It would help if we had less of the bitching. We are all just in interested in the science here.

If you have results Shake, I would love to hear them. I understand you have had some success with the Wacker oxidation of safole in DMA. It would be great if you could provide some more information about the reaction vessel you have used. What was it made from and in what way was it heated? Do you know what kind of yields of ketone you got?

If you have personal issues I feel you should work them out via the PM rather than cluttering topics with flames. Looking forward to hearing some more experimental results from this promising method! It looks like you have put quite some work in getting it to this stage.

Ketone made from the DMA wacker was never worked up, i said that above

The DMA wacker has been done, the ketone was never worked up its in storage!

One thing noticed WAS the precipitation of Pd(0) or palladium black. The smells were spot on though, the extracts were clean, DMA isnt as harsh as DMF

I have no way to test the resulting ketone right now plus it is in storage.

The conditions were just like a normal SRV. no heat was used, no CuCl2, 1%molar PdCl2 the shaker was a jigsaw, which i figured would make up the the lack of heat..

the DMA didnt melt the bottle like DMF likes to, so it was a bit better in that way, the spent PdCl2 precipitated out of solution, which usually isnt a great sign, but the smells were spot on like ketone.

There have been no more attempts without using a vessel that fits the refs a bit better.


15% water to DMA means, 300mL DMA 45mills water, and i used roughly 45mills olefin.

the refs all say 1% molar PdcL2, not 5%

to be honest, i would measure the PdCl2 by eye, but 1% means for every 100g saf, you used a gram of Pd

Add the DMA, water and PdCl2 to the vessel, charge it with o2 and shake it (jigsaw works well) half an hour to an hour of shaking and 02 filling and purging, then the 45mills saf was added.

the shaker was set to run for hours and hours, with refils of 02 every so often..

after a long time of shaking like 6 hours, the ketone was extracted with naptha directly, the vessel was recharged with a further 45mills olefin, charged with 02 and ran again.

let me say one thing, the smell of ketone was really strong, stronger than any DMF wacker..

the al/hg frothed HEAPS aswell, which was a good sign, but something else went wrong down the track and that was that, the remaining ketone has never been processed

Thanks for the information Shake. I really like the jigsaw idea. The shaking is definitely going to get more O2 into the DMA than simple stirring. Your saying you got some precipitation of Pd(0)? From reading the reference again it appears this is a result of not enough oxygen being available to reoxidise the Pd. Was your O2 pressure consistently around 5-6 ATM or did it drop significantly at points? If it did that could be the cause of your palladium black precipitation.

How are you planning on purifying your MDP2P. It appears the primary by product of this reaction with safrole as a substrate is piperonal. It would probably be pretty difficult to separate from the ketone by vacuum distillation. If it is left in during reductive amination it should form methylenedioxyphenylmethanamine. Just something to bare in mind.

Sorry to hear about your interpersonal troubles. Hope they can be resolved amicably. Best of luck with your dreams! Be sure to let us know how the reductive amination goes!

Also here is the reference again so that people can find it easier!

Palladium-Catalyzed Aerobic Oxidation of Naturally Occurring Allylbenzenes as a Route to Valuable Fragrance and Pharmaceutical Compounds
Luciana A. Parreira, Luciano Menini, Joyce C. da Cruz Santos, Elena V. Gusevskaya
Advanced Synthesis & Catalysis
DOI: 10.1002/adsc.201000050

Abstract:
A palladium-catalyzed, aerobic oxidation of naturally occurring allylbenzenes, i.e., eugenol, methyleugenol, safrole, and estragole, in dimethylacetamide/water solutions under mild conditions has been developed, in which palladium(II) chloride is used in the absence of co-catalysts or special stabilizing ligands as the sole and recyclable catalyst. Methyl ketones that are important for the flavour and pharmaceutical industries have been obtained in good to excellent yields with low catalyst loadings (1–2?mol%) and high average turnover frequencies. This simple catalytic method represents an ecologically benign and economically attractive route to industrially valuable compounds starting from renewable substrates easily available from essential oils.

fresh1, you have contributed nothing to this thread with your monologue.

It seems pretty clear to me now what conditions Shake used. The optimium conditions require heating the reaction at 60-80C under 6atm of pure O2 for about 6 hours. Shake states quite clearly that he hasn't found a vessel which he can heat at those pressures safely. Therefore his trials were carried out at room temperature under pressure, using a jigsaw shaker to promote a greater uptake of oxygen by the solution. As far as I can tell a simple PTFE bottle was used which can handle the pressure when there is no heating. The solution was shaken for 6 hours with the oxygen being recharged occasionally as it was consumed.

