Sciencemadness Discussion Board - cadaverine

cadaverine

jhonthebaptist - 28-1-2015 at 06:50

I have been trying to log in for a few weeks, it appears I forgotten my password so I made a new account.

I have spent much time devoted to making a famous cyclic secondary amine from various sources. I settled on the decarboxylation of lysine to produce cadaverine dihydrochloride and
cycilize that by strongly heating with direct flame.

The results were disappointing. From 50 grams lysine about 15-20 ml of cadaverine were produced. (yellow thick oil) I neutralized with dil. hcl to make the hcl salt and evap. to dryness. Then strongly heated this salt (200 C -- 250 C). Copious white smoke was produced as I thought ammonium chloride would sublimate. After it cooled down was then Ph adjusted to alkaline with sodium hydroxide in isopropyl alc. (75% alco. 25% water.) The mixture was then distilled., at the end vacuum was applied. I smelled ammonia so I assumed the reaction must have produced (some) of what I wanted. After distillation the alcohol amine mixture was again neutralized and evaped to dryness. When the brownish/off white
yellowish salt was reacted with other reagents it failed to work as expected. SO Im gonna put this to bed right now. This method of production for the sec amine is not practical at all.

[Edited on 28-1-2015 by jhonthebaptist]

Bert - 28-1-2015 at 08:52

What was your old user name?

jhonthebaptist - 28-1-2015 at 11:10

was pickardjr, bert.

CuReUS - 29-1-2015 at 00:15

Quote: Originally posted by jhonthebaptist

I have spent much time devoted to making a famous cyclic secondary amine from various sources. I settled on the decarboxylation of lysine to produce cadaverine dihydrochloride and
cycilize that by strongly heating with direct flame.

where you trying to make piperdine ? I didn't know piperdine could be made by strongly heating cadavarine ? do you have any literature for the reaction ?
here is a good video to make cadavarine
https://www.youtube.com/watch?v=V4D5aTNYalQ

jhonthebaptist - 29-1-2015 at 06:09

[Edited on 29-1-2015 by jhonthebaptist]

[Edited on 29-1-2015 by jhonthebaptist]

[Edited on 30-1-2015 by jhonthebaptist]

jhonthebaptist - 29-1-2015 at 09:55

[Edited on 30-1-2015 by jhonthebaptist]

Etaoin Shrdlu - 29-1-2015 at 10:39

Quote: Originally posted by jhonthebaptist

Yes Cureus, I was attempting a piperidine synthesis. I wanted to see who would recognize what I was doing, looks like you are the only one that did.

Everyone else ignores ambiguously phrased drug-related synthesis questions.

jhonthebaptist - 29-1-2015 at 14:19

[Edited on 30-1-2015 by jhonthebaptist]

smaerd - 29-1-2015 at 19:50

So, how awful does cadaverine smell?

Edit - Again considering the thread title was about cadaverine it would be nice to see what your conditions were for the decarboxylation.

[Edited on 30-1-2015 by smaerd]

jhonthebaptist - 30-1-2015 at 07:31

Well after etaioin posted that remark about drug cookery , I dint think anyone wanted to know what my procedure was or conditions of the reactions I posted. I undertook this project to find out IF it could be done, that is to make piperidine from cadaverine. I have experience with piperidine from many years and if I really wanted to buy it I could get it by the gallons. So please don't accuse me of illegal activities.
One would need to decarboxylate 5 pounds of lysine to get enough cadaverine to get the reaction to produce any workable amount of piperidine the way I did it.
I used an old 500 ml boiling flask with a stopper and a bent length of pyrex tubing, it was tilted to the right at about 2-3 o'clock. The tube ran into a 50 ml flask in ice. The lysine was mixed with sodium bicarbonate and dumped into the flask. The size of the rxn was limited to 10-20 grams of lysine because any bigger and reactants wouldn't be all used and would waste alot. At first the mixture is white as heat is applied from a bunsen burner it turns black, then grey, the cadaverine dont smell like dead bodies. It smells like the amine used in epoxy kind like jb weld in a way. However it has a strong smell that is nasty to be around for some time.

Etaoin Shrdlu - 30-1-2015 at 07:55

Quote: Originally posted by jhonthebaptist

Well after etaioin posted that remark about drug cookery , I dint think anyone wanted to know what my procedure was or conditions of the reactions I posted.

Noooooooooooo. I didn't mean it that way, okay? Exactly the opposite. Your initial question was phrased to deliberately avoid mentioning the product by name, and that makes a question look more shady than scientific. If you look around the board you'll find all kinds of drug-related synthesis threads. They get a better response if you're forthright about what you're working on.

