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A “Things I Won’t Work With” Request

I’ve been putting together a revised-and-expanded “Things I Won’t Work With” collection, which I hope to release first as a Kindle e-book (with other platforms following close behind). Each entry in the series has been revisited, with more useful (or not so useful) information and raised-eyebrow opinions added, and I’m throwing in some bonus chapters that haven’t appeared on the blog yet.
But I’d like to expand the list, both for the e-book and for future blog entries. So, what will you not work with? I’d be glad to take suggestions for the unpredictably explosive, alarmingly toxic, overwhelmingly stinky stuff that everyone with any sense avoids on sight. There have to be a lot of them that I’ve never come across, and I’d be glad to give them the full TIWWW treatment!

91 comments on “A “Things I Won’t Work With” Request”

  1. Anon-Amos says:

    1. dimethyl mercury (reputation precedes it)
    2. hexamethyl ditin (hate the smell)
    3. HF (gas or freshly condensed) (Why use Meerifield resin anyway?)
    4. diphenyl diselenide (hate the smell)
    5. HMPA (hate distilling it)
    6. NaK (boom boom pow)
    7. 3-mercaptopropionic acid (hate the smell)
    8. skatole (hate the smell)
    9. sodium amalgam (hate sacrificing glassware)
    10. hydrogen cyanide (hate the drama, love reading the Org Syn Prep)
    11. pyrrole (hate the smell, klutzy labmate once broke a full 100-mL bottle in lab)

  2. Xmas says:

    Oh! Let me know when you’re going to release it on B&N. I’ll buy it.
    I got a bootleg PDF of Ignition, and it was a fun read. I love reading about chemistry that I’d never do.

  3. Anonymous says:

    1,5-pentanediamine (stench)
    dialkyl zinc(s) (good fire)
    benzyl bromide (I had a grad school labmate drop a 500mL on the floor and had to help it clean up)

  4. eugene says:

    “So, what will you not work with?”
    Multi-ring natural products that take a four year PhD with KCN and still won’t get you a job. Bam!
    But seriously… from the stuff that hasn’t been mentioned… maybe PH3? I know other people work with it and I often looked it up since I wanted to use it as a reagent, but the safety precautions and stories of others have always made me choose much longer alternate routes.

  5. OrganicExtract says:

    I used O-(tertbutyldimethylsilyl)hydroxylamine at one point in my graduate work. It smells nasty!

  6. opsomath says:

    ZOMG so excited.
    I spent a good bit of my grad school time making p-phenylene bis(diazonium) salts. You need a non-nucleophilic counterion for those, and the old school one is perchlorate. Yes, you heard right, you combine a famously touchy explosive cation with the Grand Old Man of pyrotechnic oxidizer anions. The results are here:
    http://www.youtube.com/watch?v=SwUlYzP1oF4
    Needless to say, I went with bisulfate for my compounds.

  7. patentgeek says:

    1. Triethyl phosphite (cringing at the cellular level from the memory of the odor)
    2. Carbon disulfide /liquid N2 temp. bath (a postdoc I worked with set himself on fire twice in one day with this)
    3. Diazomethane in refluxing trifluoroethanol

  8. See Arr Oh says:

    Hey Derek!
    Two submissions:
    Propargyl dichlorides – I’ve twice had them explode during distillation
    Short-chain nitro-olefins – Only compounds that make me burst into tears with just a slight whiff

  9. Donough says:

    @ Anon-Amos. Dont go to near PV processing then if you dont like gaseous HF.
    Also from PV processing (but also other areas like gold mining), I have seen KCN used. The cyanide is a pretty good cleaning agent. However its smell is not detected by everyone. I also have it on good authority that the smell is the last thing to worry about. An ex collegue was taking fresh samples that had not been cleaned properly. His described the sensation of the body shutting down within seconds. Fortunately he was not knocked down.
    PS. When moist it emits small amounts of HCN.

