Sciencemadness Discussion Board - Things I Will Never Make

Things I Will Never Make

JJay - 8-3-2017 at 12:29

There are a few things as an amateur chemist that I won't make. Many of these are things that I probably could make, but in my mind, their production is very hard to justify. These include:

1. Methylamine

Methylamine undoubtedly has its uses, but it has a definite stigma among non-chemists, and I don't have a use for it as a hobbyist.

2. Nitroethane

Nitroethane also has uses and carries much less of a stigma, but again, it's hard for me to justify making any.

3. Monohalogenated acetone derivatives, chloroacetone and bromoacetone.

While they are not DEA-listed chemicals, they seem to have few uses except as drug precursors. If you aren't making drugs with them, exactly what are you doing?? "Your honor, I wasn't making any drugs; I was just experimenting with war gases." I mean sure, Nile Red made some chloroacetone in a YouTube video, but he also destroyed it immediately.

4. Piperonal, safrole, and isosafrole.

These are also obvious drug precursors. I consider their manufacture from natural products to be rather easy and know where there's a big sassafras grove where the spicebush swallowtails flit and flutter... but I am not very interested in methylenedioxy aromatics, though I've been invited to testify on them to government commissions due to knowledge on the subject that is apparently uncommon (???).

5. Benzaldehyde, phenylacetic acid, benzyl cyanide, phenyl-2-propanone.

Also obvious drug precursors. Benzaldehyde is said to have a lot of uses and it smells delicious, but I'm not really sure what I would do with it, and while there is some cool chemistry there, a lot of people have made it already.

6. Methamphetamine, MDMA, MDA, amphetamine, benzylpiperazine, PCP, opiates, cocaine, androgens, etc.

Seriously. It's not worth it.

One thing I *do* plan to make is phenylacetaldehyde. While it can be used as a drug precursor, that's extremely uncommon, and I like the way it smells.

A couple of things I'm on the fence about include alkali cyanide salts, and benzyl chloride. Together these could be used as drug precursors, but separately, they are very interesting compounds. I haven't made any, but the thought has certainly crossed my mind.

I'm sure I'm not the only one who has an aversion to making certain chemicals. Is there anything you will never make?

DraconicAcid - 8-3-2017 at 12:35

I refuse to work with osmium.

JJay - 8-3-2017 at 12:47

One of my sisters did a dissertation on osmium... she was a lot more concerned about anhydrous hydrazine, but I understand that osmium compounds smell awful and are extremely toxic.

My brother did one on selenium, which I guess also smells bad, although it's not really in the same ballpark.

A Halogenated Substance - 9-3-2017 at 11:08

How about organic peroxides? On nearly every thread I read about them, there is a reference to some unfortunate accident that occurred when someone worked with them.

One reoccurring example I found was one involving someone with the username 'phone'. (>100g scale of AP?!)

I never attempted making organic peroxides before but the stories and warnings I've read on this forum ensures it'll stay that way.

DJF90 - 9-3-2017 at 11:26

Not really sure what the point of this thread is?

A Halogenated Substance - 9-3-2017 at 11:32

Quote: Originally posted by DJF90

Not really sure what the point of this thread is?

Sorry, did I do something wrong? I thought of this as just adding to the list...
The beginning of the thread states that this is a list of things that was capable of being made by a home chemist but hard to justify the means of actually making it.

Or did I get what you meant completely wrong as well?

DJF90 - 9-3-2017 at 12:26

It seems to be a list of things that JJay feels the need to claim he'll never make. What thats got to do with anyone else, I'm not sure. Sure, some of the later items on the list are explicitly illegal in most (all?) jurisdictions, but theres no need to villify the other potentially useful reagents for the sake of a few ill-intentioned cooks.

DraconicAcid - 9-3-2017 at 12:42

Quote: Originally posted by DJF90

It seems to be a list of things that JJay feels the need to claim he'll never make. What thats got to do with anyone else, I'm not sure. Sure, some of the later items on the list are explicitly illegal in most (all?) jurisdictions, but theres no need to villify the other potentially useful reagents for the sake of a few ill-intentioned cooks.

It's something interesting to discuss. Although it should really be in whimsy.

JJay - 9-3-2017 at 12:51

The original post is most definitely an invitation for discussion.

DJF90 - 9-3-2017 at 12:54

Deleted my last post as I missed the last line of the OP. Sorry.

