frost (Hive Bee)
10-05-00 15:10
No 57481
      o2 is the shit  Bookmark   

fellow bees,
swinf would like to encourare the benzo loving bees to give the o2 wacker another look, swinf has had a few good o2 runs in the past but some that sucked and contained alot of iso. swinf with help finally has it down ands not looking back.
got a 40lb welding o2 cylinder with a 150psi self adjusting regulator = 170
used a 4ltr heavy walled filter flask this is awesome for adding the o2 with the clamp on hose
prestirred pdcl2 in denatured for 8 hours with a 3in eggbar
added cucl let stir for 1 hour, added olefin, put on rubber stopper strapped it down with plastic pullties, the strong kind, while friend put all his weight on the stopper then wrapped it up thouroughly with hose wrapping tape. 
added o2 up to 50 psi set the regulater, ran at room temp for 9-10 hours with high speed stirring.
the pressure dropped 12 times over this time frame the flask got very warm so obviously the exothermic reaction was doing its groove thing.
recommended ratios 1g pdcl2 to 5g of cucl to 100g olefin to 200ml of solvent. this one was scaled up, keep these ratios the same with the scale up.
ends up looking blackish with strong ketone smell,with no more pdcl2 being reabsorbed into the solution. hit with dh2o/hcl in sep, red ketone falls to the bottom, then wash water level with dcm to get what u missed, buchner through celite add to dcm/ketone, buchner again, looks greenish red now, strong ketone taste if ur brave enough to sample, when distilling little fore run then it comes over at pretty much the same temp, clear with a green tint,
very high yielding reaction, aminated some and boom u know what it did.
additionally,
using 2x solvent to safrole really helps to oxidise it much better with the hardstirring,was using too much before. no h2o was added.
thank you bees that have helped swinf work the bugs out of this. f-man, semetex, etc
frost over and out


 
 
 
 
    PVnRT_NC8
(FMAN)
10-06-00 22:03
No 57901
      Re: o2 is the shit  Bookmark   

??//


A010
 
 
 
 
    FarQ
(Hive Bee)
10-06-00 22:33
No 57918
      Re: o2 is the shit  Bookmark   

He wants to know what I want to know?
That is, what did you learn from him?


Stonium is a bitch, and yes, I love her.
 
 
 
 
    scram
(Hive Bee)
10-08-00 15:35
No 58442
      Re: o2 is the shit  Bookmark   

See man, told you this 02 tank shit is the bomb. For all of you cheap bee's flying with broken wings, you need to break down and put out the measly $70 for a 22cu ft 02 tank and $40 for a new regulator at Home Depot. All OTC, no names, no prescriptions needed for refills.
Frost,
How much actual ketone did you get from this reaction, how much actually aminated? I want to know because I have no glassware and have to guess/assume at my yields before the al/hg. Right now, got 250ml oil running in a reaction. Will let you know results soon.
 
 
 
 
    KrZ
(Hive Bee)
10-08-00 15:56
No 58449
      Post deleted by KrZ  Bookmark   

 
 
 
 
    frost
(Hive Bee)
10-09-00 01:52
No 58560
      Re: o2 is the shit  Bookmark   

KrZ,
did it in a room that the temp was 70f, the glass got very warm, have done it in ice bath but the yields sucked for swinf. how much longer should it go if done in a cooler enviroment, read on the old board the best yield u ever got was in a cold 55f room.so the longer the colder the better. sounds cool to swinf. remember you and os discussing the temp vs o2 absorbtion. love the o2 now, only getting a little whitish forerun before the goodies start flowing over.
thanks for the wisdom,
frostcoolwink
 
 
 
 
    buchiguy
(Stranger)
10-12-00 13:45
No 59537
      Re: o2 is the shit  Bookmark   

I read about this procedure on Rhodium a while ago from Spiceboy. I was wondering if anyone has tried using a paint shaker to get that major agitation that is needed to create oxidation? I was also wondering what would happen if we beefed the pressure up to 100 psi?\

 I also do NOT like the benzo/wacker because it uses a relatively hard to get, highly toxic substance, that creates a huge amount of difficult to dispose of waste. I can only get this stuff shipped by ground and it is kind of expensive, although the palladium is the real killer.
 
 
 
 
    psychokitty
(Stranger)
10-12-00 18:52
No 59631
      Re: o2 is the shit  Bookmark   

The only two times SWIM has tried this reaction with all reactants in the correct proportions was in the "bad-ass" soda-keg.  Both times a yellow oil was obtained that did not aminate and when put through several performic reactions, after dehydration of the intermediate, gave the desired ketone.  So, if one is interested in isoalkene, this is a good way to go.

My theory is that SWIMM's use of CuCl2 in this reaction was having a corrosive effect on the surrounding stainless steel.  KrZ has never reported this problem, so the only conclusion that I can draw is that he has either been lying all this time about the feasibility of this method (not likely) or his kegs are made of a type of stainless steel (possibly 440) that is absolutely resistant to corrosion.

SWIM is going to give this one another shot, but this time is going to coat inner sides of keg with epoxy paint, which is practically invulnerable to all solvents and reagents that it might be exposed to.

Comments?

--PK
 
 
 
 
    KrZ
(Hive Bee)
10-12-00 19:34
No 59654
      Post deleted by KrZ  Bookmark   

 
 
 
 
    Semtex
(Hive Elder/ Old Fart)
10-12-00 19:57
No 59665
      Re: o2 is the shit  Bookmark   

I have to side with the KRZ kid on this one, I was in the thread that he speaks of...


crazycrazy
 
 
 
 
    KrZ
(Hive Bee)
10-12-00 20:07
No 59672
      Post deleted by KrZ  Bookmark   

 
 
 
 
    zooligan
(Hive Addict)
10-13-00 06:51
No 59791
      Re: o2 is the shit  Bookmark   


Not only that, I was the one saying it didn't work, citing journal ref's, and then getting suckered into wasting goodies on it 2 more times by some dildo who said it worked like a charm!



What doesn't work?  O2 in metal, 02 with this set of reactants, or O2 in general?

 
 
 
 
    KrZ
(Hive Bee)
10-13-00 08:36
No 59818
      Post deleted by KrZ  Bookmark   

 
 
 
 
    frost
(Hive Bee)
10-13-00 18:26
No 59953
      Re: o2 is the shit  Bookmark   

glass seems to be the way to go for most unless u can have a ss tank teflon coated the pdcl2 will react with anything else thats metal. as far as solvents meoh, denatured, ipa, even everclear or diesel all work but the best imho is lab grade etoh. ipa works well but for some reason it seems to work better with a little meoh, or etoh mixed in. that will help predissolve the pdcl2. everything but ipa labgrade etoh or everclear makes a blackish post reaction mix color itll be clearer and sometimes green with those. this thing works well especially at low 3atm pressure every time swinm tries to go high 60+ he starts to oxidise the solvent and the glass will get really hot using the 2:1:1:5
solvent to safrole to pdcl2 to cucl2 ratios. but with the lower pressures the ratios work every time with no tar or crap except for catalyst in the work up. the good vs bad ketone that hes seen always go like this if its very pure and strong itll be clear with a golden tint to it. all the bright green stuff that hes seen come from it looked like good benzo stuff does sometimes but it aminates poorly. resulting in crystals that when gassed look big and fluffy but when buchnered out are tiny, strange stuff man! but for swinf the clearish golden stuff always aminates perfectly with nice white xtals in high yield.
oh yeah dont try to pressurize those 4ltr filter flasks much over 45psi he saw one explode the other day at 65 psi thank god for tape! lots.....and lots. and that thing is fucking thick.
the best o2 container swinf can think of would be a pyrex media bottle with a screw on  top and have a glass blower attach a heavy duty vaccum pressure pyrex inlet like on the big f.f.'s for the 300psi welding air hose to clamp on to.

 
 
 
 
    zooligan
(Hive Addict)
10-14-00 10:17
No 60146
      Re: o2 is the shit  Bookmark   

What about PP or PE vessels?  One of those smaller water cooler bottles, perhaps? Or even a 3-litre soda bottle?  Will that material take the reaction?  It works in the SRV/KRV scenario...

z
 
 
 
 
    terbium
(Hive Bee)
10-14-00 10:33
No 60149
      Re: o2 is the shit  Bookmark   

I have gotten some pretty good explosions from reactions with high pressure oxygen. The O2 Wacker seems to be a good route but I wouldn't try to push the envelope with oxygen pressure - stay at no more than 1 to 3 atmospheres of oxygen. Glass vessels are good in a way, if there is an explosion then they will rupture at a relatively low pressure.
 
 
 
 
    frost
(Hive Bee)
10-14-00 11:00
No 60155
      Re: o2 is the shit  Bookmark   

ptfe vvessels or coke bottles will work if u have an orbital shaker but for magnetic stirring which swinf prefers with an eggbar it will wear a hole in it and cause a rupture. o2 is definately a viable route for oxidation. 45psi is enough for an 8-10 hour conversion, if using a glass vessel and highspeed eggbar stirring. also if using stirring make sure the bottom is wide enough so that when using 1:2 safrole to alcohol ratio you can see the bottom of the vessel while the eggbar is stirring this assures that all the mix is being exposed to the o2 for better, faster oxidation. start small like 100ml safrole in a 1ltre
filterflask the best way to cap one is to use a rubber buchner stopper with the small hole it fits flush with the top put a rubber cork in the hole that wont go through it and epoxy it in place wrap it with hose tape clamp on the o2 hose to the vaccum nipple and stir with a 3 inch eggbar for 8 -10 hours this works and works damn well, and you wont make a great big mess like with the benzo nonsense.
its not uncommon to get 85-90g mdp2p out of 100g of starting material and the work up is clean and takes no time
try either one of those with the benzo.
you can make ketone in no time and it will be very aminateable.
hope this helps
frost
 
 
 
 
    Lino
(Newbee)
10-14-00 12:26
No 60176
      Re: o2 is the shit  Bookmark   

Not dreamt the O2, but have been thinking about other pressure rxns and Zooligan's thoughts on PP/PE are valid. The garden sprayer could be the ideal low cost vessel of choice. It has a built in safety valve that blows @ 45psi, (could be tweeked higher maybe). The screw on top of the sprayers widely available where I live are easily modified to make a gas tight seal. Use a silicon bung (like the rubber ones from chem. suppliers) you fit it from the bottom of the screw on top so pressure helps the seal. Gas can be added via the threaded outlet for sprayer tube, or drill the silcone bung to accept a threaded adaptor for your T piece. The self tapping properties of the silicone bung should be adequate. The thickness of these garden sprayers should be safe at these pressures. Mag stirring is poss. if you somehow make the bottom of the spayer concave or flat. Maybe a resin soln dribbled in while rotating sprayer on a turntable to produce slight centrifugal force??? Whaddya think?
 
 
 
 
    FarQ
(Hive Bee)
10-14-00 12:39
No 60180
      Re: o2 is the shit  Bookmark   

I think the coke bottle with a tyre valve is the easiest safest way, there was talk on the old board of these things being capable of 100psi. So you would be relatively safe at 60psi. But one needs to be able to rig up something for serious agitation. I imagine getting a paint shaker would be difficult and expensive, but if you are good at making things, it shouldn't be that hard to rig up a small motor spinning an eccentic shaft for agitation.
Or you can always shake by hand, it has been done, but not by this bee, I wouldn't even attempt it. But making a shaker sounds like fun.

What size rxn would be possible in a 3L vessel (by safrole amount)?
 
 
 
 
    frost
(Hive Bee)
10-14-00 16:05
No 60216
      Re: o2 is the shit  Bookmark   

old frost has something that could possibly make the bees smile and flap their wings. the best of both worlds= one of the two harware store supersites has a galvanized steel tank that holds 2 gallons, and is epoxy coated thick epoxy called endurall tm. says its coated to with stand most chemicals and substances under pressure. its called the commando this made swinf think of all the cladestine acts he could accomplish with one of those. so you know he bought 2. btw clamped an o2 hose on 1's hose outlet and it holds 80psi easy!
 
 
 
 
    FarQ
(Hive Bee)
10-14-00 18:58
No 60241
      Re: o2 is the shit  Bookmark   

What is this vessel you speak of?
What is it's original purpose?
Please elaborate.
 
 
 
 
    frost
(Hive Bee)
10-14-00 19:17
No 60246
      Re: o2 is the shit  Bookmark   

it is a sprayer for chemicals it has a pump handle its black its made by hudson who made a teflon coated sprayer of this kind a year back which was pimp for o2 work also until the teflon coating wore off. its called the commando sprayer its withe the other sprayers at l***s swinf likes this one even better because of its endurall nonreactive epoxy inner liner only modifications it needs are clipping the inner tube and clamping an air hose on its outlet. it has a good enough seal to hold 80psi swim tested this for 6 hours soo far rock solid. it looks like it could bee the concorde of ghetto reactors!
when he gets through with his new high speed hotplate and robinater vaccum distilling imaginary ketone hes gonna give it a go.
btw the bottom is very flat and about 10 inches across good stir action!
 
 
 
 
    chinacat
(Stranger)
10-15-00 11:19
No 60371
      Re: o2 is the shit  Bookmark   

As to the glass qstn./debate....mason jars..you can get them in many diferent sizes..they're cheap, and of course, made to withstand enormous pressures. Also come with hany-dandy metal vacume seals..somethign to think about I guess..I have always belonged to the Mason jar/snapple jar labware contingent myself,,,much easier to explain to nosy roomates..ect..
   But,,Frost..I'm intrigued, the Commando Sprayer??/.the Hell you say!...how much did it cost? Sounds very cool.
 
 
 
 
    frost
(Hive Bee)
10-15-00 14:42
No 60403
      Re: o2 is the shit  Bookmark   

28.50 + tax
 
 
 
 
    scram
(Hive Bee)
10-15-00 14:49
No 60406
      Re: o2 is the shit  Bookmark   

oK bro, I get jealous when my ideas get improved (I believe I'm the first to try to garden sprayers here). You gotta let me in on this since the garden sprayer I was using in March can not be found in my town anymore as it went to 90 psi and I'm sick of explosions with others at a mere 65psi. If you got a sprayer that is lined like you mention and the epoxy doesn't crack given the abnormally high pressures we are putting in these things then you have hit the bulls-eye with the whole problem KRZ has been talking about with using the wacker in SS (standard pump pressure is meant for ~20-40psi by the manufacturersi). This would be a revelation. You could do big ass oxidations in a 2gallon deal and with a flat bottom it could be kept to stay upright without have to use hook straps to contain it to the stir-plate. Cum-on guy, spill the beans (pun intended). If you can email me at jerryspringer@hushmail.com
 
 
 
 
    scram
(Hive Bee)
10-15-00 14:54
No 60407
      Re: o2 is the shit  Bookmark   

BTW, I have used a paint shaker and it worked very well in a 3 liter bottle. The only problem is that a paint shaker, despite weighing some 75+ lbs still tends to move around a concrete floor by itself given its jolting action. It also has to be reset every 15 minutes as this is the maximum timer limit. You can do 2 at once. It creates one hell of a soapy looking mix while in action. I broke the damn thing thoug. Fucking knob got stuck and it stayed on and the only way to turn it off was to unplug it. A real hassle and very noisy overall.
 
 
 
 
    FarQ
(Hive Bee)
10-15-00 15:12
No 60408
      Re: o2 is the shit  Bookmark   

Just bolt it to the concrete, very easy with masonry drill and a few ramset bolts. ANd its not permanent, just put in place and tighten down, remove when finished. If its not your house remove bolts as you leave. The timer should be taken out of the circuit and just controlled with a switch, also easily undertaken. But yes I imagine it would be quite loud in any normal living environment.


"ML"
 
 
 
 
    scram
(Hive Bee)
10-15-00 15:22
No 60410
      Re: o2 is the shit  Bookmark   

Excellent find frost. Will check this out. Let us know if its successful
http://www.hdhudson.com/catalog.html#Comandoģ
 
 
 
 
    FarQ
(Hive Bee)
10-15-00 15:37
No 60412
      Re: o2 is the shit  Bookmark   

That looks awesome, you will have to let us know how that goes, SWIM might get one sent over if they can't be found here.


