Author Topic: trans-4-MAR synth w/o cyanogenbromide writeup!  (Read 11789 times)

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Bandil

  • Guest
trans-4-MAR synth w/o cyanogenbromide writeup!
« on: September 08, 2002, 08:03:00 AM »
Experimental procedures:

28,2(150 mmol) g (-/+)-norephedrine was dissolved in 141 mL's tap water at rt. in a 500 mL FB. erlenmeyer flask.
 The whole lot dissolved without any problems. Next 12,0 g of KOCN was dumped into this soln. No heat evolution was noted. With some stirring with a mag bar, 75% of the KOCN dissovled.

The bottle was rigged for reflux and submerged in an oilbath at about 140 deg. cel. After the temp. of the liquid in the bottle reached 35 deg. everything had dissolved and it looked like plain water. Soon the whole thing began to reflux nicely. The smell reminded a bit of old wet clothes, but swim is not sure that it was the reaction that caused this.

After 2½ hour the apperance of the liquid had not changed. The erlenmeyer flask was removed from the oil bath and allowed to cool at RT. When the flask reached 70 deg, swim believed it was ok to cool it with running water. Almost immediately when the cold water touched the surface of the flask, a clear oil precipitated on top of the water. With further cooling, more appeared. Soon white flakes started to appear at the bottom. The flask was placed in the freezer for ½ an hour, till the temp. inside the liquid has droppet to 5 deg. cel. At this point the flask was white with something that did not resemble PPA nor KOCN  8) . The product was allowed to dry somewhat, but swim did not have enough time to let it dry completely, so he estimated there where 18 grammes(according to the original patent)(86,6 mmol). It should be noticed here that swim probably SHOULD have compensated for the missing CH2 group in the PPA to eph with 6% wt, but he did not bother as the last reaction uses only hydrochloric acid.

The wet carbamyl was put into 275 mL of water in a 500 mL FB flask and dissolved only lightly. Next 172 mL of 2M hydrochloric acid was added. No reaction could be noted. A stirr bar was put in and the whole lot was refluxed for about 2,5 hours. When the temp of the water reached about 50-60 deg celc, everything had dissolved and the liquid seemed like water again.

After 2,5 hours, swim removed the bottle and let it cool to RT. a soln of 20% Na2CO3 was added, while stirring, til no more white powder appeared. Swim was of course VERY thrilled when the white stuff precipated as an amide would not have done whis and PPA would be oily on freebase, so something had happened  ;) . The white precipitate was gravitity filtered and some of it was dried. Swim does not have an exact yeild, but will post it later, when the whole mass has dried. It sure did look like ALOT :D

Test of the compound:
Chemichal:
With marquis no reaction was noted

Bioassay  :) :
Swim suspected that the compound would bee 8/5 times stronger than the cis/trans-4-mar, because it should be pure trans, so the doses where scaled down by this. 10 mg was placed in a test tube and smoked. Swim's pink lungs could not hold down the harsh smoke, so swim only got a light head buzz. Swims fellow chemist smoked the full 10 mg's and got really nice effects. Next 20 mg of the freebase was ingested. Within ½ a hour, swim got all warm and fuzzy in the stomach, and one hour after the ingestion swim could no longer doubt that the synth had been a 110% success. Communication was extremely easy and the mood was generally like pure euphria. Even after ingesting 25 beers, swim was really clear headed(this stuff kills any drunken state far more that meth). It also had a quite MDMA like quality to it, but it was not forced upon as with MDMA. One could rather focus on another being and get the emphatogenic effects, while "the crowd" was not loved in the same quite stupifying manner as MDMA.

The effects was strong for 6 hours and the faded. As swim was to attend a great huge concert the day afte, no sleep could be had, but the day after a funny thing was noticed: no hangover from the beers and NO seretonin/dopamine depletion like feel was notet. In fact swim could hardly tell that he had been out partying all night...

Conclusion:
This is THE most beutifull synth ever. The reactants are rather non toxic and swim really loves to use water as a solvent. The product seems really pure and the effects are way better than that of meth and MDMA. All in all: swim has found a new favorite stim ;)

Regards
Bandil

foxy2

  • Guest
oops
« Reply #1 on: September 08, 2002, 11:12:00 AM »
Nice work!  :)


Those who give up essential liberties for temporary safety deserve neither liberty nor safety

ChambeRed

  • Guest
Norephedrine synthesis?
« Reply #2 on: September 08, 2002, 12:10:00 PM »
Great work man!,Swim would love to try his hand at this synthesis,anybee know is there any realistic way to rearrange psudoephedrine or ephedrine to norephedrine?this synth sounds really cool but how the hell to get norephedrine is a drawback :( .Peace bee's,Chambered

Bee's don't die,we just multiply.

seelite

  • Guest
Excellent Bandil!!!!!!!!!!!!!
« Reply #3 on: September 08, 2002, 01:50:00 PM »
Man, you did it!
Thanks to Bandil the Hive now has a comprehensive write up for 4-MAR complete with vital experimental details and psychological comments! And without the nasty cyanogen bromide (icky)

Way cool dude! :)

Freedom is a matter of electron density.