JJay - 9-3-2017 at 12:59

Quote: Originally posted by A Halogenated Substance

How about organic peroxides? On nearly every thread I read about them, there is a reference to some unfortunate accident that occurred when someone worked with them.

One reoccurring example I found was one involving someone with the username 'phone'. (>100g scale of AP?!)

I never attempted making organic peroxides before but the stories and warnings I've read on this forum ensures it'll stay that way.

Lots of organic peroxides have uses. Some are dangerous. Peroxy acids look useful, certainly.

Melgar - 1-5-2017 at 13:15

I've made methylamine regularly, but only to test reducing agents with nitromethane. The reduction to the amine is very quick, and it's easy to smell whether it was successful or not, without doing more extensive testing, and without any real risk of danger.

Nitroethane, I haven't needed for anything, and have no plans to make.

Chloroacetone, I accidentally made once, by acidifying a hypochlorite mixture that I'd planned to use to make chloroform. I don't ever intend to do it again; it's a rather potent tear gas. Luckily, it doesn't have that tendency to linger, like benzyl chloride does.

I kind of want to make piperonal from catechol at some point. I made it once by ozonolysis of black pepper oil, and although it was too little to quantify, it smelled amazing. Like maraschino cherries and vanilla. Safrole, I'm not interested in, except as a precursor to isosafrole, which I'm only interested in because it's a precursor to piperonal. Making piperonal from safrole seems kind of dumb, except that it's so easy for me to get sassafras essential oil, and that may actually be the easiest way to do it.

Benzaldehyde is almost essential if you're ever trying to reproduce the results of various papers. There are probably hundreds of papers out there describing the selective oxidation of benzyl alcohol to benzaldehyde, and benzyl alcohol is very cheap.

I wouldn't mess around with acetone peroxide or anything of that nature, and nitroglycerin I made once, then diluted it and poured it down the drain immediately after testing. I wouldn't do it again, when ETN is so much safer, and essentially the same reaction. I also wouldn't mess around with mercury or lead, just because they're cumulative toxins. No matter how careful I am, labels can get erased from organic solvent spills, and vials mixed up during a rush to move them away from unexpectedly vigorous reactions.

Of course, making illegal drugs is very illegal, and can get you years of prison time. However, during the several incidents where I was questioned by police, they've actually been pretty understanding when I explained what I was doing, even though some of it could easily have been related to drug chemistry (but wasn't). One time, I even had some ETN, and although they confiscated it, I wasn't charged with anything. In most cases, if you have chemicals that can be used for something illegal, police still have to prove that you intended to use them for some illegal activity in order to charge you with anything. There are very few chemicals that possession is all that's necessary to prove intent, and I think those are mostly just ephedrine, pseudoephedrine, ergotamine, and possibly phenylacetone and derivatives. This may also vary by state, and between state and federal law though.

clearly_not_atara - 1-5-2017 at 13:23

I will never synthesize calicheamicin.

I know this because the synthesis is very hard.

bis(chloromethyl)ether also makes the list because everyone who works with it gets cancer.

JJay - 1-5-2017 at 15:28

I've been known to mess around with mercury and lead, not to mention barium, but I keep the amounts small and avoid working with them when possible.

I was joking here when I was discussing how to make precursors out of illegal drugs, of course: http://www.sciencemadness.org/talk/viewthread.php?tid=73711
I know a lot of otherwise law-abiding people think that making MDMA is totally cool and hip and moral, but I don't look at it that way. ...and I'm certainly not the one who asked gdflp for benzaldehyde, haha.

Most of the people who have real life knowledge of my chemistry activities are government officials, in particular, school board members and legislators, some of whom could actually regulate them if they thought it appropriate. I did run into the chief of police the other day, who oddly enough, was doing a traffic stop with a bunch of other cops, and he said hi. I also know the local SAIC, although he and I have never discussed anything chemistry related.

The advice I generally get from government officials is something like: "Don't make any illegal drugs. Don't make any large bombs."

ninhydric1 - 1-5-2017 at 16:16

I'll never work with organometallic methyl compounds. Just the thought of it kills me. I'll probably never work with cadmium or mercury, but that might change with mercury since it is an interesting element.