Shake claims to have had success producing the ketone but having relatively low yields due to the lack of heating which is why he wants to delay further trials until a more suitable reaction vessel is found which can be heated under pressure.

The conditions were just like a normal SRV. no heat was used, no CuCl2, 1%molar PdCl2 the shaker was a jigsaw, which i figured would make up the the lack of heat..

the DMA didnt melt the bottle like DMF likes to, so it was a bit better in that way, the spent PdCl2 precipitated out of solution, which usually isnt a great sign, but the smells were spot on like ketone.

You really can't get much clearer than that. Please spend more time reading fresh1 before firing back a content less rant.

I don't know how you can claim the references are mixed up or vague. If you look at my previous post I have posted the exact reference that Shake is basing his work off. It even included safrole as one of the tested subtrates. It really can't get much clearer.

  Also much of what Shake posted was so 'mixed up' and/or vague or mixed up and complicated (with 50 refs attached ) that it was rather confusing and basically unusable for most wasps,
  who imo are more "Creative Cooks" than the "committed chemists"  more interested in refining known synths rather than trying to theoretically work out 'new' ways that don't have any 'real' benefits for use in the home lab.

Please share any and all experimental work but deal with your personal issues with one another in private.

Po

what if you use a glass coke botle? the 1250ml then instead of shaking can use some magnetic stirring and heat under boilling water?
i believe these botles can hold some pressure and with insulation i believe some heat also

what if?  there's a good chance it will blow up    The reaction vessels in this procedure were notorious for their catastrophic failures    fresh has read about plenty of explosions doing this procedure, but has never come across someone talking about a reaction vessel they used "countless times" successfully (or even multiple times)  hence why I have been asking here

 Some have suggested success with a variety of containers designed to hold pressure (such as garden sprayer bottles and the like) BUT fresh hasn't found anyone who has reported using anything (including a Spiceboy Reaction Vessel) "countless times" with great results and NO problems.

  And forget 5-6 atm from an O2 bottle WITH heating (even though most agree O2 absorbtion was better at cooler temps )
 under even just 2-3 atm = 28-42 ft/lbs ( pressure from a bicycle pump, and with not so vigorous mechanical shaking at RT)  things can go BOOM!.

  Apparently cracks become visible in 'plastic' bottles after an hour or so of shaking when doing all this by hand, and so I guess this 'hands on' approach gives one more of a chance to regulate the pressure and keep an eye on the RV and stopping things from getting out of hand, as

 Esp if the bottle is polycarbonate (as many are) coz the 'ketone' produced WILL react with it (ketones are good solvents of polycarbonates) most probably weakening it enough after the first run or two as to make further use prone to malfunction and an unnecessary risk

 I can't recall reading about a KRV 'going off' in someones hands, but there are a number of reports of rxns left to 'proceed by themselves'  exploding for reasons unknown.

Having a read around the forums about this procedure and you will find several reports of (unwanted) explosions 

 Actually NBC, it would pay if you UTFSE a bit more matey, both those in general, and also the one here 
 you would find the answers to your questions as there is quite a bit of data on this procedure floating around


Here's a very interesting and informative article on Pd catalyzed DMA/O2 wackers for those who are interested

     http://www.ncbi.nlm.nih.gov/pmc/articles/PMC2929811/

the reason for the flaming of fresh1 AKA hypnos is because if, during the peak of my studys if i hadnt met him and if he hadnt blackmailed me and threatend to call the police if i didnt send him drugs, i would have completed my research into the DMA wacker and i would not have had to give up everything i had spent so long researching..

TRUST NO ONE .. should be a no brainer

HOLD UP! What?

If this is true I am going to do anything I can to make sure you never show your face around here again hypnos and that's no fucking joke.

Yes it is somewhat concerning Sedit, I was very surprised when I read that. We cannot blackmail each other for such insiginificant gains. "Drug moneys' easy money, not grief."

Politely asking if said co-conspirator can sell or trade you some safrole is the better way to go about it I think

United we stand against the inquisition; Divided we fall.

Going to be synthesizing some CuCl2 today from CuSO4 and Na carbonate followed by rxn with HCl. Bugger these laboratory corporations, I'll make it all myself...

fresh1 you are a bitch. Shake should shoot you.

I agree it looks great but I'm not sure I get what's being said ... the author is not a native english speaker that's for sure   I mean what is MeONO? 

and what exactly is being bubbled where?   seeming I already dont know what MeONO is alluding to....I'm kinda fuckt

1.75 liters of drugstore methanol and 6 grams of PdCl2 was bubbled with MeONO produced with a solution of 110 mL of methanol, 225 grams of NaNO2 and 300 cc of water (110 cc of H2SO4 and 200 of water, chilled was added to the NaNO2 in 2.5 hours ). With stiring, of course, and with a homemade bubbler made with a piece of glass sponge (for feet) welded to a glass tube. After the adition of about 200 grams of NaNO2, 100 grams of safrol (100 cc of single distilled safrol) was added. Catalyst was not dissolved, but the reaction went to 35-40 degrees, with a great bubbling of NO and after a while all catalyst dissapear. In 30 minutes or so reaction was done, I think, and palladium appear again, but all MeONO was bubbled, and reaction was kept 2 hours from the safrol addition.

huh? 

