Author Topic: 2-hydroxy-5-MeO-BA: the continuation of the saga.  (Read 10338 times)

0 Members and 1 Guest are viewing this topic.

GC_MS

  • Guest
helpful hint?
« Reply #20 on: August 24, 2002, 01:16:00 PM »
Maybe this is helpful to get rid of your pMeO-phenol: from experience, SWiM found out that the latter easily solidifies when it comes in contact with air and is free from solvents as DCM and likes. Maybe Antoncho could remove all solvent and allow his benzaldehyde to stand for a bit (about 1 hour) and see if the pMeO-phenol solidifies. If it does, it might be usefull to reduce the amount of pMeO-phenol impurity in your sample in an easy manner. Remember: it is just a thought based on experiences SWiM had, never tested. He can also imagine that the benzaldehyde is easily oxidized by air...

Doped(TM) since 19.... euhm... a long time  :)

Antoncho

  • Guest
An update.
« Reply #21 on: August 25, 2002, 02:01:00 AM »
After drying, the product weighed only 2,7 g  ::) .
However, it can bee fairly certainly said that the actual yield is much better - the chief reason to blame is the impurity of the starting material (it also contained some CHCl3, which's hard to remove completely on a waterbath).

Obviously, the main loss of yield happens at the formylation stage. SWiHKAL is fairly certain that the way to go is to use Karl's original proc., but for longer time, to react the starting phenol completely.

Monomethylation of HQ also needs to bee improved - it yields 60% at BEST, as of today. Bisulfite purification fof it would bee a good idea.

2 GC_MS: no, it doesn't crystallize out, SWiHKAL tried that. It could bee cleaned thru bisulfite (that's the way SWI-Vitsh did), but SWiHKAL decided not to bother w/this yet and "kill both hairs with a single shot" in the final bisulfite purification.

Vitsh reported his yield of bisulfite-purified 2-OH-5-MeO-BA to bee ~40% of the unpurified cmpd's weight - which gives you an idea of how pure it was :)  ::)  :(  - however, SWIVitsh didn't use inert gas protection during formylation so probably the loss of the product was partially due to its oxidation w/air.



Any ideas, commentaries? Questions? C'mon, friends, gimme some input :)  :-[  ;)




Antoncho

Mountain_Girl

  • Guest
Good work once again
« Reply #22 on: August 26, 2002, 07:39:00 AM »
Antoncho
Um..sadly I've no intelligent comments or suggestions cos my psychotic aunt is still 2 steps behind yours and not so focussed at the moment.
(she itches to methylate and formylate
but instead rants and raves
the hydroquinone hasn't been delivered yet)
However I can congratulate on work done so far. Im really pleased your aunt is pursuing this righteous path, please tell her to keep it up.

Antoncho

  • Guest
Further adventures of SWiHKAL.
« Reply #23 on: August 27, 2002, 09:33:00 AM »
The latest notes from my crazy aunt's diary:





Into a test tube there were placed:

a) 1g of 2,5-diMeO-BA

b) 0,5mls MeNO2 (distilled, but not quite dried  - half of it distilled over at ~90 C - MeNO2's azeotrope w/water, 76% MeNO2)

c) 3,5mls MeOH


And the solution was placed into an ice/salt bath at -7 C, where it shortly turned into a fine suspension.

In the same bath 0,9mls of 40% NaOH soln in a small syringe were pre-chilled.

Also one should prepare bee4hand the following things:

a) A 2-5cm3 syringe fitted w/a pipette long enough to extend to the testtube's bottom; chilled in a freezer.

b) Ice-water and a freezer-chilled 10cm3 syringe (chill syringes' parts separately!)

c) A soln of 7mls HCl in 13mls water, kept at RT.



When the temp of the mixtr in the bath falls to -5 C, alkali was gradually added in 3 portions, with vigorous hand-stirring w/thermometer - the 1st time the temp jumps up by ~10 C - make sure that temp falls back to -5C each time.

The mixtr beecame homogenous. It was left in another icebath - temp rising from 6 to 10 C - for an hour.

Then it was chilled back to -5 C and 10mls of ice water is added thru syringe - all turns cloudy-white. As fast as possible, it was dripped thru the pipetted syringe into the acid soln with vigorous stirring.

Contrary to the documented on Rh's site similar prep'n of MDP2NP, no 'spectacular color shift' was observed - yellow color appeared immediately, and by the end of the add'n the mixtr represents a slurry of bright-orange nitrostyrene xtals of very fine consistency. They are filtered, washed w/water 3 times and air-dried on a saucer to give 0,7g (56%) of product, which has indeed a SPECTACULAR color - each time SWiHKAL looked at it his heart smiled, so cheerful and bright it was :)






Maybee, somebee will have SOMETHING to say about this? ;D

Any ideas on why the yield was so crappy? Well, still acceptable for a hallucinatory kitchen chemist, i guess.



