BMK glycidate (sodium salt) synthesis from benzaldehyde

[Ra226]

I encountered a problem. I followed the article. After adding sodium ethoxide, I stirred for an hour under a strict anhydrous environment below 10°C. After that, I started to raise the temperature to 60°C to prepare for the option of stirring for an hour. But after a little heating, the temperature in the device spontaneously rose out of control and quickly, and after only a few minutes, my thermometer showed a breakthrough of 130°C, so I want to ask, is this normal? Has anyone encountered it?The first picture is the process of stirring for 1 hour below 10°C after adding sodium ethoxide. I inserted a drying tube filled with anhydrous magnesium sulfate on the device to maintain anhydrous conditions. Since my circulation device can only cool down, I transferred the second stage of heating to the flask. The heating method is oil bath heating, but I just used the temperature of 65°C for a few minutes, and the temperature in the flask was out of control. As it rises, the thermometer shows that it exceeds 130 ℃ very quickly, so fast that I don't even have time to start the condensate water cycle in the condenser pipe, and then it becomes the state in the second picture.

Optional: As an option, an external gradual heating is set up to 60°С. With this method, the reaction yield will be reduced. A reflux condenser is installed on the reactor. RM is stirred at 60°С for additional 1 h. A heating is carried out with help of a reactor jacket and a thermostat.

G.Patton

 

[G.Patton]

I encountered a problem. I followed the article. After adding sodium ethoxide, I stirred for an hour under a strict anhydrous environment below 10°C. After that, I started to raise the temperature to 60°C to prepare for the option of stirring for an hour. But after a little heating, the temperature in the device spontaneously rose out of control and quickly, and after only a few minutes, my thermometer showed a breakthrough of 130°C, so I want to ask, is this normal? Has anyone encountered it?The first picture is the process of stirring for 1 hour below 10°C after adding sodium ethoxide. I inserted a drying tube filled with anhydrous magnesium sulfate on the device to maintain anhydrous conditions. Since my circulation device can only cool down, I transferred the second stage of heating to the flask. The heating method is oil bath heating, but I just used the temperature of 65°C for a few minutes, and the temperature in the flask was out of control. As it rises, the thermometer shows that it exceeds 130 ℃ very quickly, so fast that I don't even have time to start the condensate water cycle in the condenser pipe, and then it becomes the state in the second picture.


View attachment 12911 View attachment 12912

Ra226

After that, I started to raise the temperature to 60°C to prepare for the option of stirring for an hour. But after a little heating, the temperature in the device spontaneously rose out of control and quickly, and after only a few minutes, my thermometer showed a breakthrough of 130°C, so I want to ask, is this normal? Has anyone encountered it?

Hello, has the self-heating happen violently or slowly? It is quite interesting.

 

[G.Patton]

I did it again yesterday, this time the reaction is normal, but I think the yield will be low as far as the process is concerned. Finally, after adding ice water and standing for an hour, there is no obvious layering, so I use dichloromethane The mixture was extracted and I will analyze this extract today and post the results later. In addition, I just bought a patent for this process. The conditions and operations seem to be simpler and more optimized than your article. It shows that benzaldehyde (CAS 100-52-7) and methyl 2-chloropropionate (CAS 17639- 93-9) to the total yield of purified P2P is as high as 82.9%. I have already purchased related reagents and will try it in a few days

Ra226Have you tried to change water layer density by NaCl? It would be cheaper than DCM extraction.

Finally, after adding ice water and standing for an hour, there is no obvious layering, so I use dichloromethane

Can you link this potent?

In addition, I just bought a patent for this process.

 

[Ra226]

Have you tried to change water layer density by NaCl? It would be cheaper than DCM extraction.


Can you ling this potent?

G.Patton

Have you tried to change water layer density by NaCl? It would be cheaper than DCM extraction.

