Bullshit Thread - Part Zoklet

[Hydroponichronic]

Doncha just hate it when a two-phase extraction inexplicably precips two extra phases?

[Gun Lover]

Fucking adrenochrome, how does it work

http://en.wikipedia.org/wiki/Adrenochrome

How does it form the indole ring from epinephrine. I demand mechanisms

[Hydroponichronic]

So, let's say one had a solvent mix of 2 parts heavy aromatic naphtha, 1 part cyclohexanone, and 1 part pyrrolidone, held at 80C for 12 hrs with excess aqueous Mg(OH)₂ (so to hydrolyze the pyrrolidone into Mg(GABA)₂). One then decanted the nonpolar, and washed twice with equal parts heptane to pull the residual cyclohexanone and heavy aromatic naphtha, theoretically leaving an aqueous containing only residual Mg(OH)₂ and fairly pure Mg(GABA)₂).

Then, to one's unpleasant surprise, one instead yields a light yellow aqueous that does not xtalize even after drying at 60C for 3 hours. Instead it becomes the consistency of thick maple syrup, with a film on top preventing further dehydration. One then thinks to resolvate with hot 91% iso and xtalize from that, only to finds that instead of xtals coming out of solution on cooling, only a thick light yellow liquid precips. This would lead one to believe that Mg(GABA)₂) was deliquescent; however a quick search of the literature proves this not to be the case.

[Gun Lover]

Originally Posted by Gun Lover

Fucking adrenochrome, how does it work

http://en.wikipedia.org/wiki/Adrenochrome

How does it form the indole ring from epinephrine. I demand mechanisms

Perhaps oxidation of the catechol moiety to 1,2-benzoquinone, then michael reaction to form the heterocyclic ring

[Hydroponichronic]

Originally Posted by Gun Lover

How does it form the indole ring from epinephrine. I demand mechanisms

TBH, I would think that like all biotransformation it is enzyme catalyzed magic. I mean, once you've got enzymes at your disposal, you have the ability to literally RIP atoms off of a molecule and stick new ones on. They don't really follow rules like mortal chemistry.

[baffler]

haha mortal chemisty...

[Irukanji]

Originally Posted by Hydroponichronic

Doncha just hate it when a two-phase extraction inexplicably precips two extra phases?

So you have 4 phases? In one container...
4/4 = 1
1 phase
yfw

-------------

Ok serious talk now, started a lab course at school(I guess it's like a technical college or what have you) down here and learning some useful stuff. Bit slow for my liking, too much paperwork, but whatever. I'll consider it punishment for never doing the work in high school. Learning how to use volumetric pipettes and make solutions is ok, but easymode. Beats paperwork hands down.

But fuck I hate OH&S, the amount of common sense shit which we have to cover is just like...were these people dropped on their heads repeatedly? Class full of short cunts all complaining about the height of the glass cabinets and how they might hurt themselves...I'm 6' maybe 6'1 with shoes and they are like...4'6-5', with the exception of a few guys who are in the same boat as me. Rest of the class is female. Female teacher. Pretty sure they are sucking up to her early, but the blokes will unite and conquer with our superior height.

[Hydroponichronic]

Originally Posted by Irukanji

So you have 4 phases? In one container...
4/4 = 1
1 phase
yfw

nonpolar on top, a foamy, gelatinous interlayer, an aqueous layer, and a heavy foam/gel on the bottom (different from the interlayer). Also, what's "yfw"?

Originally Posted by Irukanji

Ok serious talk now, started a lab course at school(I guess it's like a technical college or what have you) down here and learning some useful stuff. Bit slow for my liking, too much paperwork, but whatever. I'll consider it punishment for never doing the work in high school. Learning how to use volumetric pipettes and make solutions is ok, but easymode. Beats paperwork hands down.

But fuck I hate OH&S, the amount of common sense shit which we have to cover is just like...were these people dropped on their heads repeatedly? Class full of short cunts all complaining about the height of the glass cabinets and how they might hurt themselves...I'm 6' maybe 6'1 with shoes and they are like...4'6-5', with the exception of a few guys who are in the same boat as me. Rest of the class is female. Female teacher. Pretty sure they are sucking up to her early, but the blokes will unite and conquer with our superior height.

Welcome to real life kiddo.

[Gun Lover]

Originally Posted by Hydroponichronic

TBH, I would think that like all biotransformation it is enzyme catalyzed magic. I mean, once you've got enzymes at your disposal, you have the ability to literally RIP atoms off of a molecule and stick new ones on. They don't really follow rules like mortal chemistry.

