Author Topic: extraction and washes on the ketone syntesis.  (Read 247 times)

sassa

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extraction and washes on the ketone syntesis.
« on: June 09, 2010, 01:24:17 PM »
hi.I´m on the middle of the ketone wacker this afternoom. :D
     I wouldl very gratefull if i received any suggestion about what solvent  use to make the extraction of the post reaction mix ,and how to proper make the washes.
      Like i said,i,m doing that now along this day,so a hurry answer will really great,because when i made the wacker using DMF as solvent,the extractions runned better.Latelly, i´m doing the wacker on methanol ala Methyl´s man,and last time the extractions,washes  and post Naoh washes runned  with   tricky emulsions that never separeted.It´s posible that methanol causes it?
       i noticed too that make the extractions by strirring the whole mix 5 min with a big stribar on a big beaker reduces emulsions quite well in comparison to make it by shaking on a separatory funell.any problem with that?My questions are:

1.Since i saw extractions with dcm using methanol as solvent were not good,would i use other solvent like toluene.?will the extractions and post washes run easier?...i have now good amounts of toluene,not so much of DCM.

2.Need  amounts to make correctly the saturated solutions ,and will be fine a order or secuence on the washes to make it as easier as possible.First 2 washes of water to neutralize,then baking soda and finally Nacl??are strictly necessary these water washes on the ketone synthesis?any problem going directly to the NaOH wash?

3.Final Naoh washes with 5% or 10% ??seems articles varies about this concentration.

     Any suggestions about your tips making this reaction will be very fine.It´s like one time all run easy,and other are really a painfull of dcm that dont separate completly,emulsions on the water washes,... ???
    
                    THank´s
« Last Edit: June 09, 2010, 04:55:24 PM by sassa »

sassa

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Re: extraction and washes on the ketone syntesis.urgent!
« Reply #1 on: June 09, 2010, 02:35:28 PM »
i´m doing the extractions today with toulene and are going way better than DCM. ;D ;D
Supossed no problem with that on the next steps?

lugh

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Re: extraction and washes on the ketone syntesis.
« Reply #2 on: June 10, 2010, 02:43:33 AM »
This very old thread has some thoughts on the subject:

"Bubble Gum Wrapper" benzo wacker writeup by Strike
      Methyl Man
      Member  posted 04-14-99 06:19 PM           

      Every time I try to find this apparently quite important post, I come up with nothing. The search engine produces nada for me despite using many
      different search terms/filters. Can someone please post a copy of it here in this thread? Thanks!
      ChemHack
      Member  posted 04-14-99 08:15 PM           

      Try this:
      hive.lycaeum.org/ubb_board/Forum7/HTML/000004.html

      Methyl Man
      Member  posted 04-14-99 09:32 PM           

      Oh that one! Shit, I had that already. I was thinking that it was an original post with a name like "found on a bubble gum wrapper." Duh. Thanks Chemhack.
      But tell me this if you would, someone: why do some benzo wacker texts say to flood the mixture with plain water, and others say to use 3N HCl-water?
      Both ways work?
      thanx
      ===============================
      "There's a methyl to my madness"

      Xerxes
      Member  posted 04-14-99 09:59 PM           

      Getafix had a good finish for this, which he posted. It was then lost. Then I reposted it, and now it's lost again. good christ, this "Ultimate" BB is getting to me. I guess we can't expect better unless we contribute. Like I said, I'd gladly give some money...but will it help? enough griping. Rhodium I don't know if this up to the usual quality of your selections, but maybe you could post this workup?


        quote:


        Author Topic: Hint for Benzoquinone Wacker
        Getafix posted 02-18-99 03:02 AM
        Member
        ----------------------------------------------------------
        Found this note under my windscreen wiper yesterday:
        " After dumping your rxn mix in 1.5L 3N HCl and extracting with DCM, wash the DCM with water a couple of times. Then wash with Sodium Bicarbonate twice.
        After that, wash with 5% NaOH three times. The first wash will cause both phases to be completely black, so separation is really difficult. Not even a torch will         help.  But some solids form on the interface, so you can stop the separation as soon as you see solids going through the neck. The second wash will result in a nice emulsion, but with a bit of swirling it will break in about 15 minutes. The DCM layer will now be more red than black. The last wash is quite easy. You will notice that the NaOH layer will contain a lot of tarry shit, but it is water soluble and can be washed away easily.