I personally don't care in the slightest whether you or anyone else is cooking drugs.

Darkstar - 30-1-2015 at 08:16

What's with all of these edited-out posts? Looks preeeeeeety suspicious if you ask me.

Just kidding. Seriously, though, even if you were up to no good, no one ever really makes a big deal out of it as long as you at least show some genuine interest in the actual chemistry involved.

[Edited on 30-1-2015 by Darkstar]

jhonthebaptist - 30-1-2015 at 09:07

ok no problem. If thats how it appears than thats an assumption the reader makes, wasn't my intent to look suspicious , or be sub-verse. I see quite a bit of flaming on this forum, from various posts, some have merit while others have none. I have never come here asking HOW to do anything, or to get any items. I am interested in actual chemistry and have gone to school for that subject. I may be in the wrong place, for actual science and get the impression most people are not welcome here.
If I cant be welcomed as a member then I will not stay.

[Edited on 30-1-2015 by jhonthebaptist]

Zombie - 30-1-2015 at 09:18

Dude... I'm an idiot, and they have been very understanding with me. Just sayin'

I'm aware of what piperidine is, and it's use but I took note at the cadaverine. I'd be interested in following this if you stick around.
It's obvious (as you stated) you can't make enough piperidine to make this worth the effort.

jhonthebaptist - 30-1-2015 at 09:52

Thanks zombie, This has gone as far its gonna go though. I mean I dont intend to even make anymore cadaverine or piperidine from it. There is a video on youtube of the cadaverine synthesis from lysine. The only thing I did was scale it up and did three separate runs, totaling 50 grams lysine and about 24-25 grams of sodium bicarb. Use a flask instead of a test tube.
Take note , it makes a mess of the flask. alot of tar and crap Most will come out when cleaned but not all, and the stresses it puts on the glass makes the flask almost unfit for much else. It is easy, just got to be safe when working with high temps and glass, wear eye protection if you do.

blogfast25 - 30-1-2015 at 10:00

In most cases of tar it will dissolve in hot, 20 - 30 w% NaOH with some detergent mixed in. A combination of chemical cleaning with mechanical abrasion will get rid of the junk. Superficial etching doesn't render glassware unusable either.

[Edited on 31-1-2015 by blogfast25]

smaerd - 30-1-2015 at 10:57

Thanks for the experimental. I've always been interested in decarboxylation reactions of common chemicals. Believe it or not I was considering using a cadaverine type linkage in a project that's why I asked. Interesting to hear that it doesn't smell as awful as it is often reported to be. I can actually see a good amount of interesting chemistry coming from this compound in a DIY setting so I'm glad you made this thread all the banter aside. If I were to recreate it, I'd do the old coffee can disposable destructive distillation rig, as done in benzene from sodium benzoate synthesis.

Honestly I don't think anyone cares what you plan to use the intermediates for. I think it's a little rude to speculate unless well its one of those ridiculous precursors to an illicit substance. I can comfortably say that I wish I had piperidine around many times, and if someone can't think of a legitimate reason why that might be they are probably cooks themselves.

I do have a suggestion though. Maybe for your next post to avoid scrutiny, share more of the chemistry/experimental, and less of the things you maybe aren't so eager to share. Everyone here loves to see an experiment especially one that worked.

Darkstar - 30-1-2015 at 12:18

For the record, I don't honestly believe you're doing anything illegal. And even if you were, who cares? I surely don't. This is a forum about science, not politics.

Piperidine has plenty of legitimate uses and there's nothing wrong with trying to synthesize it, even if it's just for the hell of it. That's what amateur chemistry is all about. Which is also why you should have just come out and admitted what you were trying to do in the beginning and moved on. Between the ambiguous "famous cyclic secondary amine" line and you getting all defensive and deleting your posts, is it really a surprise that someone thought your thread looked a little shady?

Anyway, I do look forward to reading more about your experiment. :cool:

jhonthebaptist - 30-1-2015 at 15:47

I agree and darkstar you are right, Im sorry for the word drama. You put the situation in perfect perspective , it was just for the hell of it. thanks for the support, I hope to contribute as much as I can.

CuReUS - 31-1-2015 at 06:27

but why did you delete your posts,what did you write in them that was so incriminating ?
also,I cant understand how you would get even a bit of piperidine,pls post the reaction mechanism or the lit-sup.

