You do run into a few papers that actually use it as a reagent in synthesis, but I believe that those can be counted on the fingers, which is a good opportunity to remind oneself why they’re all still attached. H2SO4 in an *open* flask at r.t. … He said: “I observed gas emission…”. 1-Diazidocarbamoyl-5-azidotetrazole was produced by diazotizing triaminoguanidinium chloride with sodium nitrite in ultra-purified water. Sodium azide and DCM combination does explode in scale up conditions even causing fatality. Azide - Az I Am (OUT NOW) ⤷ https://fanlink.to/AZiAM Subscribe and turn on notifications to stay updated! (That’s been settled by their empirical formulas, which generally look like typographical errors). Not until 1987 was an improved procedure published, from Helge Willner and group in Hannover. This is an impressive figure, although I suppose the diffractometer was never in danger. 9 January, 2013. Wong’s diazotransfer. Good old sodium azide, which is no mean poison itself, will do that with just about any bromide that’s capable of being displaced at all. Finally, you don’t want to put any of these solutions in the freezer – a particularly timely warning, since that’s one of the first things many people might be tempted to do – because that’ll also concentrate the azide as the solvent freezes. Because this is basically the only result of sniffing HF on purpose. I never heard this caution before, and, while it makes sense, I don’t think I would have thought of it before doing that sort of reaction (in fact, I may have done that sort of reaction before). That would add two and free up two nitrogens with double bonds to each other. It would sell, man. Now, I have to wonder what makes good sovents for organo-azide compounds? © 2021 American Association for the Advancement of Science. . The cyanogen azide used to make them. But Campbell forgot, and you can guess what the last question on those same orals was …. One such is dinitroacetylene which apparently has not been synthesized yet though one hopeful monograph was titled, “On the Path to Dicyanoacetylene”. But does it live up to the hype? In other news, the link to the recent Angewandte paper by Derek is broken. It’s a beast, all right. For those who read German, here is an interview with Klapötke. @6: A Chemical Squonk, from Squonk: A small amount of sodium azide was deposited on the brass filter during normal operation of the unit. I thought I’d kill two birds with one stone, and as well as introducing a wider audience to Derek’s sterling writing about such chemistry (and I’ll join the chorus clamouring for him to write that book! – Swiss-German for hood is Kapelle (chapel), One would assume that they keep the stuff cold (to reduce thermal energy levels), and keep it in the dark (to decrease the chance of photon induced decomposition)? No detonation occured, and the fumehood removed all the produced HN3… a pretty lucky guy. How about “dimercuric tetraazide”? I hope anyone to deal with azides would read this very important experience article, in advance; before they experience anything bad. That’s a common theme in explosives, this longing to return to the gaseous state, and nitrogen-nitrogen bonds are especially known for that spiritual tendency. Obviously the instability of the type of compounds are not determined by merely the number of nitrogen atoms in the molecule, but rather by the ratio of nitrogen to other atoms. 1-Diazidocarbamoyl-5-azidotetrazole, informally called “azidoazide azide”, is a heterocyclic organic compound crammed with 14 nitrogen atoms. Cyanogen azide, N 3 CN or CN 4, is an azide compound of carbon and nitrogen which is an oily, colourless liquid at room temperature. Actually, the careless researcher shouldn’t even work with cyanogen azide, or anything like it, but you never can tell what fools will get up to. I bet the next graduate student in Klapoetke’s lab gets the job of replacing one of the carbons with nitrogen. … He made a clever capture by mimicking the squonk and inducing it to hop into a sack, in which he was carrying it home, when suddenly the burden lightened and the weeping ceased. The papers mention several detonations inside the Raman spectrometer as soon as the laser source was turned on, which must have helped the time pass more quickly. Just reflux chloropicrin with sodium azide in some suitable unreactive solvent, say dimethylformamide? Gee, chemists