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All 106 posts Subject: trans-4-MAR synth w/o cyanogenbromide writeup! Please login to post Down

Bandil
(Hive Bee)
09-08-02 15:03
No 354295
      trans-4-MAR synth w/o cyanogenbromide writeup!
(Rated as: excellent)

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 cool . 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 wink . 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 smile :
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
(Distinctive Doe)
09-08-02 18:12
No 354337
      oops

Nice work! smile

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

ChambeRed
(Hive Bee)
09-08-02 19:10
No 354346
      Norephedrine synthesis?

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 frown .Peace bee's,Chambered
Bee's don't die,we just multiply.

seelite
(Stranger)
09-08-02 20:50
No 354369
      Excellent Bandil!!!!!!!!!!!!!

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! smile
Freedom is a matter of electron density.

Rhodium
(Chief Bee)
09-08-02 23:16
No 354408
User Picture       Red: No, you cannot make norephedrine out of ...

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
(Official Hive Translator)
09-09-02 10:26
No 354566
      Wow! I can't beelieve my eyes!

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
(Hive Bee)
09-09-02 11:31
No 354572
      Very nice!

I can´t say anything else than hats off!!.... laugh laugh

Bandil
(Hive Bee)
09-09-02 14:22
No 354593
      update

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
(Hive Bee)
09-10-02 17:30
No 354931
      well done

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
(Official Hive Translator)
09-10-02 18:43
No 354941
      PPA

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 blush )!

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
(Chief Bee)
09-10-02 20:10
No 354971
User Picture       PPA synthetic routes + 3,4-DMAR Note
(Rated as: good read)

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
https://www.rhodium.ws/chemistry/ppa.html

Propenylbenzene -> Propenylbenzene chlorohydrin -> PPA
https://www.rhodium.ws/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
(Official Hive Translator)
09-11-02 07:20
No 355255
      Yeast. And N-methyl-MAR.

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! smile

Antoncho

SPISSHAK
(Hive Bee)
09-14-02 04:48
No 356191
      Possible 'easy' PPA

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).

Patent US4501919

Vitus_Verdegast
(Newbee)
03-06-03 01:31
No 414140
      reduction of phenylacetylcarbinol oxime
(Rated as: excellent)

........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.

"There are many things under the sun."

bottleneck
(Hive Bee)
03-10-03 10:30
No 415352
      Shouldn't this have made it onto rhodium.ws a...

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
(Official Hive Translator)
03-10-03 16:21
No 415391
      Yes, indeed, WHY?

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
(Hive Bee)
03-10-03 19:08
No 415416
      Who failed the synth?

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
(Hive Bee)
03-10-03 21:11
No 415445
      A bit lower yeild than in the original patent,

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 frown .

Bandil
(Hive Bee)
03-10-03 21:41
No 415458
      Its the patent discussed in the original 4-mar

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
(Hive Bee)
03-12-03 11:00
No 416097
      Does anyone know why it's not on Rhodiums...

Does anyone know why it's not on Rhodiums site?

bottleneck
(Hive Bee)
03-12-03 15:51
No 416152
      There was also the reference by Rhodium to an...

There was also the reference by Rhodium to an article on related reactions of ephedrine.

Journal of the Chemical Society;1952;;850-4;Fodor & Koczka;The Stereochemical Course of the Conversion of 2-Ureidoalcohols into Oxazolidines. Part I.pdf (http://www.geocities.com/botero56/JCS.1952..850-4.Fodor_Koczka.pdf)

Of course it works! I can't believe anyone could fail at this! Trust me, I wouldn't (be able to) write this if it didn't work!!!

Megatherium
(Hive Bee)
03-12-03 16:46
No 416168
      This is rather funny.

This is rather funny. Today I went to the library to fetch exactly the same article.

I don't know why it isn't on rhodium.ws ... As far as I am concerned, this is one of the best synthetic routes here on The Hive. Especially since the PPA precursor can easily be made from scratch.

Rhodium
(Chief Bee)
03-12-03 21:54
No 416268
User Picture       4-Methylaminorex Review

I am working on making a 4-Methylaminorex Review article, where this and all other published syntheses are detailed, that's why the addition of this particular preparation has been postponed.

Megatherium
(Hive Bee)
03-13-03 21:49
No 416696
      I need a verification for this statement: 'Is...

I need a verification for this statement:

'Is (1R*,2S*)-phenylpropanolamine = dl-norephedrine = (+/-)-norephedrine = the precursor needed in the KOCN route for the trans-4-MAR syntheis?'

Rhodium
(Chief Bee)
03-13-03 22:51
No 416724
User Picture       stereochemistry

Yes, see Post 404474 (Rhodium: "Better pictures", Stimulants).

You want the chiral centers to be different to each other (1S,2R or 1R,2S), if they are the same (1S,2S or 1R,2R) you've got the pseudo form.

viki
(Stranger)
03-17-03 04:37
No 417874
      Can phenlyethanolamine and HOCN be used?

Could phenylethanolamine be used in this reaction. see post 22556 psychokitty.Could HOCN be substituted forKOCN?Cheers

vicki

Megatherium
(Hive Bee)
03-17-03 16:36
No 418082
      Could phenylethanolamine be used in this ...

Could phenylethanolamine be used in this reaction

Yes, this would generate straight aminorex.

see post 22556 psychokitty

Post 22556 (Orbital: "Re: AMT, Alpha methyl-tryptamine", General Discourse), this ref. doesn't check out. What do you mean?

Could HOCN be substituted for KOCN?

No. HOCN is generated in situ: phenylethanolamine.HCl + KOCN --> KCl + HOCN + phenylethanolamine freebase.
Furthermore, one can't prepare and keep (or buy) an HOCN (aq.) solution since HOCN hydrolyses in contact with moisture to NH₃ and CO₂. Even in dry organic solvents isocyanic acid readily polymerizes to give a mixture of cyanuric acid and cyamelide.
The stoichiometry of this reaction seems to be VERY important: if an excess of isocyanic acid is used, the biuret reaction kicks in ... effectively destroying the carbamate precursor   R-NH-CO-NH₂ --> R-NH-CO-NH-CO-NH₂ frown What can be more easy than using a balance to accurately weigh the needed amount of NaOCN or KOCN?

