Cure for alcohol Wacker?

[dunkel]

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]

More than interesting, thank you dunkel.

[sassy_sucker]

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]

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:

https://www.thevespiary.org/rhodium/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 20°C or so.

https://www.thevespiary.org/rhodium/Rhodium/pdf/wacker.propenylbenzenes.pdf

https://www.thevespiary.org/rhodium/Rhodium/chemistry/wacker.cyclodextrin.html

   New Catalytic System for Ketone-selective Wacker Oxidation. HolyShit!!!!  LT/

[Osmium]

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.

[raffike]

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 (missing)

(psyloxy: "Re: practising on legal substances", Newbee Forum)

[Barium]

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.

[raffike]

an aldehyde?

[Barium]

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

[raffike]

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.

[Rhodium]

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]

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 yielding  and gives purer product.
BTW. 1-MDP-3-P is an aldehyde,MDP-3-P is a propiophenone.

[Rhodium]

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]

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 (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.

________________________________________


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.

[raffike]

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...

[LaBTop]

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 (missing)

(Osmium: "Re: Boiling points chart", Chemistry Discourse),
To confuse you even more:

Post 102339 (missing)

(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.    LT/

[abolt]

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

[Barium]

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.

[Argon]

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.

[LaBTop]

""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 165°C. Or from 145 to 162°C, 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.  
Stay off the boose. LT/

Btw, enough tasted of my chemistry?