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| Author | Topic: Question for KrZ |
| ChemHack Member |
posted 10-28-1999 09:41 PM
quote: I didnt think CuCl would go into EtOH. Was it CuCl2 ? |
| KrZ Member |
posted 10-29-1999 12:04 AM
It was indeed CuCl2*2H2O, now that I look back at the notes I found in the library. Sorry about that. |
| Eigenfxn Member |
posted 10-29-1999 02:28 PM
Just a note to ask wether the hydate actually works since my friend said that she has never tried it ... She has always used just straight Cupric Chloride ... She said she sees no reson why it shouldn't work since there is most likely some water in the EtOH, or MeOH in her case, anyway .... actually she thinks that this reaction needs water just in stoichiometric amounts ... this is where the oxygen comes from I am sure both of you know this anyway .. just a side note while I ramble on Anyway she uses in her dreams the SRV with 40 lbs of O2, 1g of PdCl2, 6g of CuCl2, 100g of ketone, and 500ml of MeOH ... 8hrs of continuous shaking on a machine with occasional repressurizing 8 to 10 times she was just wondering if the hydrate works as well she really loves this method!! |
| KrZ Member |
posted 10-29-1999 04:27 PM
If she ain't doin' that ghetto react0 thang she ain't down wif da KrZ hommies. Soda Kegs |
| K.C.
Nicolaou Member |
posted 10-29-1999 08:57 PM
KrZ - What's up with the plans for making our very own Ghettoreactor(tm) that you keep tempting us with? I don't neccesarily need exact specs, but it would be nice if you gave some indication of what the thing is made out of, how stirring is performed, how rxn components are introduced/removed, and why your rxn mixture doesn't react with the stainless steel(at this point I'm guessing it's a 5 gal, teflon-coated soda-water dispenser with the top cut off and something else welded on). As for the question about the role of H2O in the O2 wacker, it is a neccesary part of the catalytic cycle and some needs to be present, but it is neither consumer or produced in the rxn. The balanced equations (reacting species are not the ones shown, but this gives the general idea) for the different reactions occurring in the wacker are as follows: 1) 1 Safrole + 1 PdCl2 + 1 H2O -> 1 MD2P + 1 Pd(0) + 2 HCl 2) 1 Pd(0) + 2 CuCl2 -> 1 PdCl2 + 2 CuCl 3) 2 CuCl + 2 HCl + 1/2 O2 -> 2 CuCl2 + H2O Overall 2 Safrole + O2 -> 2 MD2P Give me Ghettoreactor plans or give me death!! |
| prickleberry Member |
posted 10-30-1999 04:58 AM
From everything KrZ has posted, its pretty clear to prickleberry what the ghetto reactor looks like. 
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| KrZ Member |
posted 10-30-1999 01:08 PM
Does the wacker react with SS? Better get one of those other parr metal then... *sigh* |
| KrZ Member |
posted 10-30-1999 04:40 PM
Type 316 Stainless Steel Type 316 Stainless Steel is an excellent material for use with most organic systems. A few organic acids and organic halides can, under certain conditions, hydrolyze to form inorganic halogen acids which will attack T316SS. Acetic, formic and other organic acids are routinely handled in T316SS. T316SS is not normally the material of choice for inorganic acid systems. At ambient temperatures it does offer useful resistance to dilute sulfuric, sulfurous, phosphoric and nitric acids, but sulfuric, phosphoric and nitric acids readily attack T316SS at elevated temperatures and pressures. Halogen acids attack all forms of stainless steel rapidly, even at low temperatures and in dilute solutions. Although T316SS offers excellent resistance to surface corrosion by caustics. Caustics can cause stress corrosion cracking in stainless pressure vessels. This phenomenon begins to appear at temperatures just above 100° C and has been the most common cause of corrosion failure in stainless laboratory vessels. T316SS does offer good resistance to ammonia and to most ammonia compounds. Halogen salts can cause severe pitting in all stainless steels. Chlorides can cause stress corrosion cracking, but many other salt solutions can be handled in stainless vessels, particularly neutral or alkaline salts. At moderate temperatures and pressures, T316SS can be used with most commercial gases. In scrupulously anhydrous systems even hydrogen chloride, hydrogen fluoride and chlorine can be used in stainless steel. That sounds pretty good. Oxidation: Minimal reaction with Pd and Cu, no pH extremes. Hydrogenation of MDMA; strongly basic methylamine, Pt shouldn't stick to the walls or anything. Hydrogenation of nitropropenes; Even better, just nitropropene and Pd/C are all that is used. Hydrogenation of alpha-hydroxys (meth); Not good, strongly acidic H2SO4 might cause compromise the vessel, although if the reaction is carried out and room temp. it might still be feasable. I'll see what else I can find. |
| K.C.