Quote from: fresh1 on June 14, 2012, 12:11:16 AM

Quote

fresh1 you are a bitch. Shake should shoot you.

Why?  becoz of some bullshit written by a dude who thinks he's gods gift to home drug chemistry?    Great first post (not!)

Quote

It widens the range of suitable reaction vessels if only 20-50 PSI needs to be reached with heating.

Even though the dissolution of gases in organic solvents does improve with increased temperature by the time you get to RT it's already a a sufficient level for this procedure to proceed...I don't know why folks (who haven't looked into this properly) just want to make it harder 

see this is you showing your ignorance twofold. In private communication to me, a while back, I was told in detail of this by Shake.....do you want me to spill some of your personal info, you fucking twat?

you should be banned for life.....I wish you would have done that shit to me, you would be in a barrel with a sack of lye you ratbastard.

Hahahaha... yes I don't take kindly to blackmail either, but I stay out of this kind of shit.

I took a look at that alkyl nitrite wacker. Honestly, it looks very much akin to a fucking chocolate cake recipe; a total joke.

"Mix up your methyl nitrite (meONO) with this sulfuric, MeOH and nitrite. Shake that shit up and let it fizz, doesn't matter what yields you get or how you do it. I like to add a pince of salt and nutmeg too, just to embolden those flavours and leave a taste on the palette that'll make your guests eager for more!"

There's a procedure on the-collective.ws :
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This is the highest yielding Wacker but it requires more work than the rest...

Making the  Ethyl Nitrite

Mix 288g of 95% ethanol (190 Proof/Everclear) with 290mL of dH2O and 300g 98% H2SO4 and chill in the freezer.

In a 2L RBF with a magnetic stirbar, dissolve 227.7g sodium nitrite in 725mL dH2O and cool in the freezer for a few hours, without freezing the solution (some precipitation will occur).

Place the RBF in a -10C ice bath. Add the ethanol/water solution to an addition funnel positioned above the RBF. Add the ethanol solution dropwise to the nitrite solution over a period of 1-2h {with gentle stirring}, and monitor the temperature of the solution, assuring that it does not rise above 6-9C.

Once the addition is complete, allow the solution to cool in the bath, and filter out the precipitated sodium sulfate in a chilled buchner funnel/filtering flask (use very low vacuum, or the ethyl nitrite will boil away), and wash the filter cake with a little ice-cold 95% ethanol.

Remove the flask and pour the contents into a 2L separatory funnel which has been chilled in the freezer, remove the aqueous layer, and wash the nitrite with 500 mL of a 5% sodium bicarbonate solution which has been chilled in the freezer.

Drain the nitrite into a 2L RBF and add anhydrous, denatured ethanol to bring the final volume to 1L. Dry over 100g sodium sulfate for 15 minutes, filter, and rinse the cake with ~100mL ethanol. {You must dilute before filtering or the ethyl nitrite will froth violently and you will get loopy tongue}

Nitrite Wacker


Take the ethyl nitrite solution from above, bring the total volume to 2L with anhydrous ethanol {Used denatured anhydrous, 5% MeOH, or make your own from 95% and CaO}, and place in a 4L filter flask, stoppered, with a tube leading from the outlet into a jug of 2% HCl.

Add 2.65g PdCl2 (0.015 moles) and 10.08g CuCl2 (0.075 moles, anhydrous) to the flask and gently warm the flask to ~30C.

Add 325g of fractionally distilled safrole (2 moles) to the flask, and continue stirring for 8h at 30C.

Once complete, add 500mL H2O to the flask and raise the temperature to 50C, holding it there for 40 minutes.

When this is done, filter the contents over celite, rinse with 100mL EtOH, and optionally roto-vap off ~1200 mL of the EtOH.

Flood the contents with 1200mL of 5% HCl and extract the precipitated ketone 3x with 400 mL of DCM.

Wash the pooled extracts with water, saturated sodium bicarbonate solution, and brine.

Filter the organic phase through celite to remove some residual, precipitated metals.

Dry the extract over sodium sulfate, filter, and rinse the cake with DCM.

Rotary evaporate the solvent at atmospheric pressure at the steam bath, then fractionally distill the piperonylacetone over a 300mm column packed with glass beads at 10.0 mmHg (149-152C).