"ML"
 
 
 
 
    scram
(Hive Bee)
10-15-00 17:06
No 60422
      Re: o2 is the shit  Bookmark   

I just came back from the hardware store and took a look at this model. Frost if you look closely with a light you'll see the the epoxy coating tends to diminish just 2 inches from the top of the sprayer. It seems that additional epoxy (also avail at the same hardware store) would be needed to cover the upper inside lid area if the unit was laying on its side. Otherwise it looks good if your doing the oxidation with the unit standing upright. In fact the bottom is slightly bevelled with the apex of the bevel just reaching right at ground level. 3 boxes were opened and looked at, one of which you could see the run marks where the epoxy ran down the sides to the bottom and hardened. They had a display model that was up and when I took out the pump to that one it seemed as if it was a returned model that had be chemically abused inside. The epoxy was completely corroded off. I hope this doesn't happen for our useful purposes. If that epoxy is not strong enough there are several epoxy and "Appliance finishing" epoxies available at the same place. There must also be a way of somehow rigging a spray wand to allow the can to spray evenly inside the container without having to make it difficult. Man, let us know what that finish looks like once you wack the bitch!
 
 
 
 
    frost
(Hive Bee)
10-15-00 18:34
No 60452
      Re: o2 is the shit  Bookmark   

frost was g'd out and had a very groovy dream, it was about this new find of his.he first clipped the tube in the pump with some angled blade steel cutters. then he clamped on a 3/4 inch welding hose. so it would work upright.then into the vessel went 150ml labgrade etoh, 1gpdcl2 goodstuff! prestirred for 2 hours then added 5gcucl dihydrate, 100ml fractionally distilled starting material premixed with 100ml meoh and 5 ml dh20, mixed for an hour sealed up and added 40 psi set regulater and let it run for 12 hours because of the lesser pressure (usually 45-60 psi) in a 70c room. with highspeed stirring and a 3in eggbar it stirred well.
the mix was extracted had a blackish green color and spelled spicy/sweet put in a 2liter sep and added 1ltr dh20 with 50ml hcl 37% the black oil fell out and was collected.
85ml of it swimfs dream was so real! so he tasted the stuff! it was the stuff he buchnered this 3x through celite, then mixed with 300ml tolene, that he had washed the aquous level with 150ml/2x then buchnered 2x
he noticed no tar in the workup and it was a nice reddsish color with a green yellow tint, he decided to skip any washes since it was a small amnt and already looked good.
this was fractionally distilled and after collecting the tolene 25ml peanut oil was added, and vaccum was attached.
approx 2ml forerun was collected and thrown out. then at 125c(strong vac) it began to flow and it was soo beautiful (you know how dreams can be) almost clear with a golden tint,
definately the stuff!
92 ml total!
too bad this was only a dream, noone can make mdp2p that otc! and the o2 dosent work without dmf and a shaker! this must bee true since only a few bees on the new board have done it, they must all be lying myself included! but i dident lie my dream was like that.
frost over and out!
 
 
 
 
    FarQ
(Hive Bee)
10-15-00 19:05
No 60459
      Re: o2 is the shit  Bookmark   

If it needs to be re-epoxied then that sort of defeats the purpose, as one could just epoxy a better steel vessel that would be much safer and more practical for other applications as well.
The real test for this will be after several runs to see how the coating stands up.
The way frost does things I am sure we will have an answer within a couple of weeks.

Frost,
With that size base on the vessel. How big do you think you could scale up before stirring became in-effectual?


"ML"
 
 
 
 
    frost
(Hive Bee)
10-15-00 19:22
No 60463
      Re: o2 is the shit  Bookmark   

i believe it depends on the stirring power of the hotplate some are srtonger than others with a strong one and removing the pump piece 1kg could be achieved with 4inch eggbar. and 1:2 safrole to solvent ratio with 60-80psi it could bee done! the coating held up in the dream but after many maybe just buy another?
frostsmile
 
 
 
 
    Osmium
(Stonium's / Changer)
10-16-00 04:13
No 60552
      Re: o2 is the shit  Bookmark   

1. Prestir the PdCl2 and CuCl2 together for a few hours.
2. No additional water needed in this reaction.
3. The poly versions (I guess the tank is made from PP)  are probably much cheaper and should work just as well.
4. It only works good for small batches, O2 absorption is too slow when you fill it to the top with the reactands.
 
 
 
 
    KrZ
(Hive Bee)
10-16-00 09:25
No 60593
      Post deleted by KrZ  Bookmark   

 
 
 
 
    Fuchem
(Hive Addict)
10-16-00 13:12
No 60624
      Re: o2 is the shit  Bookmark   

Take a sodakeg to an industrial finish house. Tell them you are working with high temp corrosives. Ask them about vitrified coatings (duraglas, quartzite, etc) it's not cheap, but not too expensive either. Tell them you are a chemical engineering student working on your masters project and you would appreciate any discounts they would provide or even offer to assist doing the shit work/prep work.


"To be the sum of all parts, in one place, at one time" - Andrew Graybeal
 
 
 
 
    scram
(Hive Bee)
10-16-00 14:03
No 60636
      Re: o2 is the shit  Bookmark   

You nigga's are so Kool when I'm high!  This is going to be a kickass devise. KRZ, how much water do you think needs there to be per 100g oil? If your getting 80% yields, thats amazing. I'm only getting about 35% based on weight/weight but I can't say for sure that's correct since this is a very impure nondistilled product going into the al/hg which could be accounting for much lower yields due to impurity and a false impression of actual ketone content.
 
 
 
 
    Osmium
(Stonium's / Changer)
10-16-00 14:20
No 60642
      Re: o2 is the shit  Bookmark   

KrZ, read that 1969 ref again in case you still don't know it inside out wink. It clearly says that reducing the water content speeds up the reaction. Exactly my observation too.

If water was necessary for the reaction it would be necessary in molar amounts. Adding 5ml of H2O to a 100ml safrole reaction isn't even 0.5 mole. Maybe you can tell us why water is needed in the reaction at all. Everybody knows that the product of the MeOH Wacker is the ketal, which is hydrolysed in a few seconds, maybe minutes afterwards as soon as you quench the reaction with acidic water. If only a half a mole of water is present per mole of alkene you end up with some ketal or semiketal anyway, meaning you have to hydrolyse the rest during the workup. Now please show us where in your opinion during the Wacker reaction sequence water is needed. I don't know who came up with that BS idea that water is needed here. I did it without, all reagents of the highest grades available to me back when I did that experimentation, and guess what, it worked. With way less than 0.1mole of H2O/mole alkene.
But of course I live in Europe, the place where amine hydrochlorides are acidic (contrary to the meth board parallel universe, where amine hydrochlorides are neutral....). Maybe that explains it all. wink
 
 
 
 
    Fuchem
(Hive Addict)
10-16-00 15:10
No 60656
      Re: o2 is the shit  Bookmark   

http://www.blome.com/ds220.htm
http://www.tycon.com/
http://www.indobase.com/web/aquadra.htm
http://business.vsnl.com/aquadra/products.htm This lists the Fo-Poxy formulations.
http://business.vsnl.com/aquadra/coldweld.htm More Fo-Poxy info.
Perhaps ceramic glaze could bee used. Pour it into container, slosh it about, pour out, toss into the oven. I don't know if a home oven is capable of the heat required. If not, bring it down to an industrial heat treating company and see if they will fire it for you. I've had a HT shop heat all manner of weird stuff for me. I've never had to pay. Just told them I'm a mad scientist and working on my mad scientists degree. Smaller stuff they throw in with one of their batches if it's the right temp, others they do a special run for me. The guys get a kick when they see me coming wondering what the hell I'm up to now. One of them calls me "the nutty professor".
Fuchem


"To be the sum of all parts, in one place, at one time" - Andrew Graybeal
 
 
 
 
    frost
(Hive Bee)
10-16-00 16:29
No 60684
      Re: o2 is the shit  Bookmark   

osmium,
swinfs new to the organic chemistry thing, but he's learning at a fast rate, he's always added 5ml/100ml to the o2s if using something otc like heet won't there be a few mls of h2o present anyway? the reason he asks is when doing a nitro amination there has to be some h20 present to form the amine so isnt it coming from the meoh.laugh also dident spiceboy from what he had learned from you use 5ml in his experiments or did he just add that on his own? i hear thar stirring won't work from your debate with KrZ on the oldboard, but spiceboy reported good results with the eggbar as well as KrZ. i'm assuming its  working because of the eggbar and the large flat area and only 200ml alcohol to 100ml safrole will force the o2 into the mix. if totally anhydrous conditions are used how fast would conversion occur at 45psi? this will bee tried next.also what causes the yellow oil phenomenon? the stuff that looks like ketone but will freeze, i used to get it alot at first. thought it was iso nut it would aminate(low yields) is it some kinda iso/ketal azeotrope it would come over at the same temp as ketone. this happened when using air and orbital shaker. and has happened only once with o2 and stirring.

thanks for the wisdom,
frost
 
 
 
 
    KrZ
(Hive Bee)
10-16-00 16:50
No 60689
      Post deleted by KrZ  Bookmark   

 
 
 
 
    frost
(Hive Bee)
10-16-00 18:23
No 60713
      Re: o2 is the shit  Bookmark   

Nuff said!
frost
 
 
 
 
    frost
(Hive Bee)
10-16-00 18:29
No 60717
      Re: o2 is the shit  Bookmark   

KrZ,
do you have a link to that 1969 journal ref handy for swinfs notes?
thanx
frost
 
 
 
 
    Semtex
(Hive Elder/ Old Fart)
10-16-00 21:34
No 60763
      Re: o2 is the shit  Bookmark   

"Oh my GOD, it's full of stars..."

All I can say is THANK YOU!!!

KRZ for Prez!!!



crazycrazy
 
 
 
 
    frost
(Hive Bee)
10-16-00 21:57
No 60766
      Re: o2 is the shit  Bookmark   

sidenote:
isoheet is 99%ipa according to the manufacturer!
wonder where this could be used? shocked
 
 
 
 
    Osmium
(Stonium's / Changer)
10-17-00 02:56
No 60834
      Re: o2 is the shit  Bookmark   

KrZ, you said:
> Here is the wacker mechanism;
>   R-CH=CH2 + PdCl2 + H2O -----> C(=O)-CH3 + Pd + 2(H+) + 2(Cl-)
>   Pd + 2 Cu(2+) + 6 Cl- ------> PdCl2 + 2 (CuCl2)-

This is the mechanism for the real original Wacker procedure, where lower alkenes are oxidised in an all AQUEOUS solution. This reaction is much slower that the one in alcohol.
When the solvent is an alcohol and no water is present something else takes place:

R"-CH=CH2 + PdCl2 + R'-OH -------> R"-C(-OR')2-CH3 + Pd + 2(H+) + 2(Cl-)

The product for anhydrous conditions is R-C(-OR')2-CH3, the so called ketal. Semiketal would be R"-C(-OR')(OH)-CH3, a side product when sub-stoichometrical amounts of water are present.

Note the following similarity:
H---O---H
R'---O---H
Meaning the reaction doesn't mind if it is done in H2O or ROH solvent, it just happens that the latter is much faster. In that 1969 ref they clearly found that increasing amounts of water slow down the reaction considerably.

So, the product of an all-ROH-no-H2O Wacker will be R2-C(O-R')2-CH3. This is quickly hydrolysed in acidic aqueous media. Since the Wacker mix is slightly acidic adding water alone would already work, but everybody uses diluted HCl for that step anyway so the hydrolysis to the ketone is very fast, forming two moles of the alcohol and one mole of the ketone.

I'm not doubting your results, but in my experience no water is needed in that reaction. It worked well without for me. The catalysts recycled well in the alcohol solvent, or with that little water that was preent due to CuCl2.2H2O usage.

The DMF wacker needs water because the DMF can't add across the double bond like water or alcohols can. Haven't thought about it yet but I think that benzoquinone reduction needs some water too, since DMF is dipolar-APROTIC. Besides nobody has posted a DMF Wacker with reduced water yet. Everybody just used the literature numbers for H2O/DMF 1/7 or whatever they are, nobody tried to reduce the water to the bare minimum yet. It might run much faster with reduced water content, or slow water addition during the reaction.

And at least in my corner of the world the tech grade MeOH and IPA I bought were close to reagent grade purity, but I used barreled stuff from a chem supplier (still cheapest grade available) not some OTC source. But I still doubt that they contain 1% water. Purity statements on the label are usually guaranteed minimum purities, don't take them too literally thinking when it says it's 99% the it must be exactly 99% pure. That purity also depends on how it was determined, GC for example can't detect H2O. When I buy tech grade MeOH there will be EtOH in it, along with formaldehyde, acetone, other alcohols etc, making up that missing 1%.
 
 
 
 
    Antibody2
(Hive Bee)
10-17-00 08:34
No 60873
      Re: o2 is the shit  Bookmark   

Now weíre talking bees! Awesome thread.

Would the ketal or semiketal have a boiling point similar to ketone? If it did would it be possible that ketal could be mistaken for ketone when distilling?

Could this account for poor amination yields from seemingly good ketone?



Jimi loves ya
 
 
 
 
    frost
(Hive Bee / Eraser)
10-17-00 09:42
No 60885
      Re: o2 is the shit  Bookmark   

the ketal will turn into ketone when the ketamine injects.....woah. when it hits the dh20/hcl solution ikt will hydrolyse into ketone within minutes. damn did somebody,
antibody see that K TRAIN that just ran over mee.
anyway, ab2 ketal is the post wacker ketone before the hcl addition. then and only then will the KETONE appear.
digging deeper and deeper into that hole........
guess who's off today!tongue
 
 
 
 
    Antibody2
(Hive Bee)
10-17-00 11:48
No 60909
      Re: o2 is the shit  Bookmark   

Yeah, know that already, doesnít answer either of my questions though.


Jimi loves ya
 
 
 
 
    scram
(Hive Bee)
10-17-00 13:52
No 60953
      Re: o2 is the shit  Bookmark   

Yeah FIGHT, FIGHT! This is a interesting reaction. I've notice better yields with pressure either at 40-50psi or 75+. For some reason yields were always less between 50 to 75 psi. Frost that water in the al/hg comes from the nitro reaction because it produces water by itself.
 
 
 
 
    KrZ
(Hive Bee)
10-17-00 15:01
No 60968
      Post deleted by KrZ  Bookmark   

 
 
 
 
    Precursor2112
(Newbee / Eraser)
10-17-00 15:57
No 60986
      Re: o2 is the shit  Bookmark   



The Vacuum filtration of this reaction gives me reason to pause....

Could I throw a couple hundred ml's of DCM on it and just gravity filter?



(By the WAY I've been looking for the WACKER aliens to abduct me and cart me away from BENZO land.)

Benzo sucks.
 
 
 
 
    Osmium
(Stonium's / Changer)
10-17-00 16:07
No 60989
      Re: o2 is the shit  Bookmark   

Define "most effective": fastest, cleanest or highest yielding? Or most cost-efficient? Or anything else?
What kind of alkenes did he use? What chain lenght?
I'm not familiar with that ref, BTW.

When doing a chemical reaction which is unwilling to proceed you usually have two options: you can either push it from the left side of the equation (for example by using an excess of one reactand) or you can pull it from the right side (e.g. by removing one of the products by distillation or extraction or chemical means). That's what that guy obviously did, extracting the alkene into the water layer and removing the product ketone after the reaction back into the organic layer where it will stay unchanged for the rest of the reaction. So he kept the alkene concentration pretty much constant in the water layer throughout the reaction (concentration is determined by solubility of the Pd--alkene complex), and drove the reaction to the right by completely removing the product from any further attack into the organic layer since it is pretty much insoluble in the water layer and won't form soluble complexes anymore.
By using a biphasic system he still performed the reaction in the water phase, and used the organic phase as a reservoir for the reactand and the products. Of course that way the organic phase doesn't contribute to the reaction. The catalysts love water way better than the organic layer, so that's where they will be (I guess). And how did he achieve phase separation with the lower alcohols?
Did that guy use some sort of PTC in that reaction too? If he did then things really get complicated, because there are many different reaction modes possible depending on a shitloads of factors and any comparison to our topic here becomes pure speculation.

Ketals are pretty efficient protective groups, but I don't know for sure just how good they are under oxidative conditions like the wacker.

That 1969 ref clearly says that the lower alcohols were the fastest solvents, with the highest reaction rates found.
One of the original Wacker refs by Jira et. al. from the fifties even contains an example where they used safrole in the aqueous Wacker, yields were definitely worse than the ones you describe for the alcoholic Wacker.
 
