Thank´s a lot Shake for the info(..and there is no second sense behind that ).
    If you have read some post from me,you can see i´m a guy that one day "wow...that method rules...." and weeks after cooment about the same..."that method sucks"...
    Posibly i´m not too constant about chemistry theory....and prefer allways to follow practical experiences insted theoricall explanations,but of course can be an error of mine,but i´m used to believe only on things that i or othesr have seen directly instead of hypothesis,theoricall fundaments about a reaction....but i repeat it´s my fault.
   For example,i was extracting  my last benzo wackers since moths ago with toluene,after i got freaking emulsions using DCM to extract both from DMF and Methanol on my begining.Now,i consider me a lot more formed about that process and others(a lot),and since last times i extracted with toluene and get a lot of tar on the ketone distillation every time,and last time got a very clean distillation after use DCM,....we can think it´s related about less benzoquinone used....but i have made exactly the same batch using toluene and DCM,and without doubt the extractions and distillation were way more clean and easy,and since that,yields were higher.Explanation?i don´t have it yet.But like said,i think i mastered the benzo at this moment,and to me the best,will be go with DMF and DCM.
   I can talk about how pure it´s the ketone,but like said,i think very pure.Like i use now to redistill the ketone,i don´t worry too much if first ketone distilled it´s not too much pure.
    Anyway,i will reduce some of that ketone these days,so posibly amine yields can talk about it.
   I´m planning too since now i have a strong vacuum,distill first the amine base before gassing to get product as pure as posible.
   I´m plannin too on go a little into the old scholl gassing methods, since both DCM and Toluene are not cheap and easy to get to me,and try to gas into dry cold acetone like old bees i´ve read used to do.But of course it´s a question i will treat on the "SHORT QUESTIONS THREAD"
    THANK¨S MAN!

   I thinking to on the freezing quality of isosafrole,so any crystal on freezzed ketone must be isosafrole and can be filtered on cold to get ride of it?
 

Keep in mind that ketones are generally excellent solvents and the odds of the isosafrole precipitating are slim to none.

Im more apt to believe those crystals your seeing are water before I believe they are some organic substance. Have you ever tried to cold filter them to find out what they where?

Yeah,,,i used to have little amount tiny crystals on my ketone when stored freezed when distilled it on normal set-up and not fractionally,suposed both little water,isosafrole,...but after redistilling i get a ketone that does,nt present crystals at all and yields on Al/Hg and Cyano route exactly the expected amount of salt.
   But one thing i´ve observed it´s that re-distillation of ketone it´s not as good as i thinking,because i´ve started with clear green-yellow ketone and finished with little tint of orange colour on it,probably from scrothing,and with little black tar on the distilling flask again,and i´m doubtingnow  if that tar comes from impurities that still being on ketone before distillation or the proper ketone scorched ecause continued high temperature manteined on distillation process on a big batch.So maybe i understand that controversy about less yields on big batches because that,because to distill 400 gr ketone you have to keeo temp high too much time for it and that scorched more ketone than on little batches.Of course,that can be easy solved distilling on portions.
    Obviously,i will not make ketone again in much time,but  if wold  make again the wacker,i would take much care of temperature of oil bath.I have bad defect to overheat the bath to speed things and that have to be very bad about scorching no matter how intense stirring used.And a good idea would be distill it on 150 ml portions fractionally on the begining and don´t redistill.

  New things not related to that are new experiments on the cyanoroute to MDA,and have to say it´s now a keeper!...but using only 24 hours reaction and helium atmosphere=85 % yields on small batches as 30 gr. ketone.The key it´s using dry methanol,time reaction and inert amosphere.That traduces on no conversion of the amine to the alcohol and 100% activity of the cynoborohydride.I talk only about mda and ammnium acetate process. Experimented about that because a post on The Hive by Labtop about that time ,that claims after 24 hour(like strike said too),analisys by TLC,only detected final product and ketone complelty dissapeared.When i´ve done on the past,i let the rection 36-48 hours ,and saw mix starting clear yellow-green and very soon ,after that 24 hour period, the mix was almost complety clear without colour,and since that 24 hour too 36-48 becomed more orange coloured.
   I´m learnig know about using Sodium triacetoxiborohydride as a cheaper alternative,but cyano makes work so well that price it´s worth it.
     

also, does anyone believe that a bisulfite on the ketone (then recovering) before destilation will improve on the tar issue? or maybe even skip the destilation process?
seem at the old hive that adding np to the ketone then to bisulfite solution, with hark shak and low temp. helps to crystalize only the loved ketone, no chicken fat crystals...
any thoughts?
peace

Just to confirm theory that 0.75:1 molar ammount of p-benz:olefin in DMF works as good as wast excess that BrightStar used!
That is allmost exactly 1:2 mass ratio.
Used fresh p-benzo that I made using H2O2/I2/hydroquinione method.

