peracetic oxidation of asarone to ketone

[goiterjoe]

http://goiterjoe.homestead.com/tmp2p.html

I finally got around to testing this out the other day, and it seemed to work fairly well.  from 20ml of starting asarone, 14.5ml of suspected ketone was returned.  the ketone is slightly viscous with a reddish tint to it.  I didn't wash the aqeous layer from the peracetic part to reclaim the epoxide still in it, so there is the possibility of a better end return from this synthesis.  Does anyone have any experience with using Al/Hg type reductions for amphetamine derivatives?  I was also contemplating making TMMA-2, but wasn't sure about the pharmocological properties of this substance.  has anyone tried this?


If pacman influenced us, we'd glide around dark rooms eating pills and listen to repetitive music.

[blue]

i don't think TMMA2 is very active joe, have alook at randolph carters tma2 synth on Rhodiums page, he details a high yeilding leukart rxn for the ketone >> amine step.

stranger? muahahahaha

[Osmium]

I don't think you made TMA2-ketone. All bees trying this reaction have failed.
How do you know that red goo is ketone at all?

[goiterjoe]

I have yet to read of any bees trying this synth, or otherwise I might have been a little more skeptical about trying it.  I have heard of bees trying the performic route before, but performic is a stronger acid than peracetic.

If pacman influenced us, we'd glide around dark rooms eating pills and listen to repetitive music.

[Dr_Sister]

goiterjoe - actually i'm not convinced it isn't ketone. my reasoning is based on an observation of asarone in GAA while attempting a Toennies style nitrosation and the decomposition product was a blue/purple not red. and it sat in undiluted GAA for 18 hours.

Have you triied a sodium bisulfite test? if you do my experience with 2,4,5TMP-2-P is that is forms a much finer crystal than does MDP-2-P. keep us posted on the reduction.

[goiterjoe]

That was SWIM's reasoning for trying the peracetic oxidation, because he had heard of people letting asarone sit in acetic acid unharmed.  SWIM has had technical difficulties lately due to random carpenters working around the house, and had to temporarily relocate a lab.  (thank god he went through the trouble of sewing up a carrying case for all his glassware and equipment, or he would have been fucked royally when they showed up).  Hopefully he will be able to aminate some in the upcoming couple of weeks if things calm down around here, but for the mean time his nerves are kind of shot.  do you have any suggestions for an amination route that should be somewhat high yielding?

If pacman influenced us, we'd glide around dark rooms eating pills and listen to repetitive music.

[blue]

NaBH4CN redxn (probably highest yeilding)

Oxime via SnCl2 followed by oxime redxn in Al/Hg or with Na (next best)

NaBH4 redxn  (moderate yeild)

Leukart conventional or microwave (hard to say what kind of yeild to expect here)

then there are all those K10 clay redxn's w NaBH4

stranger? muahahahaha

[psychokitty]

The only detailed write-up that I have seen posted for reducing the ketone to the amine is the Leukart (sp?)  The non-microwave-using proceedure, that is.

--PK

[boppesz]

Osmium. Can you explain why asarone can't be oxidized to the ketone with the performic/peracetic acid process? I mean chemically explain. I can't believe that safrole is readliy oxidized and asarone is not. The three methoxygroups dont differ that much chemically from a methylenedioxygroup. Both types of groups are moderately activating. Three methoxys alltogether activate more than a methylenedioxy. So reaction time will be shortened. One thing I can come up with is polymerization. Asarone will polymerize at more ease than safrole. But it will be oxidized at more ease too I thnik (I can be wrong) So I think that reaction times and/or temp should be respectively shortened/lowered so no polymerization will occur But with which factor? I dunno, don't have any experiences with this.

[Osmium]

Asarone dimerizes under acidic conditions. I don't know exactly what the structure of that dimer looks like, seen it once in an obscure ref I haven't been able to find again (didn't look too hard though).
Isosafrole (or was it safrole? shit too many dugs) too can be destroyed by refluxing with e.g. formic acid, but this reaction is slower. This dimerisation business isn't that uncommon.

[boppesz]

Do you have experiences with making TMA2 from asarone? If yes, how did you oxidize it?

[cilliersb]

Just do a pseudonitrosite Asarone (Pugsley or Pseudonitrosite Faq) to obtain the Beta-Nitro compound of asarone. this can be reduced using cyanoborohydride method.

Have fun.

[zooligan]

Just do a pseudonitrosite Asarone (Pugsley or Pseudonitrosite Faq)

Um.... read AntiBody2's practical trials of this process in the Lowdown on Pseudonitrosites thread.  It'll save you a lot of wasted precursors.

z

"And if we don't get some cool rules ourselves, pronto, then we'll just be bogus too!"

[boppesz]

yeah right. And if I don't have cyanoborohydride?

[Osmium]

You don't need cyanoborohydride. Read that thread.

[Dope_Amine]

I say you O2 wack it and then leukart it.  Or if you are able to, hydroaminate it w/ n-buLi cuz it DOES work.
something for your mind.......

[Chromic]

Excuse my ignorance, what functional group dimerizes? Is it the double bond?

[Chromic]

Ok, I UTFSE... and found out that it's an acid catalysed polymerization of the double bond, Osmium said it prior posts that all propenylbenzenes are suspectible (inc isosafrole), but asarone is apparently the most sensitive. Does this mean that a buffered peracid would form the epoxide, and that the epoxide wouldn't be turned into red goo after being hit with 15% H2SO4? This looks attractive. TMA-2 sounds like fun, I want some.  

[sYnThOmAtIc]

Wouldn't electrochemcal oxidation be a suitable means of oxidation?
 The supplies are cheap, reusable, and only requires the starting oil and a couple acids. It is a very high yielding method for sure on the isoeugenl and isosafrole the only ones tested by my monkey (89&93%).   

 Isoeugenol, isosafrole, asarone, anethole, and other similar compounds can be made into their epoxides via electrochemical oxidation and refluxed with Libr for high yields of ketone or just with formic or sulphric acid.

[Osmium]

The "buffered" performic is still acidic as hell, don't think it will work.

That electrochemical epoxidation sounds like a much better idea.