All the resulting molecules from the O2 wacker form bisulfate adducts.
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LabTop recetly e-mailed me this:
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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 (missing)
(LaBTop: "Successfull DMF O2 Wacker", Methods Discourse),
and especially this remark from Antibody2 there :
Post 171802 (missing)
(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 (missing)
(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:
https://www.thevespiary.org/rhodium/Rhodium/chemistry/wacker.cyclodextrin.html
New Catalytic System for Ketone-selective Wacker Oxidation. !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!
PS4:
https://www.thevespiary.org/rhodium/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 20°C or so.
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you must keep the oxygen available.
you must keep it cool. Not cold, just cool...say around 20°C 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.