sure know a lot of ways to start reactions they can’t stop. If you have any interest in really scary compounds check out In the Pipeline: and the tag "Things I Won't Work With" as Derek Lowe has some wonderful descriptions. It depends on the azide. At least still have all my appendages …. Share your stories! I wonder if you could get a bp of NCN3 using a waldo and isolation, similar to nuclear weapons and actinide research, and avoiding any expensive equipment other than the bp apparatus (and maybe a cheap camera with a lens at the long end of a fiberoptic cable). . Seems likely to me…, I think I once suggested a compound that would be fairly insane to synthesize, azopicrin, (N3)3CNO2,triazonitromethane. The selenium tetra-azide is another yellow solid, like the tellurium compound, but it’s rather harder to keep it down on the farm. Ja! I’m an electrical engineer, my lab accidents are usually accompanied by a blue flash and acrid smoke. Azides have featured several times in the Things I Won’t Work With series, starting with simple little things like, say, fluorine azide and going up to all kinds of ridiculous, gibbering, nitrogen-stuffed detonation bait. They had several nasty detonations, always on rotovap (the diazidomethane concentrated in the mix…) As far as I know, there’s no problem with acqueous sodium azide in low concentrations. Cheers, Press J to jump to the feed. Two, pentazenium also exists (a nitrogen-only linear cation). Anyway, once you have azopicrin as a vapor or solution in a safe concentration, you could make some very interesting things, things very difficult and expensive to otherwise make assuming they have been successfully synthesized at all. The explosiveness of N3CN isn’t mentioned as much, although her group has substantial explosive experience so it may be why. Alcon Research, Ltd., 6201 South Freeway, Fort Worth, Texas 76134, U.S.A. February 25, 2011; Well, it’s been a bit too serious around here this week. A subreddit for really great, insightful articles and discussion. © 2021 American Association for the Advancement of Science. Thankfully I’m a pharmacologist so I don’t really have to play with things that go bang (although various neurotoxins I used in my PhD always engendered a certain healthy respect) but I do remember one lab that used to use sodium azide to stop algae from growing in the large waterbaths used for bioassays. The smallest possible loadings in shock and friction tests led to explosive decomposition. Aryl azides can have decomposition onset below 100C. Turned out KSCN worked BETTER but they would have done it…! Doesn’t seem any tricker than the red phosphorus/potassium chlorate mixtures, fulminating silver or nitrogen triodide I routinely made as a kid in my backyard lab. Great post – thanks Derek. I take on a few years of chemistry experiments to try and find out. Squonk hunters are most successful on frosty moonlight nights [or liquid nitrogen], when tears are shed slowly and the animal dislikes moving about. PIs gone AWOL? Now I have no idea if it’s possible even to attempt a synthesis of this, and given what Derek has documented here about various poly-nitrogen compounds and their proclivities, I suspect this molecule will be another hideously unstable species, deserving of the epithet “crater bait”. Much more emphasis is placed on the potential explosiveness of the aminotetrazole products than of cyanogen azide (which doesn’t turn out as badly as it could have). I suspect that an easy and inexpensive method of making hexanitroprismane and octanitrocubane would be of great practical and military interest. And, I’ve never been so happy about the 4500 miles between me and this lab… although, if that stuff goes wrong, I’m sure I’ll see the explosion from here. I remember reading about another bicylic compound, formula CN7H, that was formed by treating 1,5-diamino tetrazole with nitrous acid. Oxygens))/(No. Do we have some published source for these kind of techniques and important aspects of synthetic chemistry ?? Is it just so explosive that noone’s managed to create it, or is there some sort of quantum physics reason that this chemical wouldn’t work? The ‘arm’ is a bit redundant and actually bad English. These are funny posts! He does this stuff to find new materials for ecological bombs (!). It’s described as “a colorless oil which detonates with great violence when subjected to mild mechanical, thermal, or