2,5 gr palladium.
cca. 160g benzoquinone
100 ml water
cca. 400 ml DMF....That is all I had handy,everything was mixed for 15-30min
310g safrole was added over 50min,and glass was washed with 50ml DMF.
let it react 12h with reflux (just in case)
stick it in the freezer and vac. filtered to recycle some Pd and PdCl2.
Flooded everything with 2l slightly acid water (5-15%,weather was too hot and to do math),
stirred well and sticked it in the freezer shortly.(Ammount was divided in 2x2L bottles to make work easier.)
Red acid water was decanted from organic layer which was this time MUCH less spongy and more like an oil
thanks to reduced p-benzo ammount!
Extracted red acid water from each 2l bottle with xylene 2x150ml.
Extracted each bottle again with 1x75ml DCM.
Let the DCM extract on hot water bath until it evaporated and combined that,xylene extracts and organic layer from the begining.
Washed combined extract 2 times with 10% NaOH solution (300-500ml I don't remember) and got allmost green solution on second wash,
again,much easier with less p-benzo!
Washed with brine (that was mistake since it pulled a lot of ketone so I put second brine wash back together)

Vac distilled to get cca 225ml most clear/clean neon green isosafrole/ketone mixture,that contains at least 200ml ketone.

I allways had problem with any other solven exept xylene if even trace of water was present during distilaltion
while some water present in xylene extract actually helps to get cleaner ketone with sharper b.p.
Nasty emulsions carying even ketone at low temp. resulted from using toluene and DCM previously.
With xylene,you can simply distill it and it comes along with water if you have a good stirring,it doesn't matter if you have water layer.
It's kind's odd since you get few fast drops of water that sinks and than stream of xylene carying other crap with it somewhere between 100 and 150°C,
and cycle continues until you see only xylene comming out,then it's time to plug in vacuum.
Some more xylene will come out (probably with slight hint of green) and when nothing else comes for a few minutes it't time to
switch flask. When temp and vacuum are good again neon green liquid starts to come out.
You can switch flask again when you see swirlss in green liquid,that means that isosafrole is all out and ketone starts comming.
Last fraction (ketone) tends to change color to yellow when very pure.

You are probably right Sedit,I tried it and failed.

Maybe it's off topic,but what is legitimate use for MDP2P?!
This substance has UNBELIVEABLY familiar smell,something I remember from early age. Bubble-gum or something like that...
Safrole on the other hand is not familiar to me or anyone I showed it. (One firend actually said:"Ecstasy!" LOL)
I realize you use safrole in USA for candies and some drinks in miniscule ammounts so situation might be oposite for Americans.

hey there beeeeesss

first of all, im NOT looking for a spoon feed.

well..... shake posted many references on DMA/pdcl2 oxidation, but i acctually havent seem many bees trying it at all!!!
i am NOT a graduated or even a chemistry major. as a matter of fact due to personal choices i quit school a whilllee back. (not the best choice) hehehe

i´ve read MANY papers on DMA wacker but im very limited to chem literature.
even tho i was able to absorve some interesting notes.

all papers on this new oxidation seems to be fairly new around 2006-2011.

well......i would like to give it a try, since it seems very straight foward. could be done at a pressure reactor no problem, and found a small one that would be great, hold the most 250ml, so small scale.

if i got it right,only takes pdcl2,dma,h2o,o2.... i can get everything at the supermarket hehehe jk

http://repo.unair.ac.id/data/jurnal/kimia/pdf/Recent%20Progress%20in%20Wacker%20Oxidations%20Moving%20toward%20Molecular.pdf

