. This can do devastating damage when it goes off. I've seen a picture of the aftermath of such an event. In this case I believe the ether in question was THF (tetrahydrofuran, a common cyclic ether used as a solvent, in particular, I and others, use it for performing reductions using LAH (lithium aluminium hydride, LiAlH4) and other hydride reducing agents, as a polar aprotic solvent.
It had peroxidized, and gone off with an almighty wallop. Ground zero, took the form of a fridge. Or rather what was left of a fridge after the bottle of peroxidized ether inside went off like the bomb it was, blasting the fridge to pieces, which were subsequently blown through the ceiling, not few of those pieces of discombooberated fridge actually embedded IN the ceiling, straight up blown through the fucking roof like armor piercing bullets in fridge-innards form.
And not to mention, as an aside, the shockwave blew out every damn window in the lab of the poor bastard who's lab it was.
Thankfully, that was a laboratory other than mine own well nigh life-long labour of love, thank fuck, mine own pride and joy remains un-blasted by peroxidized THF-bottle-bombs and it lives to research another day (as of course, do I
)
To test for peroxides beginning to form in ethers, such as diethyl ether, THF, dioxane (a cyclic diether with more than one positional isomer, however 1,4-dioxane, where both oxygens are oriented para to each other, is the commonly used lab solvent), and diisopropyl ether, a nifty solvent useful especially for extracting polar compounds from polar solvents, but which should be handled with great caution because diisopropyl ether has bought advance tickets for the peroxide prom. Its even bought it's own peroxy-prom dress way in advance, wearing a sexy pair of secondary carbon atoms adjacent to the ether bridging oxygen, ethers that are slutty and wave a pair of secondary carbons right up in lil' miss oxygen's face, are well known for being particularly naughty and can be explosive when challenged.
Before entry to the ball they, and especially naughty old diisopropyl, should be rigorously searched for concealed weapons lest the shifty sod be concealing peroxides and the intermediate hydroperoxide, this search can be accomplished by means of test papers made by soaking potassium iodide solution into starch-rich paper; if peroxide is present it turns iodiney violet-black and then the peroxides can be destroyed by means of addition of manganous salts, or ferrous (not ferric, ferrOUS) chloride. Then the ether needs to be distilled once the peroxide is destroyed. Then test again and once peroxide free, distill and keep in an airtight bottle. I degas mine by means of sparging with a tank of argon, the hose connected to one of those fishtank airstones to bubble it through, then fill any deadspare in the bottle with the heavy, inert argon gas too, and store cool, away from direct sunlight. Direct sunlight, sparging the distilled ether with inert gas, its not vital, hell its probably overkill, but I don't want my lab blasted to smithereens by a massive shockwave. It is the work of a lifetime, and I've had to put it together and repair it twice thanks to illegal abuse from the fucking pig filth donutmunching cunts.
What I've put together, my lab setup is truly, a labour of love, I like nothing better than with the money I do not consume as food and beverage, or drugs of course, to purchase new equipment, love it when solvent refill days come and I go and restock bigtime after saving up lots, and of course ESPECIALLY, I can think of nothing non-human that I adore more, than either buying, or being bought, new lab glassware. (such as, I was positively fizzing with delighted gleefulness and grinning like a dirty great big grinner that just shot up a huge line of coke and started grinning wide enough to tear its own grin off to reveal the big fat grin below, the time my old man got me a new vacuum pump and pump oil for a recent years barfday
)
Moral of the story, watch your ethers, don't be afraid of them, remember the volatility and flammability. Treat diethyl ether for peroxides using iodide test strips and if peroxidized to a dregree as shown up by the strips then go in with ferrous iron salts or manganous salts. Store the treated ether, after distillation to purify, with a decently sized coil of copper wire in the bottles, this will help prevent more peroxidation from occurring.
Diethyl ether-inspect yearly.
Diisopropyl ether peroxidizes especially rapidly, inspect it every three months.
THF also peroxidizes somewhat quickly, but not nearly as demoniacally fast as iPrOiPr, I'd test it every somewhere in the middle and remember, secondary alcohol ethers with the secondary carbon snuggled up next to the bridging oxygen atom peroxidize fast. Also when USING ether, THF or whatever (whatether, rather...see what I did there
) they should never be distilled to dryness, don'l let a still with ether in it boil dry, because this concentrates the peroxides if present and can induce explosion. Its better to when taking off the last of the ether of whatever kind, to test for/treat for peroxides, a drop withdrawn with a pippette on the iodide/starch paper is all you need, if you get a reaction with it, then treat as usual, add some more of a less volatile, higher boiling solvent, then evaporate the ether from that, finishing, if you need the solvent gone and cannot extract from it, actually need it evaporated, by doing so with the higher boiling solvent once the ether has gone from it. Remember the possibility that some solvents form azeotropes; mixtures that once a certain concentration is reached distil at a constant ratio respective of each other.
There, hope the tips and wee niblet of safety advice regarding the cheap way to prepare, and best, safest ways to store, use and handle diethyl ether and other ethers you may come across in the lab proves useful.
LC