Yours truly,


Antoncho

yellium

  • Guest
Congratulations! I hope that you can make it to ...
« Reply #24 on: August 27, 2002, 10:07:00 AM »
Congratulations! I hope that you can make it to the end compound (probably 2cb, although the 2cc and 2ci are just as interesting), and post a bioassay here.

Antoncho

  • Guest
Oh, Yellium, thanks....
« Reply #25 on: August 27, 2002, 11:01:00 AM »
I hope so too :)  :)

Well, the experience shows that SWiHKAL is habitually unable to do smth the 1st time and not to fuck up :)  This was one of the very few occasions when it started working right away, so.... :)

It was to compensate for this sudden luck, i guess, that the destiny presented another, shall i say, 'surprise' for him: while preparing to run that same rxn w/the remaining 1,7g of his aldehyde, he broke the test tube w/the thermometer while stirring :-[  ::)  >:(  >:(  >:(  and the contents, naturally, flowed into the ice-bath :)  :)  :(  

...hehe - what would you say if that happened to you? - right, that's what the stupid hallucination said too, among many, many other words - fortunately, Russian language is extremely rich and flexible in its means of constructing really obscene and dirty cusswords ;D


Anyway... less than a gram was recovered from the catastrophe, it was reacted w/MeNO2 right away w/out prior drying - w/the only differences that:

a) The mixtr was incubated for an hor at -5-0 C rather than 5-10 C.

b) The end product was washed w/20mls IPA on filter - and, DAMN IT - there was an evident dissolution, the filtrate turned yellow and cloudy (mixed w/water), some fluffy solids pptated....

WTF? I thought it wasn't soluble in IPA.... Does that mean SWiHKAL's totally fucked?

Or - is this an admixture of undehydrated nitroalcohol (seems possible since stirring wasn't very good) - ?

Or maybee, the nitrostyrene was so soluble beecause of its very fine consistency? Can anyone share his/her experiences regarding this nitrostyrene's solubility in IPA, PLEASE!



Sincerely,


Antoncho

yellium

  • Guest
Too bad. I've had my share of stupid mistakes too ...
« Reply #26 on: August 27, 2002, 01:42:00 PM »
Too bad. I've had my share of stupid mistakes too :=)

Nitrostyrene is soluble in IPA. Some more than others; when I worked with some 3,4,5-trimethoxynitrostyrene, half of the stuff would dissolve instantly in IPA. Snce I didn't want to lose to much by recrystallizing the stuff, I skipped the filtering stage, and simply reduced everything with xs LAH, then did an AB (followed shulgin to the letter). NMR showed about 99.5% clean mescaline.

So, basically, if you're so lucky that you can use LAH, don't waste your yields on making perfectly clean nitrostyrene; instead, clean everything at the A/B stage.

Beaker

  • Guest
IPA solubility
« Reply #27 on: August 27, 2002, 10:10:00 PM »
At room temp that nitrosyrene is slightly soluble in IPA, but not very much so. 20mL was maybe too much to wash 1g in, or your nitrostyrene was very impure. Also, yellium is right, rigorously purifying the nitrostyrene is usually a waste of time. How are you going to reduce?

Mountain_Girl

  • Guest
SWiHKAL has past the 1/2 way mark Antoncho!
« Reply #28 on: August 27, 2002, 10:11:00 PM »
SWiHKAL has past the 1/2 way mark Antoncho! I'm pleased and inspired by this.

Just one Q/idea:
Cold temps were maintained throughout SWiHKAL's procedure. In

Post 320904

(Rhodium: "2,5-Dimethoxynitrostyrene w/ NaOH catalyst", Methods Discourse)
conditions were different, allowing the mixture to eventually reach 60°C. I haven't really studied this reaction yet so I'm not sure what the reason for low temps are, but is it possible it may have adversely affected your yield ?

Antoncho

  • Guest
FUCK! FUCK! :-( :-( :-(
« Reply #29 on: August 28, 2002, 09:45:00 AM »
Well, guys, just as i said, SWiHKAL is, in his essense, a retarded dumdfuck, who can't do anything properly the 1st time and not to fuck it up :)  Which he did.

Sadly, the cause of failure was just the same that in the previous accident. Only this time, a mechanical stirrer blew a hole in the flask's side :o  and the contents,  note this - again - floated freely in the icebath :(  :(  :(


An attempt to resque the remnants of the orange shit was made, but judging from the previous xperience, a qtty less than necessary for reduction amt will bee recovered :( .


So i guess the next chapter of this story will have to wait for some time.... First SWiHKAL will repeat this all over again, starting from hydroquinone ;) .



Fuck!

Oh, well..... Worse things have happened.





;) ,


Antoncho

Chimimanie

  • Guest
another CHCl3 formylation
« Reply #30 on: January 16, 2003, 03:20:00 PM »
see

https://www.jatox.com/jat.mar02.pdf



p 61 contain info on metabolism of 2c-b and a reimer tielman on the benzyloxy derivative from benzyloxy phenol