        After that, wash with water again, and then with a saturated NaCl soln.

        By now the DCM should be more red than black and not as viscous.

        Dry the DCM and distil of DCM and then add about 50% peanut oil or any other high BP oil. (50% of weight of safrole used)

        Vacuum distil the mix and you will find the oil coming over will be nice and clear. No red hit coming over, or crystals forming in your condenser.

        And when the MD P2P has finished coming over, the temp will drop drastically. No orange or black oil coming over.

        AND when you check in your flask there will be nearly NO TAR. A quick rinse with some toluene will clean it up completely. No struggling with
        rock hard tar for days. Just wash and dry. And the yield is quite nice too!"  And there ends the note.
        Hope this helps!
        -getafix

        Osmium posted 02-18-99 05:06 AM
        Member
        ----------------------------------------------------------
        Osmium told you weeks ago to remove the hydroquinone with NaOH. Nice to see somebody listened.


      r2d3
      Member  posted 04-15-99 05:24 AM           

      MM: If you extract the 3N HCl "wash" with DCM, you can reclaim any unreacted safrole. Depending on your conversion percentage, this may be
      well worth the time. This process also is effective after an Al/Hg animation to reclaim unreacted MDP2P.
      Casper58
      Member  posted 04-15-99 07:49 AM           

      Another way to simplify the benzo wacker is after the 8 (or 9-9.5) hours flood the sol'n with water and the oil will drop out into tar.. let it stir and all these black crystals will form.. vac filter it all real well, add some DCM to the tar and filter.. wash the filter cake real well with DCM.. All this can be done within 30-50 minutes.. sure cuts down on the time.. doing all the washes takes a couple of hours, depending on skill.. distill  off the DCM and safrole and the not-ketone should come over..      however, beware of hydroquinone crystals that MIGHT come over and crystallize in your condensor.. also the purity of the ketone isn't the best, but it'll work
      peace
      Casper


 8)
Chemistry is our Covalent Bond

sassa

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Re: extraction and washes on the ketone syntesis.
« Reply #3 on: June 10, 2010, 07:20:28 PM »
thank´s alot for the info.very usefull.
Proved without doubt that for me all goes better ussing toluene and not DCM as extraction solvent.Really easy separations.But......
I am distilling today the ketone, and for my amazement, this one going out without color ??? ???.,only with a very little green, almost invaluable reflection .Ever have obtained ketone with a color between yellow and green fluorescente.I don´t believe that it could be safrol or isosafrol, because that nothing for the quantity that i´m gathering.It´s posible to be safrol-isosafrol?temperatures not mach with that. I have been attentive to the different temperatures of exit, and I could see  the safrol-isosafrol  coming at lower temperature and he was presenting certain turbidity as alway,not like the ¿ketone? i´m recovering at usual temperature(200-210).(yes,very high).
 It is possible to obtain a colorless ketona, or wants to say that I have been wrong??? :( :(.i´m have seen an multimedia article on Rhodium with people achieving blue ketone.... :o
 If the information is useful for something, I have done the wacker with benzoquinone and methanol ala methyl's man and have extracted the ketona with toluene.Is the first time that I use the toluene as solvent to extract... can it be related to this??.
     It is the only new variable that I have introduced with regard to previous occasions.
  I´m doing to the distillation with columm(fractional),really a painfull, but good to obtain more pure `product.
   What do you think??
« Last Edit: June 10, 2010, 08:18:34 PM by sassa »

Dongle

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Re: extraction and washes on the ketone syntesis.
« Reply #4 on: June 12, 2010, 11:38:02 AM »
THere was a post at the Hive, which discussed that the color of the Ketone was correlated to the extent of NaOH washes done. I can find it and post it later. I wouldn't sweat the color like people used to.