 
 
 
    dunkel
(Stranger)
10-17-00 16:23
No 60998
      Re: o2 is the shit  Bookmark   

Osmium, when you did the Wacker in the old days using MeOH as solvent, didn't you add some acidic water after the reaction was completed, then distill off the MeOH or EtOH? I think this added heat and time is necessary for effective conversion of the ketal to the ketone. In the US patent 4638094 for making phenylacetones when they perform the reaction in anhydrous conditions, at the end they add water and heat to convert the ketal to the ketone. Otherwise they add water to the reaction in the begining to end up with just ketone at the end without having to heat.

I'm not sure if just adding water at the end and immediately extracting (which most people are doing) will spontaneously convert the ketal into the ketone. The water that is already present during the course of the wacker reaction will convert some of the ketal into the 'tone. While the majority (if NO water is added) will be in the form of the ketal.

As far as quickness, since you are using alcohol as solvent and nucleophile, -0R addition (aka ketal formation), will be the fastest compared to the water.

Just my $0.02. Only one way to find out...
 
 
 
 
    Antibody2
(Hive Bee)
10-18-00 06:35
No 61118
      Re: o2 is the shit  Bookmark   

Precurser2112. Vac filtering this rxn sux. But is greatly facilitated by the use of 2cm of silica sand in buchner funnel. Usually put 1cm of 20mesh and 1cm of 50mesh on top. If the filtration slows down. Stir the sand up a little. Also works well on other wackers with more demaning work-up.

Antibody has also wondered whether the ketal --> ketone is in fact spontaneous.  If it werenít that would certainly account for some mediocre aminations with O2 wacker ketone.


Jimi loves ya
 
 
 
 
    Osmium
(Stonium's / Changer)
10-18-00 07:25
No 61130
      Re: o2 is the shit  Bookmark   

Yes, I worked up the post-Wacker reaction by adding a few drops of HCl and a little water and removing the bulk of the MeOH on the rotovap until a phase separation was visible (mixture became milky). Then more water was added and the ketone extracted with ether, followed by shaking the extract with conc. bisulfite solution.
MeOH removal was done under vacuum, so the temp wasn't that high (~40įC). Flooding with water and a little bit HCl should work just the same, as far as I know these ketals are easily hydrolysed.
But I agree, that is a very good point. The ketal is pretty stable in basic pH and will not aminate.
 
 
 
 
    KrZ
(Hive Bee)
10-18-00 07:57
No 61136
      Post deleted by KrZ  Bookmark   

 
 
 
 
    frost
(Hive Bee / Eraser)
10-18-00 14:26
No 61198
      Re: o2 is the shit  Bookmark   

isnt that kind of like the ts11
100g safrole
150cc tol
100cc h2o2 30%
"              " added at 6 hours
"               " 12 hours
"                " 18 hours
2.5cc gaa
1g pd (aco)2
60c
dual phase reaction that takes 24 hours and yields 80%
dosent h202 degrade over time so wouldent more be needed if time was increased?
if temp is decreased reaction time is inmcreased, so  wouldent adding more catylyst be a good idea even in the o2 if running colder 55f push it in the right direction and prevent side resctions like isosafrole?
wouldent 500ml tert butyl alcohol be better than tol, and just omit the a.a. add all the h2o2 (400mls)over 30 mins to 200g safrole and 1g pd(aco)2 at 78-80c maintained over 6 hours ending up with a ph of 2  and ketone not ketal?
seperate with equal vol of water then extract with dcm.
this reaction is highly selective so no iso would be produced  i'm assuming according to refs on it.
frost
 
 
 
 
    psychokitty
(Stranger)
10-18-00 21:10
No 61324
      Re: o2 is the shit  Bookmark   

KrZ, please refer me to the appropriate thread.  I hope you didn't delete all of your posts.

Now, the only gripe that I have is with the inconsistency of your reports regarding this method.  If the stainless steel interior of the "soda-keg" does indeed react with the PdCl2 and CuCl2 in solution (as it did on my FIRST and SECOND try to yield a high content of 2-alkene) how were you able to process the amounts of ketone (how much, I won't say) that you claimed you did (via e-mail and such) over a period of over 3-4 months? 

All that time, before the advent of the new Hive, you were reporting high conversion factors, accidental hose ruptures  -- the O2 heating up and the hose going BOOM!, remember? -- so when exactly did this stainless steel problem arise exactly?

I'm not pointing fingers.  Just would like an explanation, that's all.

--PK
 
 
 
 
    KrZ
(Hive Bee)
10-18-00 21:40
No 61335
      Post deleted by KrZ  Bookmark   

 
 
 
 
    frost
(Hive Bee / Eraser)
10-18-00 22:46
No 61357
      Re: o2 is the shit  Bookmark   

As i read it the good yields you were getting were with the rossi g-reactor tm at 80psi and the only prob was only 1 kg could be processed at a time. Probs were with the ss. in the all o2 probs solved thread was where the carboy idea came up there were pics and everything.on that same you were suggesting the use of ipa at a cool temp in glass with less psi. and os was saying that ipa wasent a good idea since everyone was getting such good results with meoh, and the discussion went on to arguing about the temp thing with os,then pressure, and then about a page of flaming.
good thread though alot of momental o2 breakthrus came for the o2 with that thread.blush
still peddaling
laugh
 
 
 
 
    frost
(Hive Bee / Eraser)
10-19-00 01:13
No 61400
      Re: o2 is the shit  Bookmark   

o2 was done again on a small scale 100ml 99% ipa 50gm safrole 1/2pgcl2 2 1/2g cucl2 1n 1 liter filter flask.
pd, cucl ipa prestirred for 4 hours done in cool water bath 55-60f temp was monitered carefully. alkene was added, along with 2ml dh2o, had the old 12/12 highspeed plate back in action so stirring was faster this time. 2 hours 10 minutes later stirring was stopped when pdcl2 quit going back into solution. mix wasent black this time but reddish green much clearer and less viscous than before. work up was same except added hcl directly to mix first and stirred for 5 min, then h20 was added stirred then added to sep funnel extracted as usual. distilled an got 47g ketone which was aminated with nitro,via balchemist method(thanks pal) gassed with hcl yielding 45g xtals.
swinf was very impressed. only a 5 g loss from start up! the whole thing only took 16 hours!
damn this place rocks
time for the scale up! gonna have to break out the pyrex 10L media bottle for that one though. just came back from the glassblower with the heavy duty air inlet now.
stirplate helped alot imho with the speed of this reaction the thermolyne cimatec wasent fast enough!
side note just as krz said there was no exothermic reaction with the ipa.
frost out!  smile
 
 
 
 
    Osmium
(Stonium's / Changer)
10-19-00 02:38
No 61431
      Re: o2 is the shit  Bookmark   

Wow frost! Good post! Only two hours of reaction time?!
Bee careful with that big bottle! They don't like pressure like the small ones do. Better pressure-test it in a safe location first! I'd rather buy a second stirrer and work with two batches, having them running all the time you are in the lab. 16h/2:10h= ~7 runs. 7*45g*2=~650g ketone per day. Make the reactions 30% bigger and you end up with close to a kilogram. What more do you want?

All I said back then was that MeOH is a better solvent than IPA accoring to the refs. But it seems like IPA works just as well if not better. Very cool.
 
 
 
 
    Semtex
(Hive Elder/ Old Fart)
10-19-00 05:40
No 61453
      Re: o2 is the shit  Bookmark   

So frost, your maxing out your stirplates then?  At the highest setting(s)?  What is the RPM difference between the two(if there is one) or do you mean the magnet is stronger in one...?  Nice post, any MORE luck with that epoxy coated bastage yet...? crazy


crazycrazy
 
 
 
 
    KrZ
(Hive Bee)
10-19-00 07:48
No 61464
      Post deleted by KrZ  Bookmark   

 
 
 
 
    sassy_sucker
(Hive Bee)
10-19-00 08:05
No 61467
      Re: o2 is the shit  Bookmark   

Frost: What happened to the commando idea?  Did you find a problem with it?  If so, what?  What made you decide to use the filter flask?

 -SS


how would you fuck me?
 
 
 
 
    DiethylEtherMan
(Stranger)
10-22-00 11:35
No 62431
      Re: o2 is the shit  Bookmark   

Hey guys. I know I am a newbee and shouldn't even be close to this thread, but I have to ask a few questions (and yes, I have done my research, but am still a little confused). I have been reading much from Strike's book TS II and I am interested in making MD-P2P from safrole via O2, Palladium Chloride and Cuprous Chloride.

1) Has Dimethylformamide been deleted from the process altogether? In it's place can we use IPA or MeOH now?

2) In Strike's book 26.5 g Palladium Chloride was used for 500 g safrole...has this amount been lessened to 2g per 200 g safrole?

3) Is it possible to use Palladium Acetate in an O2 Wacker? (but not the H202 and tert butyl alcohol method mention in TS II)

Thanx guys, in advance! Please, no flamming had enough of that shit. I have really spent like 6 months reading books on this, and have just recently begun my own experiences. So it's not like I am just some young punk trying to bug the shit out of all of you experienced people before I try and find the answers myself. So, plese bear with me. (I have posted these questions on the newbee forum a bit back, but no one seemed to answer them, so this is a repost, sort of) Thanx in advance. And I would like to say that Strike's book TS II is an incredible book. Without it I may have been lost for longer than I was. Here's to Strike, for an extremely informative and step by step book.

If ya wanna see the rainbow, ya got to be prepared to put up with the rain!
 
 
 
 
    FarQ
(Hive Bee)
10-22-00 11:56
No 62435
      Re: o2 is the shit  Bookmark   

All your answers are here, read and thou shall find.


ML<--Meth Loser
 
 
 
 
    LaBTop
(Daddy)
10-22-00 18:46
No 62523
      Re: o2 is the shit  Bookmark   

Let's try all to come up with ideas to scale this beautiful MF up, it would by far be a better method then the performic.
The only reason to choose for the performic is it's infinitely upscalable nature. But you are left with a LOT of waste. And this one has a far better yield, and nearly no waste.

Frost, I will try to write your researchings up for the masses, and put it up high there where it belongs in the "Detailed Methods for Non-Chemists", combined with all the neat stuff provided by KrZ, Osmium and Baalchemist.
Exellent thread, to say the least! Good old Hive feeling comming back again. LT/

PS1: anyone ever tried ultrasound transducers in this method? Eventually combined with slow stirring and a commercially available high pressure seal, or just the big-ass egg stirrbar. Ultrasound accelerated Brownian motion in the reactionmix will provide for optimal agitation, let's hope.

PS2: glasslined SS reactors, second hand, lay around all over the world, in any amount and size.
I saw a beautifull full Pyrex-glass roundbottom 150 liter high pressure device (~5cm diam. wall), with 1 Hp magnetic stirrer motor on top of the lid and a magnetic stirrer plate under the lid with a shaft+mixer attached (so no leaking possible), hung up in a cradle for easy decanting.
It was rated for 5 atm ! Used, but looked brandnew, prize: $ 1500 !


WISDOMwillWIN
 
 
 
 
    DiethylEtherMan
(Stranger)
10-23-00 00:53
No 62586
      Re: o2 is the shit  Bookmark   

Hey, guys...I know I am a newbee and I am just barley following you guys by the skin of my teeth, but I think I found a really cool sight (in the future for me) with plenty of glass linned SS vessels from 1L to 600L. As well as all the pressure flanges & stirrers that you guys may need. I hope this helps people. Have fun and good luck. Thanx for all the very informative posts.

You can't steal second base and keep one foot on first.

When a man succeeds, he does it spite of everybody, and not with the assistance of everybody. <-- Edgar Watson Howe

http://www.qvf.co.uk
 
 
 
 
    Antibody2
(Hive Bee)
10-23-00 12:32
No 62676
      Frost is shit  Bookmark   

Older bees - antibody is not doubting the viability of the O2 wacker, but is antibody really the only bee in this hive to smell some BS in this thread?

The really sad thing aboput it is Antibody imagines that a whole herd of newbees are right now running off to try and duplicate the horseshit that frost claimed to have done. Antibody is not talking through his hat here either, he triied a very controleed reaction almost exactly as frost described, it ran for 3.25 hours . It yielded 20% ketone 70% safrole the other 10% was lost through polymerization during distillation and in the 24inchs of glass (column and condenser).

Antibody knew better before he even started, but could not tolerate having to listen to crock of shit the FROST is spreading all over the hive. So it was rerun overthe weekend  and yields were NO WHERE near what frost claims. If anybee is interested antibody kept excrutiating notes of this one for just such an eventuality.

Anyone remember frost claiming 90% on another O2 wacker, or his claim to 90% mda  (not mdma) yield from NaBH4 (NO ONE HAS PULLED THAT OFF YET!), or his claims of outrageous yeilds of pseudonitrosites and in his description he was claiming to be using Sodium Nitrate in a synth calling for sodium NITRITE! Antibody has received numerous dumb assed questions via PM that give ly to his ignorance. he even claimed that DCM would work in the 2phase pseudonitrosite synth, and it is the BOTTOM LAYER.

In fact all Frost is is a fucking parrot, agood number of his posts is plagerized from somewhere else in the hive.

DEA must bee busting thier guts laughing as all the old respected bees of this this hive lend thier credibilty to this little bullshit artist and not even a very good one. Search through some of his posts, it is apparent to anyone with the capacity to reason. LabTop you donít really fall for this do you? Os? KrZ? Semtex n Sunlight? Antibody was under the impression you guys had it togather. This is a sorry day for the hive.

Love the refs you guys put up here and alot of the discussion is valid. But christ jesus , be careful what you beleive. Bad eneough some bees posting nonsense without the hive elders validating it.

Has anyone else been able to duplicate Frostís miracle? Think there is more dupe involved here than miracle. Antibody has $200 for anyone who can prove that he has.

Sorry to rain on this parade but antibody cannot go another day without screaming out FROST IS FULL OF SHIT!mad


Jimi loves ya
 
 
 
 
    buchiguy
(Newbee)
10-23-00 17:26
No 62749
      Re: Frost is shit  Bookmark   

Hey man! Think your being a little hard on this guy! He's not the first Bee to claim good results with this wacker you know! This idea was brought to my attention quite a while ago with the so called "Spiceboy Reaction Vessel" and he claimed over 50% yields with just manual shaking and compressed air. It seems logical that pure O2 and automated shaking would provide much better results. Frost is not the first guy to use this idea and claim it is viable buddy, so just because YOU didn't get decent results doesn't mean that it doesn't work, only that YOU must have fucked something up! So why don't you try to be part of the solution and not the problem?

I don't think the DEA is laughing too hard at this one, far from it, as if this method can be perfected it presents a major achievement in MDP2P production and will be much more difficult to trace chems as these are almost entirely OTC.

So why don't you just publish your results from an objective point of view, not slamming something until you are absolutely certain it is wrong.
 
 
 
 
    buchiguy
(Newbee)
10-23-00 17:28
No 62750
      Re: o2 is the shit  Bookmark   

I've been told by numerous experts that the H2O2 wacker does not work at all so I wouldn't waste any time with that Frost. It sounded like an excellent method but no one has been able to get it to work.

IMPORTANT QUESTION! Earlier in the thread we were talking about pressurizing pesticide sprayers, as they are almost entirely plastic, but I have not heard any success stories. This is the method SWIM will soon try but would like to know if people had any difficulties before SWIM goes ahead, as SWIM may just opt to get a soda keg teflon lined if this is the only way to go, as SWIM thinks glass vessels are a bad idea for larger scales.
 
 
 
 
    scram
(Hive Bee)
10-23-00 18:37
No 62781
      Re: o2 is the shit  Bookmark   

7.6 liter (2 gallon for US citizens) max pressure 50psi (don't go higher)
4.2 liter max pressure 60psi (possible to go up to 80 psi, but over 65psi prepare yourself for possible injury)
Best bubbling action w 4.2 liter is a total volume of 600-700ml
Best bubbling action w 7.6 liter is a total volume of 1100 to 1300ml
Its best to get a regulator that maxes out at 60psi, you can even set it so that it won't fall below a given psi. Use belt straps (hook type) to strap the vessel nicely around the stirrer. Use only egg shape stirbars of 62mm or longer. Purge twice before starting the reaction to maximize volume of 02.
I had one of the 7.6 liter explode on me due to a faulty regulator which had worked the prior time. As a result, the bitch must have pumped up to 80 psi before blowing with a shotgun like sound and certainly would have broke my leg had it been aimed there instead of the wall. The whole HDPE was ripped with a 1/4 meter tear going lenghtwise. From now on, I double up and make sure psi 60 doesn't show psi 10 using a secondary inline psi gauge. I will not be fucking with glass anymore. Im not smart enough and should have heeded KRZ's advise on using 'vacuum' type carboys instead of the typical $10 carboy. Pumped a 3 gallon up to 35 psi, no problem. Before pumping to 45 psi the carboy was place under a hugh furniture box because of fear the stopper would blow-out. Not realizing the situation was going to much worse than that, it was pumped to 45 psi and about 1 minute later KABOOOOM, loud as a shotgun, really loud. Blew the MF in hundreds of pieces with the largest piece no bigger than my hand. Fortunately, shards were pretty much constrained to th inside of the box. I'll leave the dangerous work to the big boys from now on. I notice that after it broke there were significant varying thicknesses of the carboy throughout.
 
