dunkel (Stranger)
02-14-01 00:34
No 173179
      Cure for alcohol Wacker?     

Bees that are interested in performing the alcohol Wacker with high yields may want to check out the following patents: US 3410807 and 3475461.

Both are by the author of the original paper describing the wacker process using alcohol.

The info:

the first patent gives a detailed description (example 6) of the oxidation of styrene (the closest relative to our favorite alkene). He indicates that there are a number of side products, including the aldehyde as well as isomerization that hurts yields. He concludes that the best solvent for styrene is methanol which produces the highest conversion and least side products. In this example H20 concnetration was 0.7 percent.

In the 2nd patent he admits that the previous method (above) produced the desired product (ketone) but in poor yields due to side reactions and other products (isomerization and aldehydes, etc.). To correct this he uses an inhibitor to prevent side reactions and improve the yield. These happen to include hydroquinone and benzoquinone among others.

In an example using styrene, by simply adding hydroquinone to a typical wacker oxidation  using O2, CuCl2 and ethanol the yield jumped from 59% to 74% and also decreased side reactions. In this case no water was added so the final product, an acetal, had to  had to be hydrolyzed with acid to form the desired ketone.

We all know the wacker works. With DMF and O2 or benzoquinoe the yields are good. With MeOH and benzo the yields are good. But with alcohol and O2 the yields aren't so hot. Maybe this can help? Use MeOH, add hydroquinone and hydrolyze at the end.
 
 
 
 
    Antibody2
( )
02-14-01 21:08
No 173328
      Cure for alcohol Wacker?     

More than interesting, thank you dunkel.
 
 
 
 
    sassy_sucker
(Hive Bee / Eraser)
02-14-01 21:52
No 173338
      Re: Cure for alcohol Wacker?     

Someone care to try this and report back?

I don't have any pressure vessels, unfortunatly.  If this were to work well, it would still accomplish the same goal of it being very OTC.  (hydroquinone is sold at every photo store)

 - ss


how would you fuck me?
 
 
 
 
    LaBTop
(Daddy)
06-05-03 01:34
No 437839
      Did anyone ever tried this??     

And what would the product(s) be from a methanolic wacker: PdCl2, CuCl2, MeOH and Safrole with a touch of hydroquinone (and NO water addition!) pressurized with O2 where safrole were used and not the styrene?
Read both patents!
If you use the wacker oxidation to make your MDP2P, a common byproduct is  Methylenedioxyphenylpropanal (also called "MDP3P"), and as this also will form a bisulfite adduct, you cannot remove that with Bariums new procedure to clean up impure ketone. All impurities with a carbonyl function (aldehydes/ketones) will form bisulfite adducts (piperonal and Methylenedioxyphenylacetaldehyde are other examples).

How exactly would you hydrolize that product(s), with how much and what diluted acid?

See f.y.info:
../rhodium/chemistry /wacker.krv.html
See his remarks: Dont heat this stuff in any way while preparing. Heat favors aldehydes. The refs say that isomerization is decreased with control over 2 factors:
you must keep the oxygen available.
you must keep it cool. Not cold, just cool...say around 20C or so.
../rhodium/pdf /wacker.propenylbenzenes.pdf
../rhodium/chemistry /wacker.cyclodextrin.html   New Catalytic System for Ketone-selective Wacker Oxidation. HolyShit!!!!  LT/

WISDOMwillWIN
 
 
 
 
    Osmium
(Stoni's sexual toy)
06-05-03 12:43
No 437946
      You have to heat it, otherwise the reaction...     

You have to heat it, otherwise the reaction won't take place.

Hydroquinone addition only makes sense with styrene because styrene polymerizes easily. Since our precursors don't undergo radical polymerisation this is not an issue.

I'm not fat just horizontally disproportionate.
http://www.whatreallyhappened.com
 
 
 
 
    raffike
(Hive Addict)
06-05-03 12:52
No 437948
      If you use the wacker oxidation to make your...     

If you use the wacker oxidation to make your MDP2P, a common byproduct is  Methylenedioxyphenylpropanal (also called "MDP3P"),
Is MDP3P an alcohol or rather substituted propiophenone?
and as this also will form a bisulfite adduct
Somebee just mentioned propiophenones doesn't form bisulfite adducts.See Post 57305 (psyloxy: "Re: practising on legal substances", Newbee Forum)

For those about to synth,we salute you
 
 
 
 
    Barium
(Hive Addict)
06-05-03 13:25
No 437950
      No     

MDP3P is a aldehyde. I've been taught that propiophenones doesn't form bisulfite adducts due to steric hindrance. I've never verified this myself though.

Freaky
 
 
 
 
    raffike
(Hive Addict)
06-05-03 13:31
No 437953
      an aldehyde?     

an aldehyde?


For those about to synth,we salute you
 
 
 
 
    Barium
(Hive Addict)
06-05-03 14:23
No 437960
      That damn nomenclature.     

That damn nomenclature. I call MD-propiophenone MDP1P not MDP3P. Well well!

Freaky
 
 
 
 
    raffike
(Hive Addict)
06-05-03 14:34
No 437961
      MDP-1-P is an aldehyde,i agree.But according...     

MDP-1-P is an aldehyde,i agree.But according to that we may easily say that MDMA made from wacker ketone is about 15% some wierd product.Amines condense with aldehydes also right?MDP1P bp is about 5-10 C higher than MDP2P's but most bees distilling ketone collect everything over 20-30 C range so that aldehyde comes probably also over.