  10. Harry says:

    Here are a few of my candidates:
    Carbon Diselenide- STENCH!
    Isocyanides- Stench
    Diazomethane
    HF, especially anhydrous
    2-bromopropionaldehyde- incredibly strong lachrymator

  11. Indy says:

    1) Phenylacetic acid… That thing has a particular smell that sticks with you down the pores!
    2) 10 M BuLi… Try it out and you’ll see what a beautiful flame you get off the tip of the syringe!
    3) Ni(CO)4… My PhD mentor wanted to use it for carbonyl insertion reactions. Sure… Never touched the darned thing and might still be in his lab ever since (20 years ago and going!).
    Gee… the things one had to avoid to survive the PhD program! 🙂

  12. James says:

    Fluorine gas
    Trimethylphosphine
    nickel carbonyl
    HMPA (although it’s sometimes necessary)
    hexamethylditin
    organomercurials
    H2S (condensed) is lots of fun

  13. billswift says:

    >You need a non-nucleophilic counterion for those, and the old school one is perchlorate. Yes, you heard right, you combine a famously touchy explosive cation with the Grand Old Man of pyrotechnic oxidizer anions.
    Maybe that’s the old school way of keeping out/getting rid of the “klutzy labmates” several commenters have mentioned 😉

  14. rhodium says:

    Unfortunately my list is things I won’t work with again.
    1. Nickel carbonyl. And yes, it does smell like newly mown hay. Not as well known as its carcinoginicity is its ability to burst into flame in the air if enough of it decomposes to finely divided Ni.
    2. Diphenylcyclopropenone. The synthesis goes through the dibromodiphenylacetone. Either that or the final product introduced me to the concepts vesicant and contact dermatitis.
    3. Any methytin comounds due to the small and headaches.
    4. Not really something I won’t work with again, but benzoyl peroxide and aniline gives of, after a variable delay, copious white smoke. A trail of this may be what one sees in old Keystone Kops films.
    5. Four liter flasks with THF, benzophenone and pieces of sodium, due to the getting rid of sodium problem. Perhaps you have covered this problem in a different context.
    Continuing this list is hard, since I am now wondering how it is I am still alive.

  15. bbooooooya says:

    Phenylethanethiol: foul foul foul, permeates nitrile/vinyl gloves, seeps into skin, never goes away. Awful Awful stuff.

  16. nova1966 says:

    tetramethylenedisulfotetramine (in the kitchen)
    castor bean allergen (after sensitization, unless air stops moving)

  17. Clarence gatemouth brown says:

    I have a variety of current and former colleagues/supervisors and bosses that would fit the bill here – unpredictably explosive, alarmingly toxic, overwhelmingly stinky etc. Just say the word…..

  18. sigma147 says:

    I’m surprised no one aside from Harry has mentioned isocyanides. Nasty little beasts, those…

  19. Eric says:

    Silver azide. Used to work with it, now I’m typing this with 7 fingers.

  20. Laura says:

    I still remember thinking that I was going to die a horrible flaming death when smoke billowed out of the bottle of trimethyl aluminum that I opened. Time to recharge the glove box!

  21. skatesailor says:

    Pass up the chance to work with 2-chlorobezalmalononitrile (CS, C10H5Cl2), the riot control agent. Your wrists and neck will burn for hours when a dirty lab coat shares its contaminant with you. I hate to imagine the pain felt by someone sprayed in the eyes, nose, or mouth with CS.

  22. quintus says:

    methyldichlorophosphine MePCl2. Especially upon distillation, if it goes wrong you get a horrendous smell which pervade everything, not to mention the pyrophoric byproducts.
    9-BBN is another one trying to prepare it on scale caused a cloud of smoke and what may have been a flame!

  23. myma says:

    the supercalifragiliciousexpeali boom boom
    from last week

  24. Acme_Rocket says:

    1,2-ethanedithiol (awful smell)
    alpha-bromo-phenylacetonitrile (tear gas/potent lachrymator)
    There are many more, but these two stuck out.

  25. Lisa Balbes says:

    Can I put “stupid people on the list? 🙂

  26. Anonymous says:

    Trimethyl thallium (There was a guy called Dr. Hub in Prague in 70s who was preparing Me3Tl from Me2Hg as a starting material. He had a runaway spill one night and he fell ill with CNS damage symptoms next morning, and died in horrible spasms few weeks later). Thallium(III) salts in general – they generate organothallium compounds from tyrosine residues in your skin.
    Volatile organolead and trimethyltin compounds.
    Carbonyl sulfide – COS is a gas that even in trace amounts makes carbon disulfide smell like carbon disulfide. Pretty neurotoxic too.
    Ni(CO)4 and FSO3Me. They put quite a few people in hospital ICUs.
    Me2AsCN – neoroparalytic warfare agent-like properties. Work with cacodyl cyanide cost Bunsen his right eye (from an explosion) then caused his nearly fatal poisoning. “The vapor from 1 grain (0.0648 g) of cacodyl cyanide in a room produces sudden numbness of the hands and feet, and dizziness and insensibility to the point of unconsciousness. The tongue becomes covered with a black coating. ”
    Diethyl tellutium, it taints your body and makes you a smelly social outcast for many months after. Or even inorganic tellurium compounds – when absorbed in trace amounts they give you tellurium breath.
    Beryllium compounds
    Radioisotopes by default.
    NCl3, N2O5, Cl2O7, Mn2O7 and BrF5

  27. luysii says:

    Patients with ‘multiple chemical sensitivity syndrome’

  28. xyz says:

    methyl iodide (large scale), I would not use.