 
 
 
    Semtex
(Hive Elder/ Old Fart)
10-23-00 19:45
No 62795
      Re: o2 is the shit  Bookmark   

Well I guess Osmium's full of shit, and the KRZ kid too, damn, should have known better... shocked

FOR THE LOVE OF HONEY, where the hell did you get that rant?!?  Give us some rxn details of these complete failures you are talking about.  There are NUMEROUS bees, much more knowledgeable(sp?) than you or I that have had success with this rxn, I really don't see what the problem is with frost having done the same.  I remember back in the day when Osmium and Spiceboy were fine tuning the SRV, hell when SWIM tried it for the first time he got a 20-30% yeild, and that's with AiR and hand shaking for a couple of hours!!!  I would honestly have to say to all that if you give this method the chance it deserves, you won't be disapointed. <----  That's a PERIOD...wink


crazycrazy
 
 
 
 
    DiethylEtherMan
(Stranger)
10-23-00 21:05
No 62818
      Re: o2 is the shit  Bookmark   

Hey, New Bee, here again. Someone please F**kin' tell me that Antibody2 is not telling the truth. Becasue I have been studying all of FROSTS posts to the F'in T and was soon planning on sending my researchings to a friend so he could try the synth. Someone here...anyone....a rubtle for FROST?

Dear Anti-Body, no disrespect to you, but I hope to god your not too sure of what your saying. Don't let it be true, brotha. But if it is, I suppose I would want to know since I spent alot of time reseaching this method and aquiring many items.

More comments, please!

kpjr.

If some of us were not so far behind,
The rest of you would not be so far ahead!
 
 
 
 
    KrZ
(Hive Bee)
10-24-00 05:04
No 62920
      Post deleted by KrZ  Bookmark   

 
 
 
 
    Antibody2
(Hive Bee)
10-24-00 06:48
No 62933
      Frost is the shit  Bookmark   

Antibody Did not say the O2 wacker does not run, It Does run! Antibody has gotten high from using this synth.
The BS antibody is talking about is the yield Frost is claiming.

Antibody dxoesnít think s0omeone with the amount of experience the Frost has is going to go out and trip over a 90+% yield


distilled an got 47g ketone


Lets look at this staetment for a second. Didnít KRZ say earlier that the theoretical yield for this baby is 92%. Yet here is frost claiming 96%. Did pixies give him that additional 4%, and what about losses during distillation and work-up. You lose an ml in your distilation flask, you lose an ml in your condenser, you loss an ml or two AT LEAST during work-up, some in the funnel, some in the sep funnel. There is usually a little polymerization, NO? To get a yield like frost is claiming taking standard work-up and distillation losses into account he would have probably needed a  yield in excess of 100%. Where does a bee get those? In his imagination, thats where.

There arenít many kitchen chemists that have those kind of work-up skills, and as antibody knows from the PMs he has received from Frost, that he doesnít fall into that category, Sorry!

Antibody knows that this synth can run, he isnít discounting what KRZ and Osmium have said, NO Way. Nor is antibody trying to discount the entire thread, it has a ton of merit as antibody has already stated earlier in this thread.

[/quote]Awesome thread[quote]

Antibody will get the details at lunch and post them.





Jimi loves ya
 
 
 
 
    KrZ
(Hive Bee)
10-24-00 08:36
No 62955
      Post deleted by KrZ  Bookmark   

 
 
 
 
    placebo
(irritable and cranky / Eraser)
10-24-00 08:56
No 62961
      Re: Frost is the shit  Bookmark   

Thankyou KrZ, I was going to say that's a weight yeild not molar.
Secondly, how bout Frost gives us a super duper write-up in incredible detail, so that all us retards can follow it and not fuck up like antibodyshockedj/k.
I am also sick of Frost's vague posts.
If it's that easy Frost, please take the time to make a detailed write-up.
Just think....
If you do, and it is so easy to follow that all the bees suddenly start producing MDP2P in good yeilds. I am pretty certain all your previous stories wil be forgotten, and you will be a hero to the masses forever!



Hi Honey, I'm home!
 
 
 
 
    KrZ
(Hive Bee)
10-24-00 09:09
No 62963
      Post deleted by KrZ  Bookmark   

 
 
 
 
    zooligan
(Hive Addict)
10-24-00 09:57
No 62971
      Re: Frost is the shit  Bookmark   


On a truly interesting note are those reactions using propylene glycol etc.  Now, if you aren't into those, which they say provide "total recovery of the catalyst system", they also mention another trick, extracting the post-reaction mix with DMSO to recover 50-75% of the catalyst system!


A retardo-ready-riteup (R3) describing this will make you even more of a hero than you already are K-man!  Especially with the prices and decreasing availability of PdCl2.

 
 
 
 
    DiethylEtherMan
(Stranger)
10-24-00 10:03
No 62973
      Re: o2 is the shit  Bookmark   

Dear KrZ:

 If you get a moment, could you post some links to some of the references you speak about. Something to get me going in the right direction. I have no idea where to find them online (or, if not online, where)?? Also, about the 'molar' form of measurment...I don't have the slightest clue about that. If you could post a link to a description of how to calculate molar weight to gram weight and how to calculate actual yeild percentages acccounding to molar weight I would be extremely grateful. Thanx again! I know, this newbee's a pain in the ass now. Sorry, guys!

This thread is getting better & better!

kpjr.

The reward of a thing well done, is to have done it well. Ralph Waldo Emerson
 
 
 
 
    zooligan
(Hive Addict)
10-24-00 10:16
No 62976
      Re: o2 is the shit  Bookmark   

Unobtanium posted a few links to some good molarity, molality, and concentration tutorial pages a while back, but that thread seems to have gotten clipped in the last pruning of the data tree (repost please, U-nob you).

Try this link for some basic chem concepts http://pc65.frontier.osrhe.edu/hs/science/hchem2.htm

Mods, this question (and ones like it) seems to get asked a lot.  What happenned to LaBTop's sticky thread with all the educational links in it (I mean why is it not sticky anymore)?

z

 
 
 
 
    CrystalDaddy
(Newbee)
10-24-00 10:24
No 62979
      Re: o2 is the shit  Bookmark   

KrZ is a known liar as well as part time drugstore clerk.

 
 
 
 
    KrZ
(Hive Bee)
10-24-00 10:53
No 62991
      Post deleted by KrZ  Bookmark   

 
 
 
 
    scram
(Hive Bee)
10-24-00 13:40
No 63015
      Re: o2 is the shit  Bookmark   

LOL, I believe Frost. He's been speakin' to the man and getting good advise from him. Frost and I spoke about 5 months ago of which I traded alot of info on the sprayer method and said he was going to start doing it this summer. He got a source from me (if I still remember correctly) of which I thought the man would have already been aware of,  in which I would have traded that source with the an for some of this valuable information myself. If spiceboy claims 70% yields like mentioned earlier and being repeatable with just arm shaking, its not that much of a jump from 70 to 80% and luckily even 85% for a beginner. I'm beginning to think that ISA is a big factor of the high yields over MeOH.
 
 
 
 
    Semtex
(Hive Elder/ Old Fart)
10-24-00 17:33
No 63062
      Re: o2 is the shit  Bookmark   

That may bee, but I believe that Osmium(feel free to correct me if I'm wrong) got good yeilds with MeOH(80%+...?) so it's not to say that MeOH isn't A good solvent for this rxn, but I do agree that from what the pimps are saying that IPA(what the hell is ISA?tongue


crazycrazy
 
 
 
 
    psychokitty
(Newbee)
10-24-00 17:38
No 63065
      Re: o2 is the shit  Bookmark   

Epoxy paint is probably a much better coating material than teflon.  More resistant to weathering, that is.

--PK
 
 
 
 
    Antibody2
(Hive Bee)
10-25-00 06:16
No 63180
      Re: o2 is the shit  Bookmark   

Pychokitty - antibody has wondered about the viability of the epoxy coatings everyone is talking about. Acetone is a solvent that goes through epoxies like no tomorrow. Antibody assumed that ketone would have similar properties.

Scram -you missed my point, Didnít say the wacker doesnít run or that 80% is impossible, just that the way frost described it in 2.25hrs was what antibody had the problem with. Notice there hasnít been a rebuttle from Frost.

Placebo - WTF, it never would have come to that if you werenít asleep on the job, or moonlighting at totse or whereever.

KRZ - to extract catalysts into DMSO you would first need to get rid of your alcohol, right? DMSO is a polar solvent isnít it?


Jimi loves ya
 
 
 
 
    KrZ
(Hive Bee)
10-25-00 07:52
No 63203
      Post deleted by KrZ  Bookmark   

 
 
 
 
    Acme
(Hive Bee)
10-25-00 20:09
No 63405
      Re: o2 is the shit  Bookmark   

IMO Frost is not full of shit.  Anyone who says he is, or KrZ too, dont have the sense God gave a mule.
I posit that the water, whatever it is doing, is not being incorporated into the product, that oxygen I am sure comes from O2
 
 
 
 
    LaBTop
(Daddy)
10-25-00 21:19
No 63426
      Re: o2 is the shit  Bookmark   

Last email received from a friend who isn't very fond of posting practical tests here:


-- I carefully fractionated the oil from the water-added O2 wacker and it's only isosafrole and a few ml's ketone.
The only thing I did different from KrZ's is : I used MeOH instead of IPA and shaker agitation.
Might try exactly one more trial using IPA and hand and shaker agitation just to be sure.
Really,  I'm just glad the benzo is almost here. --


For your info:
He allready checked out all possibilities mentioned in this thread from the first date of this thread and before that, and got very bad yields of ketone for the elevated (higher = 50 C) temperature O2-wacker,
then send me a very enthousiastic email about the results of the water-added O2-wacker, which was an oil, which he did the Frost-way, 2.5 hrs and KrZ's, 8 hrs,
then send me a pessimistic next one where he tried to aminate the oil with 4 different aminations, ALL shitty results.
And this was his last one.

He explained to me he did the Benzoquinone wacker many times before with a consistent >80% yield of ketone, and excellent aminations thereafter.

I don't think the IPA will give much or noticable better results, so it seems to be a very complicated way of making isosafrole from safrole.
 
It's a pitty, looked like a nice find, but as usual, the only real proof is amination and subsequently oral tests, in case you have no better techniques, like TLC, GC or NMR available. LT/



WISDOMwillWIN
 
 
 
 
    Semtex
(Hive Elder/ Old Fart)
10-25-00 22:24
No 63452
      Re: o2 is the shit  Bookmark   

Are you saying that he tried an elevated temp wacker this time or prior to this time...?  I think the word around is that 55F not 55C was shown to give good results.  Other than that, I am not sure what the acual numbers are/were but I think Osmium's had some good exp with the MeOH/O2 wacker, maybe he could point out some hints/tips...?


crazycrazy
 
 
 
 
    LaBTop
(Daddy)
10-25-00 23:10
No 63470
      Re: o2 is the shit  Bookmark   

I'm re-reading his mails to find out if he used a glass or plastic vessel.
Osmium quote: Everybody knows that the product of the MeOH Wacker is the ketal, which is hydrolysed in a few seconds, maybe minutes afterwards as soon as you quench the reaction with acidic water. end quote.
Perhaps there could be a major mistake, but I doubt it, he mentioned quenching with the right amount of acid.
For your info: The elevated wacker was done in a warm water bath, before this thread.
This time he tried the Frost and KrZ methods, and both gave exactly the same results as them, O2 uptake measured :
Water added O2 trial O2 uptake fore each hour: 5, 4, 0. Rapid color changes.
No water added O2 trial, O2 uptake for each hour: 2, 4, n.a.(vessel breach), 5, 3, 3, 2, 2, 0.
So he worked with plastic vessels. Glas explodes, does'nt breach.
I still have hope.....LT/


WISDOMwillWIN
 
 
 
 
    Antibody2
(Hive Bee)
10-26-00 06:52
No 63550
      rxn notes  Bookmark   

Here are the notes that were kept during the rxn antibody discussed above (please note that an american thermometer was used during rxn)

1l heavy walled filterflask in a waterbath fixed with a 1.25" victor tire valve, was charged w/0.5g PdCl2, 2.5g CuCl2, 100ml 99%IPA, 2.5 " egg shaped stirbar. Stirred overnight.

9:30: flask  was charged with 50g safrole (0.28 moles), pressurized to 50psi, set stirrer on high, cooled bath from 61deg F->55deg F over 0.5hr

10:00: Stopped stirring, pressure had dropped to 40psi, opened flask charged with 3.5ml dH2O, resealed flask and repressurize to 50psi.

10:30: Pressure had dropped to 38psi bath temp had risen to 62Deg F, added two more ice cubes to bath, repressurize to 50psi.

11:10: Pressure had dropped to 43psi bath temp had risen to 66Deg F, added three more ice cubes to bath, repressurize to 50psi.

11:40: Pressure had dropped to 45psi bath temp had risen to 66Deg F, added three more ice cubes to bath(bath tempo dropped to 56F), repressurize to 50psi.

12:20:  Pressure had dropped to 44psi bath temp had risen to 64Deg F, added two more ice cubes to bath, repressurize to 50psi.

12:55: Pressure had dropped to 45psi. Stirring was stopped.

Total pressure drops 45psi or 3atm. In this flask with the reactants there remained 1.1litre headroom.
1l of Oxygen @1atm =1.42g
3.3l Oxygen @ 3atm =4.686g
0.2947moles of oxygen was consumed by reaction, a slight molar excess relative to safrole.

IPA was distilled at 45degC under medium vac, the remaining oil was passed through .25" 50mesh silica sand in a vacuum filtration set-up to recover catalyst.

Stirred filtrate with 200ml dH2O and 20ml 31% HCl for 15 minutes. Red oil that fell out was separated and the aqueous layer is extracted with 20ml DCM which is pooled w/ previous extract and placed in a 250ml rb flask in an oil bath, DCM is stripped off @ 760ttorr.

High Vac attached and applied
4mls of forerun are collected and discarded
30mls of safrole collected at 102-104 deg C
7mls ketone collected at 104-138 deg C
bit of polymerized crud in flask

Notes: the 2nd two fractions were tested with sodium metabisulfite 1ml each. The 3rd fraction crystallized immediately in the normal fashion, the 2nd fraction initially did nothing, but upon vigourous shaking finally began become turbid forming fluffy cystals over 1hour period at RT. (Crystals unlike any previously witnessed in similar rxns)

The 2nd fraction was reacted in a MM nitro Al/Hg, used the Ritter work-up, pregassed toulene was added to the washed and driied toulene extract until ph5 is reached. Nothing An hour later additional pregassed toulene added bringing PH down to 2 yield=0.0g+ONE PISSED OFF BEEmad


Total time elapsed 11.5hours.

So there it is, flames welcome, Placebo?



Jimi loves ya
 
 
 
 
    LaBTop
(Daddy)
10-26-00 10:28
No 63593
      Re: rxn notes  Bookmark   

O2 is SHIT. LT/


WISDOMwillWIN
 
 
 
 
    zooligan
(Hive Addict)
10-26-00 11:01
No 63600
      Re: rxn notes  Bookmark   


O2 is SHIT. LT/



How eloquent.  Can you elaborate?

z

 
 
 
 
    KrZ
(Hive Bee)
10-26-00 11:09
No 63605
      Post deleted by KrZ  Bookmark   

 
 
 
 
    Antibody2
(Hive Bee)
10-26-00 11:51
No 63614
      Re: rxn notes  Bookmark   

KRZ, if its antibody you ask, he beleives the pressure of distillation to have been 5-10torr. 1st time this pump was used, so that is calculated by plotting the 2nd fractions BP on a nomagraph.

The pump was rated at 5millitorr ultimate vac , but it is not new. KRZ to be honest this was antibodies 1st crack at calculating mass of gases, so he fully expected after posting that to be told he had fucked up and calculated wrong.

