Author Topic: Safrole -> MDP2Pol -> MDP2P  (Read 5069 times)

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Bandil

  • Guest
Safrole -> MDP2Pol -> MDP2P
« on: September 26, 2001, 04:37:00 AM »
Hi!


I have read a lot of posts on the Safrole -> MDP2Pol -> MDP2P synth using sulfuric acid hydration followed by ammonium nitrate and some cuprous catalyst. None of them seem to agree. Does anyone have a definite answer on the reaction? Does it work at all or is it BS?

Thanks!

Regards
Peter

Rhodium

  • Guest
Re: Safrole -> MDP2Pol -> MDP2P
« Reply #1 on: September 26, 2001, 05:06:00 AM »
There are no theoretical obstacles to the method in question, but I don't know of anyone who have succeeded in practice with it.

Antoncho

  • Guest
Re: Safrole -> MDP2Pol -> MDP2P
« Reply #2 on: September 26, 2001, 08:19:00 AM »

There are no theoretical obstacles to the method in question, but I don't know of anyone who have succeeded in practice with it.




But what of tBOC's write-up on your page - it seems to bee very practical... Was it a fake? Did he fail eventually? How did you know?

Please, elaborate - sad news for me, i used to put much hope into that method...

Antoncho


sunlight

  • Guest
Re: Safrole -> MDP2Pol -> MDP2P
« Reply #3 on: September 26, 2001, 08:35:00 AM »
I'll believe in it when some reliable bee post he did it, and worked, and the ketone was aminated and the product had at least the correct melting point. May be it works and we are so silly, but I've not seen a good reason to try it, specially after seeing all the fiascos in mdp2pol with dichromates, dual phase etc... it supposedly worked for some bees, but...

Semtexium

  • Guest
Re: Safrole -> MDP2Pol -> MDP2P
« Reply #4 on: September 26, 2001, 10:33:00 AM »
I have to agree, if we've all been fucking around using up expensive PdCl2, etc if this method proves viable then perhaps we should all be sitting in the corner with a dunce cap on our heads.  The fact remains however that if this method is ever GOING to work it's going to require some research and a bunch of trial and error.  Now luckily we have access thru the hive to a LOT of notes on the subject, if we can wade thru them and pick out the really relivent bits then perhaps this method will in the future lead to un-Godly amounts of honey being produced easily and safely and without alot of eviromental impact...

I think the cold H2SO4 route has been proven to produce the MDP2Pol, as long as the temp is kept down and one doesn't try to distill it(thanks Brightstar).  Have any of the MDP2Pol --> MDP2P routes been proven...?  I've seen examples with AA and cupric salts as well as a purposed route with Permaganate, but I've seen nothing conclusive as to the outcomes, sure Tboc said it worked as did a couple others, but when asked questions about it they quickly disapeared...

::)  ;D  :)  :P  ;)     Mean People Suck     ;)  :P  :)  ;D  ::)

Rhodium

  • Guest
Re: Safrole -> MDP2Pol -> MDP2P
« Reply #5 on: September 26, 2001, 11:43:00 AM »
The problem is that some bees have reported success, but that the success wasn't measured with any analytical equipment, and only one or two unknown bees said the produced ketone aminated fine to a working amine. But then again, several who have tried it have failed.

Bandil

  • Guest
Re: Safrole -> MDP2Pol -> MDP2P
« Reply #6 on: September 26, 2001, 01:14:00 PM »
I think my cat might give the synth a whirl this forthcoming week. Any suggestions on how to test the products? Is it not the common practise to check for sec ketones using 2,4-Dinitrophenylhydrazine and the primary using fehlings? I have no access to nmr, MS etc. Perhaps some TLC will be possible.

Ideas anyone?

Thanks!

Regards
Peter

PEYOTE

  • Guest
Re:Safrole -> MDP2Pol -> MDP2P - about hydratation
« Reply #7 on: September 27, 2001, 12:58:00 AM »
If you make an hydratation using only conc. H2SO4, your product cannot be only MDP2Pol. The best way is oxymercuriation/demercuriation using first HgSO4/H2SO4, then NaBH4.

The reason is: there will be appreciable rearrangement of the secondary carbocation that safrole will form when a H+ attack the double bond.

Ar-CH2-CH=CH2 + H+ ==> Ar-CH2-CH+-CH3 ==> Ar-C+(CH3)2 =(H2O)=> Ar-CHOH(CH3)2 + H+

This is a bad stuff.


Just a Touch Of Mojo Hand

Bandil

  • Guest
Re:Safrole -> MDP2Pol -> MDP2P - about hydratation
« Reply #8 on: September 27, 2001, 01:54:00 AM »
Im aware that the final MDPxPol intermediate is a mixture of MDP1Pol/everything else and MDP2Pol. I will just have to live with this. If i carefully keep the temerature of the mixture around zero degrees celcius, do you have any idea of the ratio of the two compounds? 80:20 i can live with.

How about the final oxidation using ammonium nitrate, do you have any comments on this one?

Thanks, my cat really appereciates your feedback before he gets going!

