Limpet_Chicken
Bluelighter
- Joined
- Oct 13, 2005
- Messages
- 6,323
Feeling fucking frustrated. I've been searching hard for some carbon disulfide, CS2; and I am having a lot of trouble. I keep my eye open of course on the likes of ebay and amazon just to see if any CS2 turns up. I think I COULD make it, but it requires passing sulfur in the gaseous form through a tube-furnace, basically a metal pipe heated from the outside with multiple high-temperature flames or with electrical resistance wire wrapped externally in asbestos to keep the heat in, and internally, the space packed with coke (as in the coal-derived carbonaceous fuel) heated to a red heat, then passing the sulfur, heated itself until it becomes gaseous, and propelled with an inert gas to push the sulfur gas though the coke. This forms, apparently, although as of this particular moment I have never performed the task, carbon disulfide.
Problems being that its EXTREMELY flammable. So much so that according to my reading, there mere act of holding a glass rod that has been dipped in hot water, close to CS2 is enough to set carbon disulfide ablaze. VERY very flammable stuff, and its one of the most acutely toxic solvents going, not counting extreme reaction conditions that involve things like electrolysis in anhydrous cryogenic liquid hydrogen fluoride gas or other truly hazardous in the extreme situations like that, things not even I would attempt due to sheer deadliness and utter lethality, things performed using magic methyl (methyl fluorosulfonate) which is fucking heinously toxic and carcinogenic as you can get, and the preparation isn't anything pleasant either, involving distillation of a mixture of fluorosulfonic acid and dimethyl sulfate, both being VERY toxic, and extremely dangerous, fluorosulfonic acid hydrolyzes to hydrofluoric acid and is a very powerful acid, CHLOROsulfonic acid I would handle, even though its an extremely corrosive, powerfully acidic chemical, toxic and moisture-sensitive giving off seriously nasty fumes, but at least it doesn't destroy glass, chlorosulfonic acid is vicious and dangerous stuff and dangerous to prepare too, but it is something I can manage and handle, but fluorosulfonic acid is something I want nothing to do with whatsoever. And dimethyl sulfate is a HIGHLY toxic methylating agent (and it will methylate DNA, and methylate YOU as well as methylating whatever substrate one wishes to methylate, and poisonous enough that there is a record of someone eating a hamburger close to where someone was working with Me2SO4 in a fume hood. They died days later. (this wasn't a hobbyist or/and clandestine chemist, this was in a professional lab). I avoid using DMSO4 myself, I've never used it so far, I will if I have to, but rather than dimethyl sulfate, I'll use methyl iodide, which is more manageable and although still highly toxic and carcinogenic, mutagenic etc. its a lot safer than dimethyl sulfate, although more expensive if bought. Although I'd not buy it, but rather, make it, since the fundamental ingredients are cheap, if one buys iodine in bulk, which I do when I need to re-buy iodine whenever I run low and buy more. The 'ingredients' being simple, very cheap methanol, dried first with quicklime, distilled from it, then a catalytic quantity of red phosphorus to form phosphorus triiodide in-situ, which is continually regenerated from more methanol, whilst elemental iodine is added, to form methyl iodide, which is then carefully, and wearing full protective gear, distilled in vacuo and stored out of light, after purging with argon inert gas or nitrogen, in amber glass bottles in the fridge (no, not the one used for food, hell no!, there is more than one fridge in the house, and while one of them is used for food storage of course, another is dedicated to storing things you'd not want to have near food, such as say, my iodine monochloride, chromyl chloride (both home-made), my tubs full of elemental iodine since its volatile and likes to escape through containers, or sublime onto the top with some remaining in the vapor phase unless its kept cold, keeping bottles of bromine, solvents like acetonitrile (methyl cyanide), ethers like THF, diethyl and diisopropyl ether, and various other solvents, as well as volatile oxidizing agents and corrosives that need special containment and are best kept as cold as possible in storage.
And I use MeI as much as possible when I need a powerful methylating agent, since its much more safe to handle, as long as proper safety precautions are followed, than Me2SO4. I can get all the iodine I want, and obviously, buy big 4 gallon drums of things like methanol, dry the latter with conventional dessicants like anhydrous sodium or magnesium sulfate, distill it, then dry by distillation over CaO (or if I want it ABSOLUTELY anhydrous, then distill again and distill it once more over calcium carbide, which chemically reacts with water and forms acetylene gas, driving off the last traces of water), then react with iodine, catalyzed by a little bit of red phosphorus, and of that I've no little supply, got about 2kg of very high quality red phosphorus (came originally from sigma-aldrich, through a couple of contacts, cost me just 80 euros a kg, would be more but I got a deal from my supplier, who themselves has to go through a contact of their own, so there is a little markup since both have to earn their crust, which is fair, but my to-supplier contact gave me a discount, since minimum order for red phosphorus is one kilogram, and I purchased two at once so each cost me less, and the total came to just 80 eur/kg. No, not for meth making, I've more than one way to skin amphetamine-shaped members of the order Felidae if I wished to do so, but phosphorus based reagents have a very large variety and a great deal of interesting and highly useful compounds, both common and less well known; from triphenylphosphine to phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide/pentabromide, the less stable phosphorus triiodide, and the stable but little known diphosphorus tetraiodide, a most useful sounding reagent prepared via disproportionation of PI3 generated in-situ in diethyl ether, or else through another phosphorus halide.
