The Vespiary

The Hive => Novel Discourse => Topic started by: sunlight on September 27, 2001, 01:29:00 PM

Title: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: sunlight 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.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: PEYOTE on September 27, 2001, 01:30:00 PM: Whoa!!!! And, will it go with ANY nitrostyrenes?

:) :) :)

have you got any ref for this procedure?
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: sunlight 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?
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: Rhodium on September 27, 2001, 04:15:00 PM: Great work sunlight!
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: Lem2 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
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: Antoncho 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
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: Rhodium 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!
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: Antoncho 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
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: sunlight 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.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: Rhodium 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.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: sunlight 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 ?
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: Rhodium 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.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: sunlight 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.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: zooligan 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!"
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: sunlight 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.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: Prdy2GO 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?
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: Rhodium 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.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: sunlight 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.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: sunlight 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 ?
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: Antibody2 on September 29, 2001, 02:47:00 AM: far out sunlight! hats off
"All those memories lost like rain..."
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: Rhodium on September 29, 2001, 03:20:00 AM: An accurate estimate of purity with a melting depression can not be made, but I would say that the purity is relatively good anyway, it is certainly 95%+.

I'd guess that the impurity is mainly the N-hydroxy amine, which is known to be formed in some Zn reductions. It should also be active, se all the HOT compounds in Pihkal.

Regarding the amount of solvent needed, I am sure we can tweak the reaction to use less if we experiment a bit.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: sunlight on September 29, 2001, 07:27:00 AM: Thanks Antibody2.
Rhod, there's a misunderstanding. The brominated sample is from a previous small batch a la Beaker and brominated a la Shulgin. The procedure usually stops in the hydrobromide, but the liquors of washes where worked to get 600 mg of de hydrochloride. What I wanted to mean is that this conditions of workup, a first test or a minimum amount, seems that as you said there's no mistery that the mp is depressed. I have always thought like you that purity is 95+%.
About OTC, well, I remeber that when I was a boy the bateries for light were made with graphite and Zinc, may be it could be recovered, washed and moltered, but I wonder how if someone can get the aldehyde and a few things more, he can't get 1 kilo of Zn dust. Anyway it seems that there are hard places in this world.
Ok, let's stop to talking about it, I'm tired and can't sleep thinking all the time in it. A few days more and we'll have more information.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: Semtexium on September 29, 2001, 07:38:00 AM: A few days MY ASS!!! Your a research ADDiCT!!! ;) Get some help or some sleep, GHB works wonders in just such a case old friend... :) Can't wait to hear some more good news... 8)
::) ;D :) :P ;) Mean People Suck ;) :P :) ;D ::)
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: Prdy2GO on September 29, 2001, 09:28:00 AM: Might we have a bit more details on the Zn?
" You said "About OTC, well, I remeber that when I was a boy the bateries for light were made with graphite and Zinc, may be it could be recovered, washed and moltered," are you telling us that you ripped appart some battries for the Zn?
If so what are the details type, manuf., part, processing steps?
What other sources do you think would work?
Thinking about stripping the copper plating from a few pennies and using a dremal and the small drum sander or a grinding wheel? Do you thank that will work what else?
Thanks
...
..
.

Hum did you get that?
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: sunlight on September 29, 2001, 03:29:00 PM: No my god, I bought it in my regular-chems shop. Zn is nothing especial.
What I wanted to mean is that I broke bateries when was a child and get the Zn foil (0.5 mm or so ) to make electrochemical experiments, in the school. I know nothing about pennies, may be if you ask for euros...
And yes, I'm addict and I'm too much excited, almost ill, and can't work till Monday...
I've done a lot of failed tests with the nitro, a lot.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: Semtexium on September 29, 2001, 06:33:00 PM: Your still my favorite addict Sunlight... ;)
::) ;D :) :P ;) Mean People Suck ;) :P :) ;D ::)
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: KrZ on October 08, 2001, 09:21:00 AM: Not sure if this has been mentioned already, but British Patent 793,965 details this reduction quite nicely. While they use a thio-derivative, the conditions are clearly applicable.