  29. nucleofuge says:

    Nickel Boride: Requires too much finesse for what you get.
    DCC: Better coupling reagents have been developed, plus it tends to form a rock-solid brick in reagent bottles.
    DDQ: Generates byproducts with problematic water and organic solubility.
    Thiophosphoryl chloride: Burning stink.
    DAST: Too smokey.

  30. Hap says:

    Since I don’t work in lab, this is sort of arbitrary, but…
    Thallium salts, dimethylmercury, et al. – anything with irreversible toxicity is a nonstarter.
    1-methyl-4-aryl-1,2,3,6-tetrahydropyridines (MPTP analogs) – see above.
    Interhalogen compounds (and their cyanogen and azide analogs), selenium and tellurium compounds – they’re not all horrific, but since they vary between icky to nasty to uncontrollable, I don’t see enough of a point in them to worry about them.
    Nickel tetracarbonyl – I suggested it for an allyl-allyl coupling on a synthesis exam, and if the professor had wanted to end my career, he could have actually bade me to follow my own route.

  31. Hap says:

    I thought it was phosgene that smelled like newly-mown hay. Speaking of which…
    Phosgene, dimethyl sulfate, methyl fluorosulfonate, and mustard gas/nitrogen mustards all seem like good choices – the first three particularly because their toxicities are not immediately apparent but are easily fatal.
    The diazomethane twins (diazomethane and trimethylsilyldiazomethane) – even if only the unsubstituted one likes to detonate, they’re both pretty toxic (as for the first three above).

  32. Hap says:

    Anon26’s paper (Milkshake also suggested it a while ago) is a fiesta of TIWWW goodness. Arsenic compounds have lots of good reasons to be on that list, and the paper with that quote gives many of them.

  33. quintus says:

    How about management?

  34. CMCguy says:

    Anything with Radioactivity has always scared me.
    OsO4: although have used myself and know is “popular” in many labs not sure all who use treat with proper respect (particularly in regards to disposal)

  35. Bunsen says:

    Yay, more superneurotoxexplosivexotherminoxious compounds to read about! (That adjective can probably be improved upon, but it fits the meter better than hexanitrohexaazaisowurtzitane did. Might make a good intro title or something. Noxious is a bit hard to rhyme, though…)
    It looks like diazomethane was already the subject of a How Not to Do It entry, though that could probably be adapted for the book. In fact, I’d bet there are a few other things in http://pipeline.corante.com/archives/how_not_to_do_it/ that might be useful.

  36. B says:

    Cycloproparene, C7H6 of stinkyness…

  37. metaphysician says:

    *goes to look for a way to read Kindle e-books without a Kindle*

  38. Handles says:

    re: cycloproparenes
    I dimly remember seeing Brian Halton give a lecture once, I think he mentioned a bromo-substituted cycloproparene as being the stinkiest thing ever made. I wish I had access to his reviews (e.g. DOI: 10.1021/cr010009z) in case he published any anecdotes.

  39. Martin says:

    trimethyltin hydride. Used the chloride many many times in PhD. Mentioned to boss I wanted to make some of the hydride for alkyne additions and that my initial attempt in fumehood hadn’t worked as gas too volatile. He said no in a _very_ clear way (with explanations)

  40. rural says:

    phenylphosphine, that smell will hunt me for the rest of my life.

  41. Chemcat says:

    Isovaleraldehyde — a stinky bugger, although I read once that almost 40% of people cannot detect its stench. Would you like to see if you’re so lucky? 😉

  42. Lu says:

    Iodoacetic acid: volatile and very irritating even in miniscule quantities.

