P2P synthesis from BMK Glycidic Acid (sodium salt) - modified version

[G.Patton]

Distillation adapter

Hello, do you mean Claisen adapter?

Pour 100 - 150 ml of Phosphoric acid

What concentration of the acid have you used? Why have you added so much acid? 100 - 150 ml is 3.5 - 5.2 fold excess.

Why don't you added the acid into glycidate aqueous solution and did in vice versa? I guess, It takes a lot of time.

 

[Heisenblack]

Hello, do you mean Claisen adapter?


What concentration of the acid have you used? Why have you added so much acid? 100 - 150 ml is 3.5 - 5.2 fold excess.

Why don't you added the acid into glycidate aqueous solution and did in vice versa? I guess, It takes a lot of time.

G.PattonYes Claisen adapter.

I used 100 ml for 50 gr batch, excess acid is to prevent the formation of layers in the flask and to make the reaction go on immediately, this minimizes the formation of byproducts. The amount of acid can still be optimized to make it economical. When I had less acid, I could see the brown glycidate layer in the flask. I forgot to mention the pH of p2p in the receiving flask was 5.5 - 6.

The process takes about 1 hour to complete.

 

[w2x3f5]

I think it has no sense. An excess of the acid (too big) will not change the reaction way.


Have you tried a bigger than 50g scale?

Thank you for your experience report here!

G.Pattonit does not change the reaction path, but the rate of the reaction

 

[metux]

Am already hidrolized bmk oil,and its floats on surface,i folow G.patton,extraction method,100gr glycidade 20gram naoh with 300mil water,affer reflux 1h,and cool to room temp,added hcl about 28% 200ml,then refluxed again,for 3hours,with mixing,after finish all,i get brown oil,and white salt on the botton,i try to disstill without extraction,becose i doint like messing with extraction,it worked for a while,i can't distill all stuff from the reaction flask becose its starts exploding,with big bubbles,and gasses,my termometer cracked,and stuff almost not exploded into face.

 

[metux]

Am already hidrolized bmk oil,and its floats on surface,i folow G.patton,extraction method,100gr glycidade 20gram naoh with 300mil water,affer reflux 1h,and cool to room temp,added hcl about 28% 200ml,then refluxed again,for 3hours,with mixing,after finish all,i get brown oil,and white salt on the botton,i try to disstill without extraction,becose i doint like messing with extraction,it worked for a while,i can't distill all stuff from the reaction flask becose its starts exploding,with big bubbles,and gasses,my termometer cracked,and stuff almost not exploded into face.

metuxIts a bich to work with,yield is shit also for my.

 

[w2x3f5]

Am already hidrolized bmk oil,and its floats on surface,i folow G.patton,extraction method,100gr glycidade 20gram naoh with 300mil water,affer reflux 1h,and cool to room temp,added hcl about 28% 200ml,then refluxed again,for 3hours,with mixing,after finish all,i get brown oil,and white salt on the botton,i try to disstill without extraction,becose i doint like messing with extraction,it worked for a while,i can't distill all stuff from the reaction flask becose its starts exploding,with big bubbles,and gasses,my termometer cracked,and stuff almost not exploded into face.

metuxuse boiling stones (pieces of porous pottery) and your mixture will boil much more evenly if it is not thick
steam distillation won't save you from solvent extraction of the ketone...

 

[metux]

Am extracted as well with petrolium ether,but results its not worth to try a gain,best result then i distill into ether.

 

[metux]

Some people get 65%,its true or not,i can't tell.

 

[w2x3f5]

Some people get 65%,its true or not,i can't tell.

metuxtry the technique from this topic, it will be great if you publish your result

 

[metux]

For every 20 mil to distill needs a lot off water,then i doint added it starts bubling like Chernobil,i think stainless steel distiller, with gas heater full power,and River water for cooler,its the best choise for distiling,in large scale.