I guess the sodium chloride may not be effective anymore, because when I use dichloromethane to extract, the dichloromethane is abnormally in the upper layer, which means that the density of the water layer is already very high, and the sodium chloride may no longer be able to extract it. Increase density.Also, since I have a rotary evaporator that makes large-scale solvent recycling possible, I don't incur much cost in using solvent extraction reagents in large quantities.

Can you ling this potent?

regarding the patent, I found a patent published in 2009 and bought it. Its process looks very mature and simple. I plan to try this method after the added reagents arrive. The raw materials are still benzaldehyde and 2 - methyl chloropropionate.

 

[G.Patton]

I guess the sodium chloride may not be effective anymore, because when I use dichloromethane to extract, the dichloromethane is abnormally in the upper layer, which means that the density of the water layer is already very high, and the sodium chloride may no longer be able to extract it. Increase density.Also, since I have a rotary evaporator that makes large-scale solvent recycling possible, I don't incur much cost in using solvent extraction reagents in large quantities.

regarding the patent, I found a patent published in 2009 and bought it. Its process looks very mature and simple. I plan to try this method after the added reagents arrive. The raw materials are still benzaldehyde and 2 - methyl chloropropionate.

Ra226

I found a patent published in 2009 and bought it.

Can you write full name, number or/and doi please?

 

[Ra226]

Can you write full name, number or/and doi please?

G.PattonThis is a patent applied for in China. It seems that the scope of validity is only in China, and there is no English version of the full text, so I did not find the DOI number of this patent. The original text is written in Chinese, and the publisher is from Modern Times, Xi'an City, Shaanxi Province, China Institute of Chemistry, the phone number and email address left by the author are 029-88291460 and [email protected]. But you can pay attention to the content I will post next. Once I verify the reliability of this process, I will post all the detailed processes and precautions. This will take about a week or so from now.

 

[Ra226]

Can you write full name, number or/and doi please?

G.PattonIf you need it urgently, I can translate the operation part of the original text and send it to you in private chat. But from a responsible point of view, please do not publish it on the forum before verifying its reliability.

 

[Davidrobinson]

This is a patent applied for in China. It seems that the scope of validity is only in China, and there is no English version of the full text, so I did not find the DOI number of this patent. The original text is written in Chinese, and the publisher is from Modern Times, Xi'an City, Shaanxi Province, China Institute of Chemistry, the phone number and email address left by the author are 029-88291460 and [email protected]. But you can pay attention to the content I will post next. Once I verify the reliability of this process, I will post all the detailed processes and precautions. This will take about a week or so from now.

Ra226Just post the patent, your asking for help on a patent no one can see

 

[Ra226]

Can you write full name, number or/and doi please?

G.PattonI have published the patent process and practice.

Patented process from benzaldehyde to BMK glycidyl ester to P2P

This article provides you with a patented synthesis process from benzaldehyde to BMK glycidyl ester to P2P. This process comes from a patent published in 2009. The original text used 4-methoxybenzaldehyde to synthesize 4-methoxyphenylacetone. I replaced it with benzaldehyde to synthesize...

bbgate.com

 

[Ra226]

Results released: After a catastrophic failure, I had my reaction rerun yesterday. The reaction strictly follows the procedure of the article, using the optional option of heating to 60°C and stirring for 1 hour instead of stirring at room temperature for 12 hours. Figure 1 and Figure 2 are photos of the cooling stage and heating stage, respectively. Figure 3 is the output. Due to the slow separation after adding 1L of ice-distilled water according to the article, 300ml of dichloromethane was added for extraction and dried with anhydrous magnesium sulfate, so this is the dried extract. Figure 4 is the output TLC (Thin Layer Liquid Chromatography) test performed today, I manually transcribed the results because the operator could not take a clear and recognizable picture.