Fluorosulfonic acid itself is prepared by reacting hydrogen fluoride (anhydrous) with sulfur trioxide, HF being outright deadly poison, and sulfur trioxide, that I CAN handle if I have to but it IS nevertheless most dangerous and great care is required in its use, production and handling, SO3 being the acid anhydride of H2SO4 (sulfuric acid), or alternatively fluorosulfonic acid can be made by reaction of reaction of calcium fluoride and oleum (a solution of sulfur trioxide in anhydrous, 100% sulfuric acid, basically sulfuric anhydride in sulfuric acid, known as fuming sulfuric acid, and extremely corrosive, water-sensitive giving off extreme heat if moisture gets to it, and billows off fumes of sulfur trioxide), and then purging the resultant liquid with argon or nitrogen to free it of hydrogen fluoride (the gas corresponding to, when in solution, hydrofluoric acid and likewise extremely dangerous, with even a small area of skin contact being potentially fatal, and requiring IMMEDIATE response in the form of injecting the area with calcium gluconate and slathering calcium gluconate topical gel over the area, to cause the HF to react with the calcium gluconate rather than have it chelate the calcium from blood, forming insoluble calcium fluoride, and leaching calcium from your bones causing massive hypocalcaemia which results in a fatal heart attack), that must be done whilst one waits for the paramedics to arrive in the ambulance.)
Definitely not nice to make, not nice to store, not nice to use, nothing nice about it whatsoever. Its one of those things that I'd be REALLY unhappy and uncertain about making or using at all, save for the most extreme circumstances. Chlorosulfonic acid, sure, although dangerous stuff, but fluorosulfonic acid is just bad news. And even in professional labs, magic methyl (methyl fluorosulfonic acid ester) is banned in many of them methyl trifluoromethylfluorosulfonate (methyl triflate) being used instead now, with that triflate group being an excellent leaving group, as triflate groups are [triflate being the common term for trifluoromethyl fluorosulfonate as a leaving group, or triflyl for a substituent, the OTf group is a super leaving group, much better than even iodine, like the tosylate group which is perhaps more often used, that being derived from the far safer and easier to handle toluenesulfonic anhydride or toluenesulfonyl halides]
Alkylating agents of all kinds are never friendly as a rule, but methyl iodide is a much safer alkylating agent for introducing the methyl group. And besides its easy to make with that methanol iodination using catalytic quantities of red phosphorus. And since I already have kilos of red phosphorus of top notch purity, none of that crap recovered from matchbox striker pads by desperate meth cooks, but of the very best quality from a chemical company renowned for its excellence in produce and service, although one that will not sell so much as a drop of distilled water nor a stick of chalk or piece of paper to a user other than a formally accredited organization or governmental department. Sigma-Aldrich are cunts like that. If I myself contacted them directly they'd doubtless not even reply to an email. Not even to tell me 'no', they'd just ignore it. (rude if you ask me, at the very least they could acknowledge a refusal of service to be polite and civil)
Thankfully I have a guy who has a guy who can get things from them and sell them on to the guy I have, who can then sell the products I need on to me. Both of course do not do it for nothing, so its not the base price from sigma I pay, but there is a markup for each to make some earnings, which given they are providing an otherwise extremely difficult service to access to hobby chemists, that I do think is more than fair, that they get to earn from their services, they can't be expected to have charity demanded of them. But said service IS useful. Someone that can get all the things they need from Sigma, get them to the hobbyists, and are happy to be.....lets just say very, very, very discreet about what they send things as. (for example a bottle of trans-cinnamyl chloride, and one of n-butyric anhydride both came described as 'glass cleaner and glass polish' and phosphorus as 'red terrarium sand' and at a customs value of next to nothing
I'm certainly not complaining, and the contact does do truly excellent service.