SPISSHAK
(Hive Addict)
03-17-03 23:11
No 418180
      you have a good explanation there

What I am wondering is why water is used as a solvent in one of those examples, when it decomposes HOCN to CO2, and NH3?

Megatherium
(Hive Bee)
03-17-03 23:24
No 418189
      Well, I don't know, but I think the ...

Well, I don't know, but I think the Encyclopedia of Reagents for Organic Synthesis is a reliable source.

I read further:

"Preparative methods: by the depolymerization of cyanuric acid or by heating urea. The gas can be absorbed in ether, THF, CHCl₃ or CCl₄. Aqueous solutions of HNCO can be prepared in situ by reacting NaOCN or KOCN with 1 equiv. of dil. HCl or AcOH at temperatures of approx 0 - 15 °C".

Probably, the HNCO won't react immediately with the water and it slowly decomposes (hence it is generated in situ). It 's all a matter of kinetics tongue .

dennis_pro
(HyperLab Bee)
03-19-03 07:47
No 418966
User Picture       It's me...

I'm personally failed this synthesis.
The substituted urea is produced fine, but final HCl condensation always fails for me. I have using pharm. grade PPA. Have tryed two times - the yield is zero.
P.S. I have worked accordingly to method posted here by Rhodium.
P.P.S. Sorry my terrible english :)

With best regards,
Dennis Prochko aka Wolf

Bandil
(Hive Bee)
03-19-03 08:53
No 418978
      Are you using the right isomer?

Are you using the right isomer? Norephedrine that is? It is the only place where one is able to fail, as far as i can see. That would explain why you got the carbamyl, but to amine that falls out!

Regards
Bandil

Cops are not there to help you, they're there to bust you.

dennis_pro
(HyperLab Bee)
03-20-03 03:10
No 419255
User Picture       Are you using the right isomer? I'm not sure.

Are you using the right isomer?
I'm not sure. I have used pharmaceutical PPA (GB pharmacopea). It should be racemate or right isomer, according to Rhodium, didn't it?

For me: After refluxing subst.urea with HCl, the solution becomes clear, after adding NaOH it becomes clody and some white precipitate forms. But after extraction with hexane, nothing go to organic phase... Is it amide or amine or what?

With best regards,
Dennis Prochko aka Wolf

Bandil
(Hive Bee)
03-20-03 08:54
No 419368
      Instead of basifying with NaOH, try to use...

Instead of basifying with NaOH, try to use carbonate as described originally. Why are you extracting with an organic phase? Just suction filter the precitiapate. It's pure and ready to use(unless you want the HCl)...

But try to skip the last step and see what happens!

Good luck
Regards bandil!

Cops are not there to help you, they're there to bust you.

Rhodium
(Chief Bee)
03-20-03 21:47
No 419520
User Picture       PPA British Pharmacopoeia

http://www.pharmj.com/Editorial/20001202/letters/Moffat.html

dennis_pro
(HyperLab Bee)
03-21-03 05:36
No 419695
      So, GB PPA is racemate...

If it is racemate (50% of right isomer) I have expect 20% yield. But practically obtain less than 1%. And nobody knows why :(

Is SOMEBODY other than Bandil tried this method, or not? Can SOMEBODY confirm ICE yields and identity? Post your methods with comments please.

With best regards,
Dennis Prochko aka Wolf

Vitus_Verdegast
(Hive Bee)
03-21-03 07:16
No 419724
      melting point

Dennis_pro :

what is the melting point of your PPA ?

From the Merck Index:

Phenylpropanolamine (racemic mix of d- and l-norephedrine)
base : 101-101.5°
.HCl : 190-194°
.HCl (+)-form : 171-172°

Norpseudoephedrine
base : 77.5-78°
.HCl : 180-181°

http://www.metafilter.com/comments.mefi/21638

Prometheuz
(Stranger)
03-21-03 11:11
No 419773
      Confirmation

SWIM can confirm that SWI Bandil and himself ran the synth 2 times, at different scale, with no deviations from the first write-up. The yield for the second synth has not been established yet, but I am positive it's at least at good as for the first synth.
Hopefully there'll be opportunity to get a NMR done soon. laugh

To fathom Hell or soar angelic
Just take a pinch of psychedelic

SPISSHAK
(Hive Addict)
03-21-03 19:46
No 419879
      maybee when you based it

The ph got too alkaline and hydrolysis ensued.
That could explain not getting any yeilds.

silenziox
(Stranger)
03-22-03 18:19
No 420224
      (1R,2S)-phenylpropanolamine = l-ppa, not dl-ppa

Username: Megatherium
Post: I need a verification for this statement:

'Is (1R*,2S*)-phenylpropanolamine = dl-norephedrine = (+/-)-norephedrine = the precursor needed in the KOCN route for the trans-4-MAR syntheis?'

Good grief shocked .. Didn't anyone check this out?
Rhodium also verified that 1r,2s-phenylpropanolamine is dl-ppa ...
The thing is that 1r,2s-ppa equals to l-ppa (cas# 492-41-0).

Rhodium
(Chief Bee)
03-22-03 19:34
No 420246
User Picture       The * means that the chiral center can point...

The * means that the chiral center can point either way, as long as the other one is also changed. By not including the * in your nomenclature you have locked the centers into a single position, and the statement is no longer true.

Vibrating_Lights
(Hive Addict)
03-24-03 06:04
No 420740
      Nitroethane

WHere is the ref for PPA with nitroethane/benzaldehyde. Also Can KOCN be found over the counter. or can it be generates from potassiumferrocyanate

Start thinking more like a chemist and less like a criminal

Prometheuz
(Stranger)
03-24-03 08:08
No 420785
      KOCN availability

KOCN is non-toxic and not a suspect chemical to order. If you can buy basic chemicals somewhere, you should have no problem getting KOCN. It's cheap as well. smile

To fathom Hell or soar angelic
Just take a pinch of psychedelic

Rhodium
(Chief Bee)
03-24-03 22:40
No 420919
User Picture       WHere is the ref for PPA with ...

WHere is the ref for PPA with nitroethane/benzaldehyde

Search for posts by Barium. He has made several substituted PPA's recently.