For those about to synth,we salute you
 
 
 
 
    Rhodium
(Chief Bee)
06-05-03 20:04
No 438020
      MDP1P = MD-propiophenone, MDP3P = aldehyde     

No, MDP1P is the propiophenone and MDP3P the aldehyde. For correct numbering, the MD-Phenyl ring is placed in the 1-position and not in the 3-position.
 
 
 
 
    raffike
(Hive Addict)
06-05-03 20:17
No 438024
      Maybe so,but that aldehyde,call it P1P,P3P or...     

Maybe so,but that aldehyde,call it P1P,P3P or whatever you like still finds its to final product as a secundary amine amine,it might not make any noticeable difference but still...
People get upto 80% w/w yields(rarely more) from Wacker and say it's higher yielding than peracid oxidation(upto 75% w/w yields,rarely more) but if this 80% yield stuff from Wacker contains 15% of aldehyde,it makes total yield of ketone 15% lower,like 68% w/w or so and in that case the performic acid oxidation is higher yieldingsmile and gives purer product.
BTW. 1-MDP-3-P is an aldehyde,MDP-3-P is a propiophenone.

For those about to synth,we salute you
 
 
 
 
    Rhodium
(Chief Bee)
06-05-03 20:27
No 438031
      MDPxP     

1-MDP-3-P is an aldehyde,MDP-3-P is a propiophenone.

That makes no sense to me... Go back and check the usage of MDP3P and MDP1P over the years at the Hive - as good as everyone uses the nomenclature I described.
 
 
 
 
    Argon
(Stranger)
06-05-03 21:00
No 438040
      bisulfite adduct formation     

All the resulting molecules from the O2 wacker form bisulfate adducts.

___________________________________________________________

LabTop recetly e-mailed me this:
--------------------------------------------------------------------------------
________________________________________

Subject: Copy: Re: what is your point?
From: Argon
Received: 06-05-03 01:39


In reply to:
I read the link that you have suggested, and what is your point?

You are saying that you conspired with other Hive members to modify info throughout the Hive and Rhodium in order to confuse the same people that you trying to teach?
LT/: Where did you get that idea from in any of my texts???


*************************************************

Now first read Post 171271 (LaBTop: "Successfull DMF O2 Wacker", Methods Discourse),
and especially this remark from Antibody2 there :
Post 171802 (Antibody2: "Re: my exploited private email", Methods Discourse)  :
""Ahem, actually the reason I beleive those rxns failed was because KRZ posted 50 deg Farenheit when it was supposed to be 50 deg Celsius. Everyone who followed those directions applied cooling and the results were completely uniform - fuck all(or close eneough).
KRZ then went in and deleted all his posts (the one above came much later) to destroy the evidence.
I still don't believe frosts post in that thread he also claimed it happened in 2 hours and 50F.
Prestir was NOT the issue. And the DMF and Alcohol wackers are two different rxns. No one ever has doubted the DMF wacker, that I am aware of.
The reason those chemists failed was because they were stupid eneough to blindly follow either KRZ or Frost's advise. Whether thier dis-info was posted intentionally or by accident I don't know. They should have checked the refs themselves. Yes antibody included. It was actually a very cheap lesson in trust. DON'T. Get it from the horses mouth. I learned my lesson I hope the others did as well.""


I think I found the moment in that thread of yours where I have lost you, and most of us btw:
Post 434362 (Argon: "REPLY To SPISSHAK", Methods Discourse).

Imagine yourself what I see when I look at the thread list in a forum and click at your thread, because there's a (1) behind it, meaning there's one new post:
I see solely your former post(434360), and your new one (434362). I opened that post at my time 24:00 hr.
Then it took me 7 hours to construct and post my answer (Searched a lot on the topic and inbetween read several other forums!), so I missed the 3 later posters inbetween, especially your next post (434467)!

You put me on the wrong leg with that sudden link to the DMF/O2 wacker, where lots of people in the past have discussed if this one should be externally heated to 50 C!
Thus, when you say in the next line that"" Also, I read someone saying on this board that if you don't run this hot"", I interpreted this as related to that DMF/O2 post at Rhodiums.

So, back to that famous post of you:
""""SPISSHAK, I fucking love you man!

I think you nailed it with the ketone problem.
I never was able to find an MSDS for the commercially available ketone, not where I shop anyway. But after your reply I was forced to search about 20 minutes. Internet search produced an MSDS from some Korean company. I could not understand what the fuck it says there, but what I did understand is: b.p. 132 @ 2mm/Hg, 141 @ 4mm/Hg. Fuck, you have to run the shit hot And I am pulling about 6mm.

I guess terbium is full of shit. Fuck, Rhodium too? NO
And half of these lyeing motherfuckers on the Hive. 25 degrees higher then the saf...
If I ever run into them...... """"


Let's see what you probably mean there to explain:
(Take in account I am just now realizing you must be Argox)
You were referring there to the first Spisshak post, not the one just above this post of yours.
Where he doubted you'd made MDP2P because of your mentioned Bp for MDP2P.(This I realize just now, thought then you referred to Spisshaks post just above, which did not give me a clue what the hell you were referring to).
But this line is still a mystery to me:
""b.p. 132 @ 2mm/Hg, 141 @ 4mm/Hg. Fuck, you have to run the shit hot And I am pulling about 6mm.""

WHAT shit you have to run hot? The MDP2P to test the Bp at atmospheric???
Or the whole hydrogenation of MDP2P in the reaction vessel???
And where does that ""And I am pulling about 6mm"" refer to??? That your measured Bp at 6mm should be even higher than the mentioned two from the MSDS at 2 and 4mm/Hg???

Then I lost you totally on the connection to Terbium and Rhodium beeing full of shit after that mysterious line!
BUT Especially: 25 degrees higher than the saf...