Rhodium

  • Guest
Red: No, you cannot make norephedrine out of ...
« Reply #4 on: September 08, 2002, 04:16:00 PM »
Red: No, you cannot make norephedrine out of ephedrine or pseudoephedrine eassily. Make it from scratch, there are instructions at my page.

Could somebody dig in the literature to find the melting point for N-carbamoyl-norephedrine?

Antoncho

  • Guest
Wow! I can't beelieve my eyes!
« Reply #5 on: September 09, 2002, 03:26:00 AM »
Man! Finally someone tried this so-much-talked of thing!


Bandil, you definitely earned yourself an entry in The Hive's Hall of Fame! Congratulations!



Antoncho

Barium

  • Guest
Very nice!
« Reply #6 on: September 09, 2002, 04:31:00 AM »
I can´t say anything else than hats off!!.... ;D  ;D

Bandil

  • Guest
update
« Reply #7 on: September 09, 2002, 07:22:00 AM »
Swim just finished measuring out his/hers yeild. From the original 28.20 g PPA HCL, there where formed 15.34 g trans-4-MAR freebase.

A bit lower yeild than in the original patent, but in the next run swim will attempt to improve the technique!!!

Enjoy!

Regards
Bandil

starlight

  • Guest
well done
« Reply #8 on: September 10, 2002, 10:30:00 AM »
this looks very easy!

of course finding PPA HCL seems 100 times more difficult than it was three years ago.....

spent a whole day searching for medications on the Web and found none at a reasonable price.... also most that did were stacked with other ingredients that did not look that easy to separate.

You can get the PPA, but you need a prescription (for your dog, or for you in some parts of the world).

Looks like those that aspire to this may have to make the starting material themselves....

Antoncho

  • Guest
PPA
« Reply #9 on: September 10, 2002, 11:43:00 AM »
PPA can bee easily made by condensation of benzaldehyde w/EtNO2 (under specific conditions - UTSE) and reducing the formed a-hydroxy-phenyl-2-nitropropane w/ Al foil or some such (as found by AB2).


If one's to use some subst'd BA in this rxn we soon might well get some reports of novel psychodelic MAR derivatives (maybee :-[ )!


I mean, that would still bee a rather short synth, even if you include making EtNO2 - only 4 steps! From scratch!


An amazingly interesting area!


I wonder though if the 'size factors' (the ones that prevent, e.g., substituted benzylpiperazines from being active and require shortening of the chain to fit into receptor and gain activity) would apply here - while in case of BP's we can shorten the chain, here there's seemingly nothing one could do about it...


And then, what about the N-methyl MAR derivative?



Many avenues leading in all directions...




Antoncho

Rhodium

  • Guest
PPA synthetic routes + 3,4-DMAR Note
« Reply #10 on: September 10, 2002, 01:10:00 PM »
There are also many other ways of making PPA, which are superior if you happen to live in a country where nitroethane is List 1.

Propiophenone -> alpha-bromo Propiophenone -> Cathinone -> PPA

../rhodium/chemistry
/ppa.html



Propenylbenzene -> Propenylbenzene chlorohydrin -> PPA

../rhodium/chemistry
/ppa.synthesis.html



Propenylbenzene --Peracetic Acid or Oxone--> 1-Phenyl-1,2-epoxypropan --NaN3--> 1-Phenyl-2-azido-1-propanol --Zn/NH4Cl--> PPA

BTW, the N-methyl analog (3,4-dimethylaminorex, gotten from KOCN/ephedrine) is a weaker stimulant, and has a much higher risk of causing irreversible harm, as in acute hepatic insufficience (liver failure) or that thing with the larger heart blood vessels going haywire (whatever that is called in latin).

Antoncho

  • Guest
Yeast. And N-methyl-MAR.
« Reply #11 on: September 11, 2002, 12:20:00 AM »
Rhodi, thanx a lot for the clarification on 3-methyl-MAR.

But i didn't mean that. What i meant was actually the 2-N-methylamino derivative. If i am not mistaken, it is the 2-aminogroup (not the one inside the ring) that is crucial for binding to the receptor - analogous to the ethylamino group in PEA world. No?

That 2-methylamino-4-methyl-5-phenyloxazoline could, probably (i'd bee grateful for any opinions from the more knowledgeable bees) bee made by reacting 4-MAR w/equimolar amt. of formaldehyde and reducing the imine w/Al or some such. As described for N-methylation of amphetamines on Rh's page.

What do you think?


........and we forgot about that biosynth of l-PAC from benzaldehyde - hopefully, the alpha-hydroxyl won't interfere with oxime formation in the next step.