Vibrating_Lights
(Hive Addict)
04-11-03 23:40
No 425843
      MORE HELP

an you be a little more specific about where to look for the ppa from nitroethane patents. I cant sem to find them.
vl_

Start thinking more like a chemist and less like a criminal

starlight
(Hive Bee)
04-12-03 18:17
No 426118
      US2151517

Patent US2151517

Wouter
(Stranger)
05-12-03 21:28
No 432852
      precipated amine

Bandil wrote: SWIM was of course VERY thrilled when the white stuff precipated as an amide would not have done this ...

If the amide wouldn't precipated, will this means when you use a mixture of norephedrine and norpseudoephedrine, that you can easily separate the formed amine from the amide?!?! Instead the VERY DIFFICULT separation of norephedrine from norpseudoephedrine before.

Rhodium
(Chief Bee)
05-12-03 22:35
No 432857
User Picture       Yes.

Yes.

Bandil
(Hive Bee)
07-01-03 13:04
No 443774
      Edit to the synth

After some PM's from different bee's i've noticed that i missed the original amount of water in the synth. The post is too old(or something like that) for me to edit...

The first line should read:

28,2(150 mmol) g (-/+)-norephedrine was dissolved in 141 mL's tap water at rt. in a 500 mL FB. erlenmeyer flask.

Maybe some really cool, kickass, king of the world mod could be so kind as to edit my original post?

Regards
Bandil

Size doesn't matter, it's the sound you make when hitting the ground after smoking it, that matters!

Osmium
(Stoni's sexual toy)
07-01-03 13:17
No 443775
User Picture       Done.

Done.

I'm not fat just horizontally disproportionate.
http://www.whatreallyhappened.com

moedank
(Newbee)
08-10-03 05:41
No 452718
      it works

Swim followed this synth. to the letter and everything went fine. Swim only did a small bit and has been up since thursday! Couple foils every now and then . Way better than meth and it takes alot less. Swim hasnt even done a half gram and been up for 3 days.

AND YOU CAN EAT!!!!!!!!!!!!!!!!!your not hungery, but unlike meth, you can eat a cheeseburger!!!!!great, great, sythn.

Also sex is Great! My girlfriend.......well anyway

SWIM DID ALSO wash the white crystals by dissolving them in ISO. 70% and letting evaporate. Nice clear pecies that burn clean.

Dont use TOO MUCH sodium bicarbonate in the last step cause it will come out in your 4mar. If this happens just dissolve as much as you can in Room Temp. ISOPRO. then filter the iso from the white shit that wont dissolve. Evaporate iso and there you go......

meanest mother fucker in the valley...

Rhodium
(Chief Bee)
08-12-03 16:09
No 453121
User Picture       Just the Hydrochloride salt left

Now the only thing we need is a working procedure for producing the hydrochloride salt of 4-MAR... HCl in IPA added to an etheral solution of the freebase does not produce a crystalline product.

Bandil
(Hive Bee)
08-12-03 18:35
No 453137
      true

yeah, that's definately true. Swim tried to crash some salt crystals by titrating an IPA soln. of 4-mar and adding acetone without a fleck of a crystal. Quite disapointing actually. Drew of the solvent with some vacuum and heat, which produced goo.

I think that the old fester journal suggests gassing in benzene. Does anyone know if that actually works?

But other than that, would the only reason for making the hydrochloride be to enable the user to snort it without to much pain?

Regards
Bandil

Size doesn't matter, it's the sound you make when hitting the ground after smoking it, that matters!

Rhodium
(Chief Bee)
08-12-03 19:12
No 453148
User Picture       Advantages of trans-4-MAR Hydrochloride

That is one reason, other reasons include better storage stability, and probably even higher purity upon recrystallization of the salt (even though the substance is ~95%+ pure on ¹H-NMR after recrystallization of the freebase).

moedank
(Newbee)
08-13-03 05:46
No 453250
      Even beeing a person that has a hard time...

Even beeing a person that has a hard time sniffin anything, the bite wasnt that bad. Rather snort this than cut coke or mdma. Meth has a worst drip than the 4mar, but i still like meth better. wink

Rhodium
(Chief Bee)
08-13-03 12:33
No 453305
User Picture       It's not all about pain, but also effectivity

Even if it doesn't hurt that much to insufflate the freebase (4-MAR being a relatively weak base), the water solubility is low enough for the absorption to not be especially effective.

Bandil
(Hive Bee)
08-13-03 12:42
No 453310
      To get back on track:

We'll i can see that we need the salt somehow. Swim's quite willing to experiment to find a suitable method.

Any bright ideas? How about forming the sulfate in IPA/Acetone perhaps?

The original Eleusis used benzene to form the salt in, which is quite non-polar. Maybe pet. ether could be used to crash the salt?

Regards
Bandil

Size doesn't matter, it's the sound you make when hitting the ground after smoking it, that matters!

Rhodium
(Chief Bee)
08-13-03 17:19
No 453372
User Picture       How to form the HCl salt of 4-MAR

I think that slow gassing of the freebase (dried in a vacuum desiccator) in chilled ether (dried over sodium or molecular sieves) with rigorously dried HCl gas (bubbled through a few cm of H₂SO₄ in a gas washing bottle) will do the trick.

If it still oils out, then chilled toluene should be tested (but not as the first option, it is hard to remove without multiple recrystallizations from low-boiling solvents).

Dextrose
(Hive Bee)
08-16-03 15:17
No 453919
      Acetate

SWIM made fine glass-like, indeed snortable crystals, using Acetic Acid...

Make Drugs - Not War!

The White House needs Acid!

Rhodium
(Chief Bee)
08-16-03 16:25
No 453926
User Picture       4-MAR acetate?

How? From what solvent did you precipitate it, and/or recrystallize it from?

Dextrose
(Hive Bee)
08-17-03 18:14
No 454143
      Re: 4-MAR acetate

Sorry for the lack of details.

SWIM was at a friends house, and had brought a little of the freebase with him... A few hundred miligrams was put in a test-tube, with a little denatured ethanol, and concentrated (32%) AA (the only acid SWIM could find in the house tongue ) was added, until the freebase dissolved in the alcohol...

It was then poured onto a plate, and evaporated in the oven.

No recrystallization was done, since time was a factor in this particular case... (Crashing would probably had worked, but SWIM wasn't sober blush )

Make Drugs - Not War!

The White House needs Acid!