  43. Canageek says:

    No one has mentioned noble gas compounds yet? Some of those are rather energetic. I’m not sure I wouldn’t work with them, but I’d sure be doing it on a small scale– I recall hearing about someone getting hurt working with 50 mg of the stuff.
    Lets see, also on my ‘handle with oh so much care’ list is anything that randomly explodes. I had to read about this gem for a class I took last year:
    “Although violent detonations occasionally occurred when BrO3F was brought into contact with CH3CN, the […] make CH3CN a useful solvent for the synthesis of anions derived from strong oxidative fluorinators.” –John F. Lehmann; Gary J. Schrobilgen; J. Am. Chem. Soc.  2005, 127, 9416-9427 10.1021/ja0402607

  44. Susurrus says:

    Allyl mercaptan. It smelled like a skunk even before I opened the can containing the bottle.

  45. Tanith says:

    Hydrofluoric acid – scared the **** out of me when I spilt the stuff

  46. Anonymous BMS Researcher says:

    Google Yale Sabia Virus NEJM for a case report — free full text — of a 1994 incident when a researcher was treated with ribavirin after exposure to an exotic virus. I was at Yale when this incident happened — in a building just across the street.
    Fortunately it wasn’t Ebola for which there is no treatment. I’d also be reluctant to work with hantavirus or some highly pathogenic flu strains, among others.
    A much less dangerous virus — the 2009 H1N1 flu — gave two Canadian government inspectors a stern lesson about infection control rules. They were investigating an outbreak at an Alberta pig farm — I believe the likely vector was a farm worker who had been on vacation in Mexico. Anyway, it was hot and humid among thousands of pigs and the face masks got very unconfortable so they took off their masks. A few days later they had reason to regret having taken those masks off!

  47. Hurin says:

    You’ve written a fair amount about azides in the past, but tetraazidomethane might deserve special mention.

  48. David Bush says:

    If you might be interested in biological work, look into prion research. Since they’re just malformed proteins, they survive most things that you can use to get rid of even the nastiest bugs, like heat and radiation.
    Our group was asked to do some sequencing work on one by MS, we politely declined after hearing that one group had to move their instrument into a BSL-3 lab to work with one.

  49. Crystallographer says:

    Tetrahydrothiophene. A bottle had apparently been kept in the lab freezer previously. Several years later, you would get comments from people working at the other end of the lab about thirty seconds after opening the freezer very briefly. The stink of that stuff lingers…

  50. Chemist says:

    The most stinky thing I worked with was where we took the acid chloride of iso-buteric acid and reacted it the 2-thiopyridine to make the thipryridylester.

  51. Anonymous says:

    I’d like to second the nomination of scatole. There is a reason it is named after sh$@t!

  52. Mr. Fixit says:

    As a general rule, I prefer not to work with compounds, such as heavy metals that will silently accumulate in my system, then WHAM kill you (sorta). I am much less concerned about compounds like tBuLi, where there are definitive safety precautions one can take to ensure the ability to walk away from the reaction to live a long and healthy life.

  53. bonedriven says:

    Selenium Dioxide. I was looking into oxidizing a heteroaromatic methyl group to the acid, which called for stoichiometric SeO2 on a several gram scale. It’s MSDS is pretty terrifying : http://msds.chem.ox.ac.uk/SE/selenium_dioxide.html Of interest is the LD50 for skin contact: 4mg/kg in rabbits.

  54. OldLabRat says:

    Cyclobutylcarboxylic acid = pure sour milk.
    Iodyl sulfate + nitrohalobenzenes = large boom.

  55. Fiona says:

    @David Bush – How on Earth do you move an MS machine? I thought they were pretty fixed. (NB – It’s been years since I’ve seen an actual MS machine, they may have got smaller in the intervening time)
    Reagents I thoroughly wish never to use again – ethidium bromide, just say no to intercalating agents.

  56. Anne says:

    There are some dreadful stories about smallpox post-eradication. The Russians did biowarfare work on it, and some got loose. Worse, the work (that is, they blew up 400 g of the agent) was isolated on Vozrozhdeniya Island in the Aral Sea – which is mostly gone now, so the island isn’t an island any more. There was a case, too, where a British researcher, Janet Parker, caught it at work. She died, and the head of the lab committed suicide as a sort of apology.

  57. DannoH says:

    Any of the hydrolyzed chemical warfare agents with a sulfur in the parent compound (HD and VX)? Those two little beauties are why I cant smell garlic, onion, or skunk anymore…

  58. Ethan C says:

    Old picric acid/metal picrates. As a graduate student TA, I was told to mix up Beaujard’s etchant solution for an undergraduate steel metallography lab The absolutely ancient picric acid looked mostly-dry, in a glass bottle with a metal cap, so I NOPEd the hell out of there as fast as I could.
    This reaction may have been caused by my previous experience with this material, where during a high school track meet, I watched a bomb robot get blown up while carrying a jar of old picric acid because the operator set the jar down on the outside concrete too hard (they were going for a controlled detonation with one of those steel hemispheres, but didn’t make it that far).