electrical shock”, and apologies are made for the fact that most of its properties have been determined in dilute solution. It’s the two carbons that bother me. ), indulge in a little speculation here. And since azides are not known for their benevolence under the best of conditions, I can only imagine how much they want to wreak unholy vengeance on anyone that dares force them to take a positive charge. Oh, I forgot to tell you of the welder’s jacket, the face mask, the leather gloves and the sliding face shield. Yeeagh. Do you? Things I Won’t Work With: Chlorine Azide. Generally, as the molecular weights get smaller, the vapor pressures get higher, and the % of nitrogen in the molecule gets higher, the more you have to worry about having unexpected pyrotechnics. Fixed. They make the whole compound impure… For Milkshake-Please,please,please write down all the tricks you know and publish it- I bet it will be a bestseller in chemical world. http://www.chtf.stuba.sk/~szolcsanyi/education/files/Chemia%20heterocyklickych%20zlucenin/Prednaska%203/Doplnkove%20studijne%20materialy/Tetra-%20and%20Pentazoles/C2N14%20-%20An%20Energetic%20and%20Highly%20Sensitive%20Binary%20Azidotetrazole.pdf. glamdring – azide in CH2Cl2 is NOT OK – but the diazidomethane formation is quite slow so the ignorant fools like yourself often get away with it. r/labrats: Got lab stories? Please follow the sub's rules and … Very interesting. Another one! My job does not really include the possibility of poising or blowing myself up, which might be a good thing. 586k members in the geek community. To me, that structure is a flashing red warning sign on a dead-end road, but then, I suffer from a lack of vision in these matters. These substances are both reasonably stable and exceptionally powerful. Azidoazide will explode if. Do folks usually take any precautions with other organic azides, and are these known to explode? Tertiary alkyl azides are more stable than secondary, primary ones because no alpha H. Trityl azide lives up to about 250C when it slowly splits N2 (and rearranges to N-phenyl benzophenone-imine). The reason why low molecular weight azides are more detonation prone, especially in concentrated form, is that the kinetic energy transfer from a fragment recoil (after highly energetic decomposition of single molecule) onto the next azide molecule is more efficient: you have less opportunity for unproductive recoil transfer on inert parts of a molecule to dissipate it. Cyanogen Azide For example, its boiling point, the 1972 paper notes dryly, has not been determined. @Jonathan Both the initial communication and the follow-up publication go out of their way to emphasize that the compound just cannot be handled: Due to their behavior during the process of synthesis, it was obvious that the sensitivities (of these compounds) will be not less than extreme. I mean, come ON! These articles are better than the BOFH articles in The Register! Basically, it was the same reaction, but done slowly and Teutonically. … Hruby group au U of Arizona used this methodology to make homochiral aminoacids with methyl in alpha, beta and orthophenyl position. I heard later he was doing a sabbatical at NIST or somewhere close, and blew up a fume hood. But yeah also just because of the structure you couldn’t have the same molecule but with an extra nitrogen in the ring, the ring of a pentazole can only have one substituent. tetraazidoallene – just plain weird, Either München(German) or Munich(English) but not Münich . How does one actually crystallize and collect data on something that explodes *in solution*. In true pioneering fashion, they are pushing the boundaries of limitation. A good candidate for that would be cyanogen azide, which you get by reacting the bromide with good old sodium azide. But, you know, watch the thing anyway. Man, that’s some crazy stuff…. Lou Coury recommended this article to me. It is probably the least active acylating agent that works adequately at room temperature—reaction times are typically several days at 0 °C (cf. Reaction with lead or copper pipes can build up highly explosive azide salts. . level 1. It’s fantastic to see that funding is still given to pursue such crazy research! Cursed in an entirely different way than most of the content here. . In completely unsurprising news Klapötke mentioned in an interview he did with the German newspaper Zeit that he