Sandman
(Stranger)
08-22-03 03:37
No 454952
      More on KOCN availability

SWIM's Merk 11th Ed. doesn't list any uses for KOCN (Potassium Cyanate, correct?). Is it used in any common OTC products that anyone knows of?

moedank
(Newbee)
08-22-03 08:40
No 454992
      shit son just do a search on yahoo for info on

shit son just do a search on yahoo for info on kocn!

It was used in the FIRST ORGANIC SYNTH. EVER! The synth. of Urea. I very common synth for starting chemist and nobody even blinks when you ask about it.

meanest mother fucker in the valley

Sandman
(Stranger)
08-23-03 06:03
No 455145
      Thanks moedank.

SWIM would never just go to a Lab supply w/o knowing if the wanted item would cause any concern or be suspect to the seller.

One final question: SWIM gathered about 2gm worth of PPA from the med. cabinet, but most have Chlorpheniramine maleate in them, and the largest source (1gm of PPA) has 75mg PPA with 200mg Caffeine per cap. Would these interfere with this rxn, or could they still be used in some way?

moedank
(Newbee)
08-23-03 08:02
No 455173
      I failed HS chemistry.......

I failed HS chemistry.......

I have no idea how the caffine will effect it. Im sure Bandil can help or even Rodium so if they dont chime in I would PM one of them.

I put up a post in the stimulant forum and there is pics at the end if you want too take a look. Sorry i dont know more about chem, but im just starting out.

ONly suggestion is dont use too much sodium bicarbonate in the last step and run every reflux for as long as the OG write up says. I couldnt believe i did it the first time. Only smell was the damn veg. oil bath.

Sandman
(Stranger)
08-23-03 11:33
No 455187
      Thanks for the quick reply moedank.

Thanks for the quick reply moedank. SWIM is self educated since the 10th grade and while checking out the Hive for five years now is also only just really getting started also. Your Stimulants forum post is what brought us here.

SWIM started a thread in that forum also Re: Prescription Stims Cost, etc. which explains the real need for help. SWIM really thinks you've found the answer to the problem here, and is very glad you shared. Thanks!

Rhodium
(Chief Bee)
08-23-03 11:51
No 455190
User Picture       Pure PPA, please!

You really should extract the PPA.HCl from those so that you don't have any caffeine or chlorpheniramine left, as you definitely don't want any of that to interfer with the reactions.

You should be able to find solubilities of the other substances in the Stimulants forum, as well as removal techniques, as they have been extracting pills for years...

Sandman
(Stranger)
08-23-03 13:50
No 455198
      PPA Extractions

Do you think a STE backed up with an A/B would work then?

Rhodium
(Chief Bee)
08-23-03 21:09
No 455242
User Picture       pill cleaning

I don't know exactly which pill cleaning methods removes what - Ask geezmeister.

Newbee_2Bee
(Stranger)
08-25-03 14:46
No 455561
      i sent a reply (question) last night ...

what the hell happened to it? frown

Newbee_2Bee
(Stranger)
08-25-03 16:36
No 455580
      Do I have the right stuff?

This (Damn Yankee) bee lives in the Southern U.S.--anybee who is familiar knows that they are about 10 years beehind the rest of civilization! Having an awful time finding the stuff for this synth! KOCN...forget about it...NB2B has called every chem supply and photo supply in town - "We only sell to businesses."...checked in the major metropolis about 40 miles away...same thing. Ok...so then I'll go the NA2CO3/urea route...I go to the 2 biggest home improvement stores in the country...one says "no urea", the other "oh yes"...now mind you, I have never bought the stuff -but am fairly sure it should be in a bottle or jar...I told the man "pure urea"...so he throws a 40lb. bag in my truck..and I get home to discover it's full of little white beads with little brown "rocks" scattered throughout! Fertilizer for the lawn. I remember seeing something about Cyanuric Acid--(Cilliersb-Post# 213811 says "...isn't HOCN cyanuric acid? If so, there is lots to be found at the pool store." Rhodi replies, "I think the pool store thing is a trimer--not sure if it can be depolymerized readily." Jim-Post#213914 says "I am positive adding water will depolymerize it"), so I assume that I can use it...and I go pick some up.
Here's the ironic part...all the while I HAVE the PPA...(diet pills...just like the product "DEXA-****"), capsules with little white orbs inside. The ingredients list says "Phenylpropanolamine HCl-timed release"...that's it...no inactives!
So now, after my 4 day shopping nightmare...I sit and read all posts in this thread and then all of them on Rhodi's site...and I am so confused I could spit wooden nickels...'cuz it seems like it's saying I CANNOT use HOCN! Pleeeez enlighten this mixed up Bee...someone...ANYONE...SWINb2b dreamt of smoking her last bowlful of meth nearly 3 days ago...(yes-- imagined all by herself--THANKS to this and Rhodi's sites...and the input from all of her fellow bees wink !) To reiterate: SWINb2b has in her posession: PPA, Na2CO3, cyanuric acid hydrate, DH2O and 31.45% HCl. So can I go? Or no? tongue

Vitus_Verdegast
(Hive Bee)
08-25-03 17:42
No 455587
User Picture       well, yes

Prepare your NaOCN from urea and Na2CO3, and recrystallise three to five times (from H2O it was I believe, better UTFSE first). You want to have it very pure, with all the remaining carbonate removed.

Check the stim forum on how to extract from time-release pills, I'd guess that they probably use nasty polymeric shit for this.

A Dream Within A Dream (http://www.poedecoder.com/Qrisse/works/dreamw.html)

Newbee_2Bee
(Stranger)
08-25-03 22:02
No 455651
      The lawn fertilizer?

You mean the lawn fertilizer the guy gave me? Cuz that's as close as I've come to urea. So the cyanuric acid WON'T work?

Vitus_Verdegast
(Hive Bee)
08-26-03 00:43
No 455675
User Picture       urea

Yes, urea is used as a fertilizer.

I've bought pure urea (sold for use in dye solutions, tie-dyeing etc...), that look like small white granules, resembles styrofoam but they are pretty hard.

I don't know about the cyanuric acid, but it is so simple and straightforward to make NaOCN, even a kindergarten kid could do it. So if I was you I'd stick to that.

You probably have enough urea and Na₂CO₃ to make 1 kg of NaOCN, which you can recrystallise many times as to obtain a very pure 99+% product.

Make sure you PPA is also very clean.