The more he thinks about it, he wonders if the 2nd fraction was safrole at all, cause safrole doesnít do shit with sodium bisulfite (antibody did a test tube worth of that too), so that part is confusing, because something, maybe traces of ketone reacted with the bisulfite from fraction2 yielding those very puffy crystals, some of them so weird they passwed through a cooffee filter. Is it possible the oxygen is bonding to another part of the safrole molecule?

Antibody is NO chemist (more a monkey who look at pictures, but cannot read) So where is all that O2 going? wish he knew. He doesnít think there was a leak. If it were a leak perhaps O2 consumption would have been more uniform. IPA was used, you say that cannot be oxidized, so you tell me. Antibody is stumped, maybe a greater bee than me can solve this one.

BTW it was 50-65 Farenheit that was maintained.



Jimi is confused about this too
 
 
 
 
    LaBTop
(Daddy)
10-26-00 11:54
No 63616
      Re: rxn notes  Bookmark   

We don't talk about higher temp wackers.
Two different testers talk about <roomtemp O2 wackers with, and without water added, both got isosafrole and a minimal amount of ketone. Antibody gives the distillation pressures. My friend has a top ass lab. LT/


WISDOMwillWIN
 
 
 
 
    KrZ
(Hive Bee)
10-26-00 12:16
No 63627
      Post deleted by KrZ  Bookmark   

 
 
 
 
    Antibody2
(Hive Bee)
10-26-00 12:23
No 63629
      Re: rxn notes  Bookmark   

KRZ, the temperature did NOT get out of hand it was within 10deg of 55deg Farenheit the entire rxn. The flask never even got warm.


Jimi loves ya
 
 
 
 
    KrZ
(Hive Bee)
10-26-00 12:29
No 63632
      Post deleted by KrZ  Bookmark   

 
 
 
 
    Antibody2
(Hive Bee)
10-26-00 12:31
No 63634
      Re: rxn notes  Bookmark   

It was cold. There were ice cubes floating in the water bath. Antibody is beginning to think you are toying with him.


Jimi loves ya
 
 
 
 
    LaBTop
(Daddy)
10-26-00 12:33
No 63636
      Re: rxn notes  Bookmark   

Yep, I'm confused also, mainly by the fact that Spiceboy, Osmium, you, frost and some others reported good results at times, so it could be that the cooling of the vessel is a major point to take care of.
You clearly stated that only glas and plastic gave results, so checked that too, it was plastic.
Temp control MUST be the main issue here, the rest is simple.
But notice the exact same O2 take up ratios during the 8 hrs and the 3 hrs duplos of the KrZ and frost methods, and still ISO . LT/


WISDOMwillWIN
 
 
 
 
    KrZ
(Hive Bee)
10-26-00 12:58
No 63643
      Post deleted by KrZ  Bookmark   

 
 
 
 
    Antibody2
(Hive Bee)
10-26-00 13:08
No 63647
      Re: rxn notes  Bookmark   

KRZ in three posts in a row antibody stated the cold temps and you persisted in replying about synths where the temp was out of hand?frown ? Or did he misunderstand what you were tryying to say?


Jimi loves ya
 
 
 
 
    LaBTop
(Daddy)
10-27-00 00:06
No 63836
      Re: rxn notes  Bookmark   

Any one else who does'nt act like a child who has something worthwhile to say?
Would like to hear your opinion, Os, and if Spiceboy is around, I know you peek in, any help in solving this problem is appreciated, I still can't find anything wrong in my friends writings and certainly not in Antibody's writings. He followed exactly the outlined procedure, used IPA, the right O2 psi (the other used 45 psi, see no problem with that btw), the only thing I can come up with is the premixing of the CuCl2, PdCl2 and the solvent (IPA or MeOH), which should be done perhaps longer then the 2 hours strong mixing reported to me, an overnight mix would be 100% sure. LT/


WISDOMwillWIN
 
 
 
 
    Osmium
(Stonium's / Changer)
10-27-00 04:29
No 63893
      Re: rxn notes  Bookmark   

I can only repeat what I have said for several years now. I did it without added water, 4-5:1 MeOH:safrole, 100:1-1.5 safrole:PdCl2, 1:3-4 PdCl2:CuCl2, pressure up to 5-7bar (75-100psi), strong manual shaking for several hours. Catalysts were pre-stirred for 12 hours or longer because it took that long for all the PdCl2 to dissolve. Since O2 absorption was very slow to non-existent when done cold I had to warm it up occasionally in a water bath, and I thought that some warming up took place during reaction.
That's all I have to say. Worked for me.
 
 
 
 
    Osmium
(Stonium's / Changer)
10-27-00 05:10
No 63899
      Re: rxn notes  Bookmark   

Did somebody save immature shit's replies? PM me so I can reinsert them.
 
 
 
 
    Antibody2
(Hive Bee)
10-27-00 06:18
No 63908
      Re: rxn notes  Bookmark   

Yes, too bad KRZ took his marbles home.The last three replys from KRZ, were assertions that increasing temp over RT increases isomerization and polymerization, Or that these things occured when temp got out of hand. This why antibody got short because the temp didnít get out of hand.

And he asked what we antibody/labtop thought was being oxidized if not the safrole.

Sorry didnít save a copy, he did seem to be in ernnest before we frustrated him. Antibody even went and back extracted the whole fucking mess last night, hoping he had fucked up the extractions, no dice.

Osmium, would you be willingh to give us a blow by blow narration of one of your typical rxns? Antibody remembers how well your old Al/Hg method worked w. thick foil. Maybe we just need it SPELLED OUT for us?


Jimi loves ya
 
 
 
 
    KrZ
(Hive Bee)
10-27-00 06:23
No 63911
      Re: rxn notes  Bookmark   

Come come now.  There was nothing of any gravity in my posts.  Antibody clearly showed that the topic was worthless, and I can only agree with his results as I have never actually performed the reaction/any reactions!  Now, does anyone know where to get some yerrycans?
 
 
 
 
    sassy_sucker
(Hive Bee)
10-27-00 07:31
No 63926
      notes from frost  Bookmark   

Frost has been having trouble getting onto the board and asked if SS would post this for him:

swinf does this,
1. pdcl2 high grade eberhard  imho the best kind commercially available
no photo quality stuff used here ex. if using 200mlmeoh 1gpdcl2 5gcucl2 you will start oxidising the meoh at 3atm swinf uses less with sucessful meoh runs .90 g.
2. add ipa99% 100ml to .51g pdcl2(eberhard) with 2.5g cucl lb grade
prestir at 1 atm 14.7 to 15psi for 4 hours high speed 3 inch octogonal stirbar this is placed into the waterdish and allowed to come down to 55-60f then safrole almost clear fractionally distilled, 50ml is added
safrole temp was around 60f then 2mldh20 was added which makes for almost 10% h20 excess(including water content of cucl2,safrole and ipa.
everything was sealed up and stirred with a corning submersible stirrer
2000rpm.
2 hours 10 min(a little longer because the h20 wasent quite a 10% excess) the regulater that guy has can be set to reprussurize after drops of 15 psi this occurs 10-12 times during the reaction. then 25ml 37%hcl is added and stirred for several mins. then 3/4 h20. workup as usual the reaction is complete when it stops, stops STOPS ABSORBING O2 and pdcl2 stops going back into the solution, and isnt being recycled by the cucl2
swinf wasent there when u guys did it he dosent know what went wrong.Boo fucking hoo!
he will say that this does work the main factors are 1. correct ratios
2. constant o2 absorbtion via agitation shaking or stirring 3. doing it over and over until you finally get a feel for it. swinf is obviously no chemist, i mean fuck he just got the molar thing down, no disrespect to those who are as they are cool as fuck and know their shit.
but he is/was obsessed with this and there is no telling how many thousands of dollars and hours he's spent getting this to work.
swinf dosent know the perfect ratios but he keeps getting better and better at this.
it works with meoh and etoh but as KrZ said (who else) they both cause an exothermic reaction and increased isomerization and a longer reaction time. ipa does not!
the bottom and size of the flask and the stirring power you're using does play alot in the rate of o2 absorbtion.
increased pressure does work ex 10l carboy etoh99% same ratios etc
85-90psi 6 in eggbar 2000rpm  will do a kg of safrole in 4-5 hours at room temp( better if in water bath but takes 8-9hours) with some isomerization but decent yields (better than benzo)
and 1kg benzo run would bee the messiest shit in the world!
AB2 we've talked alot and you are a cool bee that adds alot to the hive
but how many fucking 02's have you done a couple, a few? not doubting your skills have read all your posts as well as every post that has ever been posted at least 100x ex. your washing machine trials. but others have done it. benzo works for u and swinf as well but fuck it
its too fucking messy and wastes too much shit.
all you benzo loving rp/i2 bees have at it.
who wants to fuck with all that crap for their (personal use) RIGHT!
bullshit!don't player hate because you can't do it the first  time.
Obviously there are some variables you havent properly nailed down thats all, there are some smart ass people on this board.
everyone thought the birch was bullshit at first but if you're gonna hook up kgs of gogo are you gonna rp/i2 the shit. not many us bees will.
whats gonna happen when p-benzo is like rp/i2 alot of wings will be clipped and every bee will bee doing the performic which works well,
but too messy in large stuff. urban bees would bee smart to learn the o2. damn swinf has had too run 4 benzos at the same time 3x per week some times = no sleep.

if any bees have any experience with o2 wacker they know the spicy ketone not safrole smell when its done!! hows that for a scientific explanation.
KrZ is the PIMPDOM on this and most everything, Lt's 1pot is the shit,osmium is a fucking genius, brightstar laid it all down for the masses, and methylman made it soo much easier for all us non-chemist to get the honey and aminate that shit!
I love the fucking Hive and don't know why i cant acces it, was it something i said. i wrote hey man and got no reply what is the deal.
i'm not there and everybody talks shit a coincindence? who knows
thanks for the knowledge though!
Frost


how would you fuck me?
 
 
 
 
    sassy_sucker
(Hive Bee)
10-27-00 08:06
No 63935
      Re: notes from frost  Bookmark   

BTW... this is frost's reply to Antibody2's rxn notes that SWISS emailed to him.

 -ss


how would you fuck me?
 
 
 
 
    placebo
(irritable and cranky / Eraser)
10-27-00 08:17
No 63938
      Re: notes from frost  Bookmark   

...and why did you email it to him?

Frost seems to have a few people that speak on his behalf...


Hi Honey, I'm home!
 
 
 
 
    sassy_sucker
(Hive Bee)
10-27-00 08:41
No 63950
      Re: notes from frost  Bookmark   

I don't understand your question.

I emailed it to him because I was aware that he was unable to get on the board and was curious to see if he saw something in AB2's reaction notes that would cause such a failure.

 -SS


how would you fuck me?
 
 
 
 
    Antibody2
(Hive Bee)
10-27-00 09:19
No 63962
      Re: notes from frost  Bookmark   

Frost - the reason that times were kept for the rxn was because deep down, antibody really wanted this rxn to run, and because antibody wanted to have a race with you! Ya know fun? So although he had doubts he went into it with good faith.

He was probably the most dissappointed bee about this whole deal.To answer your question though at least 12 SRV wackers have been attempted. with O2, with air, with hand pump and O2 tanks, with shaking with stirring and in the clothes dryer. While each run had some miserable tiny yeild grugingly, not once was antibody gratified by this rxn.

It wasnít a washing machine method it was a clothes dryer method with SRV.  And any run over 4 hours exploded.  Not boom but the soda bottle would split making a huge mess and big stink. Stirring the srvs exploded too! To be honest thuogh, he thinks those explosions had the best yield, he thinks it was the ketone% getting high eneough to eat the plastic. The exploded rxns always smelled better ketone wise, but it is hard to extract ketone from a clothes dryer or the pillows the srv were wrapped in, to be certain.

The fact that some ketone is formed was always encouraging, but after awhile even that wears thin.

The rxn above was the senond one where stirring was used as opposed to agitation (there was a 3-4 inch head of foam throughout), and have to say that agitation was better although but only marginally.

If some bee can tell him where he went wrong antibody would be grateful. The CuCl2 used was not anhydrous but water shouldnít affect the yield here?

The reason frost, why antibody finds your posts hard to digest is because of all the non-sequiter shit you throw in. Like what the fuck I2/RP has to do with o2 wackers is beyond antibody. It makes antibody beleive that you donít actually understand some of the stuff you are trying to discuss. And if it isnít understood, antibody thinks it a real leap to use misunderstood info to get 90%+ yields.

Maybe you arenít a total fraud frost but you havenít convinced antibody you donít exagerate an awful lot. \

And you also state as fact, things that you cannot bne certain about. (this is a very dangerous habit to get into, especially with all kinds of newbees doting on your every word - Fuck it is irresponsible to spread misinformation like that) Like the way you said DCM would work in the pseudonitrosite thread. That demonstrates a 0% understanding of an rxn you already were claiming big success with. It also demonstrates a 0% understanding of the properties of DCM, which is a solvent you claimed to have used. If you used it how can you not be aware that it is always going to go to the bottom?

These things about you do not add up and make me very wary of you. Sorry but antibody thought this needed saying. It is too badfrown antibody is very depressed about this whole thing.


Jimi loves ya
 
 
 
 
    psychokitty
(Newbee)
11-02-00 20:17
No 66114
      Re: notes from frost  Bookmark   

There is no mystery as to why Frost's and KrZ's information is inaccurate.  I just figured it out.  Both are disinformation hacks working either for the DEA or a fucking terrorist group that would like, at most, for you to waste huge amounts of oil, and at least, nothing more than to blow your FUCKING heads off after injecting too much O2 into your bottle container.

I just had my last (hopefully) e-mail exchange with "Fucking YO!" or "Lying Pig!" or KrZ as he used to be known.  I was trying to come to an understanding with him IN PRIVATE as to why it is he passed on so much experimental bullshit to me via e-mail before the collapse of New Hive. In short, after cornering him with only a few indisputable facts, he finally admitted, "Yeah, bitch, I fucking lied to you. So what?" (paraphrasal)

If anyone would like to discuss this with me, send me a message.  If you would like to read our (mine and dick-head's) e-mail exchanges, let me know how I can transpond them to a new thread, and I'll be happy to do so.

In case you didn't know it, KrZ and I are now at war.

Your absolutely loyal Hive elder,

psychokitty
 
 
 
 
    scram
(Hive Bee / Eraser)
11-02-00 21:14
No 66128
      Re: notes from frost  Bookmark   

Why the fuck, and how does KrZ's post keep getting deleted?!! I know whats going on here. KrZ and Frost are both legit. I wish I had saved the email on my computer before it got deleted. It was from frost at the beginning of this post. He mentioned to me that he had been getting alot good tips on IPA method including ratios, etc, etc for the past xx days. He told me to switch to IPA method as it really kicked ass. KrZ, of course doesn't want to give out this information freely, it just depends on what mood you get him in. And that's no guarantee that he'll help you the next day and will say goodbye to you with a big fat "FUCKOFF!" I've read virtually every KRZ posting since he has been here. Everything that he says jives with regards to content, his methods of changing techniques chronologically, his data always stays consistent with what he said in the past and so on. There are many things here I've notice bees claim he said this or that, when in fact I immediately knew that person was wrong and apparently never say xx post(s) by KRZ. He doesn't want to give out his info, he could give a shit if your new or old, its just his personality (hence more why I think Fman is his alter ego; their writing strike unusual resemblence in some sentence structures). If you look back at KrZ posts from late 99 to eary 2000, you can slowely put together a chronology of him perfecting IPA method gaining >90% yields. You can do this on anyone here in the hive and see if they are full of it or not. I just don't believe that anyone would so much theoretical experimentation would just say shit w/o doing and accomplishing. It's unfortunate for some that ask for his advise just get toyed with. I learned this way back and didn't even bother to go straight for getting info from him, but yet, systematically collected all his writing to get a complete grasp of where his secrets on success are. In my opinion, the old hive board has really good info. Not the 2nd hive that closed in April, but the one where it was just a BB with no graphics.
 
 
 
 
    placebo
(irritable and cranky / Eraser)
11-02-00 22:47
No 66158
      Re: notes from frost  Bookmark   

scram, you have claimed success from the O2 wacker for quite some time now. Yes?
Could you give your interpretation of the procedure you follow and possibly offer any insight into the failures of Antibody2 or Labtop's friend?
I can account for the fact that some people lie and make up shit to mis-inform but too many have claimed success with this method, including Osmium.


Hi Honey, I'm home!
 
