Author Topic: Russian patents works!!! Zn-HCl nitrostryrene rdxn  (Read 12398 times)

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sunlight

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Russian patents works!!! Zn-HCl nitrostryrene rdxn
« on: September 27, 2001, 01:29:00 PM »
I love you Rhod (I remember you gave the ref) and Antoncho, you translated it from russian.
I decided finally to try this single rxn, water, Zn and HCl... and it works.
In a first attempt, 6 grams of 2,5 DMNS in 64 ml H2O + 30 ml IPA + 20 HCl were stired and at 25 - 30 C were added 32 grams of Zn dust and 170 cc of HCl, stired till remained an almost colourless solution. Some insolubles were filtered (Zn) and then vacuum was applied to remove excess of HCl and some water. No acid wash, it seemed a clear solution and I was just checking rxn, and freezed 25 % NaOH with stiring was added to get a milky solution with the amine on top. Extraction with toluene and crystallyzation gave 3.9 grams, 62 % of 2CH . HCl.
Mmm, I haven't checked mp, but I'm sure it's 2CH. I'll do anyway.
It has been just a first test to see if it works, things can be better, I think 24 grams of Zn is enough, and I only made two extractions of the basified solution, so it will give probably better yields.
The rxn is very friendly, a water bath (20 C) is enough to control temperature, adding ice or removing it when necessary, and addition of Zn and HCl doesn't foam a lot, and temp is stable.
The bad part is the huge amount of solvent you get for so little product, but the best is you only need the nitro and Zn (both powdered with a coffe grinder), 36 % HCl (cheap in the drugstore), a bit of alcohol (not necessary), water and toluene.
Say goodbye to all the nightmares with anhydrous conditions, LAH, NaBH4, THF, Pd/C or poissonous Hg etc... for domestic amouts of 2CH. This rxn is very very easy, absolutely kitchen chemistry.
Next week we'll probably try a 30 grams batch and I'll post the procedure.
This is by far my best finding in kitchen and psychedelic chemistry.

PEYOTE

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Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
« Reply #1 on: September 27, 2001, 01:30:00 PM »
Whoa!!!! And, will it go with ANY nitrostyrenes?

:)  :)  :)

have you got any ref for this procedure?

sunlight

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Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
« Reply #2 on: September 27, 2001, 03:48:00 PM »
I've made the melting point and it's a bit depressed, 132-135 instead of the 138-139 C of PIHKAL. The product is not absolutely white, but a bit tany, so I hope that the reason for it is that a quick and not too much cared work-up have carried some impurities. I wanted to see the end as soon as possible !!!
We'll try a 30 grams batch trying to optimize the Zn (I think 3/4 parts it's enough) and work-up, and I'll post  it.

Theoretically it should work for any nitrostyrenes or even nitropropenes (what about 2,4,5 TMP2NP ?, isn't it sensitive to acids ?). And it will be fine for low dose compunds, but for mescaline for example, just to get a few doses.

This is the reference, posted by Antoncho after Rhodium's inquiry, if I remeber correctly:
Antoncho
(Newbee)
04-23-01 07:56
No 186076
 Re: References on nitrostyrene reduction
OK, here's what it says:
As was already mentioned, it only deals with the compounds in which either R1 or R2 or both of them are hydrogens. Unclear yet if it will make any differense.
The rxn is made with Zn powder in aqueous acid soln with heating. The conc. of acid should be 4-22%. Best choice for acids are acetic or formic, in presence of EtOH or THF. These conditions allow for increasing the yield by 19-28% - up to 76% and no HgCl2 is required.

Example 1. To the suspension of 0,627 g of 2,4-dimethoxyPEA in 18 ml H2O there's added 3 ml 36% HCl and, with effective stirring, maintaining the temp at 25-30 C, over the course of 4 hours tere is added in small portions so as not to allow excessive foaming, 7.1 g of Zn dust and 27 ml 36% HCl... stirring is maintained for 1 more h, utill all Zn is dissolved. After that the rxn mixtr is a clear, colorless soln without any solid particles. Washed w/ 2x 10 ml benzene, aqueous phase is basified with approx 90 ml 25% NaOH with stirring and cooling, so as not to allow the temp rise over 30 C; until all initially formed Zn(OH)2 redissolves. The product which is an oily subst. at this point is extr'd w/4x30 ml benzene, washed w/10 ml 2% NaOH, dried for 12 h w/ 6 g KOH, quickly (to avoid forming any carbonate) thru a dense glass filter and evap. the solvent. After drying to const weight the yield is 0.534 g. (98%)