You got your answer already in the very first line of the very first poster, ""mdp2p boiling at 120 degrees??""  Those ?? indicated nonunderstanding of: ""safrole (b.p. 97-101 C) "" and ""178g of yellow MDP2P was recovered. B.p. 122-128 C. ""
I expect you tried to put your thoughts: "25 degrees higher than the saf", in an extreem small window:
Extrapolated from 2 to 4 to 6 mm/Hg, your expected MDP2P literature Bp's must have been 132-141-150 C at those pressures, but you mentioned you'd measured 122-128 C! That's about 25 C higher, yes, the difference between +/- 150 C or +/- 125 C.

BUT, it's also about 25 degrees higher difference between your mentioned measured Bp's of saf: 97-101 C and MDP2P: 122-128 C with your pump!!!

So what is there to get so exagerated about??
And what is there to be fixed at Rhodiums DMF/O2 wacker procedure on Rhodium??
LT/

PS: Boiling points at normal pressure (760mm/Hg) :
Safrole : 233.5 C
MDP2P   : 286   C
See Post 103961 (dpHarma: "Re: Boiling points chart", Chemistry Discourse)

PS2: Post 173179 (dunkel: "Cure for alcohol Wacker?", Methods Discourse),

""""In the 2nd patent he admits that the previous method of the first patent produced the desired product (ketone) but in poor yields due to side reactions and other products (isomerization and aldehydes, etc.). To correct this he uses an inhibitor to prevent side reactions and improve the yield. These happen to include hydroquinone and benzoquinone among others.

In an example using styrene, by simply adding hydroquinone to a typical wacker oxidation  using O2, CuCl2 and ethanol the yield jumped from 59% to 74% and also decreased side reactions. In this case no water was added so the final product, an acetal, had to be hydrolyzed with acid to form the desired ketone.

We all know the wacker works. With DMF and O2 or benzoquinoe the yields are good. With MeOH and benzo the yields are good. But with alcohol and O2 the yields aren't so hot. Maybe this can help? Use MeOH, add hydroquinone and hydrolyze at the end. """"


PS3: ../rhodium/chemistry /wacker.cyclodextrin.html   New Catalytic System for Ketone-selective Wacker Oxidation.  !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!

PS4: ../rhodium/chemistry /wacker.krv.html
Read all his comments, especially this one:
Dont heat this stuff in any way while preparing. Heat favors aldehydes. The refs say that isomerization is decreased with control over 2 factors:

you must keep the oxygen available.
you must keep it cool. Not cold, just cool...say around 20C or so.

________________________________________


you must keep the oxygen available.
you must keep it cool. Not cold, just cool...say around 20C or so.


I am sorry,  but you are full of shit. It is obvious to me that you never ran this reaction. And the procedures to which you have provided links are inaccurate. And the fact that you have changed over a series of posts on the Hive and on Rhodiums page, including Pihkal relating to the properties of MDP2P and its boiling points is unacceptable.
 
 
 
 
    raffike
(Hive Addict)
06-05-03 22:42
No 438063
      That makes no sense to me...     

That makes no sense to me... Go back and check the usage of MDP3P and MDP1P over the years at the Hive - as good as everyone uses the nomenclature I described.
Yeah,me too but it seems that my chemdraw program gives wierd drawings...


For those about to synth,we salute you
 
 
 
 
    LaBTop
(Daddy)
06-06-03 04:59
No 438141
      Argon:     

You seem to have difficulties with reading dates:
I first showed you that in Sept 2001 Antibody2 at last lead the way to explaining why you need to heat the vessel to 50 C and not cool to 50 F.
Small typo from KrZ, no need to nitpick too long about that.
Does that 50 C looked like roomtemp to you? No? Ok.

Then I try to let you read an old 1998 thread which is still up on Rhodium/ws from "Ketone", the only alcoholic wacker description-line in the Rhodium wacker part, with a whole lot of personal interpretations from the writer in it, so you can see WHERE all that misunderstanding about the right temp started from.
There was a LOT of discussion since 1998 about the followup wacker-KRV procedures done by others later. Totally normal for a newly introduced procedure. It all evoluted in the O2 wackers we know of by this date.

No, you only cut and paste my highlighted exerpt from that 1998 thread and jump to conclusions. As usual the wrong ones.


Btw, I still didn't get an explanation about your attack on these helpfull people, who's help you obviously ask for and need so hard to succeed, but when you misinterpret or misunderstand their guidance you start discredit them.
Still didn't hear an explanation for your rude behavior, so you start pissing on me for a change?
 
The boiling points for MDP2P and safrole came from a quick search :
Post 103964 (Osmium: "Re: Boiling points chart", Chemistry Discourse),
To confuse you even more:
Post 102339 (Atomicdog: "Improved Boiling Points Chart", Chemistry Discourse),
just found with another quick search.
Good luck with determining the real exact MDP2P boiling point you will trust.

What the hell are you thinking? That you are a freeloading member of some unfailing top notch chemistry journal?

We just try to collect as much knowledge as possible, against all suppression, and do the best we can together to finetune all posted procedures on a daily basis and help everyone out with all their hundreds of questions per day. For free.
The only thing we ask in return is to post your experiences, so you all can learn from the good ones and the bad ones, and we can reach a consensus about the liability of as many procedures possible.
Sure there are still some uncertain procedures hanging around, we'll weed them out or correct them, whenever we find them.  tongueLT/

WISDOMwillWIN
 
 
 
 
    abolt
(Hive Addict)
06-06-03 05:37
No 438149
      Argon     

Argon, I suggest you go back and read the opening page:-

You may find information as well as misinformation about hazardous, poisonous, or explosive chemicals and methods. All information is given only for those who have the theoretical background, the practical experience, the proper equipment, and a valid permission. Any accidents or legal problems are not the responsibility of this site.

