Author Topic: o2 is the shit  (Read 21479 times)

0 Members and 1 Guest are viewing this topic.

placebo

  • Guest
Re: notes from frost
« Reply #120 on: November 02, 2000, 10:47:00 PM »
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

  • Guest
Re: notes from frost
« Reply #121 on: November 02, 2000, 11:29:00 PM »
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 (missing)

(Player 19: "keg 02 Wacker", Methods Discourse)

Post 107871 (missing)

(pHas3d: "Updates on O2 wackers...", Methods Discourse)


zooligan

  • Guest
Re: rxn notes
« Reply #122 on: November 03, 2000, 05:44:00 AM »

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

  • Guest
Re: notes from frost
« Reply #123 on: November 03, 2000, 09:06:00 AM »
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

  • Guest
Re: notes from frost
« Reply #124 on: November 03, 2000, 12:03:00 PM »

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

  • Guest
Re: notes from frost
« Reply #125 on: November 03, 2000, 12:56:00 PM »
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 srv’s? 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. :)


Jimi loves ya

Elvium

  • Guest
a
« Reply #126 on: November 03, 2000, 01:01:00 PM »
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

  • Guest
Re: a
« Reply #127 on: November 03, 2000, 01:43:00 PM »
Orbital shakers don't get quite as good agitation.  What were your bp's, vacuum, bisulfite weight, etc?

placebo

  • Guest
Re: a
« Reply #128 on: November 03, 2000, 02:38:00 PM »
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

  • Guest
Re: a
« Reply #129 on: November 03, 2000, 03:15:00 PM »
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

  • Guest
Re: notes from frost
« Reply #130 on: November 03, 2000, 04:24:00 PM »
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...


::)  ::)

psychokitty

  • Guest
Re: notes from frost
« Reply #131 on: November 03, 2000, 05:44:00 PM »
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

  • Guest
Re: notes from frost
« Reply #132 on: November 03, 2000, 05:56:00 PM »
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

  • Guest
Re: notes from frost
« Reply #133 on: November 03, 2000, 07:00:00 PM »
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

  • Guest
Re: notes from frost
« Reply #134 on: November 03, 2000, 10:57:00 PM »
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

  • Guest
Re: notes from frost
« Reply #135 on: November 04, 2000, 05:08:00 AM »
Thanks frost.

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


Wanna do the rumpy pump?

Elvium

  • Guest
Re: notes from frost
« Reply #136 on: November 04, 2000, 03:09:00 PM »
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

  • Guest
Re: notes from frost
« Reply #137 on: November 04, 2000, 03:21:00 PM »
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

  • Guest
Re: notes from frost
« Reply #138 on: November 04, 2000, 03:58:00 PM »
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

  • Guest
Let's look at the literature
« Reply #139 on: November 04, 2000, 10:13:00 PM »
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.