A Dream Within A Dream (http://www.poedecoder.com/Qrisse/works/dreamw.html)

Newbee_2Bee
(Stranger)
08-26-03 03:54
No 455700
      Thanx!

Thank you VV...and thanx for not flaming my A$$...I'm not a total ignoramous, just have no formal training in the wonderful world of Chemistry. You're a Gentleman and a Scholar! (And My...what a handsome lad, at that! wink I'll let you know how it turns out!

placebo
(arrogant bee of the day)
08-26-03 10:21
No 455750
User Picture       If one had a choice between...

If one had a choice between...

Potassium ferricyanide
Potassium ferrocyanide
Potassium thiocyanate

Which would one get?

I'm not fat, I'm just too short for my weight.
http://www.whatreallyhappened.com

Rhodium
(Chief Bee)
08-26-03 11:04
No 455759
User Picture       All three are wrong, unfortunately.

All three are wrong, unfortunately. You need potassium (or possibly sodium) cyanate).

Polverone
(Hive Bee)
08-26-03 18:20
No 455811
      the fertilizer is fine

See the little brown rocks? Pick them out by hand. You don't need much KOCN. The KOCN can be prepared more easily in higher purity than NaOCN. It's more soluble too Post 445115 (Polverone: "More cyanate info", Methods Discourse). I don't know if this is important for this application, but it'd be a shame to have this procedure fail because you didn't take the time to find some potassium carbonate.

Cyanuric acid is not deopolymerized by addition to water, at least not to any significant (pH-strip detectable) extent.

19th century digital boy

moedank
(Newbee)
08-27-03 06:03
No 455927
      I cant believe im reading this

PPA is the HARDEST PART!

KOCN you can order from ANYPLACE ON THE PLANET CAUSE IT IS NOT A WATCHED CHEMICAL! It was used in the first organic synth. EVER. It is so common first year chem students will sometimes recreate the first organic synth. EVER!!!!!!

and sodium bicarbonate!!!!!!!!!!!soda ash!!!!!!!!!!come on man youre not even trying. I saw this shit on ebay for $4 a lb. More common than dirt. The last two chems are so easy to get, nobody is gonna even ask you shit about either one of em. Find a big chem company, call and order the shit. USE A FCKING CREDIT CARD TOO IF YOU WANT! Doesnt matter ONE DAMN BIT!

ONE LINE ON THURSDAY, ONE LINE ON FRIDAY, AND ONE LINE ON SATURDAY........will i ever sleep again

Sandman
(Stranger)
08-27-03 18:57
No 456042
      Sodium Cyanate - interesting point Rhodium

Found this on a the Web-site of a mfg. in Japan:

"Potassium Cyanate exhibits the same chemical properties as sodium cyanate but its physical properties are different in that it has a higher solubility in water { g/100g H2O: KOCN75 (25°) - NaOCN 10.7 (16°) } and its melting point is lower. ( mp : KOCN 315° - NaOCN 550° )".

If anyone trys sodium instead, please post the results.

moedank: Sodium bicarbonate is just plain Baking Soda. Did you mean to say you found sodium carbonate on eBay? Can sodium bicarbonate even be used in this procedure?

Megatherium
(Hive Bee)
09-02-03 01:16
No 456788
      A word of caution ... & another KOCN patent
(Rated as: excellent)

A word of caution:

http://www.chestjournal.org/cgi/content/full/118/5/1496

Another KOCN patent:

Patent US3935300

moedank
(Newbee)
09-03-03 07:39
No 456987
      yes i meant sodium carbonate. sorry bout that

That was an OK read. Id like to know how much of the product was used by the people.

Also, i dont know about the 4 to 6hour per dose shit. You do a toothpick size line of ice and you aint gonna sleep that night. its a good 16hours per line. shit i stayed up 3days on less than a 1/4 gram.

I saw another study on rats where they broke it down into 4 isonomers(apperenty there are 4 in ice). It was a very good read with alot of shit i didnt understand. Ill try and find it again. If i do ill post it.

Sonson
(West Coast Cowboy)
09-06-03 14:12
No 457462
      Now we know!
(Rated as: excellent)

Here is some more information…and all of this is of course nothing but a dream not dreamt by me.

Cis-4-methylaminorex

To a cooled MeOH solution (50ml) of 0.025mole norephedrine freebase (3.78g) and 0.075mole NaOAc-3H20 there was added a 0.027mole CNBr in 22ml MeOH (this was made by adding 4.31g Br2 to 1.36g NaCN (97%) in MeOH) dropwise. The temperature was kept below 8°C during the addition.
The reaction mixture was the allowed to stir at the icebath for another 60mins.
The solvent was removed at the rotovap and 50ml Na2CO3 solution (sat’d) was added. The product was filtered and washed with two portions of water and dried.
The white crystals were dissolved in boiling toluene (15ml) and this solution was decanted while hot from some insolubles. Some hexane was added and the product slowly crystallized as large white plates. Mp 148.5-150. Yield 1.95g

Trans-4-methylaminorex

0.025mole norephedrine HCl (4.69g) and 0.025mole KOCN (2.09g) was added to 25ml milliQ water. Reflux for 2.5hours and the cooled in the freezer. The product was filtered and dried. Yield 4.26g.

The urea was boiled in 70ml water with 8g conc. HCl for 3h. The reaction mixture was poured into a saturated Na2CO3 solution containing some solid carbonate. This was left to stand for 2 days before it was filtered. The product was washed with water (3x20ml) and dried over magnesium perchlorate. Yield 2.1g.

The crude product was dissolved in 11ml boiling toluene and decanted while hot from some insolubles. The crystals were washed with 2x10ml petroleum ether (bp50). Mp 144-145.5. Yield 1.96g (44%)

GC/MS analysis was made on both the cis and the trans isomers on a DB-5 column (50-150°C 30°C/min then 150-320°C 15°C/min). Both were pure (99%+) with a small peak eluting shortly after the main product (at the same time in both cis and trans product.) with a very similar spectra to that of the 4-methylaminorex. The cis and trans product were separated easily, were the trans isomer eluted prior to the cis in accordance with the Cooper article in J. Forensic Chem.

Analysis of the urea in the trans synthesis proved to contain at least five different products of which the urea was present in about 45%.
The identity of the other 4 peaks is unknown.

Dextrose
(Hive Bee)
09-08-03 13:57
No 457721
      SWIM has been very curious, wether there are...

