hCiLdOdUeDn (Hive Bee)
07-24-02 09:27
No 336441
      Oxone stirring..  Bookmark   

SWIM has commenced in the Oxone method to make isosafrole-epoxide.  This is SWIMs setup.

64.8g isosafrole
600mL denatured alcohol
1500ml dH2O
80g NaHCO3
290.8g Oxone

This is stirred with a 2" magnetic stir bar in a 4L flask.
Will this stirring be powerful enough, the vortex comes down about halfway down the solution.

THANKS!

hcildoduedn
 
 
 
 
    OB1KNoBee
(Hive Bee)
07-24-02 10:58
No 336485
      40 degrees  Bookmark   

And watch your temperature, don't let it go past 40C, have some ice nearby to combat the temp if needed. Please post your ketone % yields . Very curious as to whether this is a worthy synth still.

OB1
 
 
 
 
    hCiLdOdUeDn
(Hive Bee)
07-24-02 11:20
No 336498
      hcildoduedn is away from his lab.  Bookmark   

hcildoduedn is away from his lab. He will do this as soon as he gets back! Will post results soon!!

hcildoduedn
 
 
 
 
    terbium
(Old P2P Cook)
07-25-02 04:42
No 336783
      Alcohol  Bookmark   

Any particular reason that you are using denatured alcohol instead of methanol?
 
 
 
 
    Wargasm
(Hive Bee)
07-28-02 03:13
No 337890
      I have run this synth 6 times now.  Bookmark   

OB1KNoBee, re:

And watch your temperature, don't let it go past 40C, have some ice nearby to combat the temp if needed. Please post your ketone % yields . Very curious as to whether this is a worthy synth still.
[/red]


SWIM has run this synth about 6 times so far, SWIM is a very new chemist, still finding the right teqnique, but SWIM can tell you every synth resulted in ketone (which aminated), with fairly good yields, about 65-70%(of ketone, not the final product), considering SWIM's experience (5 months, most of which spent learning basic O-chem req for synth).
SWIM is having very low yields of final product, nothing consistant, and SWIM is trying to figure out why.  Suspect it could be shitty vac resulted in a high temp for ketone dis (came over at 192C).  Waiting on a proper rotery vane pump to verify.
But every batch has resulted in active product.  SWIM's experience with MDMA limited (only twice that wasn't mine)... untill 1st batch (went a little overboard for a while... WOW, but SWIM doesn't have much to campare it to).
Because SWIM's not ready to invest in a moderately used mass spectrometer, have had to rely on the reviews of the more experienced.  The only complaint was a few people saying the 125 mg dose was too strong.  Obviously, not the worst thing someone could say.
Wanted to wait untill got the procedure down a little better before I posted, but...
I think every batch ran, at one point, above 40C.  What would happen, low quality ketone, or failed run?

EDIT-  some other interesting data:  Quite a few questions on this, though not for a while:

100% or 85% oxone?  -Used both, both work, just ajust the weight of 85% oxone to include the weight of oxone + sodium bicarb.

I experimented with adding 43% HCl, first diluted, then right out of the bottle shocked, untill the silt dissolved (I was waiting on a buchner funnel, so I couldn't suction filter).  But I want to do an identical run with and without, to see if it affects yields or ketone quality.
 
 
 
 
    Vibrating_Lights
(Hive Addict)
07-29-02 07:58
No 338385
      jesus  Bookmark   

There is alot of tricks posted here that make this rxn run well. Search my posts. The ammount of dcm used in the extractions is important.  But if the temp gets over 40 then the molocule gets chewed to shreads.  Bigger oxidations have a tendancy to run hotter than smaller ones.  water or ice bath is nescesary for over 100 gms.  >than 500 gms and it getws real hot 47.c. no ketone all bi product.  degradation product smells strongly of sweet flowers not at all chemicaly like ketone.
Vl_

!!!!!!!1I buttfucked your daughter!!!!!!!!1..............Vl_
 
 
 
 
    hCiLdOdUeDn
(Hive Bee)
07-29-02 12:45
No 338466
      Ok...here are the results..  Bookmark   

SWIMS first oxone run. SWIM was going to start the oxone run earlier when I first posted but SWIM got side tracked. Here goes...