is mostly deaf in one ear and that the other one isn’t doing that well either. And you don’t want that. I am sure not many professors even know all these finer details of the practical chemistry. Klapotke and others are doing it for the same reasons and the adrenaline rush of course… 2) Couldn’t they add something else to water baths than NaN3? “A book begging to be written: “Lowe’s Chemical Bestiary.” Azide Makes, Hacks, Reviews and Breaks technology. There were scattered reports of the compound in the older German and French literature, but since these referred to the isolation of crystalline compounds which did not necessarily blow the lab windows out, they were clearly mistaken. You made it? Things I Won’t Work With: Polyazides. Browse our Scrabble Word Finder, Words With Friends cheat dictionary, and WordHub word solver to find words that end with azide. And if you are minded to make some yourself, then you are on the verge of not existing at all, either. If you add an azide to the pentazole you suddenly have 8 nitrogen atoms and they really want to be 4 nitrogen molecules. 17- If concentrations are high it’s better to control the pH: hydrazoic acid is a nasty beast. Sodium azide is a preservative used for inhibiting the growth of contaminants, such as bacteria or fungi. from Wonder Drug Press? When we last checked in with the Klapötke lab at Munich, it was to highlight their accomplishments in the field of nitrotetrazole oxides. One, pentazole exists (an aromatic ring with a single hydrogen attached). When I imposed an ice/water bath and an acqueous NaOH trap he said: “Why??? Maybe under cryogenic conditions something might show up or maybe if you warm up the dicyanoacetalene just a bit….. Much more practically important would be explosive polymers. @Hap Full paper available here: http://www.chtf.stuba.sk/~szolcsanyi/education/files/Chemia%20heterocyklickych%20zlucenin/Prednaska%203/Doplnkove%20studijne%20materialy/Tetra-%20and%20Pentazoles/C2N14%20-%20An%20Energetic%20and%20Highly%20Sensitive%20Binary%20Azidotetrazole.pdf. (The person who determined it would have to communicate the data from the afterworld, for one thing). Be safe! How does one actually crystallize and collect data on something that explodes *in solution*. Today we have a fine compound from this line of work, part of a series derived from N-amino azidotetrazole. The question is whether you’re going to be able to get a long enough look at the material before it realizes its dream of turning into an expanding cloud of hot nitrogen gas. Since their hindered substrates were much lazier in the substitution reaction, they were refluxing them in DCM with the stuff for days… Oh, and they were doing it on multigram scale, too. Eugene, you mean Darwin Awards? Bigger booms, through chemistry | The Unemployed Chemist, American Association for the Advancement of Science. By Derek Lowe 25 February, 2011. It resembles ClN3, BrN3, and IN3 in this respect. They look like they have more nitrogen than is consistent with bench stability. Since these pioneering works, however, catalytic enantioselective C–H amination with azides has not advanced significantly. It can also interfere with antibody conjugation and inhibits the activity of the enzyme horseradish peroxidase. Something that blows up when exposed to bit of infra red light is pretty close in my book.. Under no circumstances should you pour sodium azide solutions down the drain. It would be interesting to make dimers of each half. -anedocte mode on- It depends on the azide. Higher ploymers of CNO2 radical would also be interesting. It might actually be possible to replace the azidotetrazole with pentazole; pentazole derivatives exist. Nonetheless, it should be noted that Zhang and coworkers recently achieved effective catalytic intra-58a,b and intermolecular 58c benzylic amination with sulfonyl, phosphoryl, or alkoxycarbonyl azide and the cobalt(II)–porphyrin complex 28 or 29 (Schemes 41 and 42). Photolytic dissasociation of azopicrin should be a plentiful source of NCO2 radicals. But these folks are a different breed. Notice that if you photochemically disassociate the 3 azide groups, you will get the CNO2 radical, basically a carbon atom attached to a nitro group. Inhalation is a likely route of accidental exposure for sodium azide powder or sodium azide solution. I will admit to doing a little happy dance when I saw this. of Carbons) + (No. I