Example 2: 3,4-dimethoxyPEA. 1,045 g of the nitrostyrene w/ 3.27 g Zn (10x molar excess) are ground into fine powder, suspended in 9 ml H2O, cooled to 5 C, over the course of 0,5 h 27 ml 15 HCl are added with stirrng and cooling (temp <10-15 C) Stirred for 0.5 h more at 10 C, then 31 ml 36% HCl is added (0,5 h, 10-15 C), not allowing strong foaming. Temp then allowed to rise to 25-30 C while adding 3,27 g Zn dust and 20 ml 36% HCl for 0,5 h. Stirred for 1 more h until all Zn dissolves. The rest like above, xept drying agent 15 gNa2SO4+ 2 g KOH (time not specified) Product's a yellowish oil that on standing crystall. to almost colorless crystals. Yield 0,819 g (90,5%)

Example 3. All like in #2 xept 4-metoxyPEA, yield 88%

Example 4. 4-methoxyPEA. 0.537 g nitrostyrene, 11.4 ml formic acid, 2 ml 36% HCl at 10-15 C; added 2.03 g Zn, 8 ml HCl, 5 ml formic (for 0.5 h) Stirred for 45 more min. Added for 15 min at 20-25 C 0.77 g Zn, 6 ml HCl, 3 ml formic. The rest as above (Note: when basifying, temp never allowed to exceed 30 C). Yield 87% Formic acid was employed merely to reduce the amount of foam during the rxn.

Example 5. 4-methoxyPEA. 0.537 g nitrostyrene, 9 ml acetic, 7.5 ml 36%HCl. Temp 25-30 C, for 0,5 h added 2.07 g Zn. Then added 1.5 ml HCl and stirred for 1 more h. Then extracted as above(xcept the first benzene wash is washed twice w/5% HCl and then aq. liquors combined). Yield 79%
Example 6. 4-benzyloxy,3-methoxyPEA. All as in #5. Yield 82%

Example 7. 4-PropoxyPEA. To the mixture of 15 ml EtOH, 15 ml 36%HCl w/stirring at temp 25-30 for 20 min is added finely ground mixtr of 1.035 g nitrostyrene and 1.31 g Zn (4x molar excess) During the next 15 min added are in small portions 1.66g Zn and 5 ml HCl. Stirred 55 min until all dissolved. Extraction like in #5. Yield 84%.

Example 8. 4-ethoxyPEA. All like in previous, xept THF as the solvent. Yield 88%

Example 9. 3,4-dimethoxyPEA 1.45 g styrene as fine powder susp in 16 ml aqua, then 4 ml
HCl added, then over 40 min at 25-30 C added 26 ml HCl, 3.98 g Zn, stir till all dissolves. Extr like in #1 Yield 91.5%

Example #10 3,4-DMPEA. 1,045 g powdered styrene susp in 15 ml aqua ; added 3 ml HCl. Then w/stirring over 1 h at 25-30 added 12 ml 26(?)% HCl and 2.215 g Zn. Stirring 2 h till all dissolves. Extr like in #1 Yield 90%

Examples #11 and 12 are relatively useless and used to define the optimal conc-tion of acid, which appears to be around 15 percent. The paper repeatedly emphasized that acid conc. should be between 4 and 22%.

Whoo... I finally did it. Any questions on the details of the transcription are welcome. HCl conc. is 36% where not specified otherwise.

Sweet Jesus! Now, i wonder if everything is really THAT easy. Although there has been lots of published here trials using approx the same method, i believe, this exact combination of conditions (keeping the temp and acid conc low ) was never experimented. Can't be confident with that, though. ...man... Just Zn and HCl in good old H2O... Doesn't look believable, but it's a patent, after all!

I just looked it up in PiHKAL, 3,4-DMPEA. The corresponding nitrostyrene is reduced w/LAH for 18h and it yields 3.3 g from 11.45 g ! Looks like this one is not particularly easy to reduce, huh? The 3-ethoxy,4-methoxy- yields 3.8 g from 6.2 g - not the best of yields, too. Looks like the stuff described in this patent is none easier to reduce than the "conventional" nitrostyrenes. I don't know shit about materies like that. Can anyone comment? Is there a way to tell?





Rhodium

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Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
« Reply #3 on: September 27, 2001, 04:15:00 PM »
Great work sunlight!