[Edited on 5-2-2017 by ninhydric1]

Praxichys - 2-5-2017 at 06:11

I don't think there is anything I would flat-out refuse to work with. It's not really a matter of how dangerous a compound is, but the effectiveness of your safety measures.

Obviously for legal reasons I'm not going to have any scheduled or prescription-only compounds laying about. However, I have no issues with precursors that have other uses like benzaldehyde, methylamine, red P, HI, iodine, 1,4-butanediol, piperidine, NaBH4, lithium, etc. (In fact, I have most of those already.)

Having a bunch of pseudoephedrine or helional laying around is a dumb idea though. Not saying I'd strictly never deal with them but I can't see what use they might have other than certain scheduled drugs (and I'm sure law enforcement would agree).

[Edited on 2-5-2017 by Praxichys]

unionised - 2-5-2017 at 10:40

... friends with Donald Trump.

Magpie - 2-5-2017 at 11:02

I will never attempt a Wittig reaction using triphenylphosphine.

mayko - 2-5-2017 at 12:01

Quote: Originally posted by Magpie

I will never attempt a Wittig reaction using triphenylphosphine.

Why is that? I have been given that very task at work.

unionised - 2-5-2017 at 12:53

Quote: Originally posted by mayko

Quote: Originally posted by Magpie

I will never attempt a Wittig reaction using triphenylphosphine.

Why is that? I have been given that very task at work.

That might be the most useful aspect of this thread.

Magpie - 2-5-2017 at 13:02

Quote: Originally posted by mayko

Quote: Originally posted by Magpie

I will never attempt a Wittig reaction using triphenylphosphine.

Why is that? I have been given that very task at work.

Triphenylphosphine (TPP) is incredibly poisonous. An instructor told us a story of when he was in grad school someone was doing this reaction using a vacuum line. The line developed a leak. The chemist ended up in the hospital for 6 months recovering from TPP poisoning.

Mayko I hope you are not serious.

unionised - 2-5-2017 at 13:17

No
Triphenyl phosphine is not spectacularly toxic.
It's also not a gas.

Phosphine , is nasty.
https://en.wikipedia.org/wiki/Phosphine#Toxicity
Is that what you meant?

Magpie - 2-5-2017 at 14:10

I agree that handling phosphine would be a greater hazard but with a good hood it would be manageable. I don't know the details of my instructor's anecdote. I imagine the TPP was dissolved in a solvent, perhaps ether.

I suppose these Wittig reactions are done all the time in professional labs. I can really only say that I won't be attempting this at home.

AvBaeyer - 2-5-2017 at 19:19

Magpie,

Triphenylphosphine is perfectly ok to handle. I use it quite frequently in my home lab to make stabilized Wittig reagents for synthesis. You instructor probably mixed up triphenylphosphine with phosphine as noted above. Phosphine is not something to play around with hood or no hood.

AvB

JJay - 2-5-2017 at 19:22

I'm kind of leaning against ever making phosgene, but it looks both more useful and easier to make than oxalyl chloride.

I'd say that nickel carbonyl is on the list of things to avoid making.

DraconicAcid - 2-5-2017 at 19:35

Triphenylphosphine is a perfectly safe solid that I used as an undergrad. Trimethylphosphine, on the other hand, is much more volatile and toxic, as is phosphine, methylphosphine, etc.

I had to use nickel tetracarbonyl once. Didn't enjoy it. Would never make it at home.

JJay - 2-5-2017 at 19:38

I could see possibly making it in a professional setting, but as an amatuer? Definitely not.

benzylchloride1 - 3-5-2017 at 18:27

One of the more memorable things that I have seen in my years.

[Edited on 4-5-2017 by benzylchloride1]

karlos³ - 6-5-2017 at 13:09

Is that bis-trifluoromethyl mercury??

Where did you get this picture from, certainly not shot yourself don´t you?

benzylchloride1 - 6-5-2017 at 20:42

It is indeed bistrifluoromethyl mercury, I took the picture over a year ago. Interestingly, this compound is a light orange solid as can be seen in the small Nalgene bottle, as opposed to dimethylmercury which is a colorless liquid. The large crystallizing dishes contain mercuric iodide recovered from years of chemical oxygen demand testing of waste water. Much worse stuff is still lurking on the 5th floor of the building...