~29.8 g Nitrostyrene dissolved in 300 cc Ethanol, 200 cc Acetic Acid, 100 cc H2O, and 80g Zinc dust added slowly with external cooling such that temp. did not rise above 30C. Once Zn addition is completed they add 100 cc H2O and heat to 60C for one hour. Filter off Zinc. Distill off Ethanol fraction. Basified with 40% NaOH to redissolve precipitated Zinc. Extract 3X with ether, wash pooled ether extracts with 40% NaOH to remove any Zinc. Distilled ether and crystallized in HCl/IPA.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: sunlight on October 12, 2001, 12:36:00 AM: I don't remeber it. I works with acetic acid too, I've tested H2SO4 and it seems to work as well. I still wonder how this so easy procedure has been ignored till now.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: Rhodium on October 12, 2001, 12:58:00 AM: KrZ: That patent deals with the already partially reduced phenylnitroethane, not a phenylnitroethene (nitrostyrene).

But coupled with the NaBH4 reduction of nitrostyrenes to phenylnitroethenes, this may be a good alternative to the CTH with ammonium formate to give the phenethylamine.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: sunlight on October 12, 2001, 03:28:00 AM: Yes, you are right, Rhod, it reduces a curious phenyl nitroethane. I thought firstly that the alkylthio group was added to the ring, and I was very surprised with the first reaction, but in a second lecture I saw that the alkylthio is added to the double bound of the nitrostyrene
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: KrZ on October 14, 2001, 12:06:00 AM: I know it wasn't a nitrostyrene. Same diff. though. Zinc and Protons = FUN. :P
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: sunlight on October 14, 2001, 01:17:00 AM: My mind is in a some kind of explosion. I'm thinking now about to reduce nitromethane in methanol+acetic and Zn, then add Ketone, then add more Zn, more acetic, may be it will reduce as well the imine without Hg... Any impossible in this idea ?
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: Osmium on October 14, 2001, 02:11:00 AM: I don't think the imine will form well with excess acetic acid around.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: BenWiFFen on October 14, 2001, 06:10:00 AM: 1981 and up U.S penneys work good. Just hold one with a pair of plyers. Use your propain torch and melt the penney. When it starts to melt give it one shake and the Zn will fall leaving the copper jacket in the plyers. Let it fall into a frying pan or whatever, Higher the better the Zn will make a bigger and thinner splat. Then cut with shears and toss in blender. It's sorta fun in no time at all you'll have a stack of splats.
Gear Driven ;)
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: megamole on October 14, 2001, 06:42:00 AM: Wouldn't treating US pennies with an acetic acid bath do the trick? Just let them fizz until they're bright and shiny. Modern pennies are 96.5% zinc; stripping that thin copper coating off leaves you a very pure source to work with.

Still, the problem then is that solid zinc is very different than powdered zinc. How does one reconcile this, or does it even matter?
"Give me ten minutes with your inner child, and I'll give you back an inner adult."
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: foxy2 on October 14, 2001, 02:19:00 PM: There are several methods of precipitateing highly avctive Zinc Powder from Zinc salts. I will post some details in the far future, as i am way to busy with other shit now.
Do Your Part To Win The War
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: sunlight on October 14, 2001, 06:35:00 PM: Wow, with this kind of pennies, may be your governement have definitivaly supported a new generation of home phenethylamine cookers. Copper++ will accelerate the rxn of Zn with HCl, wich in IMHO is a competitive rxn with the real rdxn that seems to proceed through a nitro-Zn intermediate (you'll see when you make it), so may be you need more Zn just reducing to pennies to dust. Copper hydroxides (Merck) seems that are solubles in alkaline solutions when fresh made and if only CuCl is formed, part of it could be filtered. Well, I'm especulating may be it won't so easy.
In other hand seems that BenWiFFen have solved the copper question, so now you need to make Zn dust.
Other way is foxy2 if works with common materials.
Anyway, how much is a penny ? Do you know why they are made with Zn ? , I believe is becuase Zn is absolutely cheap, even technical grade from Aldrich is not expensive, but I've found it 4 times cheaper from a minor company, and it's perfect. And see this Merck):