Lem2

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Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
« Reply #4 on: September 27, 2001, 06:42:00 PM »
lol, I KNEW IT!!!!!! I posted a long time ago about this, I think under the nick Lem, and every one was like "NO it won't work!!, it won't! blah,. blah blah" BUT I KNEW IT!!!!!!!!!!!!! THE DOG WILL HAVE IT"S DAY!!!!! MESCALINE FOR THE MASSES!!!!!! ;D

Antoncho

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Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
« Reply #5 on: September 27, 2001, 07:37:00 PM »
OH SUNLIGHT!

And Antoncho loves both you, PolytheneSam and Rhodium! Your post made me happy as a puppy - sweet Jesus, sweet Jah, i can't express how exhilarated i'm about this!

Actually, you know what - and it is a really strange coincidence - yesterday a very respected Russian chemist posted a message on HyperLab, that said that the patent doesn't work and that he tried it three times - to no avail. And i was just about to post his "findings" here when i saw your post - would you believe it?!!!
The guy - actually, our Founding Father - has been away for a long while, which makes me think he's probably a disguised nark :o  I'll find that out...

But - back on topic. Antoncho's ashamed to admit this, but there's a notion in the patent that he overlooked in the above translation - well worth mentioning. Quote: " when carrying the process by an established method, when the quantity of metal is more than that of acid, the yields are significantly less" Not that you did it some other way, just to make sure noone else messes it up. Kinda explains why the other's attempts at Al/Hg redxn might have been so low-yielding, i think.
And - a practical sidenote question. What exactly you mean by saying you ground your Zn in a coffee grinder? Was your Zn a foil or one can do it w/granules? (SWIM only has access to Zn in granules:)

Thank you in advance, and - HOSANNA to your revolutionary work once again!

Antoncho

Rhodium

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Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
« Reply #6 on: September 27, 2001, 07:46:00 PM »
What a teamwork! I dig up a strange reference, Polythenesam orders it from the russian patent office and scans it, Antoncho translates it to english and Sunlight finally applies the method on a useful nitrostyrene. The Hive Collective is stronger than the sum of all of our abilities when being alone... Keep up the good work, and especially the teamwork!

Antoncho

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Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
« Reply #7 on: September 27, 2001, 08:22:00 PM »
Now let me very humbly note that SunLight surely deserves some really cool title - or otherwise i'll bee forever ashamed to wear mine ::)

Antoncho

sunlight

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Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
« Reply #8 on: September 27, 2001, 09:22:00 PM »
Thanks PoliethyleneSam, I love you too, I forgot you ordered the patent.
Really this global Hive is very strong. If that chemist says it won't work, ok, let's go slow with this, but I would sure it can be only 2CH, though mp is a bit depressed. I have done Al/Hg with acetic, NaBH4 and Al/Hg, NaBH4 in THF/ethanol and Pd/C Am. formate... and god, this is IT.
Lem2, I guess nobody feeled it could work, even me, but I like to go in new things, specially in the field of kitchen chemistry, easy, accesible methods. I had the time and I bought the Zn on Tuesday. In fact I made a first test months ago with aluminium foil, but it didn't work. And I was really fed-up with 2CH and fucking solvents, pyrophoric catalyts, anhydrous conditions or mercury, bad work-up and low yields.
About acid conditions, there was a typo in my post, they were 170 cc of HCl, not 180, but I'm sure it is not really important.  I just took the example 9, and being more conservative doubled the amounts of Zn and HCl. This is not correct, the concentration of HCl (what patent says it's the essence) is not the same just doubling HCl, but ther are other differents examples, like 1 or 2 with less acid (and much more Zn). IPA was added because the nitro is hydrophobic, and adding the alcohol makes a homogeneus mess, but it can be omitted.
Zn was dust, but when the flask was opened it was in stones (aglutinated), so I started adding it by pressing it with a spoon, but particles were too big and finally I went to the grinder, and it worked fine. In other hand I started the rxn at 10 C (because the bath was too much cool and I expected a exhotermic rxn) and the first portions of Zn did'nt made too much, at 25 C is when rxn goes fine.
First it is a incredible orange messy, then it goes to orange-grey, green grey and finally is almost transparent, may be a little pale yellow, just what patent says. It works absolutely like in the paper.
Very happy, but better wait confirmation. Let's say that patent works producing an hydrochloride salt that has (right now) a similar mp to the 2CH one, and the taste is the same.
If you read the Zn/Hg rdxn in Rhodium's page, this is almost the same, but it seems Hg is not necessay, what a toxic waste...
Pioneer Researcher , thanks, it is perfect.

