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Publications / Re: ketones and stuff
« Last post by Tsathoggua on Today at 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.
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Publications / Re: ketones and stuff
« Last post by bsmathers on Yesterday at 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!
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Publications / Re: ketones and stuff
« Last post by Tsathoggua 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
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Publications / Re: ketones and stuff
« Last post by carl_nnabis 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.
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Publications / Re: ketones and stuff
« Last post by bsmathers 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.
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Publications / Re: ketones and stuff
« Last post by carl_nnabis 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  :)
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Publications / Re: ketones and stuff
« Last post by haber 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.
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Publications / Re: ketones and stuff
« Last post by bsmathers 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.
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Publications / Re: ketones and stuff
« Last post by Hanswurst 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.
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Publications / Re: ketones and stuff
« Last post by carl_nnabis 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?
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