  59. David says:

    Beta naphthylamine (and derivatives). I currently have 10 g of it sitting in my hood, as a byproduct of BINAM preparation. It’s been an unpleasant couple of days in lab. (For those of you who are unaware, they are potent bladder cancerogens and are genotoxic.)

  60. Harry says:

    @54 Bonedriven- SeO2 really isn’t all that bad. I’ve used it numerous times on a multi-kilo scale.
    The biggest nuisance is dealing with the selenium formed during the reaction. Fortunately we have a process we run on a relatively regular basis that uses selenium, and we’ve found that the byproduct selenium works very well in it, so we’ve pretty well closed the loop. We did have to figure out how to keep it from forming a bunch of solid masses in the flask, but once we did that it was smooth sailing.

  61. Hap says:

    I don’t count virii/bacteria as TIWWW – I take them as givens. It’s one thing to work with chemicals that will kill if you’re not careful, and another when you (and your family, and lots of people around you) can die horribly because someone in the same building made a mistake.
    I am reading Demon in the Freezer, and it describes much of this in disturbing (well, not as disturbing as the article Dr. Lowe linked a long time ago about Iraq’s use of chem warfare on Kurds, but not good) detail.

  62. Noel says:

    Radioactivity, unless I have my own set of equipments. We had a stupid grad student who always used to spill radioactive stuff around so whenever I used to go to that table the geiger counter used to scream at the top of its lungs. I just didn’t kill this guy, I wish I would have.
    Ethidium Bromide, yeah they say its not that harmful. But I don’t want to die of cancer just because my group leader is a cheap bastard.
    Schotten – Baumann reaction, Benzoyl Chloride always made me go nuts, it is so eye irritating.
    Mercaptoethanol, the idiot grad student always used to use it on the bench instead of fume hood and then spread the disgusting smell all over. Even I find it difficult to use it in the fume hood.
    Working alone in CO2 hood with the cell culture. I know folks who have fainted.
    Animal models with lethal mutations. Majority of the group leaders think that its not so difficult to work with such models, even though they carry lethal mutations, but these guys don’t really work in the labs so have no freaking clue what actually works and what doesn’t. They just want grad students and post-docs to bring fancy results from thin air.

  63. Brian Chalmers says:

    Arsenic trichloride
    Dichlorophenylarsine
    Dichloromethylarsine

  64. MoMo says:

    Organoselenium compounds! They make your hair fall out!
    But I save on hairdressers!

  65. MoMo says:

    Organoselenium compounds! They make your hair fall out!
    But I save on hairdressers!

  66. pete says:

    biology:
    – harvesting a large vat of primate-tropic retrovirus bearing a strongly activating Ras gene
    chemistry:
    – fuming HF in a styrofoam cup
    home:
    – spam, powdered eggs, spam n’ spam in a mornay sauce with spam

  67. Anonymous says:

    I once opened a big 1 kg bottle of cholesterol just to have a look. The SMELL!! I almost spewed my entrails. If you find a bottle, trust me, don’t open it…wrap about 1 km of parafilm around the cap and bury it….OR loosten the cap a bit and stash it under your boss’s desk!!!

  68. KevinM says:

    Antimony pentafluoride
    Dicobalt octacarbonyl

  69. Harry says:

    I never made this stuff personally, although I did end up getting in contact with it once when decontaminating a piece of equipment. The prodcut was 10,10′ oxybisphenoxyarsine, and it was used as a fungicide/mildewstat in plastics as I recall.
    Aside from using Arsenic trichloride as a starting material, the final product was unbelievable irritating to the skin. This one definitely makes my list (as does practically any arsenic compound).

  70. Anonymous says:

    pressurized HCl gas. Had to use it a lot in grad school, would never again. Nothing ever happened, just always made me nervous. Really rather avoid any really nasty gas. Phosgene is another thing I prefer to avoid. There are so many safer alternatives for most reactions, I rather just buy the more expensive reagent and limit the risk.

  71. @67 says:

    Wow, cholesterol is THAT volatile at ambient temperature and pressure? I agree with you that lipids can be quite stinky…butyric acid and caproic acid, barf!!!
    Although the smell is bearable, I despise doing any stereoselective chemistry with alpha-pinene auxiliaries (sorry Midland and Brown).