Fucking enzymes, how do they work

Also, I wonder what the trifluoroacetate ester of morphine would be like. That'd require quite a nasty anhydride/acid halide, methinks.

Edit: Are you kidding me?

Codeine ----------> Codeinone --------------> Hydrocodone

1) Swern Oppenauer oxidation
2) H₂, Pd/C

Why the FUCK do I live where codeine isn't OTC

Shit, it's one step from DHC. You can buy boxes of that shit in England for cheap.

[BungHole]

Originally Posted by Gun Lover

Fucking enzymes, how do they work

Also, I wonder what the trifluoroacetate ester of morphine would be like. That'd require quite a nasty anhydride/acid halide, methinks.

Edit: Are you kidding me?

Codeine ----------> Codeinone --------------> Hydrocodone

1) Swern Oppenauer oxidation
2) H₂, Pd/C

Why the FUCK do I live where codeine isn't OTC

Shit, it's one step from DHC. You can buy boxes of that shit in England for cheap.

That's God's way of protecting you from harm.

[Gun Lover]

Ergocornine

I've not looked at any ergoilne synthesis in years, but couldn't you hydrolyze that amide to the carboxylic acid then react it with diethylamine and dicyclohexylcarbodiimide to give ?

Is this route inferior to traditional methods? Or maybe I should ask if it even would work

[Hydroponichronic]

Originally Posted by Gun Lover

Ergocornine

I've not looked at any ergoilne synthesis in years, but couldn't you hydrolyze that amide to the carboxylic acid then react it with diethylamine and dicyclohexylcarbodiimide to give ?

Is this route inferior to traditional methods? Or maybe I should ask if it even would work

Yes, you could. But what I've heard is that extraction and purification of erogoloids to reagent grade precursors is a bitch. On top of that, where the fuck does one get DCC, or other useful peptide coupling reagents? When I was reading on such things back in the day, I was under the impression that if such a thing was to be done, it would require home-synthesis of really nasty stuff like thionyl chloride or PCl₅ and the like.

[Hydroponichronic]

Just spit-ballin here gaiz, but I had a thought the other day. Could one react acetophenone with calcium carbide to yield the thing on the left, then catalytically hydrogenate to yield the thing on the right?



And if mono-hydrogenation was not an option, could the thing on the left be reacted with dilute acid to yield β-Me-β-OH-P2P?

[typedthiswithmytits]

Originally Posted by Hydroponichronic

Just spit-ballin here gaiz, but I had a thought the other day. Could one react acetophenone with calcium carbide to yield the thing on the left, then catalytically hydrogenate to yield the thing on the right?



And if mono-hydrogenation was not an option, could the thing on the left be reacted with dilute acid to yield β-Me-β-OH-P2P?

what is all this sorcery for?

[Gun Lover]

Originally Posted by Hydroponichronic

Just spit-ballin here gaiz, but I had a thought the other day. Could one react acetophenone with calcium carbide to yield the thing on the left, then catalytically hydrogenate to yield the thing on the right?

Yeah I think so. And you could use H₂/Lindlar's catalyst (Pd/C poisoned with quinoline) or Na metal in liquid ammonia to selectively yield the alkene.

Originally Posted by Hydroponichronic

And if mono-hydrogenation was not an option, could the thing on the left be reacted with dilute acid to yield β-Me-β-OH-P2P?

Yes, but not with acid alone. The proper way to yield a methyl ketone from an alkyne is to use HgSO₄/H20, H₂SO₄ which yields the terminal enol which quickly tautomerizes to the methyl ketone

[Hydroponichronic]

Originally Posted by typedthiswithmytits

what is all this sorcery for?

Well, if the β-Me-β-OH-P2P is aminated, it would yield β-Me-Phenylpropanolamine. I suspect such a compound would have all of PPAs good decongestant properties without any of its legal troubles. Plus it could be sold freely like phenylephrine, as it can't be converted into methamphetamine. Also, the β-Me-β-OH-P2P would serve as a good starting point for research compounds.

Originally Posted by Gun Lover

Yeah I think so. And you could use H₂/Lindlar's catalyst (Pd/C poisoned with quinoline)

I have a personal distaste for expensive metal catalysts.

Originally Posted by Gun Lover

or Na metal in liquid ammonia to selectively yield the alkene.

Birch reduction however, is quite to my aesthetic.

Originally Posted by Gun Lover

Yes, but not with acid alone.