 
 
 
    KrZ
(Hallucinogenius)
11-02-00 23:29
No 66178
      Re: notes from frost  Bookmark   

Here's what psychokitty is on about, she said that I had told her the O2 wacker runs great in soda kegs or some sort of stainless steel vessel.  I then said it only works well in glass, because the SS reacts with the suspension, heating up, polymerizing product, etc. PK insists that I told her it works in kegs, and then comes back at me with this;

But if your interested one experiment you described to me via e-mail through your rcdorks@yahoo.com e-mail address, here's a paraphrasal of it:

Something like 1000 mL of 1-alkene using a pressure of 120 Ibs of O2 in the keg.  You described that the reaction gets kind-of hot and that your initial recommendation was to only use 40 Ibs of pressure and then work up to the full 120 Ibs in the last 12 hours our the required 24 hrs. 

BTW, If the reaction vessel had indeed been a carboy, like you now claim, I can't reasonably see how it could hold 120 Ibs without your suffering a massive explosion with glass fucking flying everywhere like a low-yield grenade.  Sounds a little fishy, no?

Just to stimulate your memory, this was around the time that SWIM wanted to perform your H2 pressurized catalyst reduction of eph_drine in the keg; however, you instead recommended the elimination reaction of the gamma-chloro-propyl-benzene using t-butylamide (I think). (For the longest time, I was confused because you wrote '3-chloroallylbenzene' and I assumed that you were recommending the removal of a chlorine atom in the 3 position of the benzene ring; wasted alot of time in the library on that one, but no big deal).

-------
Now, I did recommend using 40 psi in the kegs before, after some initial failure using the high psi's which some bee claimed he had succeded with.  I recommended using 40 psi because I hoped that if the reaction didn't go so exothermic, there wouldnt be so much polymerization.  Yields were obtained with the kegs, always, but they were never very good, 50 at the max on down to 35 (on a molar yield basis).

Now the second part of the message, mentioning t-Butylamide, and an allylbenzene.  NEVER did I say any of that, the post is on rhodiums site and I'm sure you all know the mistakes pk made.  The reaction was a dehydrohalogenation with K-tButoxide employed as the catalyzing base.  That reaction works, and it works well.

After I got this, I basically felt like (1) I was being called a liar without copied posts or references (2) PK couldn't remember reaction details on another post, which was just a clear example of its inability to recollect the events properly.  This pissed me off, and since PK had already told me it didn't believe me when I said I hadn't told it to run out and get 98% oxidation yields using a keg, I was pretty mad, hence;

"Yeah I lied to you bitch, so the fuck what?"

Confronted with no evidence, a clearly faulty memory, and an increasingly accusational tone, I snapped back.  And I certainly don't regret it.

PS Here are two old hive threads which I referenced to her in my defense after the initial contact;
Post 107575 (Player 19: "keg 02 Wacker", Methods Discourse)
Post 107871 (pHas3d: "Updates on O2 wackers...", Methods Discourse)
 
 
 
 
    zooligan
(Hive Addict)
11-03-00 05:44
No 66253
      Re: rxn notes  Bookmark   


I can only repeat what I have said for several years now. I did it without added water, 4-5:1 MeOH:safrole, 100:1-1.5 safrole:PdCl2, 1:3-4 PdCl2:CuCl2, pressure up to 5-7bar (75-100psi), strong manual shaking for several hours. Catalysts were pre-stirred for 12 hours or longer because it took that long for all the PdCl2 to dissolve. Since O2 absorption was very slow to non-existent when done cold I had to warm it up occasionally in a water bath, and I thought that some warming up took place during reaction.
That's all I have to say. Worked for me.



What were your yields likeon this run Os?

 
 
 
 
    scram
(Hive Bee / Eraser)
11-03-00 09:06
No 66292
      Re: notes from frost  Bookmark   

Let me put it to ya like this jeb, I ain't boasting no 90% yield, but 02 wacker is so foolproof that a chimp on crank could get yields. I've done it about a dozen times all leading to yields. Now, my shit not distilled, this goes from beginning to end processes, so maybe it's the reason for 30 to 40% molar yields I get from saf to ketone). I seriously doubt that its the purity of my oil because I can guarantee all of you that (despite the bullshit about "garbage in = garbage out" hoopla I got almost 2 years ago) my sa.. is relative pure (over 98%). I can go by look, taste and smell alone once I've freeze-purified. I got good oil though too. You'll get yields no mater if it goes for 4 hours or 50 hours, I just haven't been able to pinpoint the ideal apex of the conversion given time, pressure, temps, etc. I can tell you that I've noticed some differences once 2ml h20 was added halfway into the reaction, significant color change and more robust like popourri smell within 2 hours after water added. I just dont understand how people get ` molar yields with lousy shaking in a small 2 liter bottle with no 02. I'm busting balls over here just to get at 50%. Like I said, you cant fuck it up. Heat always seemed to produce best yields, running at ~10c for 45 hours produced the worst yields (always correlated to the smell too). Man, KRZ, I can tell you shit about your posts that not even you would know you wrote. I remember him stating ghett0 = glass = wacker. Soda keg = failures in getting etoh converting to some sort of acetone and blowing his keg (yes, if i remember correctly, that was a wacker he ran in a metal container of which he never did again, only hydrogenations for the cornealius kegs). KrZ is doing some type of addition of safrol over a period of time with lower solven/saf ratios and using IPA at pressures of 40 - 45 psi. Pressures at 100+ psi I believe he does not add water. I've noticed that addition of water in the lower pressures have made better yields for that pressure range. Water was rarely introduced in the 85 psi I was doing (before I realized pressure dangers first hand a couple times) the best yields then. I'm thinking about asking a qualified bee with access to that gps satelite crap to analyze my ketone for actual content. I usually get 80ml oil to make 17g hcl when I was having luck. Recently, since using lower pressures, my luck changed for the worse. I think that the water addition is some secret thing going on to get best yields at those pressures. I don't know jack about chemistry and I fucking hate real (textbook) chemistry, I just copy the best of the best of this sight and compare and make the best of having no distillation glass. But I like it that way, freezing is fun. Placebo, Could you post your email address, I want to get that address for the electolytic cleaner in the future. Thanks
 
 
 
 
    scram
(Hive Bee / Eraser)
11-03-00 12:03
No 66362
      Re: notes from frost  Bookmark   

   
Let me put it to ya like this jeb, I ain't boasting no 90% yield, but 02 wacker is so foolproof that a chimp
   on crank could get yields. I've done it about a dozen times all leading to yields. Now, my shit not distilled,
   this goes from beginning to end processes, so maybe it's the reason for 30 to 40% molar yields I get from
   saf to ketone). I seriously doubt that its the purity of my oil because I can guarantee all of you that
   (despite the bullshit about "garbage in = garbage out" hoopla I got almost 2 years ago) my sa.. is relative
   pure (over 98%). I can go by look, taste and smell alone once I've freeze-purified. I got good oil though
   too. You'll get yields no mater if it goes for 4 hours or 50 hours, I just haven't been able to pinpoint the
   ideal apex of the conversion given time, pressure, temps, etc. I can tell you that I've noticed some
   differences once 2ml h20 was added halfway into the reaction, significant color change and more robust
   like popourri smell within 2 hours after water added. I just dont understand how people get ` molar yields
   with lousy shaking in a small 2 liter bottle with no 02. I'm busting balls over here just to get at 50%. Like I
   said, you cant fuck it up. Heat always seemed to produce best yields, running at ~10c for 45 hours
   produced the worst yields (always correlated to the smell too). Man, KRZ, I can tell you shit about your
   posts that not even you would know you wrote. I remember him stating ghett0 = glass = wacker. Soda
   keg = failures in getting etoh converting to some sort of acetone and blowing his keg (yes, if i remember
   correctly, that was a wacker he ran in a metal container of which he never did again, only hydrogenations
   for the cornealius kegs). KrZ is doing some type of addition of safrol over a period of time with lower
   solven/saf ratios and using IPA at pressures of 40 - 45 psi. Pressures at 100+ psi I believe he does not
   add water. I've noticed that addition of water in the lower pressures have made better yields for that
   pressure range. Water was rarely introduced in the 85 psi I was doing (before I realized pressure dangers
   first hand a couple times) the best yields then. I'm thinking about asking a qualified bee with access to
   that gps satelite crap to analyze my ketone for actual content. I usually get 80ml oil to make 17g hcl
   when I was having luck. Recently, since using lower pressures, my luck changed for the worse. I think
   that the water addition is some secret thing going on to get best yields at those pressures. I don't know
   jack about chemistry and I fucking hate real (textbook) chemistry, I just copy the best of the best of this
   sight and compare and make the best of having no distillation glass. But I like it that way, freezing is fun.
   Placebo, Could you post your email address, I want to get that address for the electolytic cleaner in the
   future. Thanks
 
 
 
 
 
    Antibody2
(Hive Bee)
11-03-00 12:56
No 66386
      Re: notes from frost  Bookmark   

Osmium - Thanks, you say a few hours of hard manual shaking. Is that continuous or at intervals that you shake? How many is a few hours?

Thanks for the good post scram. You covered alot of ground there. Got a few questions. What set of conditions produced your best yield? What solvent were used? What method of shaking? Continuous or periodic shaking? How do you avoid explosions or burst srvís? You are using an SRV, correct? How do you decide when to stop?

Lets get some specifics and maybe we can wrestle this baby to the ground.smile


Jimi loves ya
 
 
 
 
    Elvium
(Stranger / Eraser)
11-03-00 13:01
No 66388
      a  Bookmark   

My trials show that the 2h, water added, cooled, O2 wacker ala KrZ does not work.. producing only isosafrole and very little ketone. But if this does it work it would be revolutionary so I leave open that possibility.

Here is a detailed writeup so others can replicate the exact conditions and share the results. It is slightly modified for simplicity so that any bee could perform it. The fundamental reaction conditions remain the same.

Ingredients:

100g Safrole
7.2mls dH2O
1g PdCl2
5g CuCl2.2H2O
200mls IPA (99%)
O2
1 SRV

Procedure:

Combine IPA, CuCl2, and PdCl2 in a flask or beaker. Apply light heat and rapid stirring until all solids have gone into solution, then allow to cool. This takes about 6hours.

Combine everything into an SRV and pressurize to 45psi with O2. Shake rapidly by hand for 3m, then place into a 14C water bath for 7m, repeat this cycle for 2h. If there is doubt as to whether O2 is in solution then the pressure can be released and the solution sloshed slightly, if O2 is in solution then it will bubble out just like pop.

Workup:

Add in enough 3N HCl to allow phase seperation and extract with solvent of choice, wash extracts with a portion of brine, dry extract, and distil to get the goods.

Results:
My results with the above only produced isosafrole and a tiny amt of ketone, the only change was use of an orbital shaker and MeOH as solvent. Double distilled to be certian and bisulphite tested -ive.

Then next trial using exact ratios. At the 2h mark there was little color change, so the reaction was continued overnight. The result is ketone as can be expected. Still to undergo the ultimate test of amination.

Conclusion:

Neither disproves or proves the validity fo this procedure.
 
 
 
 
    KrZ
(Hallucinogenius)
11-03-00 13:43
No 66406
      Re: a  Bookmark   

Orbital shakers don't get quite as good agitation.  What were your bp's, vacuum, bisulfite weight, etc?
 
 
 
 
    placebo
(irritable and cranky / Eraser)
11-03-00 14:38
No 66415
      Re: a  Bookmark   

Elvium, are you saying you left the vessel overnight under pressure or you continued with the shaking and didn't repressurise?
What yield did you get this time? Or do you not distill? ..and base yeilds of MDPDP on yeild of amination?


Wanna do the rumpy pump?
 
 
 
 
    Elvium
(Stranger / Eraser)
11-03-00 15:15
No 66425
      Re: a  Bookmark   

The shaker is strong enough to shake stress marks and breach of the bottle in 3h and in other reactions has proved adequate for uptake. 64g S in, distilled once through vigreaux to yeild 59.3g IsoSafrole with asp. vac. BiSulphite tests negative.. using saturated NaMeBiSulhpite water.. which is the first -ve result I've ever seen. Pre distil oil is clear and way too clean. Tastes and smells like saf. This trial was done at rt instead of 14c. The pre-stir time was >24h in RB flask w/o Cucl2 and most but not all of the pdcl2 was in solution. Measured O2 uptake per hour was 5,4,0. Thpose are the only changes, possibly one of them was dramagic enough to change the reaction outcome.. you tell me.. i'd really like to see it work.



 
 
 
 
    Semtex
(Hive Elder/ Old Fart)
11-03-00 16:24
No 66437
      Re: notes from frost  Bookmark   

If ANYONE can vouch for KRZ and the soda keg not being used for the wacker it's SWIM damn it.  SWIM read a bunch of posts concerning the Ghetto reactor, and thinking that was the famed soda keg tried out 2(1kg) batchs of olefin ---> ketone O2 wackers in the keg.  After FAILUURE and mass polymerisation SWIM asked KRZ about it, and nothing but help(being a good thing) was offered, and when it was pointed out that the Ghetto was indeed NOT the soda keg, SWIM went back and re-read those posts and it was a misunderstanding on SWIM's part that caused the fuck ups.  Since SWIM is currently unable to dream for a while he hasn't been able to once again go at the O2 wacker, but I do ABSOLUTLY remember that SWIM did get a 30% yeild once in the SRV with AiR, so unless you can tell SWIM why the bioassayed product of that RXN was so damn good then I wouldn't be posting shit like "O2 is shit".  As far as i'm concerned this method shows as much merit as any of the others currently floating around the hive...


crazycrazy
 
 
 
 
    psychokitty
(Newbee)
11-03-00 17:44
No 66464
      Re: notes from frost  Bookmark   

Regarding your recommendations about using reduced pressures (40 Ibs) in the keg, you are now changing your story, and to give you credit, it does somehow sound good enough to get you off the hook with everybody else. But not me.  Why?  Because now that you admit you DID tell me to try the wacker in the soda keg, I'm here to fill in one simply blank which is that you verified that the yields would still be in the 90% range.  Obviously, according to what you just wrote they wouldn't have.  Whatever.

Now regarding several old posts in the old Hive database, I know I reported carring out the wacker in the keg, getting isosa_role as the product (but I didn't know it then) which for obvious reasons didn't aminate, and for some reason, you were just fine with that report, saying nothing of the complications that you claim you've had performing such reactions in kegs.  You were just like, "Oh, that's about right".

And there are other glarring inconsitencies in your reporting such as that time you suggested saturating ethanol with methylamine HCl and then using that with "piperonylacetone" (MD-P2P) in a reductive amination using H2 and Pt to get the desired final product.  I asked you about this and you were just oh-so-happy to suggest that you sometimes test us little bees to see if were keeping up our skills.  Fuck you, dude.

And I'm not even going to get into the whole cyanoborohydride HCN evolution debate we had back when with your insisting that there was nothing to fear of the gas evolution that I and a few others were experiencing.

As for the GHETTO/SODA KEG misunderstanding, there I give you due credit.  I did misunderstand that part of it and that is indeed my fault.  But you are hardly the altruistic figure you like to portray yourself because as far as I can tell, you could have easily seen that I made this mistake and you never corrected me.

Now, as for the elimation reaction that I spoke of that you once reported to me, I never meant to imply that you lied to me on that one.  After figuring out just what you meant by 3-chloroallylbenzeze, I was like, "very clever and very sound, as potassium t-butoxide is likely to cause elimation with limited migration of the double bond".  "3-chloroallylbenzene" was your mistake; "t-butylamide" was mine.  I never targeted you on this one.  I simply meant to convey that your typo confused me.

I'll just have to find some of those old posts to prove my point:  That you are too often erratic, KrZ, thus contributing doubt to your word.

--PK
 
 
 
 
    KrZ
(Hallucinogenius)
11-03-00 17:56
No 66471
      Re: notes from frost  Bookmark   

Cry me a river.


Elvium
(Stranger / Eraser)
10-21-00 23:34
Re: Bromosafrole prep.                                                                                                                                                                                                                             Reply
HBr (28%+) in GAA gives 90% yield BromoS, even in large batches.
 