Regards
Peter

PEYOTE

  • Guest
Re:Safrole -> MDP2Pol -> MDP2P - about hydratation
« Reply #9 on: September 27, 2001, 01:59:00 AM »
If i carefully keep the temperature of the mixture
 around zero degrees celcius, do you have any idea of the
 ratio of the two compounds? 80:20 i can live with.

Maybe, I dunno the exact thermodynamic data for this reaction.

 final oxidation using ammonium
 nitrate

I dunno, do you have the rxn?

Bandil

  • Guest
Re:Safrole -> MDP2Pol -> MDP2P - about hydratation
« Reply #10 on: September 27, 2001, 03:48:00 AM »
Got this ref from rhodiums page:

R-C(OH)-R' + 2 Cu(OAc)2 ==> R-CO-R' + 2 CuOAc + 2 AcOH

2 CuOAc + NH4NO3 + 2 AcOH ==> 2 Cu(OAc)2 + NH4NO2 + H2O

NH4NO2 == H+ ==> N2 + 2 H2O

And abbreviated to one line:

R-C(OH)-R' + NH4NO3 == Cu(OAc)2/AcOH ==> R-CO-R' + 3 H2O + N2

https://www.thevespiary.org/rhodium/Rhodium/chemistry/mdp2pol.txt



Thanks!

PEYOTE

  • Guest
Re:Safrole -> MDP2Pol -> MDP2P - about hydratation
« Reply #11 on: September 27, 2001, 04:28:00 AM »
Well, N2 is formed, and this is a VERY stable compound, so the equilibrium will be totally moved to right, and I think this rxn will work very well. Le Chatelier docet

Bandil

  • Guest
Re:Safrole -> MDP2Pol -> MDP2P - about hydratation
« Reply #12 on: September 27, 2001, 04:53:00 AM »
OK, i need a verdict on what my cat should do, as it is not sure here.

a) Be a post-pioneer and try out the Safrole->MDP2Pol->MDP2P using the H2SO4 and ammonium nitrate oxidizer and post results?

b) Be boring and go with the safrol->isosafrol->MDP2P using the peracetic acid method and a lot of vacuum?

By the way, if the cat choose to go the b way... Any commenst on the safrole + CaO + KOH -> isosafrole reaction? Can KOH be substituted with NaOH??

Either way, the cat will post what it finds out!

THANKS!

Regards
Peter + cat

PEYOTE

  • Guest
Re:Safrole -> MDP2Pol -> MDP2P - about hydratation
« Reply #13 on: September 27, 2001, 05:04:00 AM »
I'd choose A  :)


Just A Touch Of Mojo Hand

Bandil

  • Guest
Re:Safrole -> MDP2Pol -> MDP2P - about hydratation
« Reply #14 on: September 27, 2001, 05:22:00 AM »
I think the cat will choose A for starters... But if/when it fails it sure will go for B.

There are just a few unanswered questions for this method. When refluxing the glycol(made from peracetic actid and isosafrole) in methanol and sulfuric acid(to obtain the ketone), is it possible to substitute the methanol with ethanol, as methanol is quite impossible to obtain?

Thanks!

Regards
Peter and Cat

PEYOTE

  • Guest
Re:Safrole -> MDP2Pol -> MDP2P - about hydratation
« Reply #15 on: September 27, 2001, 05:27:00 AM »
On

https://www.thevespiary.org/rhodium/Rhodium/chemistry/peracid.html

there is written MeOH, because, I suppose, the glycol is much better soluble in MeOH than in EtOH, or using MeOH reflux is at a lower temperature, but I dunno. Try to ask to Rhodium, the Chief...

Rhodium

  • Guest
Re:Safrole -> MDP2Pol -> MDP2P - about hydratation
« Reply #16 on: September 27, 2001, 08:47:00 AM »
I believe ethanol would work just as well.

Bandil

  • Guest
Re:Safrole -> MDP2Pol -> MDP2P - about hydratation
« Reply #17 on: September 27, 2001, 09:01:00 AM »
@Rhodium> Would you belive it is worth the effort to try out the safrole -> MDP2Pol -> MDP2P using method A?

Thanks!

Regards
Peter

Rhodium

  • Guest
Re:Safrole -> MDP2Pol -> MDP2P - about hydratation
« Reply #18 on: September 27, 2001, 09:03:00 AM »
Yes, we need someone to work out the right reaction parameters for the above to work.

terbium

  • Guest
Re:Safrole -> MDP2Pol -> MDP2P - about hydratation
« Reply #19 on: September 27, 2001, 07:32:00 PM »

a) Be a post-pioneer and try out the Safrole->MDP2Pol->MDP2P using the H2SO4 and ammonium nitrate oxidizer and post results?

b) Be boring and go with the safrol->isosafrol->MDP2P using the peracetic acid method and a lot of vacuum?



Or do both! If you do (B) first, a known good procedure, then you will have a reference sample of MDP2P. Then when you try (A) you will be able to compare.

Can you get TLC plates? Even if you can't get TLC plates you could probably use paper chromatography instead to compare your products from the two procedures. With the MDP2P from procedure (B) you could even prepare some MDP2P-ol by reduction to check the first step of procedure (A) again via paper chromatography.