The onus is on you

"We settled on the one issue that everyone could agree on." (Paul Wolfowitz)
 
 
 
 
    Barium
(Hive Addict)
06-06-03 11:53
No 438201
      Raffike     

Now I see what you are missing.

By writing (3,4-methylenedioxyphenyl)-1-propanone you have specified that the functional group (the carbonyl) is on carbon no. 1, this is where you start counting carbons. Thus the phenyl ring ends up on carbon no. 3. The more correct name is (3,4-methylenedioxyphenyl)-1-propionaldehyde since it isn't a ketone. According to IUPAC the name is 3-Benzo[1,3]dioxol-5-yl-propionaldehyde. Do you notice that their name also places the phenyl ring on carbon no. 3. The last part of a name is the "backbone" of the molecule. In this case it is the propionaldehyde.

By writing 1-(3,4-methylenedioxyphenyl)-1-propanone you have specified that both the functional group and the phenyl ring is attached to carbon no. 1. Now you get the propiophenone.

Freaky
 
 
 
 
    Argon
(Stranger)
06-10-03 20:48
No 439114
      LaBTop     

Btw, I still didn't get an explanation about your attack on these helpfull people, who's help you obviously ask for and need so hard to succeed, but when you misinterpret or misunderstand their guidance you start discredit them.
Still didn't hear an explanation for your rude behavior, so you start pissing on me for a change?


I am sorry if I was rude, but my thrustration with the bullshit on this forum, and I guess my chemistry skills is obviously spilling over.

Why did you changed over a series of posts on the Hive and on Rhodiums page, including Pihkal relating to the properties of MDP2P and its boiling points?  I really need to know.

I am going to give you a taste of your own chemistry.
 
 
 
 
    LaBTop
(Daddy)
06-10-03 23:16
No 439153
      Huh?     

""Why did you changed over a series of posts on the Hive and on Rhodiums page, including Pihkal relating to the properties of MDP2P and its boiling points?  I really need to know.""

As I said in the former posts, I did a quick search 2 times already, and didn't find any boiling point or bp of MDP2P mentioned by me. Please enlighten me, especially that "including Pihkal" remark. Or was this aimed at another member?

Search: LaBTop, "boiling point of MDP2P"  : no matches.
Search: LaBTop, "boilingpoint of MDP2P"   : no matches.
Search: LaBTop, "bp of MDP2P"             : no matches, exept Post 434498 (LaBTop: "???", Methods Discourse), from 21 May, which asks you why you can't find the "bp or boiling point of MDP2P", (--WITHOUT-- my name attached), just put that in your own Search, which should have given you the same results as I already offered you in above posts.

I do however mention trillions of times the boiling points of MDP2P at reduced pressures.
Btw, the real boiling point of   --PURE--  MDP2P is not often encountered by COOKS, caused by the fact that nearly all Hive and Rhodium procedures to get to this precious commodity will let them create a mixture of goodies and more or less impurities, which have a different combined bp.
Just as well as a bp of impure MDP2P under vacuum is affected by the same burden, and there is always a boiling traject to observe, not a specific fixed boiling point.
F.ex.: MDP2P boiling at 10 mm Hg or 10 mbar from 148 to 165C. Or from 145 to 162C, etc.

Part of the quite wastefull discussion we are having, is based in fact on the poor Search skills of yours, which I can't help for, sometimes you have to be creative, use "bp" or "boiling point" or "boilingpoint" or "methylenedioxyphenyl-2-propanone " , "MDP2P" or "MDP-2-P", etc, etc.
Even better is open a Merck and look it up. And then you still are not really helped definitely, see above.
Or use any other of the multiple links to online databases on chemicals all over this board and the internet, or just Google.
And this poor skill didn't help you eather in looking up as many posts as there are on the subject of alcoholic wackers, and put them in a TIMELY manner, so you can start doubting older posts and get more trust in younger ones.
And first do some research via Google or Scirus or Orgsyn etc, to get some insight in wacker literature, which would have given you at the very beginning the security that you need to warm up an alcoholic wacker.
You seem to accept it from others, just not from me, so I have to force you into believing the facts by asking others.
You also seem to act, and type, VERY impulsive, this is REALLY a dangerous habit for a cook, too fast working can blow you up. Take the time to retrospect on procedures, thoughts and acts, it could save you from disasters.
Must be the lengthy typing of mine which makes you aggressive in some wacky way.tongue
Stay off the boose. LT/

Btw, enough tasted of my chemistry? tongue

WISDOMwillWIN
 
 
 
 
    madprosr
(Hive Bee)
06-11-03 00:16
No 439168
      cure swim's o2 wacker?     

swim tried to follow ritter's procedure as closely as possible-

dried some IPA (forget how much) over 80g, then 20g, 10g, 5g MgSO4.1h2o
fractionally distillled some safrole at 124C, safrole had just a tiny hint of yellow in it.

stirred 275ml IPA, 1.5ml h2o, 1g photographic PdCl2, 2.8g acs-grade CuCl2.2h2o, then 50g safrole and placed in a 2L soda bottle.

swim tested the krv several times by pressurizing to 40 psi, he then measured the pressure at 35 psi, apparently 5 psi escapes when the o2 tank is disconnected.

swim pressurized the krv to 40 psi, shook 5 minutes, then 4 times he placed on a 40-45C water bath for 10 minutes and shook for 10 minutes. this was repeated a total of 6 times. when swim stopped shaking, the solution was 1/2 foamy bubbles and 1/2 liquid, the bubbles would break up in 10 seconds or so. the solution stayed dark brown the entire time.