 
 
 
    scram
(Hive Bee / Eraser)
11-03-00 19:00
No 66494
      Re: notes from frost  Bookmark   

7 ml water for 100g saf is way too much especially using dihydrate cucl2. At most per 135ml saf swinm used  4 ml water with anhydrous cucl2. 7ml would certainly require you to quad-druple the reaction time in MeOh (I dont know about ipa yet). I'm going to test 70ml oil against the normal 1/5 catylist ratios soon and the reduced solvent ipa volume with saf + 2ml water introduced in 3 increments over 1 hour. I'm hoping that yields will go above P this way. I remeber semtex post about this and that's why I decided not to try ipa but I'm willing to loose a little to gain alot of knowlege. Garden pressure sprayers are being used in swinm experiments. Coke bottles are too thin to use with the stirbar, eventually wearing a hole through the srv, particularly with 3 liter bottles. The average bug sprayer can safely handle 55-60 psi with no precautions (except keep the pump part pointed away from your face). Some sprayers will pop at 65 psi, others will bust  at 95, 2 gallon models will most certainly bust after 65psi (believe me, its not a pretty explosion either)
 
 
 
 
    pmpB_4
(Stranger)
11-03-00 22:57
No 66542
      Re: notes from frost  Bookmark   

the good o2s that swimn has seen have gone like this:
same pdcl2 cucl2 safrole to solvent ratios as everyone else is working with. 100ml safrole
with meoh and etoh at low presure 3 atm add 4ml if solvent is anhydrous. if stirring put in a cool water bath if shaking on an orbital do it in a cool room. stirring always takes longer 8-12 hours than shaking 4-5 hours.
if using high pressure 85psi don't add water
you can go by the color and the smell of the mix as to when it is done. meoh and etoh cause an exothermic reaction, hence the coolwater bath to prevent isomerization.
ipa works well also. the trick is to prestir the pdcl2 cucl2 and ipa at 1atm pressure for 24 hours. then proceed from there at 55-60c it can take from 3 to 10 hours for conversion it all depends on the size vessel you're doing it in and the power of your stirplate.
for extraction add hcl directly to the mix and stir 30 min to hydrolysise the ketal into the ketone, add water and extract with naptha for some reason this leaves the tar and iso behind.
 
 
 
 
    placebo
(irritable and cranky)
11-04-00 05:08
No 66575
      Re: notes from frost  Bookmark   

Thanks frost.

KrZ, what in your mind is the ideal O2 wacker from experience?


Wanna do the rumpy pump?
 
 
 
 
    Elvium
(Stranger / Eraser)
11-04-00 15:09
No 66655
      Re: notes from frost  Bookmark   

KrZ:

I remember a yoiung bee who hadn't had much success and asked a big bee who had. YOU stated that 50C in an UNLINED SS KEG with high pressure would work just great. So KrZ why don't you tell us just how well it works and who recommended it? 50C works well too eh..88%?

I'm just saying it didn't work given my attempt to recreate yoiur results and have given as much detail (unlike you) in an attempt to find where the problem might lay. Needless to say I won't follow your archiac advice again.

If its this easy why isn't someone out there making a kg a day using a stupid pop bottle??

Seems to me like you have all these elite 92% yeilding reactions that only you can re-create.

Tell me why HBr in GAA deosn't work for bromination? Just put in enough for a >1.2M ratio.
 
 
 
 
    Elvium
(Stranger / Eraser)
11-04-00 15:21
No 66658
      Re: notes from frost  Bookmark   

Oh KrZ, one more thing.

Your new special reaction can produce these amazing results at the 50g scale.. first try.
50g Safrole -->45g MDMA.HCL in 16 hours total for a 64%M yeild from safrole!!

At least I outline the procedure so others can attempt to re-create the XP rather than give obscure details, RVs only you can make, and the aid of 'message errased by krz'.
 
 
 
 
    DiethylEtherMan
(Stranger)
11-04-00 15:58
No 66666
      Re: notes from frost  Bookmark   

Prestirred w/ 3in egg bar: 50ml IPA with .25g pdcl2 & 1.25g cucl in 500 ml Fil Flask for 5 hours (unpressurized vessel). Pdcl2 looked fairly well absorbed. Started heavy stirring with 3in egg bar. Placed water bath on top of stirrer. Placed 500ml Fil flask in bath...Temp of bath with ice cubes came down to 40-45 F. Took temp of safrole (from frigerator) approx 60F. Added .25 ml sassy and 1ml dH20 to 500 ml Fil Flask with IPA, pdcl2, cucl. Took temp inside Fil Flask...waited til it came down to 60F. Temp of water was approx 40-45F. Sealed up with wire ties, hooked up 02 tank. (Just like FROST). Strapped on the motorcycle helmet this time. Pressurized to 45 PSI. Within 1st hour, drop of 4, down to 41 PSI. Repressurized to 50 PSI...Watched for an hour...barley a drop of 1 PSI. Went to bed for 5 hours or so. Added ice before I slept. Woke up...PSI was at 46. Again...only a drop of 4 PSI. Repressurized to 50 PSI again. Temp of bath had risen to approx 60F.  Added more ice cubes...temp came down again to 40-45F. With the next hour to hour and a half, a drop of maybe 1 PSI. Left home...continued the heavy stirring...that was 2 hours ago. Color was reddish brown with a faint haze of green...(oil probably).

Does anyone know why I am absorbing such a small amount of O2?

pmpb4: I did not pre-stir the IPA, pdcl2 & cucl for 24hours. Last time I tried with IPA (my first experience, BTW) I prestirred for 8 hours with no drop in pressure?? Will try again tonight with 24 hours pre-stirring IPA, pdcl2, cucl. Hope this works. Why does it need to be prestirred for 24 hours?

I just realized that someone said 55-60F...then someone else said 55-60C ? Which is it?

kprj.



If some of us were not so far behind, the rest of you would not be so far ahead!
 
 
 
 
    Beaker
(Hive Bee)
11-04-00 22:13
No 66738
      Let's look at the literature  Bookmark   

From JOC 34, 1969, 3949-3952


     A 50mL portion of 0.665M 1-hexene, 0.020M PdCl2 and 0.100M CuCl2 x 2H2O in 1-propanol was shaken for 120 min at 50C under 3 atm O2. The reaction mixture contained 2.0% water from all sources(salt hydration, impurity in the alcohol and water of oxidation). Of the hexene charged, 13%(by GC area) remained unreacted and 86% was converted into hexanone and 1.0% into side products. Resolution of the hexanone peak showed 75-76% 2-hexanone and 24-25% 3-hexanone.



     Assuming that the reaction rate is directly proportional to PdCl2 concentration, that the substitution of nPrOH for iPrOH does not affect the rate, and that the reaction rate is not concentration or substrate dependent, one can extrapolate a reaction time of ~11.5hr using 1g PdCl2/100g safrole at 50C.

     This is a crude approximation at best, but it may be of value if anyone is wondering why their oxidation is proceding slowly at 10-15C, which is significantly colder(slower rate of reaction) than the above example. Also, when the authors of the above article ran the reaction in with an increasing amount of water present, they observed a reduction in the rate of reaction, so the added water may be slowing the reaction down in this case.

 
 
 
 
    DiethylEtherMan
(Newbee)
11-04-00 23:41
No 66750
      Re: Let's look at the literature  Bookmark   

Beaker: I believe that was intended for me, and anyone else who needs to know since earlier in this post someone stated the water bath temp for the reaction was at 55-60F. I sincerley appreciate the tip. Thanx!

Where can one go to find this literature (journal references...college library?...Online?) that you posted above. Of course, I am a newbee. As we speak...after 24 or so hours of stirring at 55-60F...temp was brought up to 50-55C and PSI set at 45. Thanx again. Will post back with results.

How much dH20 is added after the HCI addition? (I saw someone mention 3/4??? 3/4 of what?)

kpjr.

To be loved is to be fortunate, but to be hated is to achieve distinction. --> Minna Antrim


If some of us were not so far behind, the rest of you would not be so far ahead!

 
 
 
 
    placebo
(irritable and cranky)
11-05-00 07:33
No 66832
      Re: Let's look at the literature  Bookmark   

Ok, here is an old thread I had saved, it is quite interesting and gives another idea of KrZ's for a pressure vessel.
*Note... This was prior to the soda keg idea!

Author Topic: Ketone for lazy people
KrZ
Member posted 01-12-99 01:32 PM
--------------------------------------------------------------------------------
I'll have to admit I'm pretty slak when it comes to shaking a coke bottle so recently the R&D team here has developed this vessel which has yet to be fully tested.
The stuff we used;

1 ft long 10" diam piece of PVC pipe
2 end caps for PVC pipe
2 x 1/2" male-male brass connector
Tire valve
1/2" brass screw-on endcap
PVC pipe sealer
2 nuts to attach to the male-male connectors
Gasolia Soft-Set
Thread Sealant with Teflon
Tire Pressure Gauge
Tank of Welding O2
1/2" Hi-pressure hose with screw caps (3ft or so)
Elec. tape or whatever
4l beaker, stirbar, stirplate

Take the PVC end-cap and drill 2 1/2" holes and one hole big enough for the tire valve. Put some Gasolia on the male-male connectors and screw them into the 1/2" hole. Screw the nuts onto the connectors on the inside of the PVC caps. install the tire valve and use some gasket sealer to make sure its nice and tight.
Seal the untouched PVC endcap to the pipe with the PVC compound. Place the capped pipe on the stirplate. Slide the beaker inside of the pipe (if its loose put some paper towels in there to stablize it and don't make it a tight squeeze so its hard to get out either). Place your standard list of SRV reactants in the beaker. Drop the stirbar in. Smear the Gasolia on the inside of the other PVC cap. Place the cap on the pipe and pull up and down while twisting so you ensure a good wide seal between the cap and pipe. Make a full loop with the tape around the hole pipe just do be sure (I did it twice to make an X pattern on top/bottom). Screw the hose onto the tank and brass fitting. Attach the tire pressure valve (If you've got a regulator on your O2 tank this isn't necess.). Spray the O2 into it with the other connector open, this way it pushes the atmosp. out. Cap the other male-male connector using Gasolia. Pressurize it on up to 125 psi (thats as high as I took it but who knows). Turn the stirrer on and wait 2 hours or so... You get the picture...

Anyway, the device has been constructed and pressure tested, but no runs yet. I'm assuming you would need to give it 2 hours but it could be less considering the ridiculous amount of O2 we'll be cramming in there. Its certainly alot harder to make than an SRV but once you've got it setup I think it has some minor advantages, I'll provide an update on how it goes in action as soon as I can.

...and here is how it proceeded.

KrZ
Member posted 01-14-99 11:18 AM
--------------------------------------------------------------------------------
I'm going to redistill to make sure;
In the beaker went;
3.5 g PdCl2, 45g CuCl, 295 g Safrole, 875 ml DMF.

Pressurized it up to 120psi, let it stir with a heavy ass vortex for about 2 hours(so hard a large portion of the bottom of the beaker was exposed and @#%$ was way up on the sides). Extraction as usual. Distilled off the DCM and everything else coming over before 142C, then came a fraction at 148C weighed it at 8.6g, and another one at 152C weighed it at 285g. First fraction was yellowish and had an odor, second fraction had no odor and was yellow-light-greenish with no smell. Remember this vacuum pump is retarded, it pulls safrole over at 127. I also tried using the silicone glass-joint stuff to make a seal and it didn't hold as well as the gasolia (I could hear it leaking). The room it was done in was about 50F.

...and then...

KrZ
Member posted 01-17-99 10:57 AM
--------------------------------------------------------------------------------
I went to a local welding supply place, they had regulators that went up to 100, 125, 150 and various other levels (with increasing cost the higher it was rated for) the one I got goes up to 125, as you might have guessed. It was a pain in the ass finding an adaptor to get it to connect to the 300psi presssure hose I bought, it was a 5/16" size regulator and the hose was 3/8", apparently a very uncommon combination cuz I had to go 5/16->1/2->3/8 with brass adaptors to hook it up. I'm perfectly content at 125, I didn't wash the filter cake when drying,(What filter cake????..placebo) left ml's of oil here and there in beakers, and knocked over a 250ml beaker with some oil in it, so I believe actual yields were very high. The PVC I bought only came in a 10ft piece at a time (got funny looks from the counter guy when I wanted only 1 ft) so I've got a big piece sitting in my backyard. I'm going to get an ABS pipe before I do it again as it seems Beagle was quite right (after reading up on it). Trying to think of a way to fit a big rubber o-ring around the inside of the pipe and designing some latches for quick snap-on loading ;-) I'm pretty satisfied with all yields but, I want to get something real nice and take a pic. of it and upload it for you guys to see.
Amination is currently proceding under nitrogen using 300g of MeAm in just enough MeOH to dissolve it (you need to dissolve the MeAm in methanol first and it takes an hour or so of careful checking   addn. to get it perfectly saturated, which is important!). You don't need to waste a kg!! Just wait longer, check the pH and adjust accordingly, use heavy ass stirring and you'll get the same yields!!

For removable endcap.

TheCat
Member posted 01-20-99 10:16 PM
--------------------------------------------------------------------------------
KrZ, one more thing. Have you had anyone more dreams at high preasure? If you have how were the yeilds?
Also I was a thinking. You want a nicer looking presure vessel? Go to the plumbing store and ask for a "clean-out" for you 10" ABS or PVC pipe. What a clean-out is is a section of pipe that looks kinda like an end-to-end pipe coupler with a big ass threaded plug in one side (if you go ask for one you will know what I'm talking about). What you would do is put the regular end cap on one end then attach the clean-out to the other end and there you have it. A preasure vessel with a screw on cap.

A good point by Semtex...
Semtex Enigma
Member posted 01-22-99 08:59 PM
--------------------------------------------------------------------------------
Small correction/note: The purpose of a regulator in situation which you are describing is not correct. You see when a regulator(say 125psi) is hooked up to the O2 tank, all it is doing is regulating the flow of gas through the tube from the regulator at a maximum pressure of 125psi. It does not control the pressure in the vessel, only how fast the gas enters it. To get an accurate reading of the pressure inside the pipe one would have to equip the vessel with a gauge.
I once suggested a modified version of Piglet's proposed bubbler for the wacker. You see I think that bubbling under atmospheric pressure would be uneffective, however I have reason to belive that it would indeed work under increased pressure. I will try to write up an outline for those in the position to dream of such things. If anyone is interested please let me know...

Results...
KrZ
Member posted 01-23-99 12:03 AM
--------------------------------------------------------------------------------

It was about 80%, theres still some more rexytal. in the IPA now so I don't know exactly yet. I just waited a little longer, was very careful dissolving my MeAm to assure saturation, and I filled it with nitrogn and capped w. a ballon each time, I also checked and adjusted the pH with a digital meter every 6h. Other than that its all been said before...
I told the guy at the welding place I would be injecting N2 into soil for an Ag. Exp. involving ag. engineering; oxygen/nitrogenation injection cost analysis for farms, etc. he believed every word, he said I'd need a tank and regulator, then he produced a brass piece with two pressure gages and another steel piece that fit into it with a big plastic knob and another gag, he said just hook the flow regulator to the tank and the pres. regulator up to it. Thats what you get for welding standard set up right? If the flow reg. was just on there I suppose all 1000osi or whatever that tank is at would come across, boooom! I've been looking at these stainless stell compressed gas tanks MSC direct has, 4.7 gallon capacity one for ex., some welding to attach a mechanical stirrer would be needed for anything bigger but I think a big stirbar and some fine tuning of the plate to get max spin would do it for this size. Could form alot of ketone that way....

Some wise words from psychokitty...
psychokitty
posted 02-22-99 08:58 AM
--------------------------------------------------------------------------------
As for KrZ's set-up, I have a little bit of information to offer.
I spoke recently to a machinist who know something about pressurized canisters and he told me that PVC pipe fittings are pretty resistant to corrosion and could possibly hold up to using the reactants directly in the container itself. But since one can't be sure, it probably would be best to conduct solvent tests.

The pressure and temperature ratings of PVC can be found printed on the sides of the pipe so that should make it easier to determine how much of a beating it can stand.

I also asked about the danger of explosion and he said that more than likely, there would be no danger as long as the temperature and pressure of the reaction did not exceed the limitations of the pipe's design. HOWEVER, if the pipe was dropped -- not even from very high up -- it could very likely break causing the undesired aforementioned explosion. And BTW, it doesn't matter if it is ABS or PVC or whatever as the impact from the released air alone could cause serious injury.

As for the easy access issue, the ends of the piping could be threaded, or installed with a threading adapter.

KrZ: I must admit that I am confused as to why you use so much O2 pressure when you could easily get away with less. We all know that 30 pounds is effective at transforming the alkene to the ketone in alcohol solvent in 2 hours using just regular air! So why not simply start with a little over 30 pounds and once the oxygen gets used up and the pressure goes down (to just a little under thirty pounds), simply inject more oxygen until 30 pounds is reached again?