Radium212 - 25-7-2017 at 04:05

Phosgene or chloroacetone. Acetone peroxide, as well.

j_sum1 - 25-7-2017 at 14:38

Coloured mercury

JJay - 25-7-2017 at 16:35

I've actually been considering bromoacetaldehyde. I think it will react with lithium diphenylcopper or diphenylzinc to make phenylacetaldehyde in good yield.

Loptr - 26-7-2017 at 10:51

Quote: Originally posted by JJay

I've actually been considering bromoacetaldehyde. I think it will react with lithium diphenylcopper or diphenylzinc to make phenylacetaldehyde in good yield.

Which route to the Gilman reagent would you take? This is something I have been thinking about lately, too. Not to phenylacetaldehyde, but organocuprates in general.

They can be prepared from their corresponding Grignard reagent with copper (I) salts. The counter ion would then be magnesium.

[Edited on 26-7-2017 by Loptr]

JJay - 26-7-2017 at 12:44

I'd probably use phenyllithium and copper (I) chloride. I have wondered how hard it would be to prepare organocuprates from phenylsodium.

I don't think it's a good idea to prepare phenyllithium without inert gas, but a phenyl Grignard can be prepared with a drying tube....

I think phenylacetaldehyde can be made with diphenylmercury too. But I am not going to make that.

unionised - 27-7-2017 at 04:34

I will never make a contribution to this thread consisting of information on chemicals I will, or at least hope to, make.

Loptr - 27-7-2017 at 07:55

Quote: Originally posted by JJay

I'd probably use phenyllithium and copper (I) chloride. I have wondered how hard it would be to prepare organocuprates from phenylsodium.

I don't think it's a good idea to prepare phenyllithium without inert gas, but a phenyl Grignard can be prepared with a drying tube....

I think phenylacetaldehyde can be made with diphenylmercury too. But I am not going to make that.

Yeah, forget that one. I think that would be a series of compounds I could add to this thread in good faith; organomercury compounds! I am fine with mercury salts, just be sure to clean up and recover as much of the salt as possible for reuse, and also to keep it from getting into the environment.

As for the air-sensitivity of lithium reagents, that is exactly why I considered the route from Grignard reagents. I have pretty much everything else needed to work in an inert environment, except for the gas bottle and one of those drying apparatuses that fits onto the bottle itself.

[Edited on 27-7-2017 by Loptr]

JJay - 27-7-2017 at 09:21

Same here. I need an argon tank.

I do like the Grignard route. I could theoretically whip up a batch of diphenylcopper magnesium bromide right now using materials I have on hand if I pick up some ether.

Refinery - 5-7-2020 at 11:18

Things I will never do?

In my current setup:

Any reaction that could get out of hand, is too toxic to be handled, has such strong odor it will persist. I'm also not keen on energetics because I don't have place to play with them, and also things that are highly illegal shall remain untouched for now. Every synthesis I plan, I strongly consider how I can actually deal with it, does it need any containment, does it pose contamination hazard, how do I manage the waste, what equipment I need, etc.

In any given time:

I wish I could do every chemical reaction there is. The more exotic substance, more the merrier. Blast-proof, biolab level fume hood with ability to remotely control many processes would be a nice one for a start.

Eddie Current - 5-7-2020 at 20:34

I am mostly interested in the reaction mechanisms & older chemistry techniques, and can study them without illegal drugs & poisons or designated explosives.

As for chemicals, I will never go near HF or HgC2H6 regardless of the inducement and there's a few other substances that I would avoid in the hobby setting.

Otherwise, let's do some chemistry.

Metacelsus - 6-7-2020 at 09:08

Quote: Originally posted by JJay

Fun story time. Back in undergrad I worked in an organic synthesis lab. I needed to use some phenylsilane reagent (I believe it was triphenylsilane but I'm not completely sure). It turned out the lab had an old bottle of the stuff, way at the back of one of the storage cabinets. You know, back where nothing has been touched since 1975.

The cap was pretty crusty-looking, so after opening it I took a GC-MS to check the quality. The main component was there as expected, and there were also lots of siloxane oxidation products coming at later retention times. Maybe I could distill it to clean it up, I thought.

But I also noticed a strange minor peak coming just before the retention time of the main compound. The m/z read 356. I did a spectrum database search, and guess what: diphenylmercury! It was probably an impurity from the synthesis.

Needless to say, I successfully convinced my PI to buy a new bottle.

[Edited on 2020-7-6 by Metacelsus]