Quote:

Piperidine has plenty of legitimate uses and there's nothing wrong with trying to synthesize it, even if it's just for the hell of it.

piperidine is in the list 1 of DEA,I think that means its illegal to possess of manufacture without permit

Quote:

If you look around the board you'll find all kinds of drug-related synthesis threads. They get a better response if you're forthright about what you're working on.

that is so nice,so could someone please tell me why safrole is converted to isosafrole
This question has been bothering me for a long time.Is it done to prevent polymerisation due to storage ?

turd - 31-1-2015 at 07:14

Quote: Originally posted by CuReUS

piperidine is in the list 1 of DEA,I think that means its illegal to possess of manufacture without permit...

...in some parts of the world, that are irrelevant to many of us (myself included).

Quote:

that is so nice,so could someone please tell me why safrole is converted to isosafrole

So that oxidation gives you the phenylacetone and not the phenylpropionaldehyde. The smell is also (very) different.

Zombie - 31-1-2015 at 07:20

I have to point out here fellas the a very large percentage of the forum is involved with compositions that are frowned upon.

Perhaps the matter is best suited for the forum management rather than the members.

Besides, who's to say the fella really did any of what he said he did. Could be my grandmother passing time, and stirring up cr@p like always.

Oh... nobody in the thread mentioned Safroil.

Just sayin'

[Edited on 31-1-2015 by Zombie]

blogfast25 - 31-1-2015 at 09:00

Quote: Originally posted by Zombie

I have to point out here fellas the a very large percentage of the forum is involved with compositions that are frowned upon.

A very large percentage?

Frowned upon by whom? The yokels in your local police station in Florida?

What's done here is either legal or it's not. In the former case let them frown themselves into an aneurysm.

Zombie - 31-1-2015 at 09:38

Sometimes sir... I wish. Forgot, we are the home of the worlds smallest police station. Guinness book

[Edited on 31-1-2015 by Zombie]

The Volatile Chemist - 31-1-2015 at 11:13

It's the 'energetic Materials' Section which is frowned upon. It's title is soooo funny, as it obfuscates what's actually going on inside

When I first joined SM, I just thought it meant 'dangerous chemicals'

Zombie - 31-1-2015 at 12:10

The Volatile Chemist / Energetic Materials section I fail to see the attraction

The Volatile Chemist - 31-1-2015 at 12:22

Quote: Originally posted by Zombie

The Volatile Chemist / Energetic Materials section I fail to see the attraction

Haha, I actually haven't made anything energetic. Not that I haven't tried... I'm waiting till I own an industrial lab and have excuses

Darkstar - 31-1-2015 at 12:36

Quote: Originally posted by CuReUS

piperidine is in the list 1 of DEA,I think that means its illegal to possess of manufacture without permit

It's not illegal to possess in the US. (assuming that's where you're referring to) It just means its suppliers are tightly regulated and its sale is closely monitored. Iodine, safrole and benzaldehyde are also examples of List I chemicals. Are these illegal to purchase or possess? No. Are they more difficult to purchase than most chemicals? Yes.

Etaoin Shrdlu - 31-1-2015 at 14:42

They are illegal to manufacture without a permit though.

CuReUS - 1-2-2015 at 03:20

Quote: Originally posted by turd

Quote:

that is so nice,so could someone please tell me why safrole is converted to isosafrole

So that oxidation gives you the phenylacetone and not the phenylpropionaldehyde. The smell is also (very) different.

but wont oxidation of safrole give a ketone,according to markonikoff rule or is marko not applied here at all ?
also,when you isomerise it and then oxidise it,won't it dance over to the benzylic carbon and form propiophenone instead of P2P.(I know it doesn't,but generally that's what everyone would expect it to do,as then the carbonyl carbon will be in resonance with the benzene ring)

turd - 1-2-2015 at 05:55

Formally: alkene --(oxidation)--> epoxide --(hydrolysis)--> vicinal diol --(elimination)--> enol --(tautomery)--> ketone/aldehyde --(condensation)--> tar.

Which of the two OHs is more likely to eliminate?

jhonthebaptist - 1-2-2015 at 08:53

Piperidine isn't illegal to posses, as long as its 500 grms or under and you don't have other things like, the bromobenzene, cyclohexanone, Mg, and such. (I think, not sure though) If it were totally illegal then everyone that has a pepper shaker would be subject to punishment. I have bought it before 9/11, bought a 1000ml for 80 bucks. But that was a long time ago, and I only used a few mls of it. ended up trading a wood splitter for the rest of the bottle.
Personally I was just curious about making it from cadaverine. There is a lot of scientific reports that are false, so I was wanting to verify/discredit the claim. I don't give a crap about what its used for because I like to be able to function and think.