In addition to aerobic alcohol oxidation and oxidative carbon-carbon bond forming reactions, one of the first examples of the use of molecular oxygen as the terminal oxidant in a Pd-catalyzed oxidation reaction was reported in 1959 by Smidt and co-workers.55 The authors disclosed the oxidation of ethylene to acetyl aldehyde using a PdII catalyst in combination with Cu salts under an aerobic atmosphere. This seminal report led to the development of the Wacker oxidation, which is one of the most widely used palladium oxidase type transformations and has played a key role in the development of all PdII-catalyzed aerobic oxidation reactions. In recent years, there have been a significant number of reviews on the current progress of the Wacker reaction and, thus, will not be comprehensively reviewed in this article.56 However, one important aspect of the recent advances in the Wacker oxidation is the development of direct molecular oxygen-coupled catalytic systems, which eliminate the need for co-catalysts by employing ligands to stabilize the Pd0 intermediates.57
One of the first examples of a co-catalyst free direct molecular oxygen-coupled Wacker oxidation was reported in 1998 by Sheldon and co-workers.58 The catalytic system employed the water-soluble ligand PhenS (1) in combination with 30 bar of air at 100 °C. In 2006, Kaneda and co-workers disclosed a direct molecular oxygen-coupled Wacker oxidation that utilized a mixed dimethylacetamide (DMA)–H2O solvent system at 80 °C and 6 atm of molecular oxygen.59 Interestingly, dimethylformamide (DMF), which is a common solvent employed in the Wacker reaction, did not lead to appreciable yields of the methyl ketone under these conditions.56 The authors hypothesize that DMA potentially acts as a ligand to prevent catalyst decomposition and Pd0 may have a more negative redox potential in DMA compared to other solvents leading to a more stable catalytic system.
Both of these co-catalyst free aerobic Wacker oxidations require the use of high pressures of molecular oxygen or air as the terminal oxidant, which limits the overall applicability of the methodology. In 2006, Cornell and Sigman reported the first example of a co-catalyst free aerobic Wacker oxidation at balloon pressures of molecular oxygen or air.57 The catalytic system employs the ligand (?)-sparteine and a DMA–H2O solvent system at 70 °C (Fig. . A variety of terminal alkenes can be selectively oxidized to the methyl ketone product and the catalyst exhibits excellent functional group tolerance for the presence of unprotected alcohols (35b, e, and f) and acid sensitive protecting groups (35d). An exciting aspect of this system is that the ligand (?)-sparteine in combination with DMA prevents alkene isomerization, which is a common side reaction in Wacker oxidations.60 This is showcased by oxidation of alkene 34f, which contains a homoallylic chiral center, to the methyl ketone 35f without racemization. The use of a ligand in this case increases the practicality and synthetic utility of the Wacker oxidation.


now how do i figure it out the moles, the reaction time, etc. i know it takes aroun 5%pdcl2 but what about water and DMA how do i know how much to use?
from what i seen i should mix the DMA, H2o and pdcl2 heat a lil and stirr for hour or so so everything its dissolved, then add oil add pressure and stirr....but for how long?

im trying to learn, not trying to get spoon feed please......i understand that water is a big player in this reaction, not as much when done with cucl2, right?

well if anyone have any thoughts or would like to help a bee out on this experiment i would be greatfull.
i think this new method its the future!!!! benzo its nasty... tired of working with it.

thanks alot yall

peace

ps:A typical example for Wacker oxidation: Into a reaction vessel equipped with a reflux
condenser and a rubber balloon were placed PdCl2 (5 × 10-3 mmol), DMA (5 mL), and
H2O (0.3 mL). This mixture was heated at 80 oC under atmospheric O2 pressure for 4 h.
After addition of 1-decene (0.5 mmol), the mixture was vigorously stirred at 80 oC for 6
h. GC analysis of the solution using naphthalene as an internal standard showed an
84 % yield of 2-decanone as the sole product.

http://www.wiley-vch.de/contents/jc_2001/2006/z502886_s.pdf

If you want the DMA wacker to work with no stabilizing ligands for the PdCl2, you need to run it under these conditions

50C - 60C
off the top of my head you need 15% water to DMA and yes the water is the key,
you need a few hours of reaction time and you need pure 02 under 5 - 6 Atmospheres

an SRV wont get to those tempretures whilst having those pressures without exploding

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

The DMA wacker is the smoothest looking, easiest way to ketone, all the journal refs agree. one of the refs even used saf in the examples!!

It all comes down to the reaction vessel, if you figure that out let me know!
 

do you even know what we are talking about? if you did you would understand

Maybe if you knew anything at all about chemistry and wenrt just a junkie,,,,,

Still blowflying around here hypnos? haha