SWIM has been very curious, wether there are remarkable differents between bioassays of the cis- and trans-isomer...

Can SWIS (dis)confirm this?

Make Drugs - Not War!

The World needs Acid!

Rhodium
(Chief Bee)
09-09-03 02:32
No 457822
User Picture       All 4 isomers of 4-MAR gives different effects

Yes, there are relatively large differences between the effects of the cis- and trans- isomers (as well as of the individual stereoisomers of each), at least in rat trials. Didn't I post an article about this a while ago? If not, I'll find it and post it very soon.

moedank
(Newbee)
09-09-03 07:11
No 457869
      here is the website to the text, in full.

http://jpet.aspetjournals.org/cgi/content/full/300/2/450

meanest mother fucker in the valley

Rhodium
(Chief Bee)
09-09-03 22:07
No 457980
User Picture       Behavioral effects of the 4-MAR Stereoisomers
(Rated as: excellent)

Actually, I was thinking of this article by Glennon (I'll try to scan/upload it soon): Post 407786 (Rhodium: "4-MAR isomer potency", Chemistry Discourse)

BTW, Here is the full citation/abstract for the article mentioned in the above post:

Acute Neurochemical and Behavioral Effects of Stereoisomers of 4-Methylaminorex in Relation to Brain Drug Concentrations
Aino Kankaanpää, Satu Ellermaa, Esa Meririnne, Paula Hirsjärvi and Timo Seppälä
J. Pharm. Exp. Ther. 300(2), 450-459 (2002) (http://jpet.aspetjournals.org/cgi/reprint/300/2/450.pdf)

Abstract

4-Methylaminorex is a stimulant drug of abuse that exists as four stereoisomers: cis-4R,5S, cis-4S,5R, trans-4S,5S, and trans-4R,5R. These isomers have previously been shown to differ markedly in various respects. In the present study we assessed the effects of the isomers of 4-methylaminorex (2.5, 5.0, and 10 mg/kg i.p.) on extracellular dopamine and 5-hydroxytryptamine (5-HT) levels in the nucleus accumbens, as well as behavior in the rats simultaneously. The relative concentrations of the isomers in the brain were also measured. The samples were collected by in vivo microdialysis and then analyzed for neurotransmitters with high-performance liquid chromatography/electrochemical detection and for cis- and trans-4-methylaminorex with gas chromatography/mass spectrometry. The behavioral effects of the isomers were assessed from videotapes recorded during the microdialysis experiments. All isomers elevated the extracellular levels of both dopamine and 5-HT, with the exception of trans-4R,5R. The rank order of potency for elevating dopamine was trans-4S,5S > cis-4S,5R ~ cis-4R,5S > trans-4R,5R, and for elevating 5-HT cis-4S,5R > trans-4S,5S ~ cis-4R,5S > trans-4R,5R. Analysis of the behavioral data, together with the neurochemical data, suggests that behavioral effects of the isomers of 4-methylaminorex are related to drug-induced dopamine release and, in the case of higher doses of the most efficacious isomers, to 5-HT as well. The brain concentrations of the isomers did not reflect their neurochemical efficacy, which implies that their differences are pharmacodynamic rather than pharmacokinetic.

patrick
(Newbee)
09-24-03 07:12
No 460693
      Some questions for this synthesis

First, Thanks a lot Bandil for this wonderful write-up.

1) Is it possible, for this synthesis to use PPA-freebase and PPA-HCL?

2) The 28.2g used in the synthesis are for HCL or freebase form?

3) Is it possible to use a 10% NaOH solution instead of Na2CO3 to retrieve the freebase at the end of the synthesis?

4) What is the solubility of the freebase, what is the best medium for recrystallisation?

5) Is it possible to obtain the HCL form by gassing in the right solvent (which one)?

Thanks for all

Bandil
(you can always take some more)
09-24-03 08:08
No 460698
      1) Is it possible, for this synthesis to use...

1) Is it possible, for this synthesis to use PPA-freebase and PPA-HCL?
I suppose you mean if you should use the hydrochloride or the freebase? You need one mole of HCl per mole cyanate ion to generate the cyanuric acid. This will be supplied by the HCl attachted to the PPA in it's HCl form. It's possible to use the freebase, but then you'd have to carefully titrate it to acidic equlibrium first. An excess of acid present will cause the cyanate to break down to ammonia and carbon dioxide, once added. So use the PPA.HCl, that will make everything more smooth!

2) The 28.2g used in the synthesis are for HCL or freebase form?The hydrochloride form. I supppose that's missing from the writeup; but the freebase would have been insoluble...

3) Is it possible to use a 10% NaOH solution instead of Na2CO3 to retrieve the freebase at the end of the synthesis?Yes it is. Just be more carefull with washing/recrystallizing your product in the end, as you don't want some NaOH sticking on to it.

4) What is the solubility of the freebase, what is the best medium for recrystallisation? As the freebase is quite non-polar, you want a medium that is as polar as possible, without being too polar(eg. water). If you take a peek here (https://www.rhodium.ws/pdf/solvent.miscibility.pdf) you can see that DMSO, acetonitrile, methanol, ethanol an acetone ranks among the ones with the highest polarity index. I think that acetonitrile or ethanol might be a good candidates to try out.

5) Is it possible to obtain the HCL form by gassing in the right solvent (which one)?
There has been quite some problems forming the hydrochloride. AFAIK noone has been successfull as of now. It seems to turn into some sticky goo. The chief has written some general advice on how that could be done in this thread.

Good luck!

Regards
Bandil

I just love the smell of bromine in the morning!

patrick
(Newbee)
09-24-03 14:45
No 460732
      PPA extraction

Thanks a lot Bandil for all the information, and excuse my deep ignorance of chemistry, I am working in electronic !!!

Just some more questions:

If I want to extract PPA from all the filers found in time-released diet pills, I will perform an acid-base cleaning.
In this case, I will end up with PPA freebase, witch is solid, I think (I don't find my Merck index anymore).

Is it possible to titrate this solid freebase with dilute HCL in water, until no more solid visible and pH = 7.

Is it better to disolve the solid freebase in a non-polar solvent and then to gas with HCL ? in wich solvent ?

Thanks a lot and Best Regards

Bandil
(you can always take some more)
09-30-03 10:07
No 461834
      If I want to extract PPA from all the filers...