 

[w2x3f5]

For every 20 mil to distill needs a lot off water,then i doint added it starts bubling like Chernobil,i think stainless steel distiller, with gas heater full power,and River water for cooler,its the best choise for distiling,in large scale.

metux20 ml p2p = 240 ml water

 

[w2x3f5]

For every 20 mil to distill needs a lot off water,then i doint added it starts bubling like Chernobil,i think stainless steel distiller, with gas heater full power,and River water for cooler,its the best choise for distiling,in large scale.

metuxyou can use a steam generator or superheated steam works even better. in any case, you need to watch the distillate in the refrigerator, you will see when the cloudy water runs out and clear water comes out, which means that the ketone is over

 

[metux]

You can wait and wach for 24h then clouds its finish,,but you need take some good dope,before you start,anyone is diffrent choice,what they like to dobut my choice calculate water you need.,and gas you need,and leave,untill stops pissing.,untill all distills.you will left with salt anyways.

 

[w2x3f5]

You can wait and wach for 24h then clouds its finish,,but you need take some good dope,before you start,anyone is diffrent choice,what they like to dobut my choice calculate water you need.,and gas you need,and leave,untill stops pissing.,untill all distills.you will left with salt anyways.

metuxI personally prefer the steam generator 36 kg per hour =)

 

[metux]

One pot reaction it can by done,no need to buy reactors or to many stuff, glasware or mixers,you only need stainless steel distiliator.and longer reflux time.

 

[K-Cyanide]

The method provided in this threat (thumbs up to @Heisenblack and @w2x3f5) was tested on a medium scale with 500g BMK powder (sodium salt) CAS 5449-12-7).
The only difference to the method described was the use of jacketed glass reactor.

1000ml of 85% phosphoric acid (p.a. purity) were added to the reactor, heated and stirred. In the meantime 500g BMK powder were dissolved in 6 liter boiling/very hot H2Od..

As the phosphoric acid reached 110 C the BMK powder solution was added slowly through a dropping funnel with constant pressure. The temperature was held in a narrow range of 108C to 112 C, by adjusting the dropping speed of the BMK powder solution. This addition process took appr. 5 h.

After collecting some 3200 ml of distillate the product was extracted with 2x500ml DCM. The combined extracts were dried over sodium sulfate and the solvent removed by rotovap.

So far so good. But the yield of 168 ml was quite disappointing. What went wrong? At the time being i have no clue what it is or what to change in the procedure.

 

[w2x3f5]

The method provided in this threat (thumbs up to @Heisenblack and @w2x3f5) was tested on a medium scale with 500g BMK powder (sodium salt) CAS 5449-12-7).
The only difference to the method described was the use of jacketed glass reactor.

1000ml of 85% phosphoric acid (p.a. purity) were added to the reactor, heated and stirred. In the meantime 500g BMK powder were dissolved in 6 liter boiling/very hot H2Od..

As the phosphoric acid reached 110 C the BMK powder solution was added slowly through a dropping funnel with constant pressure. The temperature was held in a narrow range of 108C to 112 C, by adjusting the dropping speed of the BMK powder solution. This addition process took appr. 5 h.

After collecting some 3200 ml of distillate the product was extracted with 2x500ml DCM. The combined extracts were dried over sodium sulfate and the solvent removed by rotovap.

So far so good. But the yield of 168 ml was quite disappointing. What went wrong? At the time being i have no clue what it is or what to change in the procedure.

K-CyanideOk, I check it

 

[w2x3f5]

The method provided in this threat (thumbs up to @Heisenblack and @w2x3f5) was tested on a medium scale with 500g BMK powder (sodium salt) CAS 5449-12-7).
The only difference to the method described was the use of jacketed glass reactor.

1000ml of 85% phosphoric acid (p.a. purity) were added to the reactor, heated and stirred. In the meantime 500g BMK powder were dissolved in 6 liter boiling/very hot H2Od..

As the phosphoric acid reached 110 C the BMK powder solution was added slowly through a dropping funnel with constant pressure. The temperature was held in a narrow range of 108C to 112 C, by adjusting the dropping speed of the BMK powder solution. This addition process took appr. 5 h.

After collecting some 3200 ml of distillate the product was extracted with 2x500ml DCM. The combined extracts were dried over sodium sulfate and the solvent removed by rotovap.

So far so good. But the yield of 168 ml was quite disappointing. What went wrong? At the time being i have no clue what it is or what to change in the procedure.