10255. Zinc.
Zn; at. wt 65.38; at. no. 30; valence 2. Group 2b element. Abundance in earth's crust: 0.02% by wt. Natural isotopes: 64   (48.89%); 66 (27.81%); 68 (18.57%); 67 (4.11%); 70 (0.62%); eight radioactive isotopes and two isomers. Occurs in   smithsonite or zinc spar, sphalerite or zinc blende, zincite, willemite, franklinite, [(Zn,Mn,Fe)O.(Fe.Mn2)O3] or gahnite (ZnAl2O4). Has been known since very early times. Commercial forms: ingots; lumps; sheets; wire; shot; strips; sticks; granules; mossy; powder (dust). Prepn: Gowland, Bannister, Metallurgy of Non-Ferrous Metals (Griffin, London, 1930); Zinc Production, Properties and Uses (Zinc Development Association, London, 1968). Reviews: Zinc, C. H. Mathewson, Ed.,
A.C.S. Monograph Series no. 142 (Reinhold, New York, 1959) 721 pp; Schlechter, Thompson, "Zinc and Zinc Alloys" in Kirk-Othmer, Encyclopedia of Chemical Technology, vol. 22 (Interscience, New York, 2nd ed., 1970) pp 555-603; Aylett, "Group IIB" in Comprehensive Inorganic Chemistry, vol. 3, J. C. Bailar, Jr. et al., Eds. (Pergamon Press, Oxford, 1973) pp 187-328.
Bluish-white, lustrous metal; distorted hexagonal close-packed structure; stable in dry air; becomes covered with a white coating of basic carbonate on exposure to moist air. mp 419.5 deg. bp 908 deg. d25 7.14. Heat capacity at constant pressure (25 deg):   6.07 cal/mole deg. Mohs' hardness 2.5. When heated to 100-150 deg becomes malleable, at 210 deg becomes brittle and pulverizable.
Burns in air with a bluish-green flame. Loses electrons in aqueous systems to form Zn2+ E deg (aq) n/Zn2+ 0.763 V. Slowly attacked by H2SO4 or HCl; oxidizing agents or metal ions, e.g. Cu2+, Ni2+, Co2+, accelerate the process. Reacts slowly with ammonia water and acetic acid; rapidly with HNO3. Reacts with alkali hydroxides to form "zincates",ZnO22-, which are   actually hydroxo complexes such as Zn(OH)3-; Zn(OH)42-, [Zn(OH)4(H2O)2]2-.
Caution: Inhalation of fumes may result in sweet taste, throat dryness, cough, weakness, generalized aching, chills, fever, nausea, vomiting. Zinc chloride fumes have caused injury to mucous membranes and skin irritation. Ingestion of sol salts may cause nausea, vomiting, purging. See E. Browning, Toxicity of Industrial Metals (Appleton-Century-Crofts, New York, 2nd ed., 1969) pp 348-355.

USE: Galvanizing sheet iron; as ingredient of alloys such as bronze, brass, Babbitt metal, German silver, and special alloys for die-casting; as a protective coating for other metals to prevent corrosion; for electrical apparatus, especially dry cell batteries, household utensils, castings, printing plates, building materials, railroad car linings, automotive equipment; as reducing agent in organic chemistry; for deoxidizing bronze; extracting gold by the cyanide process, purifying fats for soaps; bleaching bone glue; manuf sodium hydrosulfite; insulin zinc salts; as reagent in analytical chemistry, e.g., in the Marsh and Gutzeit test
for arsenic; as a reducer in the determination of iron. It is a nutritional trace element.

"At 210 deg becomes brittle and pulverizable" it sounds good. It's extensively used in galvanization and in batteries. May be it won't be a problem.

I'm veery optimistic with this rxn, may be too much, but now I'm a bit exhalted. My reasons are that the patent says that (Antoncho) "
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. (R1 and R2 are in positions 2 and 3 of the aromatic ring, respectively, and R3 is position 4).
a)   R1=R2=H b) R1=H, R2=OCH3
b)    R1=OCH3, R2=H and R3= AlkO- or PhCH2O- (Alk = C1-C3)