If I have to, I'll go through them, or else get hold of a contact in eastern europe, latvia or poland I think. Who should be a lot cheaper, otherwise it means the passing gaseous sulfur thorough an externally heated metal chamber or pipe packed with coke, and connected to a BIG and wide surface area metal custom-built copper condenser, with efficient cooling, perhaps a multistage condenser with separate coolant baths and then carefully distilling the product repeatedly under inert gas to prevent fire.
But, I really cannot dispense with the CS2. Not a solvent I like, or that I want to use more than I need, but it does have its speciality uses and some reactions where its just that solvent which must be used to get proper yields of whatever it is one is making.
Problems being that its EXTREMELY flammable. So much so that according to my reading, there mere act of holding a glass rod that has been dipped in hot water, close to CS2 is enough to set carbon disulfide ablaze. VERY very flammable stuff, and its one of the most acutely toxic solvents going, not counting extreme reaction conditions that involve things like electrolysis in anhydrous cryogenic liquid hydrogen fluoride gas or other truly hazardous in the extreme situations like that, things not even I would attempt due to sheer deadliness and utter lethality, things performed using magic methyl (methyl fluorosulfonate) which is fucking heinously toxic and carcinogenic as you can get, and the preparation isn't anything pleasant either, involving distillation of a mixture of fluorosulfonic acid and dimethyl sulfate, both being VERY toxic, and extremely dangerous, fluorosulfonic acid hydrolyzes to hydrofluoric acid and is a very powerful acid, CHLOROsulfonic acid I would handle, even though its an extremely corrosive, powerfully acidic chemical, toxic and moisture-sensitive giving off seriously nasty fumes, but at least it doesn't destroy glass, chlorosulfonic acid is vicious and dangerous stuff and dangerous to prepare too, but it is something I can manage and handle, but fluorosulfonic acid is something I want nothing to do with whatsoever. And dimethyl sulfate is a HIGHLY toxic methylating agent (and it will methylate DNA, and methylate YOU as well as methylating whatever substrate one wishes to methylate, and poisonous enough that there is a record of someone eating a hamburger close to where someone was working with Me2SO4 in a fume hood. They died days later. (this wasn't a hobbyist or/and clandestine chemist, this was in a professional lab). I avoid using DMSO4 myself, I've never used it so far, I will if I have to, but rather than dimethyl sulfate, I'll use methyl iodide, which is more manageable and although still highly toxic and carcinogenic, mutagenic etc. its a lot safer than dimethyl sulfate, although more expensive if bought. Although I'd not buy it, but rather, make it, since the fundamental ingredients are cheap, if one buys iodine in bulk, which I do when I need to re-buy iodine whenever I run low and buy more. The 'ingredients' being simple, very cheap methanol, dried first with quicklime, distilled from it, then a catalytic quantity of red phosphorus to form phosphorus triiodide in-situ, which is continually regenerated from more methanol, whilst elemental iodine is added, to form methyl iodide, which is then carefully, and wearing full protective gear, distilled in vacuo and stored out of light, after purging with argon inert gas or nitrogen, in amber glass bottles in the fridge (no, not the one used for food, hell no!, there is more than one fridge in the house, and while one of them is used for food storage of course, another is dedicated to storing things you'd not want to have near food, such as say, my iodine monochloride, chromyl chloride (both home-made), my tubs full of elemental iodine since its volatile and likes to escape through containers, or sublime onto the top with some remaining in the vapor phase unless its kept cold, keeping bottles of bromine, solvents like acetonitrile (methyl cyanide), ethers like THF, diethyl and diisopropyl ether, and various other solvents, as well as volatile oxidizing agents and corrosives that need special containment and are best kept as cold as possible in storage.
And I use MeI as much as possible when I need a powerful methylating agent, since its much more safe to handle, as long as proper safety precautions are followed, than Me2SO4. I can get all the iodine I want, and obviously, buy big 4 gallon drums of things like methanol, dry the latter with conventional dessicants like anhydrous sodium or magnesium sulfate, distill it, then dry by distillation over CaO (or if I want it ABSOLUTELY anhydrous, then distill again and distill it once more over calcium carbide, which chemically reacts with water and forms acetylene gas, driving off the last traces of water), then react with iodine, catalyzed by a little bit of red phosphorus, and of that I've no little supply, got about 2kg of very high quality red phosphorus (came originally from sigma-aldrich, through a couple of contacts, cost me just 80 euros a kg, would be more but I got a deal from my supplier, who themselves has to go through a contact of their own, so there is a little markup since both have to earn their crust, which is fair, but my to-supplier contact gave me a discount, since minimum order for red phosphorus is one kilogram, and I purchased two at once so each cost me less, and the total came to just 80 eur/kg. No, not for meth making, I've more than one way to skin amphetamine-shaped members of the order Felidae if I wished to do so, but phosphorus based reagents have a very large variety and a great deal of interesting and highly useful compounds, both common and less well known; from triphenylphosphine to phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide/pentabromide, the less stable phosphorus triiodide, and the stable but little known diphosphorus tetraiodide, a most useful sounding reagent prepared via disproportionation of PI3 generated in-situ in diethyl ether, or else through another phosphorus halide.