I know. It was a bit vague how I phrased it:

Originally Posted by Hydroponichronic

reacted with dilute acid to yield β-Me-β-OH-P2P

[typedthiswithmytits]

Originally Posted by Hydroponichronic

Well, if the β-Me-β-OH-P2P is aminated, it would yield β-Me-Phenylpropanolamine. I suspect such a compound would have all of PPAs good decongestant properties without any of its legal troubles. Plus it could be sold freely like phenylephrine, as it can't be converted into methamphetamine. Also, the β-Me-β-OH-P2P would serve as a good starting point for research compounds.

Ring forming or otherwise?

Just trying to get an idea of where you were going with this.

[Hydroponichronic]

Originally Posted by typedthiswithmytits

Ring forming or otherwise?

Where do you get ring forming?

[Gun Lover]

Originally Posted by Hydroponichronic

Where do you get ring forming?

What are looking for the end product to be? β-Me-β-OH-N-methylamphetamine?

If so, I dunno what that might be like.

nvm im retarded

[typedthiswithmytits]

Originally Posted by Hydroponichronic

Where do you get ring forming?

ppa>aminorex etc... I dunno if the methyl would hurt that or just the end product.

[Hydroponichronic]

Originally Posted by typedthiswithmytits

ppa>aminorex etc... I dunno if the methyl would hurt that or just the end product.

That I don't know. I never liked the idea of cyclizating phenethylamines, mostly because their SARs are a mystery to me.

Originally Posted by Gun Lover

What are looking for the end product to be? β-Me-β-OH-N-methylamphetamine?

That's the magic of it. From the alkyne product you could do half a hundred different things.

Originally Posted by Gun Lover

If so, I dunno what that might be like.

nvm im retarded

Retarded? hardly. There is little to nothing out there about alkylation of the β position on phenethylamines. I base all my assumptions on the very limited experiments Shulgin did in pihkal with β-methoxylated PEAs. It seems like by-and-large, a β methoxy group does little to change PEA affinities. By this logic, a β-methyl group (much smaller, less polar) should have almost no effects, save turning a controlled substance into a legal grey area.

Also, given the low cost and lack of regulation around both precursors (acetophenone and calcium carbide), there seems to be some potential here for motivated entrepreneurs. With a β-Hydroxy group one should have compounds that act as appetite suppressants, thermogenics, and antinarcoleptics, all with relatively limited abuse potential. Body builders, truckers, and overweight people would by it by the ton. Alternatively, reduction of the β-OH should yield compounds with fairly high activity in the realm of DA and 5HT, which have uses all their own...

EDIT: And that's only for plain acetophenone. Surely one could come by ring-substituted acetophenones. A version of this trick could also work magic with (ring-substituted)benzoate esters.

[Hydroponichronic]

I just logged onto WD for the first time in a few years, and it looks like the site died in nov 2010. WTF happened? Did it relocate?

and yes, I know I am slow

[Hydroponichronic]

y'all gotta check this thread more often...

[Gun Lover]

Originally Posted by Hydroponichronic

That's the magic of it. From the alkyne product you could do half a hundred different things.

You know, looking back on the original proposed rxn, I see a problem. If acetylide is a strong enough base to react with one acetophenone, I'd be willing to bet the reactant in your picture would be liable to react with another acetophenone, no?

Retarded? hardly.

Retardedly blazed is what I meant

There is little to nothing out there about alkylation of the β position on phenethylamines. I base all my assumptions on the very limited experiments Shulgin did in pihkal with β-methoxylated PEAs. It seems like by-and-large, a β methoxy group does little to change PEA affinities. By this logic, a β-methyl group (much smaller, less polar) should have almost no effects, save turning a controlled substance into a legal grey area.

That's pretty cool; my immediate thoughts were, if your proposed rxn works: benzophenone ----> β-OH-β-phenylmeff (which I always thought was a neat drug)

But then things are starting to look a bit like pipradrol...

EDIT: And that's only for plain acetophenone. Surely one could come by ring-substituted acetophenones. A version of this trick could also work magic with (ring-substituted)benzoate esters.

Hmmm

Originally Posted by Hydroponichronic

y'all gotta check this thread more often...

qft

[Gun Lover]

Oh, but I forgot I came here to check and see if this was right:



Primary alkylamines react with ketones/aldehydes to give imines. Secondary alkylamines give enamines.

AFAIK, the tertiary enamine you get after the first step is not nucleophilic enough to attack the β position of cyclohexenone as primary & secondary amines normally would. Maybe I'm permafried, but I don't see how the two molecules would interact.

Bet the professor was just being slimy

[Hydroponichronic]

Originally Posted by Gun Lover

You know, looking back on the original proposed rxn, I see a problem. If acetylide is a strong enough base to react with one acetophenone, I'd be willing to bet the reactant in your picture would be liable to react with another acetophenone, no?