If I want to extract PPA from all the filers found in time-released diet pills, I will perform an acid-base cleaning.
In this case, I will end up with PPA freebase, witch is solid, I think (I don't find my Merck index anymore).
? dont know much about pill extraction. UTFSE in the tweaker forum, they have tons of info on how to do that...

Is it possible to titrate this solid freebase with dilute HCL in water, until no more solid visible and pH = 7.
Yes it is! Just remember if you over acidify, you have to add more cyanate, as it will be destroyed by the free acid. A way of doing that, is to add the cyanate very slowly, while stirring the solution untill it stops fizzing. Then you add the amount your supposed to. Works like a charm!

Is it better to disolve the solid freebase in a non-polar solvent and then to gas with HCL ? in wich solvent ?
Toluene or ether might be good. But unless you have pregassed ether standing around, i think it's a waste of time. Your going to use the PPA.HCl in a aqueous solution anyway, so why bother making the pure compound first? Use the titration method. I think you'll be happy with the results tongue

Regards
Bandil

I just love the smell of bromine in the morning!

Megatherium
(Hive Bee)
11-03-03 00:11
No 468400
      PPA recuperation idea?

It is my impression that the factor limiting the formation of the N-carbamyl-PPA is the hydrolysis of the in situ formed isocyanic acid (the mixture is heated to 140 °C after all). The yield of the N-carbamyl ephedrine in the original article is 57.7 %.

I guess the PPA could be recuperated from the aqueous solution after the carbamyl product is isolated, by acidifying the water phase (if there is any isocyanic acid left, it will be destroyed), and upon basification the water phase could be extracted to regenerate the PPA.

Since PPA is the precursor bottleneck of this synthesis, regenerating it could be a good idea to make some more smile .

eve
(Stranger)
11-22-03 16:30
No 472497
      pinkish crystalline powder

After performed all the workup as per bandil, now swim got some pinkish powder crystalline substance on the filter paper. swim didn't do any gassing or re-crystallization, is this "powder" alright to ingest ??

Vitus_Verdegast
(Hive Addict)
11-22-03 17:42
No 472504
User Picture       purify

Why not recrystallise to achieve better purity?

Flight of the Bumble Bee (http://www.geocities.com/eric_vornoff/BumbleBee.mp3)

eve
(Stranger)
11-23-03 22:49
No 472723
      Sorry one more question.

Sorry one more question. Does the amide that form is precipitated out when an excess sodium carbonate was added in the last step ?

Rhodium
(Chief Bee)
11-23-03 23:18
No 472727
User Picture       Purification of 4-Methylaminorex freebase

Very good question, actually.

I would definitely reccommend that you wash the still acid solution (after the HCl reflux) with a non-polar solvent to remove the amide before you basify to precipitate the 4-Methylaminorex, and also that you recrystallize the freebase from DCM/ether to remove other possible contaminants (this will also turn the product into a powder rather than amorphous lumps).

Note that the amide won't form if you use pure (±)-Norephedrine as starting material (as opposed to the diastereomeric phenylpropanolamine mixture which also contains (±)-Norpseudoephedrine).

Kinetic
(Hive Bee)
11-24-03 20:41
No 472923
      Tolu-clean

How one bee did it:

Toluene was found to be excellent alternative to the benzene used for recrystallisation by Poos et. al.; slightly less than 2g freebase (as beautiful sparkling crystals, also having a pinkish tinge) were recrystallised from 5mL boiling toluene to give very pale - almost colourless - crystals which were even more beautiful than before.

THF was then used for further beautification: the crystalline mass obtained above was dissolved in an excess of THF and set aside. The slow evaporation of the solvent caused the precipitation of stunning hexagonal prisms, having an appearance rather like that of a transparent, glass-like Giants Causeway (http://www.geographia.com/northern-ireland/ukiant01.htm).

Dextrose
(Hive Bee)
11-27-03 21:53
No 473509
      Easy sulphate-conversion

SWIM decided to do another trial, preparing a snortable salt.

100 mg. freebase was dissolved in a minimum amount of IPA in a test tube (some heating applied), one drop 96% H₂SO₄ was added, and after the solution returned to RT, an equal volume of acetone was added.
The test tube was cooled in the freezer, and after 3 hours nothing had precipiated.

Another experiment was perfomed...

250 mg. freebase was dissolved in a minimum amount of acetone (again some heating was applied).
2 drops of 96% H₂SO₄ was added, which resulted in a pop & hizz and instant crashing of the sulphate salt. smile

After a few seconds, the salt had settled to the bottom - then gravity filtered and dried, yielding 175 mg. of fine-snowwhite powder.

SWIM used to much acetone (and not 100% anhydrous solvents), which without doubt was the main reason for the low yield.

Conversion from the freebase to the dry sulphate took about 10-15 minutes, and instant bio-assay ( wink ) proved IN-administration indeed effective!

(Guess who haven't slept tonight? tongue )

Bees, this is the salt of your choice!

SWIM might try recrystallizing in a dual solvent system (IPA/EtOH + Acetone) in near future.

...sorry 'bout potential grammatic errors, i need sleep! crazy

Make Drugs - Not War!

The World needs Acid!

Rhodium
(Chief Bee)
11-28-03 16:34
No 473648
User Picture       needs improvement

If you instead add a dilute solution of sulfuric acid (in ether or THF), you can measure the added quantity more exact, and determine if you have gotten 4MAR·HSO₄ or (4MAR)₂·SO₄.

And at the moment you have only a 50% yield in this crystallization step, so things need to improve considerably in this salt preparation.

trans4mar
(Stranger)
01-15-04 09:09
No 482515
      Im having some problems!

1) How should my 20% sodium carbonate(20g per 100ml water?)solution be added. Every time the whole flask goes white and looks like milk? Is that what its suppose to do?

Should i let it all settle for a few hours or just filter it then.

2)how are you filtering? I use about 3 coffee filters and a funnel. Should i get some filter paper? I tried that the last time i was dreaming this and i really didnt see a difference.

Last one!
When refluxing the last step. I can smell what smells like "dope" coming out of the condenser. Its a typical bubble one with ice water running through it, but it still has condensation all the way to the top of the condenser on the inside.

Could i put a ballon on top to help or would it matter?

