P2P synthesis from BMK glycidate ethers

[blackburn]

how come after hydrolysis with HCI in get clear yellow/dark oil on top liquid.

but after separating the oil from the HCI, and washing it with boiling water, the oil settles very thickly on the bottom and becomes cloudy almost like honey.

 

[w2x3f5]

how come after hydrolysis with HCI in get clear yellow/dark oil on top liquid.

but after separating the oil from the HCI, and washing it with boiling water, the oil settles very thickly on the bottom and becomes cloudy almost like honey. View attachment 12514 View attachment 12515

SwesweIts glycidate just without sodium, standard problem and usually its happens because HCl not so good work

 

[G.Patton]

I have gotten the same result using phosphoric acid 85%, the temperature was max, I refluxed for about 4 hours. I think the problem was that my mixing was not sufficient, plus I stopped stirring when the reaction mixture started boiling (I honestly thought the boiling would provide sufficient mixing). I extracted the brown/dark layer with toluene, washed the extract with brine solution couple of times until the aqueous layer was neutral, then I evaporated the toluene and was left with a viscous brown liquid. When I purified this brown liquid via steam distillation,only a small fraction of light yellow p2p (maybe 2 - 5ml from 100g cas 5449) came with the water in the receiving flask, a light brown residue was left after steam distillation (see picture). I assume this is the unreacted glycidic acid? View attachment 12643

HeisenblackHello, probably your problem is in a steam distillation?

When I purified this brown liquid via steam distillation,only a small fraction of light yellow p2p (maybe 2 - 5ml from 100g cas 5449) came with the water in the receiving flask, a light brown residue was left after steam distillation

 

[G.Patton]

This is the p2p oil (I think) from the receiving flask , the mixture is still cloudy, I left it to separate into layers overnight (hopefully).

With the unreacted glycidic acid, I am planning to extract it and see if I can get more p2p by hydrolising again with the acid, using strong mixing. Starting from here, can I skip the NaOH step or is it necessary? View attachment 12648

HeisenblackLooks like a not well separated solution.

P.S. you can ask me in DM. I if for free. You don't need to pay.

 

[Heisenblack]

Thank you, I have sent the message, please respond

 

[blackburn]

So we now try the phosphoric 85%

Got same result, good oil after 5h reflux , but Took some sample and wash with hot Water and the oil sinks to the bottom and gett Little lighter, check pic on the right side. @G.Patton @Ra226

 

[blackburn]

So we now try the phosphoric 85%

Got same result, good oil after 5h reflux , but Took some sample and wash with hot Water and the oil sinks to the bottom and gett Little lighter, check pic on the right side. @G.Patton @Ra226

View attachment 12752

Sweswe

 

[w2x3f5]

View attachment 12753

SwesweToday I received a short report on the hydrolysis of sodium glycidate from another user. He tried two of my options, in the first case he received 9.2 ml of p2p (after draining 8 ml, he may have lost part of p2p on the dryers) from 20 grams of glycidate and the second version of hydrolysis from 20 grams he received 12 ml of p2p (it is not known whether it is dry p2p or not ). Theoretical reaction yield 13.5 ml p2p ketone

 

[G.Patton]

View attachment 12753

Swesweare you sure that you has exactly BMK glycidate?

 

[G.Patton]

Today I received a short report on the hydrolysis of sodium glycidate from another user. He tried two of my options, in the first case he received 9.2 ml of p2p (after draining 8 ml, he may have lost part of p2p on the dryers) from 20 grams of glycidate and the second version of hydrolysis from 20 grams he received 12 ml of p2p (it is not known whether it is dry p2p or not ). Theoretical reaction yield 13.5 ml p2p ketone

w2x3f5Congratulation. Did you post it here to promote your personal advice service or want to share your minds?

 

[w2x3f5]

Congratulation. Did you post it here to promote your personal advice service or want to share your minds?

G.PattonThe hydrolysis was carried out under my guidance and according to my method Heisenblack. I think he will publish the methodology later, after up scaling

 

[w2x3f5]

Congratulation. Did you post it here to promote your personal advice service or want to share your minds?

G.Pattonbefore publishing, need to check the repeatability

 

[Heisenblack]

before publishing, need to check the repeatability

w2x3f5Yes I will publish the methodology after running 50gr batch, the 12ml p2p from 20 gr sodium glycidate was dry

 

[G.Patton]

The hydrolysis was carried out under my guidance and according to my method Heisenblack. I think he will publish the methodology later, after up scaling

w2x3f5Nice to read this =) Thank you.

 

[G.Patton]

So we now try the phosphoric 85%

Got same result, good oil after 5h reflux , but Took some sample and wash with hot Water and the oil sinks to the bottom and gett Little lighter, check pic on the right side. @G.Patton @Ra226

View attachment 12752

SwesweActually, I have no Idea what is it. I've never tried phosphoric acid method with reflux.

 

[w2x3f5]

Actually, I have no Idea what is it. I've never tried phosphoric acid method with reflux.

G.Pattonoverheating is very likely, ketone oxidizes easily, additional side reactions possible

 

[blackburn]

Yes this is 5449-12-7 @G.Patton

@w2x3f5 okey well i have to try My way ...

Thanks to both

 

[w2x3f5]

Yes this is 5449-12-7 @G.Patton

@w2x3f5 okey well i have to try My way ...

Thanks to both

Sweswewrite me in private messages, you can independently check the method, check the result. suddenly there will be pitfalls

 

[Ra226]

I will try scale synthesis from benzaldehyde to BMK to P2P in about a week, I intend to reflux the sulfuric acid mentioned in the article provided by @G.Patton , at that time I will share my opinion and post the original Experimental data

 

[metux]

Can i use brown red color oil,for reduction?

 

[Heisenblack]

Can i use brown red color oil,for reduction?

metuxThe brown red color oil is the unreacted glycidic acid, it would be best to steam distill the ketone then use in the next step

 

[Megido]

I mean then you have oil, but this oil 6 month old and becomes red color,. Do I need redistill for next step.