  72. Dangerous Bill says:

    Don’t forget us Nookies when you put your book together.

  73. Anonymous says:

    Sulfur pentafluoride ?

  74. G. says:

    hi everybody!
    Thiophenol is my archenemy, I know it’s not that bad, but when it’s a first step in 100g sugar ssynthesis it can cause a lot of head-ache
    Proline -> sperm smell, not that bad but people around won’t sit next to you in the subway.
    Octanitrocubane, kapow (the hepta nitro version is not bad either)
    thio acetone : worst smell ever, shaking a bottle of it made me sick… i didn’t even try to open it
    Acril something compound for the smell.
    CpCo(CO)2 and all the volatile metal compound

  75. Jimmy says:

    Piperidine: Take a whiff and you’ll know why. I don’t do my own money shots.

  76. FoxysMom says:

    I will leave working with human urine to my peeps…caffeine becomes a real stinker on the way out of the human body….

  77. Secondaire says:

    Someone mentioned the low-molecular weight diaminoalkanes already. Diaminobutane and diaminopentane (cadaverine) are the worst. *Heaves*
    Thioanisole is another disgusting one. Approximately ten microliters is enough to stink up your entire lab for a day if you throw it in the broken glass bin in a pipette without bleaching it first.
    I won’t touch elemental Li in liquid ammonia after my boyfriend lit himself on fire with it trying to make LiNH2.
    Also, someone mentioned MeI in large quantities. A grad school labmate nearly ate through his hand with the stuff.
    I made a nitrated phenacyl bromide in grad school. The stuff was such a lachrymator/sensitizer that even making up an NMR sample of the #$@% made me sneeze until my eyeball capillaries ruptured.

  78. Anonymous says:

    @ 71 Cholesterol is a waxy solid at room temp. crappy stuff…

  79. Anonymous says:

    Phenacyl bromide or chloride!! I believe the chloride is the active ingredient in Mace!
    Let’s push the envelope…how about phenacyl triflate, fluoromethane sulfonate, tosylate or Iodide!! Better get a gas mask handy!!

  80. ArmedAndDangerous says:

    I’m surprised nobody has mentioned diisopropyl ether. This stuff forms highly explosive peroxides fairly rapidly (compared to good old diethyl ether). While a graduate student, I came across a VERY old 1L bottle sitting at the back of a solvent cabinet (I believe it was dated 1998 – this was in 2006) and there was a sizeable layer of chunky white solids coating the sides of the bottle. Needless to say, I didn’t even touch it with a 10-foot glass stirring rod. I graduated soon after, and as far as I know, it’s still sitting back there. Gotta love academia.

  81. Anonymous says:

    @80 Did you stash that payload under your Boss’s desk?? If not, I have a few targets for your chunky white solids!! Especially at Roche!!! HAHA

  82. newnickname says:

    Compared to some of the previous offerings, the above list seems kind of weak. From Gergel’s book (“Excuse Me Sir, …”), there is the story about methyl isocyanide. ‘Professor, why the paucity of literature since Moissan?’ ‘Well, Gergel, it’s the toxicity. That’s what killed Moissan!’
    I’ve worked with plenty of candidates for TIWWW but they are all TIDWW (things i DID or DO work with).
    I’ll toss out Rieke Mg. Highly active. Use under argon because it reacts with N2 to form Mg nitride. Glows red and catches fire in air. (Don’t ask me how I know.) Of course, I needed to work with K to make a fresh batch. But, heck, I also used to distill benzene from K-benzophenone (K melts in PhH to give a Christmas display of bright silvery balls bobbing up and down in the purple-y benzene; Na just sits there all crusted up, a gift from the Grinch.)
    I’ll work with the right chemical for the right (needed or desired) chemistry under the right (safe) conditions. Things I’d rather not work with: The WRONG chemicals for the task at hand (Na in benzene = waste of time) under the WRONG conditions or circumstances (make sure I know where the fire extinguisher is!).