Thanks for the help. I REALLY need it!

PS this is moedank from the other post about trans-4-mar. Just trying to fine tune the process.

Anyone have any thought? of how to scale up the synth. to make bigger batches?

country boy

Bandil
(The Archetypical "Good Guy")
01-15-04 10:48
No 482542
      Tweaking the synthesis

1) How should my 20% sodium carbonate(20g per 100ml water?)solution be added. Every time the whole flask goes white and looks like milk? Is that what its suppose to do?

You will not get an exactly 20% solution by mixing 100 mL's of water and 20 g's carbonate. The final solution volume has to be 100 mL's, if you want a 20% W/Vol solution. Not that it really matters in this synthesis, just a nice general thing to know. But to return to you question: just add it while stirring the acidic 4-mar solution. Once basic, the solution is put in the fridge to cool to the point just a couple of degrees above freezing point. This will squeese the rest of the goodies out of the solution.

2)how are you filtering? I use about 3 coffee filters and a funnel. Should i get some filter paper? I tried that the last time i was dreaming this and i really didnt see a difference.

Get filter paper. Works much better than coffee filters!

3)When refluxing the last step. I can smell what smells like "dope" coming out of the condenser. Its a typical bubble one with ice water running through it, but it still has condensation all the way to the top of the condenser on the inside.

Pure 4-mar is odorless, so i'm suspecting you are smelling some ammonia caused by excess cyanate. And you only need a mild reflux for both steps, so crank down the temperature a bit; please!

Finally a few personal tips for tweaking the synthesis to it's absolute best:

i)
I have not emphasized in the original writeup that it is important to A/B extract the final precipitate. As with all other synthesis the product you get in the end is not totally pure. For your own sake - and your chemical pride - work the 4-mar up in the following manner:

Instead of simply basifying the water phase(after a completed reaction), wash it once or twice with a small amount of DCM. Isolate the water phase and basify it with carbonate. Extract the 4-mar freebase three times with a proper amount of DCM. This is washed twice with dH2O and once with brine(optinal really, but a good way to get rid of the last trace of water). The DCM is extracted three times with dilute HCl. The aqueous solution is basified in the usual manner with carbonate and the precipitate is collected and used in any manner suitable for the situation cool

ii)
In the last step, after the mandatory purification step, it is a good idea to basify the solution while still hot. This will give a porrage like substance. This is the placed in the fridge untill a few degrees above zero. The advantage of doing this, is that the end product will be much more grannular and easily filterable compared to the scenario where it is basified while cold(because of a slower crystallization process).

Good luck!

Regards
Bandil

Drugs = Fun; Drugs <> Money

hypo
(Hive Addict)
01-15-04 11:08
No 482543
      minor nitpick

> The final solution volume has to be 100 mL's.

well, i'm not a trained chemist wink , but
afaik 20% means 20g/100g solution, and does
_not_ mean 20g/100ml solution, so the right
thing to do would be 20g Na2CO3 + 80g(=80ml)
H20

filter(lambda W : W not in 'ILLITERATE','BULLSHIT')

Rhodium
(Chief Bee)
01-15-04 20:11
No 482629
User Picture       the final solution

Correct Mr. Hypo. When making a w/v or w/w solution the procedure is like you describe, it is only when making a solution of a certain molarity the volume of the final solution matters, as the unit M is defined as moles of solute per volume of the finished solution.

^{The Hive - Clandestine Chemists Without Borders}

trans4mar
(Stranger)
01-27-04 09:13
No 484820
      shorter high using toulene as recrystal??????????

Please for give any spelling, grammer mistakes. Long day and fucked up.........

Anyway i Took my final step powder from this reaction and gave a couple gs to a friend or two. They and i as well experienced.....fck it, we all got horney as hell. None of us even talked that weekend, but all had the same reaction.

SWIM has done this reaction several times before and some batches make you really horney. NOW WAS THAT JUST MENTAL, or does one of the 4mar isos make you horney, and due to varying experiments, at different temps, maybe one type became the majority iso. made in the reaction.

ALSO.......

I took some laqure thinner(HD shit with toulene in it)boiled the thinner, as is, on the stove in a shot glass oil bath. once boiling i put in some 4mar powder i knew had other shit(sodium carbonate,MSM and shut up this isnt getting sold so i tried the msm to see what the product would look like.)anyway

The powder almost all disolved and clouded the clear thinner. The stuff that didnt disolve all collected at teh bottom during boiling and i left it there. I let the shot glass cool a minute and poured the cloudy liquid on top onto a plate. the soilds at the bottom of the shot glass i just let dry. It burned like shit on a foil and i wouldnt take it. Not quite sure what it is, but i put 3g MSM in and its about 3 1/2g of shit.

The clouded/clear liquid put on the plate evaporated to nice clouded crystals that SHINE LIKE NOTHING I HAVE EVER SEEN!!!

They almost glowed with shine, but the high doesnt last as long as the final step product. Any thoughts on any of this?????????????????????ANYWAY i hope that made some sense.

Rhodium
(Chief Bee)
01-27-04 14:26
No 484864
User Picture       The DUH award...

The isomer ratio will be the same, regardless of how you perform the cyanate synthesis. The purity may differ though if you do not recrystallize or purify by other means. Why are you cutting the product with MSM? Of course the effects will differ if you dilute the product...

^{The Hive - Clandestine Chemists Without Borders}

trans4mar
(Stranger)
01-27-04 19:36
No 484935
      well now i know, thanks

Ill be the first to stand up and say i dont know shit about chemistry, but i came here to learn and thats what im doing.

I just put the MSM in a couple recryst. one with pure ISO and one with that laqure thinner with the toulene in it. This isnt going to anyone and i trash all the product that isnt pure or that i put MSM in, just having some fun.

I realize your mood before taking a substance has alot to do with how you experience the drug. Maybe that explains the different effects. Ill try some other things to recrystalize it and clean it up. Shit i bet i have wasted over 2oz trying different things.

Anyone have any suggestions on cleaning it up they'd like me to try or any recrystalize suggestions. People round here dont want 4mar so im just playing around with it.

Ill try whatever, but please no chems i cant get around the local area. wink

one big shit storm after the next, thanks god.....ya did a great job!LMFAO

trans4mar
02-10-04 09:20
      the SMOKEABLE myth
(Rated as: crossposted)

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