Bert - 1-2-2015 at 09:24

I've been unable to find any listing of pickardjr in member list. If I had, I could re-connect you with former ID- Assuming you were not banned or otherwise de-listed for cause.

Did you spell EXACTLY, and did you formerly capitalize or punctuate that?

Like:

Pickard jr.

for instance?

Totally missed whatever you deleted. And have no conception of why you want to "beat around the bush" & see who can figure out your actual interest...

I have used cadaverine. Part of the ingredients in a product our trainer called "Fred". Now I shall be the mysterious one!

Etaoin Shrdlu - 1-2-2015 at 09:35

Bert, he's here. https://www.sciencemadness.org/whisper/member.php?action=vie...

Bert - 1-2-2015 at 09:48

The same Pickardjr who had this as his first post?

https://www.sciencemadness.org/whisper/viewthread.php?tid=24...

If so, U2U me.

[Edited on 1-2-2015 by Bert]

smaerd - 1-2-2015 at 13:01

Yeesh the disrespect towards Solo in that thread bugs me a lot... Solo is a really respectable poster who really goes out of his way to share information with all of us. It wouldn't surprise me if the pickardjr account was banned...

Bert - 1-2-2015 at 13:29

I did not ban,did not find a ban in profile or moderator logs either.

Woelen let it go as a detritus and a warning, over 18 months back. (Before I was even a moderator!) I will not 2nd guess a senior moderator, especially on old business.

There was a story my father told about a pioneer, a mail order bride and a mule.

"That's once!".

Zombie - 2-2-2015 at 00:06

The Little Bride.

CuReUS - 2-2-2015 at 00:30

turd ,but if the conversion of alkene to ketone was carried out by the wacker oxidation,ketone will form instead of aldehyde even for terminal alkenes
http://en.wikipedia.org/wiki/Wacker_process#Wacker.E2.80.93T...
I also found that people do the wacker on safrole itself,without isomerising it to iso-safrole.But "pickler" says that during wacker process,safrole is first converted to iso and then to P2P
http://chemistry.mdma.ch/hiveboard/methods/000332297.html
I think aldehydes will form from terminal alkenes if other reactions are used

turd - 3-2-2015 at 02:20

I was obviously talking about the peracid oxidation (in reply to your answer why one would make isosafrole).

If you go the Wacker route you do not want isosafrole, but safrole. Isomerization is an unwanted side-recation, but this is not relevant with regard to your question.

I fail to see how all this relates to cadaverine and suggest you open a separate thread if you want to discuss oxidation of allyl-/propenylbenzenes to phenylpropanones.

JAVA - 3-2-2015 at 09:02

Maybe we can make a closed section: only real chemists are permitted to post with a knowledge test?
Cadaverine smells like......blurp.

There are better ways to make piperidine. //

See hyperlink below

CuReUS - 4-2-2015 at 00:23

Quote: Originally posted by JAVA

Maybe we can make a closed section: only real chemists are permitted to post with a knowledge test?

maybe you should learn to read english first.SM is primarily for amateur chemists, not ACS laureates.And why should only some people be given the power to test others.Its like racism in the scientific community.Some of the best posts here are from home chemists not PhD's :mad:

if you are so keen to write exams,let me U2U a few "questions" .We will all see how much knowledgeable you are

Quote:

Cadaverine smells like......blurp

remind me never to invite you for lunch

Quote:

There are better ways to make piperidine. //
See hyperlink below

don't click the link,Its malware

Pickardjr - 4-2-2015 at 06:17

Im not really interested in the 101 ways to make piperidine. I wouldn't and didn't click the link in the upper post. I can not figure what the big deal is about this substance. When I preformed this experiment it was to prove/disprove the literature. The procedure is claimed to work, with a whopping yield of 1%. Feasibility is 0 % to use it in another reaction, I know this.
I'm aware of all the other ways to skin a cat, Im not interested. Just wanted to see if I could do it from lysine. I found out real quick. project scrapped. Please don not perpetuate bull-crap.

Zombie - 4-2-2015 at 11:35

Quote: Originally posted by CuReUS

Quote: Originally posted by JAVA

Maybe we can make a closed section: only real chemists are permitted to post with a knowledge test?

if you are so keen to write exams,let me U2U a few "questions" .We will all see how much knowledgeable you are

Quote:

Cadaverine smells like......blurp

remind me never to invite you for lunch

Quote:

There are better ways to make piperidine. //
See hyperlink below

don't click the link,Its malware

Figured as much... The link I mean. Perhaps Mr. Java could remove it?