This means that is for 4 substituted nitrostyrenes, (R1=2 position and so on) with a CH3O in 2 or in 1 (only one) or just H in both.
It has worked with 2,5 DMNS, this is not the patent. What about 2,4,5 or 3,4,5 or 2,4,6,? and what about the corresponding nitropropenes and 2,5 DMPNP ? It can work or not, but it should work still better with the 4 substituted nitrostyrenes, and why not with the nitropropenes ? We'll se in the test bench, I'm very optimistic.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: sunlight on October 14, 2001, 06:39:00 PM: I think Zn dust is necessary, and a coffee grinder won't make the work at all. But try it.
Osmium, yes you are right, but may be the pH could be controlled in the imine reduction. May be.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: Rhodium on October 14, 2001, 09:14:00 PM: I believe the patent restrictions on the structure was made to not infringe on other patents, and not that it would be a problem with the reaction itself. The only thing I believe it doesn't work on are those acid-sensitive asarone'ish compounds. It may also work differently on nitropropenes if the reduction mechanism depends on the nitro group to be primary, but I see no real reason for that to be the case either.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: improv_chem on October 15, 2001, 05:55:00 PM: Sweet!!!! Super Sweet! Now SWIM has a good way to reduce those nitropropenes that have been forming as thoughts in SWIM's head for some time now.
This is exactly the type of research that I love to see coming from the hive.
I really do love kitchen chemistry!! ;)
-improv :)
Let's play with nature a little, I'm sure we can make her a little higher....
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: sunlight on October 16, 2001, 02:12:00 AM: I've been may be too much enthusiastic, and now I'm worried remebering my first test with MDA, that yielded a 60 % that never happened again. I've done more tests with this procedure, but with less Zn, and yield has been constantly a bit more than a 30 %. I must repeat my first test, or similar, with big excess of Zn and a accurate work up and see then what happens.
In my first I didn't dry the solvents and it was a big volume of solvent for little product, so it had (confirmed) NaCl impurities (saline wash) ... well, it was just a test. So please, wait a confirmation of more realistic yields. What I can really say right now is that a 30%+ is easily achieved with a 3:1 Zn/nitro w/w, this is totally sure, but it's not enough good. I have been very enthusiastic with the finding, it works, but the yield can be lower. Sorry if it is not so good.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene rdxn
Post by: Vibrating_Lights on December 04, 2001, 01:34:00 AM: Has Sunlight tried a Mdp2np reduction with 6:1 Zn:Nitro ratio yet. Also what is the correct procedure for the work up. Is the alcohol in the rxn removed with vacume then basified with NaOh. Followed by extraction with Toulene.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene
Post by: sunlight on December 04, 2001, 10:33:00 PM: We went to the house of a friend some days ago and we made a bit of the nitropropene from iso, with the nitrosite procedure. It was the first time for us, and the final product had a strange smell that remebered me other smells and make me think that the product was not pure. The rxn went exactly like with 25DMNS, but always with that strong smell in the flask. We made a TLC MeOH:NH3 of the rxn mixture, with 2,5 DMNS I have observed that there's a big spot at the bottom, probably all Zn salts, and a single spot a bit higher corresponding to 2CH, in this case we forgot the TLC and solvent arrived to the top, so when we rembered it some time later, we saw the spot in the bottom and a single spot, but rf was around 0.6 instead of around 0.2, and we don't know if this diference can be explained due our forgetfullness, if it was the amine, the rxn worked really well.
When finished, and aliquot was basified with 40 % NaOH and clearly appeared drops of oil floating, but I couldn't recognize the smell of amine due the strong persistent smell of the beginning and I had to come back home. After almost two weeks he have not tried xtallization, but he has told me that pH of dried solvent is not significatively basic. Too much time to process it, he should end work up the same day, now everything can be destroyed, I'm dissappointed, he works really ssllllooooowwwwwww. The rxn went apparently pefect, so I would say it worked, but I was not there in the work up and my friend is not really experienced, may be he made a mistake or may be it did'nt work.
I made at home a very small test with 3,4,5 TMPNP, the rxn worked the same, dissapearing the insoluble nitro when Zn was 2-3:1, and basifying appeared the oil with the characteristic amine smell. I'm optimistic, but I can't state it works, and I won't try it at the moment, so if you can, it would be nice to make a small test with 34MDPNP.
I would start with a 5 % HCl in the flask and I would end with a 9 % based in free HCl over total weight, 2 hours addition, better 7:1 Zn, and then evaporate alcohol with aspirator, add water to have a density that let work DCM wash (d~1.2), basify with NaOH 40 + % to reduce volumes, extract... If you want precise details, PM me.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene
Post by: Cyrax on January 07, 2002, 04:14:00 PM: Sunlight, I am glad that you tried the reaction on a nitropropene. Since quite a while, I was wondering if it could work. A method to be sure of the spot on the TLC, is to do a ninhydrine test. If you like, I'll look up how to make this spray. To use the spray is really easy: spray the stuff on your TLC, let it dry, heat it in an oven and if you have an amine, there will be a coloured spot on the TLC. Ninhydrine is a messy substance, once I had to make the spray and it was not easy to weigh the correct amount. This stuff sticks to everything and it is carcinogenic . :(

I did some quick stoichiometry and I guess the reaction goes like this:
4 Zn + 8 HCl + Ar-CH=C(NO2)-CH3 --> Ar-CH2-CH(NH2)-CH3 + 2 H2O + 4 ZnCl2

Of course, it is wise to use excess Zn.