sassa

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Re: extraction and washes on the ketone syntesis.
« Reply #5 on: June 12, 2010, 06:04:05 PM »
Ultimately I believe that possibly quite this correct, since ultimately, after the whole distillation, the obtained product if it has this pale green color.
It is as if only it was estimated well when the flask has a considerable quantity of product. At the end of the distillation, I have had to remove the column vigreaux(of course isolated with rockwool), because   the ketone that still was staying seemd to be  unable to come out. Probably i will redestill the ketone again to assure a maximum purity,because on my post aminations the yields aren´t the supossed to get,and i believe there is connection with not pure ketone,along other variables.
 With regard to the instructions of Methyl's man it brings over of adding oil to prevent the ketone from burning, i proved this once or twice (with sunflower oil and silicone oil)and results in a distilling flask with 2 phases, the superior of oil and the low one of tar, which produced that the stirbar could not move and remaining big part of the product caught in that tar.
   For my experience and results, always it has gone quite much better without adding any oil.,and begins distillation fractional until half of the ketone it´s on the receiving flask,and then continue with normal distillation without columm.Of course  for people like me with not good vacumm source and not a big stirhotplate.Allways a little tar it´s creating on the distilling flask,but way less without any oil.
  PD:a good method to avoid this tar it´s when distillation ends,empty the hot liquid tar on a milk jug or something,not by the toilet,because,when gets cold with water,it get instant hard and sticky,and it´s very hard to clean from any surface.Then,rinse the hot flask with toulene and all that tar it´s cleaned in 30 seconds.Don´t let the flask get cold....i have spent afternooms cleaning a flask from this reaction,and sometimes needs to buy another new :P :P
    
« Last Edit: June 12, 2010, 09:23:03 PM by sassa »

Dongle

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Re: extraction and washes on the ketone syntesis.
« Reply #6 on: June 13, 2010, 12:47:52 AM »
Sassa, here you go:

Quote
The Color of Ketone
(Rated as: good read) Bookmark
I think I've discovered what causes different colors of Ketone.
The last few times I ran the MM Benzo Wacker, the Ketone came out water white. Aminated fine, but I was curious as to why it the color was so light.
Looking at all parameters, I realized that the NaOH I was using was old leftover stuff, which I had diluted down with distilled H2O to have enough to run the cleanup. A pH test gave an indication of about a 3-4% strength of NaOH.

I mixed up a fresh batch of NaOH, and strength was about 7-8%.
Ran MM Benzo and cleanup. During cleanup I could see during the NaOH wash that the oil had a Greenish-yellow tinge.
Sure enough, the Ketone that distilled off had that classic Greenish "antifreeze" color.
So.... I believe that the ultimate color of the Ketone comes from the strength of the NaOH wash, and how long one lets the oil sit with it in the sep funnel ( the longer the sep, the greener the Ketone).
BTW, I have stopped washing with saturated NaCl.
I do the bicarb wash 3 times, then 3 times with NaOH, then 2 times with distilled H2O.     nitrous351
(Hive Bee)

Sedit

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Re: extraction and washes on the ketone syntesis.
« Reply #7 on: June 19, 2010, 03:52:11 AM »
THere was a post at the Hive, which discussed that the color of the Ketone was correlated to the extent of NaOH washes done. I can find it and post it later. I wouldn't sweat the color like people used to.

I feel a large amount of color change could come from the lighting involved. Organics many times react to various light sources to generate a spectrum of color. Take tea for instance and allow sunlight to fall into a glass of tea. The top layer will appear green. Having this happen with a more transparent compound could yeild a range of colors even if your compound is clear in "normal" light.
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Vesp

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Re: extraction and washes on the ketone syntesis.
« Reply #8 on: June 19, 2010, 06:11:47 AM »
However, for ketones to condense due to a strong base or an acid is very well known and can be observed with acetone to make many many things, up to 1,3,5-trimethylbenzene and some other aromatic chemicals that smell very sage like, if I remember correctly.

I'm sure it has to do with the pH -- this problem ought to be solved by using a decent buffer solution, with a weaker base? Still allowing for neutralization, etc but without the negative effects.
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sassa

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Re: extraction and washes on the ketone syntesis.
« Reply #9 on: June 22, 2010, 11:28:04 PM »
It seems that there is no problem  with this ketone lacking in an intense color. Tried  days ago on methylamine/AL /MeOH amination and  result in a perfect hydrocloride as for effects and yields.
 Ultimately, I have proved the method of crystallization proposed by a member of the forum, about  extracte the amine  on the toluene with 10% HCL ,and let  to evaporate for days the water to obtain colored crystals, which went on to the correct color after the washes with acetone. A slow, but very very secure and easy method ;D.Served me too  to discover that my problem in the low yields was the crystallization with  gas. But now I her miss! ;D