Rhodium

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Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
« Reply #9 on: September 27, 2001, 09:29:00 PM »
How did you crystallize? HCl(g) through the toluene? If you didn't recrystallize the hydrochloride afterwards, there is no mystery at all why the melting point is depressed.

sunlight

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Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
« Reply #10 on: September 27, 2001, 09:45:00 PM »
Well, having I got 350 cc of toluene for less than 6 grams of product, I added aq. Hcl and alcohol and evaporated the solution, the azeotrope removed all the water, and then I concentrated toluene till 50 cc at 114 C. When it cooled a while, crystals precipitated, then I added a bit of acetone to filter, and washed the filtrate with more acetone. Not the best crystals, amorphous and toluene smelling.
This is the problem with this rxn, may be it's better to concentrate the toluene extracts with the aspirator and then gas or add IPA + aq. HCl. Wich is your opinion ?

Rhodium

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Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
« Reply #11 on: September 27, 2001, 10:17:00 PM »
I would of course always vacuum distill the freebase, but if you don't want to do that, I believe that drying the toluene, and evaporating much of it followed by gassing would be a much better idea. Isn't diethyl ether available to you? It evaporates much easier and leaves no residual smell.

sunlight

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Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
« Reply #12 on: September 27, 2001, 11:58:00 PM »
Yes, I've thought in ether. I can get it, but I can get OTC toluene, so much as I want, with enough quality for extractions and cheap. Ether is more expensive, smells a lot and it's necessary to dry it. The ether is a good alternative, but if you have an emulsion, you can't filter it. Anyway, boiling toluene it's not a bad choice, our loved amines are not affected. It's more a "kitcheny" than academical way. We'll see.

zooligan

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Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
« Reply #13 on: September 28, 2001, 04:43:00 PM »

Pioneer Researcher , thanks, it is perfect.




I was hoping for fielded suggestions from the masses (as with KrZ's title), but some mod jumped right on it.

My suggestion wold have been "Kitchen-Chem Researcher Extrordinaire" but Pioneer Researcher certainly fits.

z


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

sunlight

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Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
« Reply #14 on: September 28, 2001, 07:56:00 PM »
Zooligan, I like your title. I prefer easy and accesible methods than sophisticated, better if done with little materials and equipmetns, because due the legal situation, it's the better way to keep things going on.
Anyway it has been to be supported by the knowledge of academical and professional chemists, with TLC controls, analysis or whatever, but the goal is to get easy methods.
Thanks.

Prdy2GO

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Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
« Reply #15 on: September 28, 2001, 10:16:00 PM »
Outstanding work!
Now for a few questions:
1. Zn dust? What about sanded copper removed pennies? OTC sugestions?
2. Do you think this would work for plane old p2np nitropropene from nitroethane and benzaldehyde? Or MDP2Np?


Hum did you get that?

Rhodium

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Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
« Reply #16 on: September 28, 2001, 10:26:00 PM »
It should work for phenyl-2-nitropropene too in my opinion. Perhaps the yields would be a little lower with 3,4-methylenedioxyphenyl-2-nitropropene, as the acids may chew a little on the MD bridge, but as the reaction is kept cool, maybe this is not such a big problem.

sunlight

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Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
« Reply #17 on: September 29, 2001, 12:06:00 AM »
Yes, I think it will work, may be even better.
About the MD bridge, I don't think it's so weak, in the rearrangement of the diol to ketone, it is boiled at least to 65 C with 15 % H2SO4, and I've sometimes evaporated strongly acid solutions (HCl) till high temps with the aminated material, and the recovered product was in the correct mp range. Some mistakes o little care with evaporations made me learn it.
In the crystallization I found than you can add aqueous HCl to the DCM or toluene+alcohol (sometimes to a very low pH) and evaporate it bringing temp till even 140 C, then add acetone, and you get good material, correct mp, and with specially good aspect (snow white) if your ketone is specially good. A friend has a TLC of this material and it used it as reference in his firsts attempts.
For me the MD bridge is not so weak, at least with HCl. It will work, but you will need lots of solvents, Zn  and patientia for the work up. But for DOB it will be holidays in the Caribe.

sunlight

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Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
« Reply #18 on: September 29, 2001, 02:04:00 AM »
Mmm, I've checked the mp of a positively brominated amine HCl, and it's depressed too, it changes in aspect getting little brown till decompose in a similar to bromine compound at 230-233 instead of 237-239, so I can conclude very happy that the russian patent works and produces 2CH.
Could Rhodium or anyone estimate the range of purity of those products wich have a depressed mp ?

Antibody2

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Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
« Reply #19 on: September 29, 2001, 02:47:00 AM »
far out sunlight! hats off

"All those memories lost like rain..."