  83. newnickname says:

    Compared to some of the previous offerings, the above list seems kind of weak. From Gergel’s book (“Excuse Me Sir, …”), there is the story about methyl isocyanide. ‘Professor, why the paucity of literature since Moissan?’ ‘Well, Gergel, it’s the toxicity. That’s what killed Moissan!’
    I’ve worked with plenty of candidates for TIWWW but they are all TIDWW (things i DID or DO work with).
    I’ll toss out Rieke Mg. Highly active. Use under argon because it reacts with N2 to form Mg nitride. Glows red and catches fire in air. (Don’t ask me how I know.) Of course, I needed to work with K to make a fresh batch. But, heck, I also used to distill benzene from K-benzophenone (K melts in PhH to give a Christmas display of bright silvery balls bobbing up and down in the purple-y benzene; Na just sits there all crusted up, a gift from the Grinch.)
    I’ll work with the right chemical for the right (needed or desired) chemistry under the right (safe) conditions. Things I’d rather not work with: The WRONG chemicals for the task at hand (Na in benzene = waste of time) under the WRONG conditions or circumstances (make sure I know where the fire extinguisher is!).

  84. newnickname says:

    Sorry for the double 82/83 post.
    @1 and @12: We were doing large scale Stille couplings and needed a lot of Me6Sn2. The company wouldn’t supply us without a signed waiver!
    I remember when you could tell who was doing selenium chemistry by the smelly odor that followed them everywhere, 24/7.
    I think the early papers of von Doering on Cl2C: from CHCl3 + KOH said something like ‘set up several small flasks rather than one large flask due to their tendency to explode unpredictably.’

  85. Nile says:

    Yeah, I’ve got a Samizdat copy og ‘Ignition’, too. And Gergel’s ‘Excuse me sir…?’ – I think that there’s a second part to Gergel’s memorable memoir, but I’ve never tracked it down: maybe that’s a good thing, because he was a clear example of a sociopath and not many of *them* get put in charge if toxic chemicals. I don’t want modern managers getting ideas from him.
    Put that one down as ‘People I wouldn’t work with’.
    Comment 38, David Bush and prions… Very few pathologists have ever autopsied a Creutzfeld-Jacobs victim. Fewer still would ever want to; by definition, everything they work with has proven to be fatal, and they are very cautious people, but a CJD case is different.
    So what’s special about working on a CJD specimen, and the tiny number of associated prion diseases, like Kuru? It’s not just the separate table and the ‘no power tools’ rule (aerosolised debris), the space suits with the external air supply and the overpressure… It’s losing your best instruments and cutting tools. You can’t clean them. Or rather: you can make them look clean, but nothing you can do – bleach, acid, overnight in the autoclave, super-pressure steam – nothing renders them safe. You either melt them down in a furnace with a certified flue temperature of two thousand degrees and no particulate emissions, or only ever use them on that one table, ever again.
    We learned that bitter lesson from experienced and cautious pathologists who died of CJD off minor cuts from instruments that were used – once – on that one autopsy, sterilised repeatedly, reused and resterilised repeatedly, free of all contamination to the limits of detection… And still fatal to the unwary and the paranoid alike.
    The prion agent is a chemical, not an organism. You can’t ‘kill’ it, and the catalytic site that causes the catastrophic misfolding cascade is as stable as the steel on your blades, and active in quantities too small to detect. It’s also damnably slow: everybody in your lab could use that scrubbing brush, and we’d only know about it a decade later.
    It’s a horrible way to die.
    Yeah, that’s TIWWW.

  86. Anonymous says:

    Yeah, I’ve got a Samizdat copy of ‘Ignition’, too. And Gergel’s ‘Excuse me sir…?’ – I think that there’s a second part to Gergel’s memorable memoir, but I’ve never tracked it down: maybe that’s a good thing, because he was a clear example of a sociopath and not many of *them* get put in charge if toxic chemicals. I don’t want modern managers getting ideas from him.
    Put that one down as ‘People I wouldn’t work with’.
    Comment 38, David Bush and prions… Very few pathologists have ever autopsied a Creutzfeld-Jacobs victim. Fewer still would ever want to; by definition, everything they work with has proven to be fatal, and they are very cautious people, but a CJD case is different.
    So what’s special about working on a CJD specimen, and the tiny number of associated prion diseases, like Kuru? It’s not just the separate table and the ‘no power tools’ rule (aerosolised debris), the space suits with the external air supply and the overpressure… It’s losing your best instruments and cutting tools. You can’t clean them. Or rather: you can make them look clean, but nothing you can do – bleach, acid, overnight in the autoclave, super-pressure steam – nothing renders them safe. You either melt them down in a furnace with a certified flue temperature of two thousand degrees and no particulate emissions, or only ever use them on that one table, ever again.
    We learned that bitter lesson from experienced and cautious pathologists who died of CJD off minor cuts from instruments that were used – once – on that one autopsy, sterilised repeatedly, reused and resterilised repeatedly, free of all contamination to the limits of detection… And still fatal to the unwary and the paranoid alike.
    The prion agent is a chemical, not an organism. You can’t ‘kill’ it, and the catalytic site that causes the catastrophic misfolding cascade is as stable as the steel on your blades, and active in quantities too small to detect. It’s also damnably slow: everybody in your lab could use that scrubbing brush, and we’d only know about it a decade later.
    It’s a horrible way to die.
    Yeah, that’s TIWWW.