This one, if made to work, would bee the OTC'est complete drug synthesis there ever was! :)




Antoncho

SPISSHAK

  • Guest
Possible 'easy' PPA
« Reply #12 on: September 13, 2002, 09:48:00 PM »
Here's a patent that got tossed around in some PM's that is interesting, it's a variation of an akabori type rxn where alanine and benzaldehyde are supposed to give a small yield of PPA.
They use a variation here with phase transfer catalyst, and use the sodium salt of the amino acid (for a phenyl serine, but the principle looks sound though), claim the best yeilds to date.
Also see the patents referenced in this patent (if you understand German, and French).


http://patft.uspto.gov/netacgi/nph-Parser?Sect1=PTO1&Sect2=HITOFF&d=PALL&p=1&u=/netahtml/srchnum.htm&r=1&f=G&l=50&s1=%274501919%27.WKU.&OS=PN/4501919&RS=PN/4501919




Vitus_Verdegast

  • Guest
reduction of phenylacetylcarbinol oxime
« Reply #13 on: March 05, 2003, 05:31:00 PM »

........and we forgot about that biosynth of l-PAC from benzaldehyde - hopefully, the alpha-hydroxyl won't interfere with oxime formation in the next step.




I'm glad to tell you that it will not !

this is taken from J. Chem. Soc. 1, 1930, p. 1233 :

The oxime of phenylacetylcarbinol was prepared by boiling under reflux for 2 hours a solution of 5 gr of the ketone, 2.6 gr of HONH2.HCl, and 1.5 gr NaOH in water with the addition of sufficient alcohol to make the solution homogeneous at the temperature of boiling. When cold, the solution was acidified and the oxime was extracted repeatedly with ether and dried. Evaporation of the ether left an oily residue, which kept in a vacuum deposited a crystalline solid (4 gr). Recrystallisation from hot water gave the oxime in white needles, mp. 112.5°.
A small quantity of a less soluble compound was also formed, which crystallised from alcohol in small white needles, mp. 231°. This was in all probability phenylmethylglyoxime.

Reduction of the oxime:
60 gr of 3% NaHg were gradually added to a solution of the oxime (2 gr) in dilute acetic acid. After 6 hours, the mixture was made alkaline and extracted several times with ether. After drying over solid caustic potash, evaporation of the ether left a colourless viscous oil, which was dissolved in warm hydrochloric acid. The solid which separated on standing was recrystallised from absolute alcohol, nor-dl-ephedrine hydrochloride being obtained, mp. 192°, after second recrystallisation.
From the mother liquor a small quantity of nor-dl-pseudoephedrine hydrochloride was obtained, which after several recrystallisations from absolute alcohol melted at 169°.


No yield is stated, but I'm sure anno 2003 we can find better reduction methods than this.

BTW, the authors used PAC prepared from dl-mandelamide and MeMgI, followed by acid hydrolysis.




bottleneck

  • Guest
Shouldn't this have made it onto rhodium.ws a...
« Reply #14 on: March 10, 2003, 02:30:00 AM »
Shouldn't this have made it onto rhodium.ws a long time ago already? Especially for those kids who come looking for "an easy, non-toxic, simple 4-MAR synth" and only find essays on BrCN by Eleusis (not my favourite person in the whole world).

What should we tell them afterwards? UTFSE? Or maybe just RIP?

Antoncho

  • Guest
Yes, indeed, WHY?
« Reply #15 on: March 10, 2003, 08:21:00 AM »
Huh?

One of our comrades tried this..... w/out much success.

But Bandil's one person here i tend to trust.

Anyone else w/any such experience? I guess a lot of people must have tried this since then. No?



Antoncho

Bandil

  • Guest
Who failed the synth?
« Reply #16 on: March 10, 2003, 11:08:00 AM »
Who failed the synth? I have never heard of anyone trying it?

Swim has made the synth multiple times, with the same ease and high yeild each time...

Megatherium

  • Guest
A bit lower yeild than in the original patent,
« Reply #17 on: March 10, 2003, 01:11:00 PM »
A bit lower yeild than in the original patent, but in the next run swim will attempt to improve the technique!!!

Excuse my ignorance ... but on which patent did you base this great synthesis.  I used TFSE a bit, but I didn't find it  :( .

Bandil

  • Guest
Its the patent discussed in the original 4-mar
« Reply #18 on: March 10, 2003, 01:41:00 PM »
Its the patent discussed in the original 4-mar w/o cyanogenbromide thread...

You can find Rhodiums original sketch here:

Post 212038

(Rhodium: "4-Methylaminorex Synth w/o CNBr", Novel Discourse)

Bandil

  • Guest
Does anyone know why it's not on Rhodiums...
« Reply #19 on: March 12, 2003, 03:00:00 AM »
Does anyone know why it's not on Rhodiums site?