Patented process from benzaldehyde to BMK glycidyl ester to P2P

Re186

Don't buy from me
Resident
Joined
Feb 26, 2023
Messages
47
Reaction score
29
Points
18
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 phenylacetone.
This process does not separate BMK glycidyl ester.
The literature indicates that the yield of this process from benzaldehyde to distilled phenylacetone is 82.9%.
Mr. G. Patton previously provided another solution for this process on the forum, and I have made some comments under this post.(https://bbgate.com/threads/bmk-glyc...p2p-synthesis-from-bmk-glycidate-ethers.4307/)


Since my English level is not very good, this article was translated by Google after writing, please forgive me if there is any grammatical incomprehension.

Practice steps:
-A 2000ml reaction device, kept clean and dry, must be completely anhydrous.
-Add 280g of 30% sodium methoxide-methanol solution. (If you are using 28% sodium methoxide-methanol solution, you need 300g)
-Start the condensing pipe, install the drying pipe above the condensing pipe to isolate the external water.
-Add the mixed solution of 104g benzaldehyde and 232g methyl 2-chloropropionate using constant pressure dropping funnel under stirring.
-After the addition, the inside of the flask will spontaneously heat up to around 60°C. At this time, adjust the heating temperature to maintain the inside of the flask at 60°C.
-Stir and reflux at 60°C for 2 hours.
-Add 1160ml of 3mol/L hydrochloric acid under stirring.
-After adding, heat to 90°C under high-speed stirring, stir and reflux at this temperature for 4 hours, please ensure continuous stirring.
-Cool to within 20°C.
-Use a separatory funnel to separate the oil layer.
-Use 3×100ml dichloromethane to extract the aqueous layer, and combine all extracts and oil layers.
-Use 200 g of 5% aqueous sodium bisulfite (NaHSO ) to wash the organic layer.
-Use 2×200ml 1% sodium hydroxide solution to wash the organic layer to ensure that the pH value of the aqueous layer is greater than or equal to 7.
-Filter the oil layer through a sand core funnel covered with 1.5cm thick anhydrous magnesium sulfate to dry thoroughly, rinse the sand core funnel with a small amount of dichloromethane and combine.
-Use a rotary evaporator to remove low-boiling point solvents at 70 °C under reduced pressure.
-Build an atmospheric distillation device, collect the main fraction from 210°C to 240°C, and obtain yellow 1-phenyl-2-propanone.
-If produced in large quantities, colorless phenylacetone can be obtained by one more vacuum distillation.

Precautions:
-Once there is moisture in the reaction device before adding hydrochloric acid, the yield will be severely reduced or even the reaction will not occur.
-After adding hydrochloric acid, it is necessary to use strong stirring to fully mix the reaction solution. Because it is an oil-water cross-phase reaction, the reaction depends largely on the contact area. After calculation, the difference in contact area between stirring and non-stirring can reach hundreds or even thousands of times!
-Please pay attention to whether the temperature is lower than 20°C before extraction. If the temperature is too high, dichloromethane will expand the separatory funnel and open the separatory funnel.
-Washing with sodium bisulfite can add to remove a small amount of unreacted benzaldehyde to improve the purity. Benzaldehyde is not easy to remove during distillation. Please do not delete this step at will.
-The process of sodium bisulfite washing and the first sodium hydroxide washing process will be more difficult to separate, and it will take a long time to stand, please wait patiently.
-Please make sure the liquid is dry before distilling, otherwise the distillation is prone to bumping.
-30% sodium methoxide/methanol solution try to buy the finished product directly, do not use solid sodium methoxide and anhydrous methanol to manufacture.


Experience:

The first step reaction of benzaldehyde with methyl 2-chloropropionate and sodium methoxide under reflux at 60°C is shown in the figure below. The process of adding benzaldehyde and methyl 2-chloropropionate to the sodium methoxide solution will boil, please control the adding speed reasonably.
98P4Sc0LVv
IyFGWkVZJh
HAgZjTyoEr


The process of reflux at 90°C after adding hydrochloric acid is shown in the figure below.
7BDLMSRuht


The oil layer after extraction and washing is shown in the figure below.
TaX6ScQdpT
CaudlVeS1g


Use a rotary evaporator to evaporate the low boiling point solvent at 70°C, as shown in the figure below.
PEkq1TWo87


The distillation apparatus is shown in the figure below.
The total volume before distillation is about 250ml to 300ml. It is the total amount obtained from two operations. During the distillation process, about 70ml of colorless distillate flows out below 110°C. It has organic solvents and some pungent odors. It should be a low boiling point solvent.
From 110°C to 160°C, about 20ml of colorless distillate flowed out, with a pungent smell. Possibly methyl 2-chloropropionate and some product esters at this boiling point.
From 160°C to 210°C, less than 5ml of a colorless distillate flows out, which has the smell of benzaldehyde, which may be benzaldehyde.
When it is close to 210°C, the distillate starts to turn yellow, and the temperature fluctuates from 210°C to 240°C. 120ml of distillate flows out, which is olive yellow and has a consistency similar to that of olive oil at normal temperature. Main fraction with P2P.
When reddish-brown steam starts to evaporate in the flask, the distillation is over, and about 25ml of residue remains in the flask.
WO3oVyamqA