In a 4L flask (1 gallon pickle jar) was added a mixture of 64.8g isosafrole in 600ml deatured alcohol. Added to this a mixture of 290.8g Oxone and 80g NaHCO3 in 1.5L of dH2O. A 2" octagonal stir bar was added and stirring commenced. The vortex came down half way down the solution and SWIM saw swirly things on top. These are my temperature readings.

0min= 21.3C
30min=28.4C
60min=32.7C
90min=35.6C
120min=38.5C
150min=38.7C
180min=37.2C
210min=33.2C
240min=27.4C
270min=23.6C
300min=21.9C

The stirbar is now turned off and there is some white precipitate on the bottom. SWIM is now waiting for things to settle...will repost soon!

hcildoduedn
 
 
 
 
    hCiLdOdUeDn
(Hive Bee)
07-29-02 12:49
No 338467
      Forgot to mention this flask was sitting in a ...  Bookmark   

Forgot to mention this flask was sitting in a stainless-steel pot with added water to cool things down if it got too hot. SWIM never added ice to this...

hcildoduedn
 
 
 
 
    pickler
(Greenhorn)
07-29-02 15:18
No 338505
      It's a lot easier to filter the precipitate first ...  Bookmark   

It's a lot easier to filter the precipitate first before adding the isosafrole. Stirring becomes easier and the epoxide is easier to extract.

I went into the business for the money, and the art grew out of it.-Charlie Chaplin

 
 
 
 
    hCiLdOdUeDn
(Hive Bee)
07-29-02 16:13
No 338527
      ^^^Too late. Ok, phew...SWIM is now finished!!!  Bookmark   

^^^Too late.

Ok, phew...SWIM is now finished!!! This is what SWIM has done.

Once the stirring stopped, SWIM let the precipitate settle. This left the bottom with some precipitate and the solution was semi-cloudy. SWIM decanted as much of the top solution into another beaker and loaded 800mL of it at a time in his 1L sep funnel. He extracted the first two 800mL worth with 3x75ml DCM. SWIM let the DCM settle from each was for 10-15min. The DCM layer was a light yellow color and was easy to distinquish from the upper layer. 

The residue/solution from the oxone stirring was filtered and the white precipitate washed with 100mL DCM and added to the previous DCM extracts.

Now SWIM had ~500mL light yellow DCM extracts. SWIM then distilled all the DCM from the extacts and was left with ~70mL of pee yellow oil.

Now this is in the freezer right now to check viscosity (sp?) and soon will hydrolyze to (hopefully) ketone.

Thanks BEES!!!

hcildoduedn
 
 
 
 
    Vibrating_Lights
(Hive Addict)
07-29-02 19:46
No 338599
      you got it  Bookmark   

That is a great return of epoxide for someone who hasn't performed the rxn before.  As a tip.  Preheat both the epoxide and the 15%H2SO4 before adding them together.  this will raise the yeilds through the hydrolosis.  Make sure there is very cold water running through the condensor.  if not some ketone will be lost with steam out the top.  good luck
VL_

!!!!!!!1I buttfucked your daughter!!!!!!!!1..............Vl_
 
 
 
 
    Wargasm
(Hive Bee)
07-30-02 04:56
No 338769
      Oxone optimization.  Bookmark   

VL, re:
But if the temp gets over 40 then the molocule gets chewed to shreads.  Bigger oxidations have a tendancy to run hotter than smaller ones.  water or ice bath is nescesary for over 100 gms.  >than 500 gms and it getws real hot 47.c.