If the trouble with this reaction persist, I have an other method that first reduces the nitropropene to the oxime with Pb - DMF/AcOH. Then, there will be no problem reducing the oxime to the amphetamine with Zn / AcOH. The problem with the Pb reaction however is the amount of solvent that you have to use (maybe you can use less solvent). If I remember correctly, for 10 mmol of the nitropropene, you have to use 2 eq. of lead powder (this is OK), but 75 ml (!) of DMF and 5 ml of AcOH.
This can be a good method for recreational use, if you want to make DOB or DOI. In the article, they get 92 or 94 % (I do not remember correctly) of phenyl-2-oximopropane from phenyl-2-nitropropene.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene
Post by: Antoncho on January 07, 2002, 05:23:00 PM: Just wanted to remind you guys this
Post 70459 (missing)
(yellium: "Syn. Comm 18(7), 693-697 (1988)", Novel Discourse), posted by Yellium - anyone knows what ever came of it? I remember someone saying that this redn was successful w/50 g 2,5-DMNS, and another one said it didn't work when he tried it. - so the question still hangs open.

Well worth trying, IMHO.

Edit:As a side note, could anyone give me a clue where one can find an experimenal procedure of a nitropropane reduction to amine w/Al/Hg - i remember someone reporting a success (think pseudonitrosite NP --> nitropropane w/NaBH4 a la Beaker :-[ ), but can't find it for anything in my life.

Antoncho
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene
Post by: Rhodium on January 07, 2002, 07:12:00 PM: Ritter said it did produce a lot of tar when performed on a larger scale than a few millimol, but on the scale in the paper it worked great. It might just be a matter of tweaking rxn conditions.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene
Post by: ___ on January 08, 2002, 04:42:00 AM: Cyrax - i'd wouldn't mind hearing more about >Then, there will be no problem reducing the oxime to the amphetamine with Zn / AcOH. can you elaborate?
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene
Post by: Cyrax on January 10, 2002, 04:34:00 PM: Sunlight's Zn/HCl procedure is EXCELLENT to convert aryl-2-nitrostyrenes to amines, but it doesn't work for nitropropenes. Thus we have to get some intermediate product like an aryl-2-oximopropane. The Pb - DMF/AcOH procedure is original, convenient, and you don't need suspicious chemicals.
Example:
Phenyl-2-nitropropene (0.1 mol) was dissolved in a mixture of acetic acid (5 ml) and DMF (75 ml), and lead powder (2 eq.) was added. The mixture was stirred at ambient temperature for 2 h. The mixture was poured into ice-water and extracted with Et2O. The ether solution was washed successively with an aq. NaHCO3 solution and an aq. NaCl solution, and then dried over MgSO4. The solvent was evaporated off and the resultion phenyl-2-oximopropane was purified by chromatography (silica gel / DCM). Yield: 92 %.
Ref.: Synlett (1990) p 477

Chromatography is tedious, but in Chem. Ber. (1981) 114;12 p 3813 they crystallize phenyl-2-oximopropane in hexane.

Then you can do different things with your precious oxime:
* a Na/EtOH reduction like in JOC (1964) vol 29 p 1419 (there is an excellent example on Rhodium's site)
* a Zn/AcOH reduction like in Vogel (5th ed.) p 1151
or like in the russian patent, this time not on the nitrostyrene but on the oxime.

I found this Zn/AcOH reduction somewhere on Rhodium's site:
At room temperature with stirring, zinc dust (74 mg) was added to a solution of the oxime (44 mg, 0.185 mmol) in 2 ml glacial acetic acid. Stirring was continued for another 15 minutes. The reaction mixture was filtered through a sintered glass funnel with suction. The filtrate was concentrated under vacuum to afford the amine as an oil (37 mg, 0.166 mmol, 90 % yield)

And if you don't like the oxime, you can hydrolyse it with HCl to the aryl-2-propanone.

I made a VERY BIG MISTAKE in my previous post ():-).
Ninhydrin DOES NOT work on amines, but on amino-acids.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene
Post by: Antoncho on January 10, 2002, 05:05:00 PM: This lead/DMF procedure - is excellent, i've been looking for it for a long while! (i collect'em ;) )

Antoncho
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene
Post by: hest on January 10, 2002, 05:30:00 PM: Ninhydrine works nice on amines (might heat it a bit)
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene
Post by: sunlight on January 11, 2002, 12:57:00 AM: Are you sure it does not work with nitropropenes ? A friend told me he got some MDA. It was a low yield, like a 10 %, but he delayed the workup weeks, and I think it could destroy some product. In other hand I have not evidence it was MDA, only his word.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene
Post by: Cyrax on January 12, 2002, 12:15:00 AM: I am not sure it didn't work. I just saw that your friend had some problems with the reaction. It would be beautiful if you or some other friendly bee could optimize the reaction for nitropropenes. This would be great and in each case much better than the 2 step procedure that I proposed. I only meant: if the yields don't improve, you could consider the Pb - DMF / AcOH reaction.