Pressure        PSI Drop
32 (+- .5psi)   3
30              5
32              3
33              2
33.5            1.5
34.5            0.5

total pressure drop was 15 psi instead of an expected 28 psi and the solution remained dark brown.

extracted 4x 50ml DCM, washed 2x 100ml, 4x 75ml brine. two days later swim distilled a few grams of forerun starting at 56C (BP for safrole) but mostly from 85-92C. distilled 29.4g suspected-ketone from 94-100C.

threw 20g in a textbook Osmium Al/Hg. the reactin got hot, but more slowly than normal, ketone was drippped in over 30 minutes and the reaction built up to a 1 drop/10 seconds reflux about 30 minutes after that.

extracted with 100ml, 5x 50ml toluene, then washed with 4x 75ml brine. dried over 20g MgSO4, toluene was clear at this point. gassed with hcl to yield a miniscule amount of crystals and some yellow toluene with a bit of brown oil sitting on the bottom.

anybody know what went wrong? safrole purity?
not enough CuCl2 used for 35psi KRV reaction with hand-shaking?
run the fucker in MeOH instead?

is this fake ketone MDP-3-P? the aldehyde...?

help swim out and he just might wack some asarone and make tma-2 for ya!
 
 
 
 
    LaBTop
(Daddy)
06-11-03 00:48
No 439180
      Photographic PdCl2     

There was someone mentioning lately he haqd never success with that grade PdCl2, then he ordered from a genuine chem source, and suddenly all went well.
That's all I can see in a quick read. LT/

WISDOMwillWIN
 
 
 
 
    madprosr
(Hive Bee)
06-11-03 01:00
No 439186
      ah, but photo-grade PdCl2 works fine for the...     

ah, but photo-grade PdCl2 works fine for the benzoquinone wacker, right?
what about the DMF o2 wacker?

the PdCl2 sure is a nasty brown-red. if one were to make it himself with Aqua Regia does it come out this color?
 
 
 
 
    LaBTop
(Daddy)
06-11-03 01:34
No 439197
      1     

I would strive to obtain chem grade PdCl2 for any wacker.

../rhodium/chemistry /palladium.chloride.txt  :

"" J. J. Berzelius prepared palladium dichloride or palladous chloride, by evaporating to dryness a solution. of palladium in aqua regia, and dehydrating
the residue by a gentle heat. L. R. von Fellenberg obtained the chloride, as a rose-red sublimate, and a garnet-red mass, by heating palladium
sulphide in a current of chlorine; and E. H. Keiser and M. B. Breed obtained it as a sublimate by heating spongy palladium to dull redness in
chlorine; the anhydrous chloride can be distilled at a low red-heat in a current of chlorine when it yields a sublimate of deliquescent, dark red,
acicular crystals. N. W. Fischer obtained a solution. of the chloride by exposing palladium to hydrochloric acid and air; the process of dissolution
is then a slow one. If chlorine is passed into hydrochloric acid in contact with palladium, the metal dissolves quickly to form the dichloride; and if
nitric acid is added to the hydrochloric acid, some palladous nitrate is formed. By evaporating the hydrochloric acid solution over quicklime, the
chloride is obtained in reddish-brown, prismatic crystals, which, if free from nitric acid, remain dry. L. N. Vauquelin found that when palladium is
dissolved in aqua regia, and the nitric acid removed by repeated evaporation with hydrochloric acid, there remains a brownish-yellow, crystalline
mass, which, according to the analyses of R. J. Kane, is the dihydrate, PdCI2-2H2O.

The dichloride obtained by dehydrating the dihydrate is a browniish-black mass; the sublimed salt appears as rose-red, or dark red, acicular crystals;
the unsublimed salt is a garnet-red crystalline mass. The dihydrate forms reddish-brown, prismatic crystals. V. M. Goldschmidt said that the crystals
are probably rhombohedral. L. Pauling discussed the structure. E. H. Keiser and M. B. Breed gave 2.5 for the sp. gr; and G. Beck, 4.00 for the sp. gr.
at 18 degrees and 44 for the mol. vol. J. J. Berzelius observed that the anhydrous salt fuses without decomposition when gently heated in a glass
vessel; when fused in a platinum vesed, it acquires a bluish-green colour by taking up platinum chloride. When.strongly heated, chlorine and palladium
are formed. F. Puche found that the dissociation begins at 600 degrees, and attains one atmosphere of  pressure at 920 degrees. ""


The sublimate appears in several methods as rose red. The sublimate should be concidered as the purest form.  So if you have nasty brown-red PdCl2, it's time to find a new source perhaps?

Realize yourself that there could be about 20 other reasons why your test failed. I just begin with the most obvious one. LT/

WISDOMwillWIN
 
 
 
 
    Osmium
(Stoni's sexual toy)
06-11-03 12:52
No 439327
      Some photo suppliers used to sell Na2PdCl4 or...     

Some photo suppliers used to sell Na2PdCl4 or some such shit.
I'd use MeOH instead of IPA as the solvent.
AND DON'T ADD WATER!!! WATER SLOWS THE REACTION DOWN!
Once the reaction is finished add water to destroy the ketal intermediate. pH should be slightly acidic.

I'm not fat just horizontally disproportionate.
http://www.whatreallyhappened.com
 
 
 
 
    abolt
(Hive Addict)
06-11-03 13:19
No 439331
      Fester PDCL2     

Whilst on this topic. Are you guys suggesting that Palladium Chloride made by conversion of a Palladium ingot immersed in a solution of Hydrochloric Acid which then has current passed through it(as commonly popularised in Festers book), would be of an insufficient quality for an O2 wacker?

