Author Topic: ketones and stuff  (Read 10986 times)

0 Members and 1 Guest are viewing this topic.

Offline carl_nnabis

  • Global Moderator
  • Founding Wasp
  • *****
  • Posts: 618
  • So long, and thanks for all the fish!
Re: ketones and stuff
« Reply #20 on: April 15, 2017, 10:53:02 PM »
Sounds like it would be a better idea to prepare directly the D- or L-tartrate or use a chirally directing amino-acid to form the salts from. Otherwise if starting with the HCl, resolution would be a bitch. And the produuct would doubtless end up as a ball of colored snot since you'd have to base it to form a chiral salt and resolve it. Either that or use a chiral synthesis in the first place.

As for cathinone, it isn't half bad. Albeit at the price of a mouthful of leaves and twigs. The good thing about khat is that it takes a while to come on, and its being slowly drip-fed transmucosally so there isn't the abrupt dropoff in activity that leads to fiending. Very different from say, synthetic methcathinone.
Damn!
You are absolutely right, I hadn´t thought of the need to freebase the cathinone to separate it´s isomers.
Thank you very much for that piece of input!  :D

Seems like chiral synthesis is the only option to obtain the purely natural isomer.

But what options do we have for that?
The FC reaction with chiral alanine derivatives, like the N-phthalimido alaninoyl chloride, the preparation of chiral norephedrine and subsequent oxidation(not as good...), and of course the very tempting reaction of R-PAC with ammonia and cyclohexanone.
The latter reaction is in my opinion the most attractive one, of course only if the preparation of R-PAC is done according to ORG´s proved method.
Also, this reaction seems to give a better yield than the reductive amination of R-PAC, at least in theory.

Tsath, I have tried the leaves already many years ago, and besides the interesting smell they have(pyrazine probably and the norephedrine maybee too? since those alkaloids aren´t present as salts like they are in ephedra species, as far as I know), they are very bitter and have a unpleasant textural feeling when chewed...(a bit like leather)
At least coca leaves are sweet and well tasting, but khat is not!  ;D

But effects? Hmm, doubtful if I´ve felt any, but I´m talking about european grown plants, very mature ones, but still, residing in our cold climate for a long time. Not sure if these plants I´ve taken the leaves from, have ever seen the somalian/yemen drought climate at all....(they were residing in a botanical garden).

This discussion just made the experience of trying cathinone more interesting and appealing...  :D

Edit: Shit I wrote analine instead of alanine... dirty thoughts out!  ;D
« Last Edit: April 15, 2017, 10:59:42 PM by carl_nnabis »
Quote
Real bees just hear the buzzing and it doesn´t ever stop. Ever.

Offline Tsathoggua

  • Spaz Tech
  • Founding Wasp
  • *****
  • Posts: 2,256
Re: ketones and stuff
« Reply #21 on: April 16, 2017, 06:32:13 PM »
Got some khat seeds. Any experience growing it? starting it off in particular.

Don't know where the khat Tsath' tried came from, but it was active enough. Didn't ask, only time the head shop in question ever had any, so snapped it up to give it a try. Not bad really.
Nomen mihi Legio est, quia multi sumus

I'm hyperbolic, hypergolic, viral, chiral. So motherfucking twisted my laevo is on the right side.

Offline carl_nnabis

  • Global Moderator
  • Founding Wasp
  • *****
  • Posts: 618
  • So long, and thanks for all the fish!
Re: ketones and stuff
« Reply #22 on: April 16, 2017, 07:35:37 PM »
I had some rooted cuttings, three times I housed this plant for myself, but it never got old, sadly.
Those plants from the botanical garden, well, I had on several occasions a nice talk to the gardener(offering him a smoke and sitting down for a few mins with him helped a lot ;D), and he told me about the hard propagation of cuttings.
But summer is coming, so I´ll take a few twigs and try my best according to him ;)

Your leaves came from a head-shop? I guess they weren´t dried but fresh instead?
Their arome is certainly interesting.
I think pyrazines are also giving roasted coffee its arome, and kath smells similar in regards of adapting to it.
Like, one has to be accustomed to it, like coffee, but then it becomes really enjoyable(if it is good coffee/kath).
Sadly, kath is a lot more bitter than coffee... ;D

Growing from seeds seem to be hard, but can be done.
Although they are slow growing.

Maybe look for a botanical garden nearby, they usually have a lot to offer, and most of the plants are able to be propagated from cuttings or seeds...

I do not want encourage picking genetic material from those sources, but have to admit to have done so quite a few times in the past...;D
Even have taken from a now sadly dead e. coca var. coca tree(its a tree if its over 3m!) some berries.
Tasted them as well... interestingly, coca berries taste like flour with a little bit of fruit acid... ;D
Quote
Real bees just hear the buzzing and it doesn´t ever stop. Ever.