Fuck.

Originally Posted by Gun Lover

AFAIK, the tertiary enamine you get after the first step is not nucleophilic enough to attack the β position of cyclohexenone as primary & secondary amines normally would. Maybe I'm permafried, but I don't see how the two molecules would interact.

Well, if pka ~ nucleophilicity, then even tertiary amines should have that part covered. Though forming anything other than a hemiaminal would require a condensation step to happen that I'm not familiar with.


Also, what did you get permafried from? Traumatic brain injury or just chronic drug use?

[Hydroponichronic]

Also, propylene carbonate:

It is possible, for example, to obtain potassium, sodium, and other alkali metals by electrolysis of their chlorides and other salts dissolved in propylene carbonate.

So, who else finds this fascinating?

[Gun Lover]

Originally Posted by Hydroponichronic

Fuck.

Well, if pka ~ nucleophilicity, then even tertiary amines should have that part covered. Though forming anything other than a hemiaminal would require a condensation step to happen that I'm not familiar with.

That's the thing, I think the tertiary amine's inherent basicity is trumped by its steric hindrance and thus will not act as a nucleophile. At least I've never heard of such things.

Also, what did you get permafried from? Traumatic brain injury or just chronic drug use?

Oh I was fucking around. I've just been on a cannabinoid binge for a few weeks now and there has been undeniable mental impairment.

It's okay though, it's not my first cannabinoid binge; believe it or not, I can attest to the fact that even if you abuse the shit hard and stay retarded for months on end, when you stop for a couple weeks your normal brain function resumes

Originally Posted by Hydroponichronic

Also, propylene carbonate:
It is possible, for example, to obtain potassium, sodium, and other alkali metals by electrolysis of their chlorides and other salts dissolved in propylene carbonate.

So, who else finds this fascinating?

Fixed your link I think

And WTF, that would be a sweet reaction to watch. Tell me how it works dammit

[Hydroponichronic]

Originally Posted by Gun Lover

That's the thing, I think the tertiary amine's inherent basicity is trumped by its steric hindrance and thus will not act as a nucleophile. At least I've never heard of such things.

Didn't think of that. Makes sense.

Originally Posted by Gun Lover

It's okay though, it's not my first cannabinoid binge; believe it or not, I can attest to the fact that even if you abuse the shit hard and stay retarded for months on end, when you stop for a couple weeks your normal brain function resumes

IME, this won't work with organically-derived cannabinoids. The half-lives are long enough that they fuck with you for weeks/month afterward.

Originally Posted by Gun Lover

Fixed your link I think

Cool. One thing I look for, though, is a process that uses common anions. Getting/making alkali perchlorates is a hassle of its own.

Originally Posted by Gun Lover

And WTF, that would be a sweet reaction to watch.

The rxn itself, not somuch. I'd be more a fan of the subsequent reactions. I'm given to understand that oxidation of potassium in aqueous media is quite exothermic.

Originally Posted by Gun Lover

Tell me how it works dammit

I'd need to get some solvent first, which I'm probably to shiftless to ever actually do. Though it is available from a chem supplier I know.

[Gun Lover]

Originally Posted by Gun Lover

Oh, but I forgot I came here to check and see if this was right:



Primary alkylamines react with ketones/aldehydes to give imines. Secondary alkylamines give enamines.

Maybe I'm permafried, but I don't see how the two molecules would interact.

God damnit

[Hydroponichronic]

Originally Posted by Gun Lover

God damnit

Now I feel stupid that I didn't see it myself. I've been getting a lot of that lately.

[Isoterrapine]

possibility check:

would it be possible to methylate (is that the right term?) Etaqualone to form methqualone?.

Am I right in thinking this would be as simple as a methanol reflux with some kind of catalyst?. (pdcl?)

Sorry for what may be the most retarded question of the month.

[BungHole]

Originally Posted by Isoterrapine

possibility check:

would it be possible to methylate (is that the right term?) Etaqualone to form methqualone?.

Am I right in thinking this would be as simple as a methanol reflux with some kind of catalyst?. (pdcl?)

Sorry for what may be the most retarded question of the month.

Methylate is an actual term, but not proper in this context. What would be going on here is actually a demethylation, as you would be removing a carbon atom from the ethyl side chain. For all practical purposes, it's a hopeless cause. It would in no way be as simple as refluxing in methanol with a catalyst. It would involve selectively breaking the C-C bond on the the ethyl side chain of the aniline ring without destroying the other functional groups. This would be rather difficult compared to simply starting from scratch and synthesizing from, say, o-toluidine and N-acetyl anthranilic acid.