Heavens just a rumor she'll dispel
As she walks me through the nicest parts of hell
 
 
 
 
    LaBTop
(Daddy)
06-11-03 13:47
No 439334
      Fester?     

Do realize that most industrial (non chemgrade) HCl solutions contain quite some impurities, f.ex. nitric acid.

See post above:
""N. W. Fischer obtained a solution. of the chloride by exposing palladium to hydrochloric acid and air; the process of dissolution is then a slow one.
If chlorine is passed into hydrochloric acid in contact with palladium, the metal dissolves quickly to form the dichloride; and if nitric acid is added to the hydrochloric acid, some palladous nitrate is formed.
By evaporating the hydrochloric acid solution over quicklime, the chloride is obtained in reddish-brown, prismatic crystals, which, if free from nitric acid, remain dry.
L. N. Vauquelin found that when palladium is dissolved in aqua regia, and the nitric acid removed by repeated evaporation with hydrochloric acid, there remains a brownish-yellow, crystalline
mass, which, according to the analyses of R. J. Kane, is the dihydrate, PdCl2.2H2O.""

When doing this Uncle Fester procedure, I would only work with highest grade 33-35% HCl solution, 99.9% pure HCl from a HCl gas cylinder, bubbled through dH2O, to get superclean HCl solution.
I would also check my Pd ingot for impurities at the maker.
I haven't done it, so that's my 0.02 cents added. LT/

WISDOMwillWIN
 
 
 
 
    Argon
(Stranger)
06-11-03 22:37
No 439419
      LaBTop     

As I said in the former posts, I did a quick search 2 times already, and didn't find any boiling point or bp of MDP2P mentioned by me. Please enlighten me, especially that "including Pihkal" remark. Or was this aimed at another member?

You admins are all in the same boat as far as I am concerned. Just look at this link. This is you talking.

Post 171271 (LaBTop: "Successfull DMF O2 Wacker", Methods Discourse)
You are reciting the Argox post, the DMF/O2 wacker on Rhodiums page. And yes, it is inaccurate. I do not know what kind of stirring you are using, but for this reaction to be over in 200 min you must have the product to catalyst ratios that are much higher than the ones listed. And on Rhodiums page for that procedure you have a boiling point of MDP2P 114C. When the reality is that the B.P. of MDP2P @ 2mm Hg is 132C. The truth is you have to run the reaction until the the O2 absorbtion is over. That time will vary depending on the efficiency of your stirring. If you prestir the catalyst for 12-24 hours the yields are much better, 90% instead of 70%, but the reaction will not get hot on it's own with prestirring. You will have to apply external heat to 50C. Now tell me I am wrong! And I know all of you admins know that by heart, but you choose to mislead. Why?

../rhodium/chemistry /dmfo2wacker.html - for those who are interested.

And you have the nerve to say a cook that I trust e-mailed it to me. What is your problem? Perhaps you can explain to me your motivation for this, you, Rhodium, the rest of you admins.

I am going to give you a taste of your own chemistry.
 
 
 
 
    Osmium
(Stoni's sexual toy)
06-11-03 22:44
No 439420
      > And I know all of you admins know that by     

> And I know all of you admins know that by heart, but you
> choose to mislead. Why?

Hey fucktard. Yeah I'm talking to you asshole. I don't like your tone. Why don't you hit the road and get lost if you don't like the information you are fucking freeloading here?

I'm not fat just horizontally disproportionate.
http://www.whatreallyhappened.com
 
 
 
 
    LaBTop
(Daddy)
06-12-03 16:24
No 439525
      Short answer     

I had posted in this spot during a few hours a much too lengthy angry answer, but have deleted it, it's not good to answer in rage.
So I'll keep it instead to a shorter, a bit more decent and calmer reaction:

Post 171271 (LaBTop: "Successfull DMF O2 Wacker", Methods Discourse) :
"" This is you talking.""
NO, it's clearly NOT me, it's Grouch's voice and later in that thread KrZ's voice, (see text of DMF/O2 wacker on Rhodium), and I stated clearly that the text from Grouch was emailed to me.
Grouch sadly enough is since last year in prison, as we all know, and I don't know if he's still there. Is his friend still reading here, could he give an update please on his status?

"" the DMF/O2 wacker on Rhodiums page. And yes, it is inaccurate. I do not know what kind of stirring you are using,""
"" I also used a 3 inch stirbar and a Thermoline heavy duty stirrer that's rated to stir up to 132 litres.""
That you can and have read in the same post, you seem to be selectively blinded and don't want to read what doesn't fit your conspiracy theories!
That's a VERY HEAVY magnetic stirrer, Grouch also told in the same thread that he had an O2 uptake drop because he didn't put the stirrer-setting back in the original highspeed setting after one of his O2-repressuring steps.
Grouch and KrZ both do not mention anywhere external heating of the vessel to 50Celsius. Only exothermic internal heating.
But still they could aminate their ketone successfully, while you couldn't.
So WHO's inaccurate???

"" but for this reaction to be over in 200 min you must have the product to catalyst ratios that are much higher than the ones listed.""
I strongly believe you are constantly switching between data for a DMF and an alcoholic O2-wacker.
I do not believe that KrZ and Grouch were both mistaken (see their posting history), while you would be right, you talk again about a DMF wacker, that one works as announced by 2 trusted members.