Offline hamsterbob

  • Pupae
  • **
  • Posts: 59
Re: ketones and stuff
« Reply #23 on: April 17, 2017, 02:14:27 AM »
Tree graph till it big enough?
Dont listen to Business Fox he's all business

Offline Tsathoggua

  • Spaz Tech
  • Founding Wasp
  • *****
  • Posts: 2,256
Re: ketones and stuff
« Reply #24 on: April 17, 2017, 01:29:33 PM »
Yes they weer fresh. Don't remember any peculiar smells, the material had been kept in a fridge, and presumably, due to its strength was reasonably fresh.
Nomen mihi Legio est, quia multi sumus

I'm hyperbolic, hypergolic, viral, chiral. So motherfucking twisted my laevo is on the right side.

Offline Hanswurst

  • Subordinate Wasp
  • ***
  • Posts: 242
Re: ketones and stuff
« Reply #25 on: May 18, 2017, 10:02:26 AM »
So, do you, friends if cathinones, see a reasonable way to get dihydroxypropiophenone. Of course the 3,4 variety, opening the experimentation to MD substituents.
Why wasnt this the subject of this research?
Is it expensive to order? Moreover, is it possible to import or buy openly? What would a legitimation for buying this be?
« Last Edit: May 18, 2017, 11:07:42 AM by Hanswurst »

Offline carl_nnabis

  • Global Moderator
  • Founding Wasp
  • *****
  • Posts: 618
  • So long, and thanks for all the fish!
Re: ketones and stuff
« Reply #26 on: May 19, 2017, 10:27:01 PM »
FC-acylation of catechol, or benzodioxole directly but then using mild catalysts like polyphosphoric acid and acid anhydride rather than acid chloride.

Yes it is expensive. But then, so are most other of the exotic substituted alkylophenones.

A legitimiation? You mean, besides you want and need it?
Don´t know, just buy it... why would you even need a legitimation for something like this?
Quote
Real bees just hear the buzzing and it doesn´t ever stop. Ever.

Offline Hanswurst

  • Subordinate Wasp
  • ***
  • Posts: 242
Re: ketones and stuff
« Reply #27 on: May 19, 2017, 11:04:54 PM »
I meant, if it rings any alarms, if for example import would.

So, just the standard pathway,  rather annoying because the anhydride is not that accessible.
Spent some time thinking about ways to dihydroxylate propiophenone but its a pain in the ass as well.

Offline bsmathers

  • Larvae
  • *
  • Posts: 22
Re: ketones and stuff
« Reply #28 on: May 20, 2017, 07:36:15 AM »
Wouldn't polyphosphoric acid cleave the benzodioxole ring instead of acylating?

The only literature report of FC on benzodioxole I've seen uses stannic chloride as the catalyst, and only then with mediocre yield. I can post the reference if anyone is interested.

Offline haber

  • Larvae
  • *
  • Posts: 4
Re: ketones and stuff
« Reply #29 on: May 20, 2017, 07:55:36 AM »
How is 3,4-MD-propiophenone made commercially? Id guess grignard on piperonal and then oxidation to the ketone.

Offline carl_nnabis

  • Global Moderator
  • Founding Wasp
  • *****
  • Posts: 618
  • So long, and thanks for all the fish!
Re: ketones and stuff
« Reply #30 on: May 20, 2017, 05:48:36 PM »
I meant, if it rings any alarms, if for example import would.

So, just the standard pathway,  rather annoying because the anhydride is not that accessible.
Spent some time thinking about ways to dihydroxylate propiophenone but its a pain in the ass as well.
I don´t think a few grams would ring any alarm, of course some larger quantity can still.
But then again, buying more than a small quantity wouldn´t be economical, as to prepare it oneself would be.

Wouldn't polyphosphoric acid cleave the benzodioxole ring instead of acylating?

The only literature report of FC on benzodioxole I've seen uses stannic chloride as the catalyst, and only then with mediocre yield. I can post the reference if anyone is interested.
No it wouldn´t cleave it, at least not to a concernable extent as for example AlCl3 would do.
Shulgin used it IIRC when Methylone(=ß-keto MDMA) was prepared first.

But of course, SnCl4 can be used too.

And please, attach reference, at least in this thread there will be some interest on this thematic!  :)

How is 3,4-MD-propiophenone made commercially? Id guess grignard on piperonal and then oxidation to the ketone.
I don´t think there is a real commercial route to it, as the need is probably negligible, and thus it remains a fine chemical with a small production scale, probably even only bench-prepared(at least this would explain the price).

But the mentioned route via Grignard is viable, as is the methylenation of 3,4-dihydroxypropiophenone(which can be in turn prepared from via thermal ketonization from the 3,4-dihydroxybenzoic acid maybe?), as is the FC-acylation of benzodioxole.
If the grignard route is chosen, the oxidation step doesn´t even have to be done separately, the phenylpropanol can be used as is in the bromination step, if the bromination system H2O2/HBr is chosen, as this way it can be oxidised and in turn brominated in one-pot.

There is a quite a bit of references to find concerning this, especially when looking through the old hive posts, you can find some treasures  :)
Quote
Real bees just hear the buzzing and it doesn´t ever stop. Ever.