Nicolaou Member |
posted 10-30-1999 07:16 PM
Okay, but what do you use to stir? Mag stirring is usually not possible through metal and I am not famliar with overhead stirring systems that will hold that kind of pressure. Any more hints you want to drop would be appreciated. |
| Icepick Member |
posted 10-30-1999 10:29 PM
K.C.....have you ever tried mag stirring thru one of those? its amazing just how powerful a good stirplate is.....mine can go thru either a soda keg or a pressure cooker...the point is: Ya dont know till you try....
Icepick ------------------ |
| K.C.
Nicolaou Member |
posted 10-30-1999 11:19 PM
Fuck, my 7x7" Thermoline hardly even stirs through a heating mantle. I have a good O2 delivery system that gives a constant 30-125psi of O2, but my reaction vessel and agitation system (soda bottle/shaker) is only usable up to 45psi, has no temperature control, and is somewhat prone to mechanical failure (mostly due to the combination of pressure and violent shaking), meaning I have to babysit the fucking thing for hours at a time. I have heard that there is brand of soda bottle with a round bottom suitable for mag stirring, but I have doubts as to whether the thing will hold up for long reaction times in a warm water bath. So I'm not really hurting for a rxn vessel, but I'm definitely looking to upgrade. I do have a good friend who is a welder, so maybe I'll see if I can buy a sealed overhead stirrer that can be welded in some way to a SS plate that can be attached and detached to a modified cutoff soda keg. How does that sound? |
| KrZ Member |
posted 10-31-1999 12:44 PM
If you like to do things the hard way, *shrug*, but you can do pretty much all reductions without a hot water bath. Soda kegs will hold pressure up to 130psi, so you can run at 125 and be fine. Just obey the rules laid out by Parr. Stirring is also not a problem with most brands. |
| K.C.
Nicolaou Member |
posted 10-31-1999 05:15 PM
So mag stirring through an unmodified soda keg isn't a problem? If so, that's nice to know. As for temperature control, I was interested in that more for oxidations than anything else. When I oxidize I find that the temperature initially goes up to about 45C and then falls after ~1.5-2 hours, and that while I get consistent 75-85% conversion (gives 70-75% post-purification yield) after 5 hours or so, letting the rxn procede for longer amounts of time doesn't result in a significant increase in yield and gives dirtier ketone. Based on that observation and your claims, I think that the rxn probably proceeds much more rapidly at somewhat higher temps and the desired rxn becomes more competetive with crap-producing side rxns. That is why I am interested in temperature control. |
| psychokitty Member |
posted 11-06-1999 01:41 PM
This sounds great as used soda kegs are pretty inexpensive. I have a few questions though: 1.) Krz: Any progress or success stories using a soda keg as a pressure device? 2.) Halogen salts? Doesn't PdCl2 and CuCl2 qualify? What about NaCl? (See the confusion) 3.) Are there different sizes of soda kegs available? I have only seen the 5 gallon size. Hope to hear from you soon. By next post I should have a soda keg to play around with. First test will be to see if magnetic stirring works through it. --PK |
| anonymous Member |
posted 11-06-1999 07:26 PM
What are soda kegs made of? Stainless steel? Is the reaction being caried out directly in the keg or what? Isn't there a problem with the steel participating in the reaction? anonymous |
| spiceboy Member |
posted 11-07-1999 04:01 PM
" All together, now...."
The bottle is DESIGNED, by coca-cola, I'm investigating a myristicin-->ketone Not to disparage KrZ's work, at all, I just felt this was appropriate. I doubt he'll agree...
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| K.C.
Nicolaou Member |
posted 11-07-1999 06:00 PM
Spiceboy - As someone who is personally familiar with the use of the SRV, I feel that it has one principle disadvantage, which is the difficulty of any useful temperature control. Experiments with the SRV agitated in a paint shaker have resulted in consistent 70-85% yields, which are somewhat lower than KrZ's impressive tales of 92-95% yields. Based on following SRV experiments by TLC and desciptions of others' experience has led me to believe that temperature is an important factor, with the desired rxn proceeding with higher selectivity at higher temps (~50C). Since these temps are obtained initially though heat produced in the exothemic rxn and temperature then begins to fall, ketone production slows down after a certain point, and further lengthening of rxn times result in diminished returns due to the continued formation of byproducts. Your procedure is good, but not quite optimized. |
| psychokitty Member |
posted 11-07-1999 07:18 PM
I just got a used soda keg made of stainless steel for $40.00. Magnetic stirring works just fine through it. --PK |
| KrZ Member |
posted 11-07-1999 11:40 PM
I agree whole-heartedly spiceboy. The soda-keg is a horrible idea, stay the fuck away from it people. It's a bad bad bad bad idea. ;-) Don't do that amination under pressure I wrote up in too it's sooooo horrible. Don't do it. Another bad bad bad idea. |
| psychokitty Member |
posted 11-08-1999 05:56 PM