[Isoterrapine]

Originally Posted by BungHole

Methylate is an actual term, but not proper in this context. What would be going on here is actually a demethylation, as you would be removing a carbon atom from the ethyl side chain. For all practical purposes, it's a hopeless cause. It would in no way be as simple as refluxing in methanol with a catalyst. It would involve selectively breaking the C-C bond on the the ethyl side chain of the aniline ring without destroying the other functional groups. This would be rather difficult compared to simply starting from scratch and synthesizing from, say, o-toluidine and N-acetyl anthranilic acid.

thanks for clearing that up.

yea I spotted your thread which is what got me thinking.

[baffler]

Originally Posted by Gun Lover

Yeah I think so. And you could use H₂/Lindlar's catalyst (Pd/C poisoned with quinoline) or Na metal in liquid ammonia to selectively yield the alkene.

or poisoned w/ lead, calcium cabronate for lyndlar's.

An don't forget the NH₄Cl in the Birch, since it's a terminal alkyne


Also, kinda off "topic" but I saw a piperonal/nitroethane condensation that involved methylamine as the catalyst in ethanol, but also I've read alcoholic methylamine ( http://www.erowid.org/archive/rhodiu...ud-lappin.html ) can cause polymerization depending on the substrate--it seems that if the wanted prduct precipitates out quick enough, it't not a problem. Have any of you tried this method and had good results/no problems??

Also, I read the paper that actually has this (not sited correctly on erowid) which is

REACTIONS OF VANILLIN AND ITS DERIVED COMPOUNDS. XII.'
BENZYL METHYL KETONES DERIVED FROM VANILLIN AND I T S RELATED COMPOUKDS pp 216–220, 1951 (Article) DOI: 10.1021/jo01142a008, by Irwin A. Pearl and Donald L. Beyer

and they say just to cool and filter the crystals (for all B-nitropropenylbenzenes tested except B-nitroisoeugenol) like without dumping into 7 Liters of water... any experience on this--a good idea to forget the water dilution step??

[Hydroponichronic]

Well I was cleaning out my kitchen and I found a test tube in the back of a cabinet that reeked of phenylacetaldehyde. I believe I was trying to synthesize an amide of phenethylamine and phenylalanine, but I'm not sure. Anyway, it had been sitting back there for at least 6 months and grew a 1cm flawless transparent crystal of something. It had two square faces (top and bottom) and had triangular faces on the sides. Wish I could get shit that cool more often.

Anyway, in case anyone's been wondering about my absence, it's mostly due to me re-discovering reddit. Now I spend all my internet bullshit time there in search of lulz. Don't get me wrong, Zoklet's great and all, but it just can't match the magnitude of content they put up there. Also, I haven't been doing much in the way of experimental chemistry anymore. Just got tired of nothing working and said fuck it.

Well, that's not entirely true. I have been conducting some experiments with e-cigs. Turns out you can solvate butane hash oil in propylene glycol (100mg BHO in 750mg PG) and load it into an E-cig and it works. It becomes and inconspicuous, smell-free way of getting baked.

[BungHole]

Originally Posted by Hydroponichronic

Well I was cleaning out my kitchen and I found a test tube in the back of a cabinet that reeked of phenylacetaldehyde. I believe I was trying to synthesize an amide of phenethylamine and phenylalanine, but I'm not sure. Anyway, it had been sitting back there for at least 6 months and grew a 1cm flawless transparent crystal of something. It had two square faces (top and bottom) and had triangular faces on the sides. Wish I could get shit that cool more often.

Anyway, in case anyone's been wondering about my absence, it's mostly due to me re-discovering reddit. Now I spend all my internet bullshit time there in search of lulz. Don't get me wrong, Zoklet's great and all, but it just can't match the magnitude of content they put up there. Also, I haven't been doing much in the way of experimental chemistry anymore. Just got tired of nothing working and said fuck it.

Well, that's not entirely true. I have been conducting some experiments with e-cigs. Turns out you can solvate butane hash oil in propylene glycol (100mg BHO in 750mg PG) and load it into an E-cig and it works. It becomes and inconspicuous, smell-free way of getting baked.

Yo I wanted to do that but I didn't have any oil.

[Hydroponichronic]

Originally Posted by BungHole

Yo I wanted to do that but I didn't have any oil.

maek soem nao

[BungHole]

Originally Posted by Hydroponichronic

maek soem nao

But now I don't have any e-cigs.

[Hydroponichronic]

Originally Posted by BungHole

But now I don't have any e-cigs.

bugger. Well, best of luck.