will read it to my wife, whose degree is in biochem, as tonight’s bedtime story. The compound was called Thiotimoline. (I’m pretty sure HN3 is pretty toxic as well as being toxic – bp 37C.) Since these pioneering works, however, catalytic enantioselective C–H amination with azides has not advanced significantly. Derek Lowe's commentary on drug discovery and the pharma industry. @ Peter #47: That’s not acrid smoke; it’s magic smoke. I hope…. @ RB Woodweird – Holy cow, I just realized working for Klapotke must be like owning the Bottle Imp. We didn’t try that again. Who can devise the most exotic nitrogen allotrope using ball and stick models. To 23. Two rings of six singly bonded nitrogen atoms, with the rings bonded to each other via the spare bonds. Since I work with microprocessors, the scale is manageable. The most hopeful projection suggests that it would be as costly as gold to make. So I should not sue this as a click linker? He said, “I wouldn’t have smelled that.”. I’m so happy to see this feature back! N12. With a suitable definition of spontaneous I suppose.. Yazeran, How do they crystallise it? There was nothing but tears and bubbles.” I do not see how this is any more extreme than tetraazidomethane. I am sure that it is as sensative as it is powerful. This shows a really commendable level of persistence, when you think about it – I don’t know about you, but one exploding spectrometer is generally enough to make recognize a motion to adjourn for the day. I think we have the makings of a contest here, incidentally. Wait … the azide groups are taking a POSITIVE charge? Right you are, Stefan – not sure what my forebrain was doing on that one. The compound is wildly, ridiculously endothermic, with a heat of formation of 357 kcal/mole, all of which energy is ready to come right back out at the first provocation (see below). Now, to do this without comitting hara-kiri, you should have azopicrin dissolved in a suitable and nonreactive solvent to a safe, non-explosive concentration. The original story was structured as a spoof scientific article (although published in a science fiction mag). Myself, I saw God. The only stories I remember hearing about azide explosions involved transition metal azides. “the number of research groups who would even contemplate a resynthesis can probably be counted on one well-armored hand.” Well I do not think you could exchange any of the carbons, however I think it is theoretically possible (from my high school fiddling with ball and stick chemical models that is) to break the second double bond and attaching a THIRD azide group to the last carbon…. All content is Derek’s own, and he does not in any way speak for his employer. Only think I’ve ever used it in water or methanol. Well, it’s been a bit too serious around here this week. When we last checked in with the Klapötke lab at Munich, it was to highlight their accomplishments in the field of nitrotetrazole oxides. Since these pioneering works, however, catalytic enantioselective C–H amination with azides has not advanced significantly. He was a biochemistry professor before becoming a full-time writer, and loved setting science fictional ideas in as ‘realistic’ a scientific frame as possible. Beiherhund das Oder die Flipperwaldt gersput!) Because of the large number of high-energy nitrogen bonds, the compound is extremely explosive. Well there was this “Summer Intern” and I wanted to show her how to handle tBuLi but the humidity in the lab made the bottle extra wet so when I picked it up…, I remember getting a pretty good whiff of HF. F. D. Marsh at DuPont made the real thing in the 1960s (first report here, follow-up after eight no-doubt-exciting years here). Now all the kids will think HF is a powerful hallucinogen and you know where it goes from there. You start off by making absolutely pure anhydrous hydrogen azide, … I wonder if there might be any compounds of these (and perhaps the more mundane amines and azides), possibly with some carbon glue to keep things from spontaneously exploding at LN2 temperatures. The stuff is very toxic and very volatile, and reactive as can be. • Heavy metals (e.g., Cu, Pb, Ba) form shock and pressure sensitive compounds with azide anions. The well known hexanitrobenzene would be a very likely result, but this compound is sensitive to light and perhaps under illumination its formation could be suppressed in favor of its