KrZ: Will you cut that defensive crap out! I'm down with the hommies, dude, but you still haven't gotten around to answering any of my questions posted above. Come on, man! You've got it going! I'm on your side! Help me out, please. --PK |
| anonymous Member |
posted 11-08-1999 07:52 PM
Won't SS participate in the reacion? anonymous |
| placebo Member |
posted 11-08-1999 09:53 PM
Kra, could you check the post in meth forum, called masterplan, by you. Please! ------------------ |
| KrZ Member |
posted 11-08-1999 10:30 PM
Oxidation, 1g PdCl2, 5g CuCl2*dH2O, 200g Safrole, 500ml EtOH, 125psi, 8hrs. 208g Ketone Nitrostyrene reductions; 2,5 - 20g Pd/C 5%, 200g Nitrostyrene, 400ml EtOH, 125psi H2, 8hrs. 124g 2CH. 3,4,5 - 35g Pd/C 5%, 425g Nitrostyrene, 1L EtOH, 125psi H2, 10hrs. 328g Mescaline. Amination, 200g ketone disolved in 400ml EtOH dripped into 500ml solution of MeAm, MeOH, and water formed from HCl->base conversion, filtered salt, 30% overall MeAm conc. Stirred for 8 hours after addition. 25g Pt/C 5%, 125psi H2, 12hrs. 214g MDMA*HCl There I said it, now leave me alone. |
| scwam Member |
posted 11-08-1999 10:47 PM
....Hmmm, so I definately need to go longer than 8 hours on my 3liter srv 1gPdCl2, 4gCuCl2, 200g safrol, 50PSI of pure 02. Thanks for the insight KRZ. |
| psychokitty Member |
posted 11-11-1999 06:54 PM
Okay, KrZ, you are the BEST!!! However, I'm still a little confused. Time and again you've posted different reaction vessels, some being made of PVC plastic tubes, others out of glass (extra-thick round-bottomed flasks). My LAST question is this: Are you saying that a SODA KEG is THE reaction vessel to use for effecting the above reactions you stated above? Sorry for the continued harrassment. --PK |
| psychokitty Member |
posted 11-14-1999 08:44 PM
You are one elusive dude, but you still have my respect . . . --PK |
| KrZ Member |
posted 11-15-1999 03:28 PM
"Yes. Those nitrostyrene reductions are currently a bitch and a half though. 200g into 3L total reaction volume (EtOH and HCl). Filter it through celite (75% catalyst recovery) then you have to wash that with 4x200ml DCM. Which takes a while to seperate. Then you have to add 1500ml of Aq. Ammonia (29%) dropwise with stirring and this time extract with 4x250ml DCM (Hopefully that is providing good recovery? The EtOH definitely screws with the big solvation gradient one would normally have). Then you just distill that off for your goodies. Thank god for the rotovap. Although it still sucks having only a 2L sep. funnel :-( I tried just filtering and then distilling the mix but something went terribly wrong, the huge mass of black glop locked up all of the amine which presumably polymerized into one huge mess. This reaction makes for costly mescaline but with the higher 2CB activity levels it's ok. PS DO NOT cool your bromine and acetic down to 0C before attempting the reaction. I did this with some 2,5 at the 150g level on the recommendation of someones post and it screwed *everything* up. The exothermic side is good, just let it go, it won't burst out or anything, just gets warm." -In the trash can at the library |
| Osmium Member |
posted 11-15-1999 07:33 PM
That person has a rotovap, and a 2L sep funnel? Why not removing some of the ethanol after the catalyst filtration? This should make the workup and separations much easier. Any special reason why that person uses aq. NH3 for basification? What's wrong with NaOH? |
| KrZ Member |
posted 11-16-1999 12:20 AM
I think if somebody were to reduce the volume of that ethanol at all, on cooling, before extraction, there would be a whole lot of precipitation of polymerized glop. I think they probably just used aq. ammonia because they were at the store and they decided to get a bunch of that rather than keep making NaOH stock solution. Those solvent volumes I posted above won't work, the nitrostyrene is not very soluble at all in EtOH. Alternative solvents? Also the reduction time on the amination might be excessive, perhaps less is necessary. |
| psychokitty Member |
posted 11-16-1999 10:16 PM
Dude, KrZ, you need to stop posting crap that hasn't been tested. I'm not in any position to try some of the stuff you recommend like reduction of 2,5-DM-nitrostyrene into 2-CH, but shit, what if I had? More likely, I'd have ended up with a bunch of crap!!! (Expensive crap at that.) I hope you don't continue to post stuff that's only theory without saying so. . . . please. And, yes, even so, you ARE still the MAN. --PK |
| KrZ Member |
posted 11-17-1999 12:36 AM
heh, sorry. Perhaps SWIM has justr discovered the wonders of this SS vessel and is in the experimental stages? Maybe, I dunno. Anyway. The nitrostyrene info was taken from an article which used the second noted solvent volume. But one can only assume that all would have been well had the reference been followed to the T, that is, filtering the reaction mix through celite to recover catalyst, washing with multiple portions of DCM until the DCM extracts were clear, then basifying with 2L 29% NH3 and re-extracting with DCM, again, until the extractions showed no signs of carrying anything with them (considering it is a clear oil though, lets just guestimate and say 3x250ml). I'll look at the library tommorow and see what I can find. :0 pk -=krz=- |
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