K-CyanideWrite in more detail what you observed during hydrolysis, whether there were layers, sodium phosphates precipitated, and others.
Acids have been little used this is the first thing I see.
The collected water is not enough, according to my calculations, 3200 ml of water will capture only part of the ketone. Were the last drops of water in your refrigerators clear?
Is the temperature of 110 degrees in the reactor jacket or the temperature of the acid?
Were stones used to form bubbles?
Wasn't it scary to start a new technique immediately for 500 grams? without prior verification
In theory, 500 grams of sodium glycidate should make 335 ml of P2P, you have 168 ml or only 50 percent of the yield

 

[w2x3f5]

The method provided in this threat (thumbs up to @Heisenblack and @w2x3f5) was tested on a medium scale with 500g BMK powder (sodium salt) CAS 5449-12-7).
The only difference to the method described was the use of jacketed glass reactor.

1000ml of 85% phosphoric acid (p.a. purity) were added to the reactor, heated and stirred. In the meantime 500g BMK powder were dissolved in 6 liter boiling/very hot H2Od..

As the phosphoric acid reached 110 C the BMK powder solution was added slowly through a dropping funnel with constant pressure. The temperature was held in a narrow range of 108C to 112 C, by adjusting the dropping speed of the BMK powder solution. This addition process took appr. 5 h.

After collecting some 3200 ml of distillate the product was extracted with 2x500ml DCM. The combined extracts were dried over sodium sulfate and the solvent removed by rotovap.

So far so good. But the yield of 168 ml was quite disappointing. What went wrong? At the time being i have no clue what it is or what to change in the procedure.

K-Cyanidewere there no backdrops to the reactor at the inlet to the refrigerator? (by type of dephlegmator)

 

[w2x3f5]

The method provided in this threat (thumbs up to @Heisenblack and @w2x3f5) was tested on a medium scale with 500g BMK powder (sodium salt) CAS 5449-12-7).
The only difference to the method described was the use of jacketed glass reactor.

1000ml of 85% phosphoric acid (p.a. purity) were added to the reactor, heated and stirred. In the meantime 500g BMK powder were dissolved in 6 liter boiling/very hot H2Od..

As the phosphoric acid reached 110 C the BMK powder solution was added slowly through a dropping funnel with constant pressure. The temperature was held in a narrow range of 108C to 112 C, by adjusting the dropping speed of the BMK powder solution. This addition process took appr. 5 h.

After collecting some 3200 ml of distillate the product was extracted with 2x500ml DCM. The combined extracts were dried over sodium sulfate and the solvent removed by rotovap.

So far so good. But the yield of 168 ml was quite disappointing. What went wrong? At the time being i have no clue what it is or what to change in the procedure.

K-Cyanideabout the lack of acid, I made a mistake in the answer, I haven’t woken up yet)

 

[qwe111]

The method provided in this threat (thumbs up to @Heisenblack and @w2x3f5) was tested on a medium scale with 500g BMK powder (sodium salt) CAS 5449-12-7).
The only difference to the method described was the use of jacketed glass reactor.

1000ml of 85% phosphoric acid (p.a. purity) were added to the reactor, heated and stirred. In the meantime 500g BMK powder were dissolved in 6 liter boiling/very hot H2Od..

As the phosphoric acid reached 110 C the BMK powder solution was added slowly through a dropping funnel with constant pressure. The temperature was held in a narrow range of 108C to 112 C, by adjusting the dropping speed of the BMK powder solution. This addition process took appr. 5 h.

After collecting some 3200 ml of distillate the product was extracted with 2x500ml DCM. The combined extracts were dried over sodium sulfate and the solvent removed by rotovap.

So far so good. But the yield of 168 ml was quite disappointing. What went wrong? At the time being i have no clue what it is or what to change in the procedure.

K-CyanideHey, brother.
The reaction time in this way is too short. Is the product obtained p2p? What about the benefits of converting to methyl?
I plan to start this experiment, but I don't quite get it!

 

[metux]

How does it possible,then you trying extract with petrolium ether, all oil from soliution,and you thinking all oil its collected,and you have left cloudy white soliutions with salt on the bottom,,,but then you still thinking is shit yield,and dreaming about to get more oil, and trying to distill,and you collecting more oil,from the same soliution!! Does this is normal?and i use plenty of ether,i did 3 times extraction with the same soliution,with every time fresh ether.,5449-12-7 distiling for my,always get more yield.,,

 

[metux]

I see, after all reaction done,if you left for longer period to stay,havy oil,in bmk salt soliution, goes down, and light more transparent oil,stays on top.

 

[K-Cyanide]

@metux

Dude, what the hell are you talking about ?