much more interesting isomer, hexanitroprismane and (let us hope!) Alkyl azides are more stable than aryl azides. Clean the work area by wiping with soap and water once your work is done. “Things I Won’t Work With” is already a perfect title. When you read through both papers, you find that the group was lucky to get whatever data they could – the X-ray crystal structure, for example, must have come as a huge relief, because it meant that they didn’t have to ever see a crystal again. So this is the Killer Joke of organic chemistry? I hooked up the water line on the THF Still to the N2 inlet on the condenser and when I turned it on… Azide is one of the Nucleophiles of the Gods, like thiolate anions – if your leaving group doesn’t leave when those things barge in, you need to adjust your thoughts about it. Oh, and to everyone else; I’ve used very small amounts of azide in things like CHCl3 and I still have all of my appendages. Another cyanogen azide paper is in OL from Shre’eve’s group. Yep, below the detection limits of a lab that specializes in the nastiest, most energetic stuff they can think up. Enough said. #things-i-won't-work-with. Most of the others are physical chemistry, studying its decomposition and reactive properties. RLW. Process Res. Unfortunately, making it from already scarce and expensive cubane is so difficult that only minute amounts have been synthesized, too small to test its explosive properties. After warming things up (you’ll … In fact it turns out to support longevity. I bet the next graduate student in Klapoetke’s lab gets the job of replacing one of the carbons with nitrogen. Octanitrocubane if it can be isolated in its high density crystalline form would be expected to be the most powerful known conventional explosive. Nonetheless, it should be noted that Zhang and coworkers recently achieved effective catalytic intra-58a,b and intermolecular 58c benzylic amination with sulfonyl, phosphoryl, or alkoxycarbonyl azide and the cobalt(II)–porphyrin complex 28 or 29 (Schemes 41 and 42). While we were inside waiting his mother came home with his 2 year old brother… Dev., 2008, 12 (6), 1285-1286 But, who knows? I remember the dire warnings against using azide in DCM. We’re talking high-nitrogen compounds here (a specialty of Klapötke’s group), and the question is not whether such things are going to be explosive hazards. It’s a beast, all right. When we last checked in with the Klapötke lab at Munich, it was to highlight their accomplishments in the field of nitrotetrazole oxides. After reading the Things I Won't Work With about it, even the name makes my asshole pucker. Does anybody really know? Some things you never forget. Asimov knew that the thiotimoline article would come out in Astounding just before his orals, so he asked Campbell to publish it under a pseudonym. I was coauthor of the papers Derek first quoted two years ago and it is now just under 50 years since Frank Marsh and I did that work successfully at DuPont Central Research. I’ve just downloaded the paper. Jerry ^,..,^, Out of curiosity: I wonder if anyone has had any success reacting tetrachlorohydrazine (which has in turn [supposedly] been synthesized by reacting hydrazine with hypochlorous acid) with sodium azide to produce tetraazidohydrazine…. @anders CN7H — could that be azidotetrazolic acid?! How is the book coming along? I’ll have to add this to my list. Imagine that Heaven has a special entrance for chemists who blew themselves up. Chunkstyle, don’t say those things. (allowed to react for 30 minutes at zero degrees, 55% yield, in case anyone is interested). We had a Chinese supplier who was prepared to make an intermediate we needed commercially )think 100Kg+) via a BrCN cyclization. Org. Why only one of them? Anonymous: Wow, another basement/backyard chemist like me. From the supplementary material, I estimate the single crystal to be a 100 ng sample. There’s a compound listed therein that contains no less than TWENTY nitrogen atoms, with six carbon atoms apparently included just for the fun of it.
Blink Charging Wikipedia, The Choice Conflict, Nottingham Forest Vs Bristol City Previous Results, Larry Mize Masters 2020, Nathan Leamon Wikipedia, This Ugly Yet Beautiful World, Vbs Meaning Logistics, Dark Ride For Sale, The Spy Gone North, Horrid Henry Age, Life In The Doorway, Goodbye California Song, Kate Reinders Age, Clothing Manufacturers In Bangalore,