Offline bsmathers

  • Larvae
  • *
  • Posts: 22
Re: ketones and stuff
« Reply #31 on: May 20, 2017, 07:27:23 PM »
Attached is the reference. The relevant passage is reproduced below.

To a mixture of 25 ml of dry CH2C12, 37 mmole of the appropriate
acid chloride, and 35 mmole of (la-IVa), (Via), (Vlla), or (IXa) was added at -10C
over 0.5 h 5.4 g (40 mmole) of anhydrous AICI3. The mixture was stirred for 1 h at 20C
then poured onto ice, acidified with hydrochloric acid, extracted with CH2Cl2, the extract
washed with water, dried, and the solvent removed. In the acylation of 1,3-benzodioxolane
(Va), 10.4 g (40 mmole) of anhydrous SnCl4 was added at 0 C.


However, I have been unable to find this Shulgin preparation of bk-MDMA via the PPA Friedel Crafts. Can you provide a reference? All I have been able to find is the patent route using propionic anhydride and iodine.

Offline carl_nnabis

  • Global Moderator
  • Founding Wasp
  • *****
  • Posts: 618
  • So long, and thanks for all the fish!
Re: ketones and stuff
« Reply #32 on: May 21, 2017, 06:48:04 AM »
Thank you!

No, I haven´t found the polyphosphoric acid catalysed FC-acylation yet, but to be honest haven´t really put effort into the search ::)

This one mentions polyphosphoric acid, but preferably uses perchloric: https://www.google.com/patents/US6342613
Uses the anhydride too, but yield is rather low. It is interesting how little catalyst is actually used.
But I am not sure if this is the right document, at least it is useful.

Quote
2. Preparation of 5-propanoylbenzo[1,3]dioxol

To a mixture of 73.2 g (0.6 mol) of benzo[1,3]dioxol and 1 ml of 70% perchloric acid, cooled to 0-5° C., were slowly added 38.1 ml (0.3 mol) of propionic anhydride, keeping the temperature at 0-5° C. during the addition.

Once the addition was complete, the mixture was left under stirring for a further 3 hours, allowing the temperature to rise to room temperature. The mixture was diluted with 50 ml of dichloromethane and 50 ml of water, stirred for half an hour, and the organic phase was then separated. The organic phase was washed with 30 ml of sodium hydroxide 2M aqueous solution and with water, and, finally dried on sodium sulphate.

The organic phase was distilled at room pressure, collecting the dichloromethane at 40-41° C., distilling the benzo[1,3]dioxol that had not reacted (44 g) at 55° C./1.3 mbar and, finally, the product (34.5 g) at 125-130° C./1.3 mbar.

To the reaction mixture containing the 44 g of non-reacted benzo[1,3]dioxol were added 29.2 g (0.24 mol) of benzo[1.3]dioxol and 1 ml of 70% perchloric acid. To the resulting mixture, cooled to 0-5° C., was added 38.1 ml (0.3 mol) of propionic anhydride. Using the method described in the previous paragraph, 44 g of non-reacted benzo[1,3]dioxol and 34.5 g of the desired product were isolated.
Quote
Real bees just hear the buzzing and it doesn´t ever stop. Ever.

Offline Tsathoggua

  • Spaz Tech
  • Founding Wasp
  • *****
  • Posts: 2,256
Re: ketones and stuff
« Reply #33 on: May 21, 2017, 08:21:50 AM »
Just   folk who aren't already, be aware that perchlorates or especially the acid, if absorbed in the  ductwork of those who do not. And they are also good for making smokebombs (40 percent sodium chlorate, rest of it salt) or using the same mixture to pack a ten foot thick wall of conrete to eliminate a Mu-meson, plasticized with mostly klindly dealingsP we'd bladt to get spitroated on aasagai.:P
Nomen mihi Legio est, quia multi sumus

I'm hyperbolic, hypergolic, viral, chiral. So motherfucking twisted my laevo is on the right side.

Offline bsmathers

  • Larvae
  • *
  • Posts: 22
Re: ketones and stuff
« Reply #34 on: May 22, 2017, 07:55:41 AM »
Hm, that is interesting, but the use of propionic anhydride is a little unfortunate here-- PPA should be strong enough to effect the acylation with just the plain acid. Keep an eye out for the PPA route if you see it!

Offline Tsathoggua

  • Spaz Tech
  • Founding Wasp
  • *****
  • Posts: 2,256
Re: ketones and stuff
« Reply #35 on: May 23, 2017, 05:20:38 AM »
Oops.. looks like several different posts intended for several different places got spliced together there. The particle physics bit certainly did.

And to clarify about the smokebomb comp, the salt isn't fuel, its there to phlegmatize the mixture, so it burns slow and intense rather than deflagrates, that mixture is mixed with equal proportions of sugar to use, or sensitized with fine reactive metal powders and bound with wax and sugar so it can be melt-cast.
« Last Edit: May 23, 2017, 05:22:51 AM by Tsathoggua »
Nomen mihi Legio est, quia multi sumus

I'm hyperbolic, hypergolic, viral, chiral. So motherfucking twisted my laevo is on the right side.