I'm running this rxn in a 5 gal bucket.  here are my ratios...
330g isosafrole
3550 ml MeOH
8500 ml h2o
1710 g oxone (85% so the mass includes the sod bicarb buffer)
Unfortunately, I did not monitor temp or use an ice bath.  raw yield was 404g epoxide, which I estimate had some residual DCM in it, ~40 g or so.
I have read several of your posts on this route to ketone, the idea to attempt to dissolve the silt with HCl was from your notes regarding solubility of the silt.
What method did you use to filter the clarifier, and what impact did this have on the final amount of silt?
I am very interested in getting this reaction optimized.
I am beginning to think my bunk ketone is from temperature degraded epoxide, and not from the HCl addition, as originally suspected.  I'd love to find a way to dissolve the silt and extract directly.



Worker bees can leave
   Even drones can fly away
      The queen is their slave
 
 
 
 
    hCiLdOdUeDn
(Hive Bee)
07-30-02 07:45
No 338841
      Hey bees! After some hard-earned sleep SWIM woke ...  Bookmark   

Hey bees!

After some hard-earned sleep SWIM woke up to find his 100mL erlenmeyer flask filled with ~70mL suspected epoxide in a ultra thick semi-fluid like state. Very close to cold honey. This was in the freezer for about ~12hours. Now today SWIM will hydrolyze...Will repost process and yields soon!!

Thanks V_L for the tips...i will use them.

Damn Wargasm!

Talk about large scale! You should have monitered the temperature, thats alot of wasted 2-alkane. Sorry to hear about your poor ketone product. I am betting that the high temperature caused your reaction to fail.SWIMs Rxn at one point did reach 41C or so, but i didnt worry much as it was in a water bath. The water bath/stainless cooled the rxn quite a bit down because it heated up during the reaction.



hcildoduedn
 
 
 
 
    Wargasm
(Hive Bee)
07-31-02 01:51
No 339131
      wasted 2-alkane  Bookmark   

Yea, I know.  The ketone aminated though, just had lousy yields.  Proceeds from the final product helped ease the pain (and paid for my new 6L sep funnel!).
I am planning on adding a coil of vinyl tubing along the inner side of the bucket next run, through which I will circulate ice cold water (I want to get my money's worth out of that aquarium pump) during the reaction.

Does anyone know if this reaction can run too cold? Perhaps I should use room temp water.

BTW, did you realy use denatured alcohol instead of methanol, or was that a typo?


Worker bees can leave
   Even drones can fly away
      The queen is their slave
 
 
 
 
    hCiLdOdUeDn
(Hive Bee)
07-31-02 07:09
No 339242
      Yes!! Seriously i did use denatured alcohol.  Bookmark   

Yes!! Seriously i did use denatured alcohol. It works too!! I also used denatured alcohol for epoxide hydrolyzing...I finally made ketone! See Post 338988 (hCiLdOdUeDn: "Hey Bees! Finished making epoxide see Post 338466 ...", Methods Discourse)

hcildoduedn
 
 
 
 
    Flip
(Hive Bee)
07-31-02 19:32
No 339434
      A good note on oxone stirring  Bookmark   

Just as an additional tip for future epoxidations;  When you are doing and epoxidation in a big bucket, 5 gal, etc, the speed and power of your stirring is directly proportional to the optimal reaction time. (i.e) If you have a 5 gal paint bucket on top of a traditional hotplate/stirrer as opposed to a larger industrial stirrer, you should compensate by allowing longer time for the reaction to take place.  However, sometimes inadequate stirring in large reactions will cause it to fail altogether. Although I doubt most of you who care are working with these types of equipment limitations.

Flip

Conclusion /nm./: the place where you got tired of thinking.
 
 
 
 
    Wargasm
(Hive Bee)
08-01-02 04:20
No 339575
      Another note on oxone stirring  Bookmark   

I did notice the reaction times differed when scaling up.  I think there is a point where if the reaction takes too long, the oxone will be used up by the buffer before it oxidizes the product, although this hasn't happened to me yet (knock on wood).  I know several people have run this reaction successfully with a magnetic stirrer, but I have found it much easier to go to overhead stirring.  For those bees who haven't read about it already, there is a very nice design for an improvised overhead stirrer  (using a kitchen mixer) on Rhodium's site.  It shakes a bit, but works well.

Worker bees can leave
   Even drones can fly away
      The queen is their slave