Keep up the good work! The Zn-HCl is a kick-ass reaction.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene
Post by: Xgoddess on January 13, 2002, 03:11:00 AM: A research professor I know attempted the Zn/HCl redn for 10 g of 345 tri-methoxy-phenyl-2-nitro propene. He got no TMA at all. He is a bit concerned that the redn does not work for nitro propenes, only nitro styrenes. The reduction needs to be tweaked a bit::for example, these professors dont care for chromatography...What about a one step LAlH redn??
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene
Post by: ___ on January 13, 2002, 04:27:00 AM: goddess, i think you are missing the point, the whole idea here is find ways around watched/controlled chemicals, otherwise this site would be a tit on a a bull.

2X now bees claiming it doesn't reduce nitropropenes, be nice to know what it is Zn/HCl doing to nitroproenes. Is it cleaving the double bond? to give the ethane, is it only reducing to the oxime? "It doesn't work" doesn't tell us much. Can your professor expand on "He got no TMA at all"?
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene
Post by: sunlight on January 14, 2002, 12:25:00 AM: I need time to check it. As it has some similarities with the Fe CLH conversion of nitropropenes with acetones I was worried about it, but when I made a 250 mg 345TMPNP it seemed to work, basifyng I smelled to the amine. I'll try it to see if it is true or not.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene
Post by: Vibrating_Lights on January 14, 2002, 09:59:00 AM: If all yall are afraid to fuck with sunlights Zn procedure and use shulagins procedure in Phikal 109 with Fe/AcOH yeilds from nitropropene to ketone 80% then a MMNitro thats pretty Otc. can't believe it is not talked about more. with 99% yeild saf ->Iso -> 85%%nitropropene ->80% ketone dont think that can be beat. Besides the nitrite all OTC. Has any one ever tried to oxidise safrole or isosafrole with a nitrate yeilding an epoxide or a ketone and nitrite much the same as the procedure using lead to reduce nitrate to nitrite. just replace the lead with alkene. Mabye use a equimolar ammount of nitrate in dh20 perhaps with a. wouldnt it be crazy if ammonium nitrate could be used and as the ketone is formed it condenses with the ammonia yeilding the oxime. Mabye swimis just high and rambling.
VL_
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene
Post by: Antoncho on January 14, 2002, 02:53:00 PM: 85%%nitropropene ->80% ketone dont think that can be beat

heh... :) Practically, it means 2 steps instead of 1...

And that means a lot (IMHO)

Also, the actual yields are usually lower that in theory. Sometimes much lower :) .

Antoncho
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene
Post by: sunlight on January 14, 2002, 07:12:00 PM: Yo are right antoncho, my yields with Zn HCl are far from the patent. And it is similar in a lot of procedures.
Title: Re: Russian patents works!!! Zn-HCl nitrostryrene
Post by: Vibrating_Lights on January 14, 2002, 10:21:00 PM: We believe that the loss in yeilds with pseudonitrosite are due mainly to high temps causing the decomp to the red goo. yeilds can remain high if the temps are closely monitered. The secret to cleaning that red goo from the flask. AcOH and Actone. or ethyl acetate. Ice Baths are the key. Ps.don-t get that shit on you. it will make your skin rough like a wart whereever it touches.
Vl_
Title: sunlight -this still blows me away :-) VL - the ...
Post by: Antibody2 on June 22, 2002, 07:01:00 PM: sunlight -this still blows me away :)

VL - the pseudonitrosite route produces nitropropenes, which have not been sucessfully reduced using this rxn. The red goo you refer to is more indicative of low grade solvent and impure propenylbenzene, although ice is still necessary.
Title: clarifications
Post by: El_Zorro on July 04, 2002, 04:32:00 AM: Please to explain the addition of Zn dust and HCl in further detail. Do you put the Zn in the HCl and drip/pour in? or do you aalternate the Zn and HCl?
Do not go gentle into that good night. Rage, Rage, against the dying of the light. --Dylan Thomas
Title: its added in small portions and aliquots ...
Post by: Antibody2 on July 04, 2002, 09:18:00 PM: its added in small portions and aliquots throughout the initial rxn, at such a rate as to maintain the rxn and acid concentration