The P2P fraction is shown in the figure below.
QBlUshpdf2
NGOIMV93db
RvU0kB8efx
VtAgkQFi7c


The TLC comparison of distilled P2P and benzaldehyde is shown in the figure below.
WFeNi25B8o



Maybe due to some mistakes in the operation of the production personnel, the yield is much lower than the yield in the literature. I will continue to update the follow-up yield. In addition, we can see through TLC that the presence of benzaldehyde is no longer visible in the distilled P2P, but it is still impure, with two very obvious components. The impurities are unknown, and it is obvious that distillation cannot remove them.
At present, I plan to separate the components and send them to the testing agency for nuclear magnetic resonance testing to determine the product components and impurity structure, but due to insufficient funds, I am here to initiate crowdfunding to netizens on the BB forum. Below is my cryptocurrency collection It is estimated that perfecting this process will require about 10 to 12 NMR tests and some consumables, and the total cost will be about 1500 to 1800 US dollars. Once the funds are sufficient, I will use liquid chromatography to separate the product components and perform NMR detection, and then post the detection results on the BB forum. Then I will make targeted improvements to the process based on the test results, with the aim of obtaining high-purity P2P using a simple and repeatable process, and then I will continue to update these progress on the BB forum, thanks.

My BTC receiving address:
bc1qq48254h6zx89hwguppwkp3kct5xg93uvkf3vdr
My LTC receiving address:
ltc1q9535jld422uq63p4ycwvr6g0l2p3fj8e9rfzy5
My ETH receiving address:
0x9e24bC2DC0873b49bEfe5807Bb489E6BE2759eAd
The above receiving address can accept the corresponding cryptocurrency and all associated tokens.
I will update the crowdfunding situation in the comment area once a week.
 

w2x3f5

Don't buy from me
Resident
Joined
Jan 15, 2023
Messages
359
Reaction score
170
Points
43
Great job and homely atmosphere =)
You got 0.8955 mol of p2p with an admixture of 0.98 mol of benzaldehyde, do I understand correctly?
p2p your oil is really very yellow, mine is more colorless (steam distillation), photos under bright light.
 

Attachments

  • mUpnukcKQY.jpg
    mUpnukcKQY.jpg
    565.4 KB · Views: 219
Last edited:

Re186

Don't buy from me
Resident
Joined
Feb 26, 2023
Messages
47
Reaction score
29
Points
18
Great job and homely atmosphere =)
You got 0.8955 mol of p2p with an admixture of 0.98 mol of benzaldehyde, do I understand correctly?
p2p your oil is really very yellow, mine is more colorless (steam distillation), photos under bright light.
w2x3f5No, it should not be benzaldehyde, because I did a TLC comparison between benzaldehyde and the sample from the end of the first stage reaction, which showed that benzaldehyde had been basically consumed. Then a TLC comparison of distilled P2P and benzaldehyde showed that benzaldehyde was slightly less polar than both components in distilled P2P, so that was an unknown impurity. The yellow color is due to atmospheric distillation in the air. If I use vacuum distillation, I will get a colorless and transparent liquid, but it cannot accurately separate the fractions under the existing equipment conditions
 

w2x3f5

Don't buy from me
Resident
Joined
Jan 15, 2023
Messages
359
Reaction score
170
Points
43
No, it should not be benzaldehyde, because I did a TLC comparison between benzaldehyde and the sample from the end of the first stage reaction, which showed that benzaldehyde had been basically consumed. Then a TLC comparison of distilled P2P and benzaldehyde showed that benzaldehyde was slightly less polar than both components in distilled P2P, so that was an unknown impurity. The yellow color is due to atmospheric distillation in the air. If I use vacuum distillation, I will get a colorless and transparent liquid, but it cannot accurately separate the fractions under the existing equipment conditions
Ra226in total there is an admixture that flies with an azeotropic mixture in with p2p. it is interesting to check whether bisulfite will eliminate it, through isolation / purification of the adduct and further decomposition of the salt to p2p.
 

Mo0odi

Don't buy from me
Resident
Joined
Aug 26, 2022
Messages
145
Reaction score
51
Points
28

rothschild33

Don't buy from me
Resident
Joined
Oct 17, 2022
Messages
69
Reaction score
45
Points
18
So it is possible to distill p2p at 1 atm with normal distillation? I thought it would degrade before it reaches its BP temp?
 

Re186

Don't buy from me
Resident
Joined
Feb 26, 2023
Messages
47
Reaction score
29
Points
18
So it is possible to distill p2p at 1 atm with normal distillation? I thought it would degrade before it reaches its BP temp?
rothschild33No, you can only use steam distillation or vacuum distillation. Normal pressure distillation will seriously destroy the ingredients. If normal pressure distillation is necessary, I think that continuously passing a weak stream of nitrogen or argon into the distillation device may protect P2P from damage. but not experimentally tested
 

ZMI_AA0B

Don't buy from me
Resident
Joined
May 24, 2024
Messages
75
Reaction score
2
Points
8
Is the sodium methoxide methanol solution 30% methanol
 
  • Free product samples

    Testing products from new vendors and manufacturers.

    Get free samples for testing now!

  • Always stay in touch with BB forum. Element/Matrix.

    Connect notifications to always stay in touch with the forum!

    Connect

Top