"" And on Rhodiums page for that procedure you have a boiling point of MDP2P 114C. When the reality is that the B.P. of MDP2P @ 2mm Hg is 132C.""
THIS SEEMS TO BE THE HEART OF YOUR "PROBLEM", so listen carefully:
That "you" is not me, that's KrZ, the one you trusted so much you start PMing him about this procedure!!! Now YOU in fact call HIM a lier, he won't be pleased eather, believe me.
""KrZ: Vacuum distilled at ~2.0 mm Hg to recover 311.22g PiperonylMethylKetone (MDP2P) fraction  between 105-114C. There was an Isosafrole forerun, and a minimal high boilingpoint and thus polymerysized glop after 114C."" He then AMINATED his product! He also sound as if he was professionally knowing his tools, and wrote down the data collected precisely!
If you should have some grey mass left over up there, you should start to doubt your OWN vacuum meter, method, vacuumpump , thermometer, and especially your whole fuckin attitude first, before accusing others!
You DID NOT MAKE ANY MDP2P TO BEGIN WITH, you admitted that you could not aminate any products, so how the hell do you have the guts to doubt those figures, based on some fuckin ALDEHYDE or whatever you made there instead of a ketone, and then start accusing me and about everybody here of misleading people???
You really seem to be on a "nailing" binge aimed at me (and even my colleagues!) without thoroughly checking your own "facts", so you start telling me for a change what triggered this behavior?
WHAT IS YOUR PROBLEM??? I don't have one.

"" The truth is you have to run the reaction until the O2 absorbtion is over. That time will vary depending on the efficiency of your stirring. If you prestir the catalyst for 12-24 hours the yields are much better, 90% instead of 70%, but the reaction will not get hot on it's own with prestirring. You will have to apply external heat to 50C. Now tell me I am wrong! And I know all of you admins know that by heart, but you choose to mislead. Why?
../rhodium/chemistry /dmfo2wacker.html - for those who are interested.
""
You have to heat an ALCOHOLIC wacker, however you don't have to but CAN add some heat to a professionally proceeded DMF/O2 wacker. As said weeks ago ALREADY. See:
Post 171802 (Antibody2: "Re: my exploited private email", Methods Discourse), where we talked then about non DMF wackers. That includes alcoholic ones too, you know.
You keep beating a dead horse.

Btw, do you start to realize the stupidity of your own above statements?  :
You did NOT succeed to aminize your "ketone", but still use all collected data from that FAILED test (nr 434171, you haven't posted any data of a SUCCEEDED one!) to try to tackle our COLLECTIVE knowledge? Are you INSANE perhaps??? In that case, get professional help.
The consensus here seems to be that the bp of MDP2P at 760 mm Hg is 187 celsius, and not 164. So your famous "25 degrees difference" remark, thrown out in obvious anger, I still don't get. I linked those posts with discussion about MDP2P bp's LATER, so what the hell was that hickup aimed at that day? You talk to yourself mainly? And that mirrors itself into your posts, leaving us with no clue what the hell you mean?
Learn to type comprehensive texts for others to understand, try to get out of your daily egoistic reasoning, and try to see through the eye of the reader when you proofread (if ever) one of your own posts before clicking Submit.

"" And you have the nerve to say: a cook that I trust, e-mailed it to me. What is your problem? Perhaps you can explain to me your motivation for this, you, Rhodium, the rest of you admins.""

Are you slowly seeing your own unscientific way of reasoning yet???? You in fact attack KrZ.
And then YOU HAVE THE NERVE to attack us?  GO FIGURE!!!


NOTES for people with more logic:

1.  See Post 436217 (Bubbleplate: "Well....", Methods Discourse)
for a sudden yield increase with GOOD highgrade PdCl2.

2.  Post 171639 (pmpB_4: "Re: my exploited private email", Methods Discourse) :
"" most asssholes(sp!tongue) here that bitched about the IPA (LT/: an alcohol)-02 Wacker only fucked up because they didn't have the H20 in the IPA/PdCl2/CuCl2 prestir. They added it during the oxidation, and it was my fault their PdCl2 didn't solvate! Go figure!! ""
Osmium told in this thread (nr 439327) to add no water in the first IPA post of this thread, is this (old)statement above (2.) right or wrong for any ALCOHOLIC wacker, so also a failed METHANOL wacker as used by ARGON in nr 434171 where he added the water after the prestirring ??
And if right, thus his PdCl2 did not solute totally perhaps, another cause of the failure perhaps?
If he (2.) was right, then the alc.wacker prestirr could be much shorter with the water added?
In the DMF/O2 wacker Grouch and KrZ added also water in the prestirr (much more related to the safrole btw). So if one changes only the solvent, Methanol for DMF, why would there be a difference?

3.  Wacker success, good and fast O2 uptake, depends mainly on HEAVY stirring, yes, got it at last? Heavy SHAKING is even better, much better gas to fluid contact.

It seems clear by now that ARGON did not heat that METHANOL wacker, so that will have been the main reason of failure in his post nr 434171.
Why the fuck he then starts rambling on and on about a well eshtablished (by many members) DMF/O2 wacker is still beyond my comprehension.

Is some mexican thug standing perhaps behind you with a machete, which he will carve in you when you don't succeed?? That's the way it starts to sound.
In that case, get out fast and start over again in a safer place. LT/

WISDOMwillWIN
 
 
 
 
    LaBTop
(Daddy)
06-12-03 16:47
No 439526
      The SHORT one:     

ARGON, you have the wrong bull at the horns!

(However, he would have never found out what was meant by that, probably forcing him to grab the poor creatures balls, so preventive extensive guidance seemed in place, producing above long explanation). LT/

WISDOMwillWIN
 
 
 
 
    Argon
(Stranger)
06-12-03 20:52
No 439569
      Osmium     

Hey fucktard. Yeah I'm talking to you asshole. I don't like your tone. Why don't you hit the road and get lost if you don't like the information you are fucking freeloading here?