Optionally, run a chaser to clear the column, or extract and distill with a smaller rig/shorter path.

Store the pure ketone in an equal volume of anhydrous methanol, under nitrogen, in the freezer.

Weight of piperonylacetone; 321.5g, 83.5%.

Don't forget to use a water-trap to prevent suck-back should it occur!!!
-------------------------------------------
Again, it doesn't outline a rough idea for the yields you're going to get for the ethyl nitrite, and quantities of catalyst differ by factors or 2 or 3 between the methyl and ethyl nitrite synthesis. I wish someone could do a proper writeup for this, because you can recycle the PdCl2 catalyst to some degree when doing this reaction as you don't have shitty hydroquinone getting in there and messin it all up.

I made some IPNO2 for this and used that instead, but my stoichoimetry was way off and I got a red ketone. EtNO2 is a bitch to make, boils away at 20C and decomposes readily into NO2 and Et compounds at room temp. IPNO2 is preferred. I have a writeup for a 66%ish yield of IP nitrite on the-collective.ws ... check it out. There's some cruicial techniques you need when making the nitrite or your yields will be 30%... also has pics for the aspies
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After spending quite some time tracking down IPA, I finally found it. In this dinky little corner of the world, we see fit to continually curtail the rights of the majority due to the stupidity of the minority. One of these such abuses is the restriction of IPA through many retailers. Hardware stores that used to sell it a year ago now deny they sold it at all, electronics stores now only sell TV wipes, electrical suppliers sell it in 100ml bottles for many scores of $, and the pharmacy tells me its been restricted because people were drinking it, after showing me the 50ml bottle they sell for $10. Fuck off, everything in your pharmacy is susceptible for abuse.

Regardless, I wasn't going to take this bullshit. Eventually I decided to phone my normal chemical supplier, a certain business which happened to sell many chemicals and solvents in a very low key manner. 1L for $15, how reasonable!
"You see all the dodgy people coming in buying the IPA for extractions, hoods up, caps on" he said with a smile, "it's been banned everywhere else but there's no real laws about it, just a lot of heresay." He wasn't a prick. That was surprising.

So I flew on home, along with my dry ice and a whole load of other crap I bought errand. Here's the Erowid synthesis I followed: http://www.erowid.org/archive/rhodium/chemistry/isopropylnitrite.html

There's a few key tips I need to outline to anyone attempting this for the first time.

1. Use a sep or addition funnel to drip the NaNO2 solution into the alcohol/acid mix. This allows slow, consistent addition of the NaNO2 and lets you leave it unattended for a while.
2. Have a tube running from the funnel drip tip 2-3cm into the aqueous layer. This really bumps up yields by more than 50%. I noticed a double in yield from 50ml (164ml IPA) to 100ml IPNO2 on the third synth I did using this technique.
3. Use a magnetic stirrer at about 200rpm to make sure reactants mix and interact immediately and to dissapate heat better. This will keep the temp down and reduce any unexpected frothing from NO2 vapours. The more NO2 released because of your impatience, the less IPNO2 you're going to have.
4. This RXN releases a lot of NO2. Do it outside, preferrably at night, because I know you can't afford a fume hood.
5. Do not let the reaction mixture exceed 30C. I had best results keeping it around 20C +/- 5C . If it begins to boil, you are LOSING IPNO2 AS IT BOILS(BP 40C). Along with clouds of NO2 filling your work area which also take nitrite with them as vapour. So do not let it exceed 30C. Especially crucial if making EtNO2, BP 20C, this stuff will evaporate before your very eyes.
6. Have the whole thing in a salt ice bath. Lots of ice, lots of salt. Cold. I tried Dry ice with EtOH, was too cold and part of the rxn mix froze. If you do have some dry ice, crank the stirrer up high to stop it freezing and speed up the addition to keep it between 0C and 30C.
7. Wash finished product with Na Bicarbonate in a sep funnel, dry with MgSO4 anydrous then drain it off and store it in a bottle with more anhyd. MgSO4, in the freezer. I put a few drops of the corresponding alcohol in with the nitrite; not sure why but I read somewhere it could be beneficial. Possibly to kill microbes?

EtNO2 really needs to be made fresh if you decide to use it. With its high volatility and its rapid decomp at room temp into NO2 etc I'd personally avoid it, but the low volatility may be handy somewhere.

The pics are pretty self explanatory; one is the setup, one is the IPNO2 chilling in an ice bath, and one is of total yield from two noob batches using 164ml IPA each for 100ml IPNO2 yield total, plus 164ml for a better synth that yielded 100ml. Total yield, 200ml. The importance of practice has become painfully apparent in this exercise.
****************************************************

Uchicuchi