  87. Harry Elston says:

    Derek:
    I have a fundamental problem with compiling a list such as this as it stands. There are plenty of chemicals out there that are extremely odoriferous, severely acutely toxic, sensitizers, reactive etc. However, that does not mean that these chemicals cannot be worked with safely, given the engineering controls, administrative controls and proper personal protective equipment. By creating a list such as this, you’re offering an opinion that there are chemicals that are “too dangerous to handle” which can, with some work be turned into a legislative ban on compounds on these lists.
    While the “slippery slope” argument does not hold water logically, it does hold plenty of water in the hearts and minds of people and legislators – especially untrained individuals or the chemophobic crowd. (e.g. “Dr. Lowe, a Ph.D. level organic chemist says these chemicals are too dangerous…”)
    Control of the chemical is the key to to safe handling.
    Best,
    Harry Elston, Ph.D., CIH
    Editor, Journal of Chemical Health & Safety
    Principal, Midwest Chemical Safety

  88. Hurin says:

    I have a fundamental problem with compiling a list such as this as it stands. There are plenty of chemicals out there that are extremely odoriferous, severely acutely toxic, sensitizers, reactive etc. However, that does not mean that these chemicals cannot be worked with safely, given the engineering controls, administrative controls and proper personal protective equipment. By creating a list such as this, you’re offering an opinion that there are chemicals that are “too dangerous to handle” which can, with some work be turned into a legislative ban on compounds on these lists.

    You seem to have a fundamental problem with literacy as well. That list is called “things I won’t work with”, not “things that are too dangerous for anyone to work with”. That turns out to be a fairly important distinction. Dr. Lowe has has explicitly said that he won’t work with cyanogen azide (for instance) but he has not opined that the graduate students in Jean’ne Shreeve’s lab shouldn’t. Those students have been carefully trained and are the subject of zealous safety regulations, because the focus of their research is the synthesis of high explosives. So far as I know (and I researched this as part of my second year lit seminar) Prof. Shreeve’s group is one of two groups in the world that currently uses that compound.

    While the “slippery slope” argument does not hold water logically, it does hold plenty of water in the hearts and minds of people and legislators – especially untrained individuals or the chemophobic crowd. (e.g. “Dr. Lowe, a Ph.D. level organic chemist says these chemicals are too dangerous…”)

    Also, your concern trolling might hold water if you had some precedent for bills coming before congress that threaten to ban the synthesis of certain chemicals by research scientists. As it stands, its just a bunch of bloviating by a pretentious clown.

    Control of the chemical is the key to to safe handling.

    Or avoiding the ones that are needlessly dangerous in the presence of alternatives, but I guess you haven’t ever heard the saying “discretion is the better part of valor”.

    Harry Elston, Ph.D., CIH
    Editor, Journal of Chemical Health & Safety
    Principal, Midwest Chemical Safety

    Anyone want to start a betting pool about the subject of this guy’s doctoral degree? I have dibs on journalism…

  89. mmol says:

    As a graduate student, for a while I regularly made chlorine azide from hydrazoic acid generated from azide and acid, and extracted into CH2Cl2, and then added to a solution (again I had to make and purify the gas) of chlorine in CH2Cl2. I kept a bottle of ethanol handy for hydrazoic acid poisoning effects- take a good sniff and that helps – but it was a fantastic way to add Cl and N3 across an alkene! It never went “bang” but that was surely just a matter of luck. It’s not a reagent one sees used too often………

  90. sepisp says:

    Generally there seems to be a propensity to select as toxic and explosive reactants as possible. For example, you could methylate with dimethyl carbonate at high pressure, or if that’s not preferable, then with dimethyl sulfate in a benign solvent. Instead, the default has to be diazomethane in diethyl ether. Even the use of alternatives such as trimethylsilyldiazomethane is blocked by the immense conservatism in university chemistry. We can continue this list: DEAD, selenium, etc.

  91. Mika says:

    Did the kindle book end up happening? I’d love to collect it for my next bus read…

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