There are few things as frustrating as an infected computer.
Just sayin'

The Volatile Chemist - 4-2-2015 at 15:38

'Dat' malware. This place'd be a good way to distribute it, link to a supposed PDF of Vogel's 5th, and you've got thirty new infected computers

Zombie - 4-2-2015 at 15:49

It's kind of a shot below the belt, and usually draws the same in return.
Not that anyone would do something like that on purpose...

sns-viral-below-the-belt-pictures.jpg - 15kB

CuReUS - 5-2-2015 at 02:44

Quote: Originally posted by Pickardjr

. Just wanted to see if I could do it from lysine. I found out real quick. project scrapped.

I have an idea.perhaps you could try it out and tell the yields
first treat lysine with bleach to get 5-aminopentanal(strecker degradation)
then reflux the aminopentanal in HCOOH.the compond should cyclise and then the imime formed should get reduced by hydride donation from HCOOH
I always wondered why HCOOH was used to reduce imimes in one reaction(eschenweiler clark) and Al/Hg+acid was used in other reactions
also can Zn/HCOONH₄ be used to reduce the imime instead of HCOOH alone .Maybe Zn catalyses the reaction

Chemosynthesis - 5-2-2015 at 03:31

Bringing back an oldie.
https://www.sciencemadness.org/whisper/viewthread.php?tid=27...
I'd been passingly curious how that ever turned out.

Quote: Originally posted by turd

Quote: Originally posted by CuReUS

piperidine is in the list 1 of DEA,I think that means its illegal to possess of manufacture without permit...

...in some parts of the world, that are irrelevant to many of us (myself included).

The United Nations Convention against Illicit Traffic in Narcotic Drugs and Psychotropic Substances ratified by 87 signatories and 189 parties in Vienna, 20 December 1988 is probably more relevant as a bit of an aside.

turd - 5-2-2015 at 04:46

Quote: Originally posted by Chemosynthesis

Pffffft. Couldn't care less. Quote https://en.wikipedia.org/wiki/United_Nations_Convention_Agai...

Quote:

Table II

acetone
anthranilic acid
diethyl ether
hydrochloric acid (hydrogen chloride)
methyl ethyl ketone
piperidine
sulphuric acid
toluene

With the exception of anthranilic acid I acquired all of the above chemicals in 250 ml+ quantitites - no questions asked. The whole notion of PCP/angel dust is completely obscure to people around these parts. Are you seriously trying to impress us by the fact that piperidine has the same legal status as acetone?

Chemosynthesis - 5-2-2015 at 05:39

Quote: Originally posted by turd

Pffffft. Couldn't care less.

I didn't ask.

Quote:

Table II

acetone
anthranilic acid
diethyl ether
hydrochloric acid (hydrogen chloride)
methyl ethyl ketone
piperidine
sulphuric acid
toluene

With the exception of anthranilic acid I acquired all of the above chemicals in 250 ml+ quantitites - no questions asked.

I don't really care, nor is it relevant to whether it was done legally or not. In that exact same spirit, I'm not going to ask if your reagent list was supposed to impress me, as that's very achievable in the U.S. as well; however, that doesn't mean it will never have consequence to even an innocent purchaser.

Quote:

The whole notion of PCP/angel dust is completely obscure to people around these parts. Are you seriously trying to impress us by the fact that piperidine has the same legal status as acetone?

I'm just pointing out a law. No need to get reactive over it. If I were trying to impress people, I'd blather on about what I can get with a Form 222 or 225, but I would hope most people wouldn't pay any mind as that wasn't what I was trying to discuss. If you're not asking rhetorically to make an off-topic point, I am actually not particularly fond of most U.N. treaties or resolutions, but they are notably more applicable than U.S. law, which is what I stated (in continuation of the points you and CuReUS made), and members or browsers of the forum should at least be cognizant of this as it does have some impact on chemistry, as regrettable as that is.
People do post on here about how difficult it is to keep up with various government watch lists, and I doubt anyone considers how the U.N. is involved in the alphabet soup.
ex. (with acetone!): https://www.sciencemadness.org/whisper/viewthread.php?tid=36...
So unless anyone is still interested in discussing what I noted was an aside to the primary conversation, chemistry, do the two of us have more to discuss?

Zombie - 5-2-2015 at 05:58

aaaa er uh mmmm... nevermind

The Volatile Chemist - 6-2-2015 at 09:20

Surprised me this reached three pages. This is kind-of like the abortion discussion that needed stopped in my classroom just now.... Just kidding