Just a thought.
--Psychokitty

What type of plastic pipe should I get?
dpHarma
Member posted 02-22-99 08:24 PM
--------------------------------------------------------------------------------
the pipe of choice is HDPE high density polyethylene.
a great deal of study has gone into plastic pipes used for launching pyrotechnic aerial shells. when a shell explodes in it's launching 'mortar', the total combustible material is comsumed at once (or nearly) and the forces are confined in the tube.
PVC and ABS shatter into many small sharp fragments. HDPE tends to deform first and producess much less shrapnel.

dpHarma

Hope this helps a bit?
I like it!




Wanna do the rumpy pump?



 
 
 
 
    psychokitty
(Newbee)
11-05-00 19:39
No 66969
      Re: Let's look at the literature  Bookmark   

That proceedure seems like it would work -- a proceedure, mind you, that was offered by "respectable" KrZ, BEFORE he was supplanted by the "hallucinogenious".

Sheesh!  I wish KrZ was as concerned for my well-being as I was about his way back in the good old days.  If I knew then what I know today, I would have recommended that he amp the O2 pressure up to 300 Ibs -- just to see if he was keeping on his toes.

I'm through ranting.  But I do believe I'm going on a post-deleting binge. Maybe then I'll be as respected as KrZ is around here in New Hive.

--PK
 
 
 
 
    placebo
(irritable and cranky)
11-05-00 22:12
No 67011
      Re: Let's look at the literature  Bookmark   

Cool, and whatever posts you can't delete, we will make the board crash and have those posts lost forever. Ok?

Don't worry psychopussy, we will get to the bottom of this!

We are all in this together and we have nobody else to help us, so we might as well try and get along and work this shit out! (Fuck, now I sound like a god damn hippy! Fuckin love-everything E-tards!)

If not, then I shall just get fucked now and save you the time. K?

But anyway, there is some interesting info in my post above, something different to what is mentioned in this thread anyway. I really like KrZ's idea for rxn vessel. Any further word/comment on the PVC pipe vessel, KrZ?

Found it by accident in some old hive info I had saved a long time ago.


Wanna do the rumpy pump?

 
 
 
 
    placebo
(irritable and cranky)
11-05-00 22:47
No 67015
      Re: Let's look at the literature  Bookmark   

I noticed this in Frost's original post...

thank you bees that have helped swinf work the bugs out of this. f-man, semetex


WTF is up with that?
Semtex, have you attepted this rxn yet and/or helped Frost at all? (I know you have followed it a long time, as have I, but any hands-on?)
...and WTF did FMAN do for him, somebody please tell me that?

...Oh and what's with Frost saying he set O2 pressure by reg. on tank and not by pressure in vessel. ...and if he ever returned, (As if he isn't already talking shit under a new name), we could ask him if he had any idea what was the total psi drop over 10 re-pressurisations. Me thinks nowhere near enough.

Personally, as much as I would love to believe him, I think he was/is and always has been full of shit, and I will stick by that till the day I see him do anything other then set geese free.

That is not to say I don't believe others here. Lets just say it is a general dis-trust and cynicism I have had about him since he arrived. I am not the first to feel this way about him, more like the 1754th actually. (the other 542 are cops) I am also wary of all others that converse, substantiate and claim to be "mates" with him!

Now KrZ, pull your fucking dummy out and tell us everything! You know I wuv you big boy!



Wanna do the rumpy pump?
 
 
 
 
    zooligan
(Hive Addict)
11-06-00 06:35
No 67095
      Re: Let's look at the literature  Bookmark   


But anyway, there is some interesting info in my post above, something different to what is mentioned in this thread anyway.



You mean the solvent??

 
 
 
 
    placebo
(irritable and cranky)
11-06-00 06:47
No 67096
      Re: Let's look at the literature  Bookmark   

O2 pressure.
Type of vessel.



Wanna do the rumpy pump?
 
 
 
 
    zooligan
(Hive Addict)
11-06-00 07:35
No 67105
      Re: Let's look at the literature  Bookmark   

Yeah, that's a lot more O2.  This thred's so long now I couldn't find it, but didn't someone mention a set up like this in which you put a glass container inside another (more durable) container and pressurize the outer container??

Solvent is different than what has been talked about so far no?  Everything up to this point has been alcohol, not DMF, right?

z
 
 
 
 
    placebo
(irritable and cranky)
11-06-00 07:50
No 67109
      Re: Let's look at the literature  Bookmark   

Yeah its a pretty old thread, methanol and IPA were later developments.
Osmium's was with denatured I think.

The vessel, yeah the concept of something like it has been discussed, I just thought the PVC pipe was a good idea that hadn't been mentioned.


Wanna do the rumpy pump?
 
 
 
 
    KrZ
(Hallucinogenius)
11-06-00 07:56
No 67111
      Re: Let's look at the literature  Bookmark   

It certainly holds up to the pressure well.
 
 
 
 
    Precursor2112
(Newbee / Eraser)
11-06-00 09:12
No 67125
      Re: o2 is the shit  Bookmark   

Son of a Bitch!

Cold Fusion comes to Roll Makin!

O2 works!!!!

The O2 WORKS

the Coke bottle works...

39ml from 75ml of safrole.

<Pre just stood up and is suggestin a standing ovation>
 
 
 
 
    sYnThOmAtIc
(Hive Bee)
11-06-00 09:16
No 67127
      Re: Let's look at the literature  Bookmark   

I read an article in mother earth news not too long ago about building a vacuum/pressure vessel out of pvc seems like it would work. SWIK will go to HDS adn get stuff to build one and give results on pressure hold. But SWIK has recently bought a four quart stainless pressure canner he plans on giving a try. Fits perfectly into paint shaker :)
 
 
 
 
    KrZ
(Hallucinogenius)
11-06-00 09:19
No 67129
      Re: Let's look at the literature  Bookmark   

You better coat it with glass if you hope to get it to work.
 
 
 
 
    zooligan
(Hive Addict)
11-06-00 10:45
No 67152
      Re: Let's look at the literature  Bookmark   

What about epoxy or teflon paint?
 
 
 
 
    Semtex
(Hive Elder/ Old Fart)
11-06-00 18:15
No 67230
      Re: Let's look at the literature  Bookmark   

All the experience that SWIM had with this rxn happened a WHILE ago, long before our queen bee departed.  I've discussed it with frost, and perhaps some of the things I've told him helped him out somewhat...?  I don't really know, you'd have to ask him about it...


crazycrazy
 
 
 
 
    placebo
(irritable and cranky)
11-06-00 22:03
No 67265
      Re: Let's look at the literature  Bookmark   

He has gone and returned under a new name, I am sure you will pick who it is pretty easily. Gee, wonder why? Coz he's full of shit!


Wanna do the rumpy pump?
 
 
 
 
    KrZ
(Hallucinogenius)
11-07-00 11:31
No 67435
      Re: Let's look at the literature  Bookmark   

3.24g PdCl2
32.40g CuCl2ē2H2O
324.36g Safrole
70mL H2O
500mL DMF

Placed everything except the safrole in a 4L reactor, stirred heavily exposed to atmosphere for 4 hours.  Added safrole, removed atmosphere with vacuum. Pressurized to 35 psi O2.

Pressure drop (psi) Time after Last Drop (minutes)
15 17
15 18
15 20
15 20
15 29
15 38
~4 30

Total Reaction Time: 172 Minutes

Added 500 mL 5% HCl solution
Seperated precipitated Ketone/Aldehyde
Extracted 3x 100mL DCM
Pooled extracts
Wash 2x 300mL Saturated Sodium Bicarbonate solution
Wash 1x 400mL dH2O
Wash 1x 400mL Brine Solution
Dried Extracts with 50g Na2SO4 for 45 minutes
Filtered to Remove Na2SO4
Vacuum Distilled at ~2.0mm Hg to recover 311.22g Piperonylacetone fraction 105-114C.  Isosafrole forerun, minimal high bp/polymerzied glop after 114C.
Molar % Yield: 81%


 
 
 
 
    placebo
(irritable and cranky)
11-07-00 12:42
No 67452
      Re: Let's look at the literature  Bookmark   

Temp please?


Wanna do the rumpy pump?
 
 
 
 
    KrZ
(Hallucinogenius)
11-07-00 12:43
No 67454
      Re: Let's look at the literature  Bookmark   

Room temp. 65F According to the wall thermometor.
 
 
 
 
    Antibody2
( )
11-07-00 12:52
No 67458
      Re: Let's look at the literature  Bookmark   

Cool. Why the switch to DMF? How big was the stirbar?
Thanx


Iím gonna die when itís my time to die. Iím gonna live my life the way I want to!
 
 
 
 
    KrZ
(Hallucinogenius)
11-07-00 12:57
No 67460
      Re: Let's look at the literature  Bookmark   

The references seemed to indicate DMF was better.  All the patents etc. that I could find with IPA didn't have as good yields, absorption was definitely quick and noticeable.  The IPA/EtOH patents didn't have as high a selectivity as DMF or the sulfalone methods.
 
 
 
 
    Beaker
(Hive Bee)
11-07-00 13:35
No 67472
      Re: Let's look at the literature  Bookmark   

Just to clarify, are you now sayimg that you never got acceptable results with IPA? What about your older posts with EtOH/50C/80psi O2?
 
 
 
 
    placebo
(irritable and cranky)
11-07-00 13:50
No 67479
      Re: Let's look at the literature  Bookmark   

Ok so....

01-14-99 11:18 AM Krz says...

In the beaker went;
3.5 g PdCl2,
45g CuCl,
295 g Safrole,
875 ml DMF

Pressurized it up to 120psi
50F.
285g MDP2P


11-08-00 05:31 KrZ says...

3.24g PdCl2
32.40g CuCl2ē2H2O
324.36g Safrole
70mL H2O
500mL DMF

Pressurized to 35 psi O2.
60f
311gm MDP2P

So it seems from studying KrZ's figures that the O2 is not very fussy in regards to O2 pressure or water content and temp will probably only affect the rate of absorbtion.

The deciding factor is SOLVENT!
Now who has a good synth for DMF?


Wanna do the rumpy pump?
 
 
 
 
    KrZ
(Hallucinogenius)
11-07-00 14:09
No 67491
      Re: Let's look at the literature  Bookmark   

The DMF was 10% water in the PVC-a-ma-jig too, I just didn't write it in. blushblushblushblush
 
 
 
 
    KrZ
(Hallucinogenius)
11-07-00 14:11
No 67492
      Re: Let's look at the literature  Bookmark   

I got acceptable results with IPA, just more polymerization on the distillation, same with EtOH.
 
 
 
 
    placebo
(irritable and cranky)
11-07-00 14:46
No 67500
      Re: Let's look at the literature  Bookmark   

Remember this KrZ?

Wacker - sort of, solvent volume was cut in half, and the surfacant was left out (500 muL of Dawn), DMF works w/o surf.


Care to elaborate? Am I deciphering this correctly, that you were using a surfactant/PTC from a detergent, or you had some detergent in the DMF that fucked things?

So do you think that the solvent is the key (and the water) and the reason for most fuck-ups?

Hmm...What solvent did Os use, and what was his yeilds?
Os?



Wanna do the rumpy pump?
 
 
 
 
    placebo
(irritable and cranky)
11-07-00 15:37
No 67509
      Re: Let's look at the literature  Bookmark   

I have been doing some reading and found this bit of information.
If the solvent is the deciding factor between happiness and misery could this be the reason?


One of the advantages of dimethyl formamide
dimethyl amide and dimethyl sulfoxide is that
they are aprotic polar solvents and greatly
accelerate the rate of bimolecular nucleophilic
subsitution reactions since they solvate
cations but not anions. The naked anions
are thus highly reactive.

An example of an Sn2 is OH- + CH3CH2Cl -> CH3CH2OH + CL-.


Also did the old "UTFSE" (old board too) thing and found that DMF is "apparently" watched, and can only aquired through chem supply.

Can it be synthed?



Wanna do the rumpy pump?
 
 
 
 
    zooligan
(Hive Addict)
11-07-00 15:44
No 67513
      Re: Let's look at the literature  Bookmark   

Cebo's quote mentions DMSO as having some of the same properties as DMF.  Could it be used instead??

z
 
 
 
 
    KrZ
(Hallucinogenius)
11-07-00 16:27
No 67523
      Re: Let's look at the literature  Bookmark   

There's some DMSO sitting here doing nothing, maybe we can see what's up w. it.
 
 
 
 
    Semtex
(Hive Elder/ Old Fart)
11-07-00 20:29
No 67586
      Re: Let's look at the literature  Bookmark   

placebo, I think Osmium used MeOH as his wacker solvent, but that's just a rumor... wink


crazycrazy
 
 
 
 
    placebo
(irritable and cranky)
11-07-00 23:00
No 67615
      Re: Let's look at the literature  Bookmark   

I sorta remember reading somewhere that Os used denatured but can't be bothered looking to confirm that right now.

KrZ, can you elaborate a little on the IPA/EtOH/MeOH deal?
Water not as important as with DMF?
...and you said yeilds not as good as DMF, in what range are we talking?
As bad as the others got, like 30%max?
Are you adding the water with these other solvents as well?

Just trying to figure if the solvent is what is making the difference, or the water addition, because I don't think others are adding water and if so, not that much anyway.

I think if one could reliably get 60-70% yeild (by weight), this method will be revolutionary.



Wanna do the rumpy pump?
 
 
 
 
    Antibody2
( )
11-08-00 11:57
No 67813
      Re: Let's look at the literature  Bookmark   

Antibody always wondered why there was never any mention of DMSO in relation to wackers, as it shares some of DMFs properties. It is also a bit easier come by. Hmmmmmm. Any other bees got opinions on DMSO as a solvent for this baby.



Iím gonna die when itís my time to die. Iím gonna live my life the way I want to!
 
 
 
 
    KrZ
(Hallucinogenius)
11-08-00 15:46
No 67895
      Re: Let's look at the literature  Bookmark   

Solvents make a world of difference when it comes to wacker oxidations, huge changes can occur by varying them.  Check out US patent 4,661,642.  They oxidize a number of items in tBuOH with a NO2-Pd type catalyst and get large predominance of the aldehyde.  However, when they switch the solvent to glycol, using the same catalyst and reoxidant, the molar selectivity towards the ketone becomes 100%!!  It's at the bottom of the data table, decene is the starting olefin.  They mention a book "Palladium Catalyzed Oxidations of Hydrocarbons" looks like a must have!
 
 
 
 
    zooligan
(Hive Addict)
02-06-01 04:49
No 171405
      Re: Let's look at the literature  Bookmark   

Just thought it might be important to bring this thread to the top with the "successful DMF O2" thread.

z
 
 
 
 
    LaBTop
(Daddy)
02-06-01 08:05
No 171420
      Re: Let's look at the literature  Bookmark   

Also, on the subject of changing solvents, did you know, KrZ, that the solvent for reducing the decomposition explosion risk in catalytic hydrogenation (according to Rylander) is 2-methoxyethanol (methylcellusolve); whether it would be compatible with reductive amination is unknown to us. LT/


WISDOMwillWIN
 
 
 
 
    placebo
(irritable and cranky)
02-11-01 05:12
No 172815
      Re: Let's look at the literature  Bookmark   

Is anybody in a position to try a little DMSO experiment or is it going to be left up to me to make the ground-breaking discoveries for the masses, like in the meth forum? I may just keep it to myself this time! Seems to be the way things are done around here! TAKE, TAKE, TAKE!


I could explain it to you, but you wouldn't understand!
 
 
 
 
    Semtex
(Hive Elder)
02-23-01 22:52
No 175207
      Re: Let's look at the literature  Bookmark   

Does anyone have the solubility data for the glycol concerning the other stuff in the mix...? 


crazycrazy
 
 
 
 
    PVnRT_NC8
(Hive Addict)
02-24-01 04:59
No 175246
      Re: o2 is the shit  Bookmark   

i maybe isso;ting the anhydride i thomk something 03-
seems to ssalt u[ e,,u;sion] ir al fe b etc? it goes attemps to go milky then cooled then warmed this is a look as ya go titration never is the same??  sometimes it just goes entirelly milky help then it fallls out over a few days???? etc??


Amethystium   See Post 175370 (LaBTop: "Fman Thesis, the Answer", Methods Discourse) LT/
 
 
 
 
    KrZ
(Hallucinogenius)
02-24-01 12:43
No 175305
      Re: o2 is the shit  Bookmark   

I'm with FMAN.  FUUUUUUUUUUUCCCCCCCCCCCKKKKKKK!!!!!!!!!!!!!!!!!!!!!!!!!!!!