Fluorosulfonic acid itself is prepared by reacting hydrogen fluoride (anhydrous) with sulfur trioxide, HF being outright deadly poison, and sulfur trioxide, that I CAN handle if I have to but it IS nevertheless most dangerous and great care is required in its use, production and handling, SO3 being the acid anhydride of H2SO4 (sulfuric acid), or alternatively fluorosulfonic acid can be made by reaction of reaction of calcium fluoride and oleum (a solution of sulfur trioxide in anhydrous, 100% sulfuric acid, basically sulfuric anhydride in sulfuric acid, known as fuming sulfuric acid, and extremely corrosive, water-sensitive giving off extreme heat if moisture gets to it, and billows off fumes of sulfur trioxide), and then purging the resultant liquid with argon or nitrogen to free it of hydrogen fluoride (the gas corresponding to, when in solution, hydrofluoric acid and likewise extremely dangerous, with even a small area of skin contact being potentially fatal, and requiring IMMEDIATE response in the form of injecting the area with calcium gluconate and slathering calcium gluconate topical gel over the area, to cause the HF to react with the calcium gluconate rather than have it chelate the calcium from blood, forming insoluble calcium fluoride, and leaching calcium from your bones causing massive hypocalcaemia which results in a fatal heart attack), that must be done whilst one waits for the paramedics to arrive in the ambulance.)
Definitely not nice to make, not nice to store, not nice to use, nothing nice about it whatsoever. Its one of those things that I'd be REALLY unhappy and uncertain about making or using at all, save for the most extreme circumstances. Chlorosulfonic acid, sure, although dangerous stuff, but fluorosulfonic acid is just bad news. And even in professional labs, magic methyl (methyl fluorosulfonic acid ester) is banned in many of them methyl trifluoromethylfluorosulfonate (methyl triflate) being used instead now, with that triflate group being an excellent leaving group, as triflate groups are [triflate being the common term for trifluoromethyl fluorosulfonate as a leaving group, or triflyl for a substituent, the OTf group is a super leaving group, much better than even iodine, like the tosylate group which is perhaps more often used, that being derived from the far safer and easier to handle toluenesulfonic anhydride or toluenesulfonyl halides]
Alkylating agents of all kinds are never friendly as a rule, but methyl iodide is a much safer alkylating agent for introducing the methyl group. And besides its easy to make with that methanol iodination using catalytic quantities of red phosphorus. And since I already have kilos of red phosphorus of top notch purity, none of that crap recovered from matchbox striker pads by desperate meth cooks, but of the very best quality from a chemical company renowned for its excellence in produce and service, although one that will not sell so much as a drop of distilled water nor a stick of chalk or piece of paper to a user other than a formally accredited organization or governmental department. Sigma-Aldrich are cunts like that. If I myself contacted them directly they'd doubtless not even reply to an email. Not even to tell me 'no', they'd just ignore it. (rude if you ask me, at the very least they could acknowledge a refusal of service to be polite and civil)
Thankfully I have a guy who has a guy who can get things from them and sell them on to the guy I have, who can then sell the products I need on to me. Both of course do not do it for nothing, so its not the base price from sigma I pay, but there is a markup for each to make some earnings, which given they are providing an otherwise extremely difficult service to access to hobby chemists, that I do think is more than fair, that they get to earn from their services, they can't be expected to have charity demanded of them. But said service IS useful. Someone that can get all the things they need from Sigma, get them to the hobbyists, and are happy to be.....lets just say very, very, very discreet about what they send things as. (for example a bottle of trans-cinnamyl chloride, and one of n-butyric anhydride both came described as 'glass cleaner and glass polish' and phosphorus as 'red terrarium sand' and at a customs value of next to nothing
I'm certainly not complaining, and the contact does do truly excellent service.
If I have to, I'll go through them, or else get hold of a contact in eastern europe, latvia or poland I think. Who should be a lot cheaper, otherwise it means the passing gaseous sulfur thorough an externally heated metal chamber or pipe packed with coke, and connected to a BIG and wide surface area metal custom-built copper condenser, with efficient cooling, perhaps a multistage condenser with separate coolant baths and then carefully distilling the product repeatedly under inert gas to prevent fire.
But, I really cannot dispense with the CS2. Not a solvent I like, or that I want to use more than I need, but it does have its speciality uses and some reactions where its just that solvent which must be used to get proper yields of whatever it is one is making.