Os, don't get angry. I mean, some of the stuff you guys have posted up is not on the money. And after a few months of fucking around, you start to get thrustrated. I asked all the right questions in the past, and got nothing gooood in return.

I am sorry, but that is what it takes to get answers around here.
 
 
 
 
    Argon
(Newbee)
06-12-03 21:13
No 439575
      LaBTop     

So your famous "25 degrees difference" remark, thrown out in obvious anger, I still don't get.

Well, let me explain. Throught the Hive and Rhodium and Erowid there are documents available for download by Shulgin, Chromic, BrightStar, Krz and many others that repetedly state that the ketone will come over ~25C higher than the safrole with the same vacuum source. I mean are we gonna play stupid??? Do you want me to give links??? That is not my famous remark, I am sorry.

And I was under impression that we reconciled on rudeness?? Or are we right back where we started?

Yes, perhaps you are right, you pesonally do not list the incorrect b.p. of MDP2P. But I would really appreciate some insight into why half these docs have that copied and pasted error. Do you know?
 
 
 
 
    raffike
(Hive Addict)
06-12-03 21:44
No 439580
      Raf's pulling his ketone about 50 degrees...     

Raf's pulling his ketone about 50 degrees higher than safrole,he doesn't know why.Safrole around 105 or so and ketone 150-160C.Isosafrole at 115 sometimes higher and sometimes lower,depends in what mood his pump is.

For those about to synth,we salute you
 
 
 
 
    LaBTop
(Daddy)
06-13-03 03:36
No 439637
      Argon!
(Rated as: good idea!)
    

Yes, I know, and I already explained that to you 3 days ago in the above post:
Post 439153 (LaBTop: "Huh?", Methods Discourse) :
""Btw, the real boiling point of   --PURE--  MDP2P is not often encountered by COOKS, caused by the fact that nearly all Hive and Rhodium procedures to get to this precious commodity will let them create a mixture of goodies and more or less impurities, which have a different combined bp.
Just as well as a bp of impure MDP2P under vacuum is affected by the same burden, and there is always a boiling traject to observe, not a specific fixed boiling point.
F.ex.: MDP2P boiling at 10 mm Hg or 10 mbar from 148 to 165C. Or from 145 to 162C, etc. ""

Now have a look at what raffike just told you:
""Raf's pulling his ketone about 50 degrees higher than safrole,he doesn't know why.Safrole around 105 or so and ketone 150-160C ""  That's in fact a 45 C jump to see the first ketone drops roll.

then Post 175260 (LaBTop: "Re: DETAILED METHODS for NON-CHEMISTS The Sequel !", Methods Discourse), in BENZOQUINONE to KETONE from RollWitMe :
""The other ones boils alkene at 92C and knows to watch for ketone @ ~ 130C. Well only 2 drops of unreacted alkene came over at ~95C and then a neon green ( very pretty, SWIM first tone runs were darker yellow w/ only slight green undertones compared to this which was practically glowing flourescent green ) fluid came over @~138-145C "" that's a 43 C jump to ketone.

then Post 23325 (LaBTop: "Detailed Methods for Non-chemists Edit: IT'sDONE!", Methods Discourse), in SAFROLE :
""S15. - The main safrole oil body (ca. 15.5-17.2 L), which boils (at~ ~130 C) and comes over at your vacuum ( should be 20 mbar or lower),""
""M14. - To get the real clean MDP2P, you will have to vacuum-distillate this dirty MDP2P-base ....and you don't let the temp go over 170 C, at ~20 mbar vacuum ""
that's a 40 C jump to ketone.

So I should say that it's pretty sure that between 10 and 20 mbar vacuum, the temp jump from the first drops of safrole to the first drops of ketone lays between 40 and 45 C.

I just quickly did a random check on some posts I remembered, and I do not see any strange anomalies. The traject is pretty much the same.

So, come up with those links, "I mean are YOU gonna play stupid"???
I am not gonna do all YOUR thinking, searching and problemsolving, no freeloading anymore.

Last but not least:
""And I was under impression that we reconciled on rudeness?? Or are we right back where we started?""
So now you try to pull our legs???
YOU were the one who started with multiple unfounded accusations, packed in exceptional rude wrappers, and we were the ones who didn't bigban you after the very first rude remarks.
I have saved your ass here, if not for me, you were already bigbanned. I know your cocky hidalgo behavior, based on uncertainty, so change your attitude wisely, or you get axed forever by some less flexable staffmember.
And that was the last serious warning. LT/

WISDOMwillWIN
 
 
 
 
    raffike
(Hive Addict)
06-13-03 07:28
No 439667
      What a whiner that guy is.Isomerize your ...     

What a whiner that guy is.Isomerize your fucking safrole(if you have safrole) and oxidise with peroxyformic acid if Wacker is way over your capabilities.Check these sticky threads for info how to exactly do that.
PS when MDP2P is distilled second time,raf collects stuff over 5C range,will this guarantee enuff pure >95% ketone?

For those about to synth,we salute you
 
 
 
 
    aleph
(Stranger)
11-09-03 15:33
No 469792
      WTF?     

Hell of a thread to find when I only needed the bp of MDP2P.  Ironically, this is where I found it - in the link to the Improved Boiling Points Chart, so keep on arguing, bees.  It makes the search more, um, shall we say interesting, but, at least in this case, provides the needed end result (even though, there still seems to be some question about MDP2P bp without vacuum....)

Tolerance is a sign of maturity.