 

[G.Patton]

Results released: After a catastrophic failure, I had my reaction rerun yesterday. The reaction strictly follows the procedure of the article, using the optional option of heating to 60°C and stirring for 1 hour instead of stirring at room temperature for 12 hours. Figure 1 and Figure 2 are photos of the cooling stage and heating stage, respectively. Figure 3 is the output. Due to the slow separation after adding 1L of ice-distilled water according to the article, 300ml of dichloromethane was added for extraction and dried with anhydrous magnesium sulfate, so this is the dried extract. Figure 4 is the output TLC (Thin Layer Liquid Chromatography) test performed today, I manually transcribed the results because the operator could not take a clear and recognizable picture.

Ra226Hi, the TLC result tells us that your benzaldehyde has not completely reacted. Have you calculated the reaction yield?

Figure 4 is the output TLC (Thin Layer Liquid Chromatography) test performed today, I manually transcribed the results because the operator could not take a clear and recognizable picture.

 

[Ra226]

Hi, the TLC result tells us that your benzaldehyde has not completely reacted. Have you calculated the reaction yield?

G.PattonNo, the color of the benzaldehyde spot is quite dark from TLC, which means that the concentration of benzaldehyde in the product is quite high. If I want to calculate the yield, I need to use column chromatography to separate and weigh the components, but I did not purchase column chromatography equipment for the point of production. But in short, based on experience, I think that the incomplete consumption of benzaldehyde has something to do with the process not adding solvent, and this problem seems to be improved in the patent I bought.

 

[G.Patton]

No, the color of the benzaldehyde spot is quite dark from TLC, which means that the concentration of benzaldehyde in the product is quite high. If I want to calculate the yield, I need to use column chromatography to separate and weigh the components, but I did not purchase column chromatography equipment for the point of production. But in short, based on experience, I think that the incomplete consumption of benzaldehyde has something to do with the process not adding solvent, and this problem seems to be improved in the patent I bought.

Ra226I think everything is easier. Just stir the reaction mixture longer. Have you tried this option? Also, try a milder heating.

 

[Ra226]

I think everything is easier. Just stir the reaction mixture longer. Have you tried this option? Also, try a milder heating.

G.PattonIn fact, after I stirred for 1 hour below 10°C, the process of raising the temperature to 60°C was very careful and slow. This process took at least about 1.5 hours. After reaching 60°C, I started timing reflux for 1 hour. After 1 hour, it was naturally under stirring. The stage of cooling down to below 35°C to add the cold water took another about two hours, so it actually had a very long reaction time, at least 5+ hours, so I don't think it was a lack of time. I observed that at the stage of adding sodium ethoxide, the sodium ethoxide aggregated and agglomerated in the reactant and was not easily dispersed, and after the sodium ethoxide was completely added, the mixture became viscous like a paste, containing a large amount of solids, and it was completely a solid-liquid mixture. Bad for the reaction.

 

[Acab1312]

Hello does anyone know a reliable supplier in Europe for Methyl 2-chloropropionate (cas 17639-93-9)?

 

[Germanium]

Is it possible to synthesize PMK by using piperonal instead of benzaldehyde?

 

[w2x3f5]

Is it possible to synthesize PMK by using piperonal instead of benzaldehyde?

Germaniumyes

 

[Germanium]

yes

w2x3f5Thanks!
Is a solvent needed to dissolve piperonal? If so, which solvents can be used?

 

[mithyl2]

Is it possible to synthesize PMK by using piperonal instead of benzaldehyde?

Germaniumis the process for synthesizing pmk with piperonal from start to finish exactly the same as the synthesis of bmk from benzaldehyde?

 

[haze2000]

Jungle method ( HDPE Barrels) wont work with this procedure because of water traces?

 

[G.Patton]

Jungle method ( HDPE Barrels) wont work with this procedure because of water traces?

haze2000Probably yes. I'm not sure about what condition are you talking about.

 

[haze2000]

Probably yes. I'm not sure about what condition are you talking about.

G.PattonI was curious about large scale production, but HDPE is not hygroscopic as far as i know.

 

[G.Patton]

I was curious about large scale production, but HDPE is not hygroscopic as far as i know.

haze2000

HDPE is not hygroscopic

What? What do u mean? HDPE is plastic. How it can be hygroscopic?