Phenylacetone (P2P) synthesis from benzaldehyde with butanone

[Ortist]

saponification in aqueous NaOH at 50 degrees ?! Thats really bad idea

 

[gmo]

saponification in aqueous NaOH at 50 degrees ?! Thats really bad idea

OrtistWhat temperature is required?

 

[mckennai]

What temperature is required?

gmoAre you already in try or just asking? I'm almost trying that recipe just Williams guiding and directing me. I think I've done obtaining first intermediate I'had 3butane2one now I'm on acetoxy synthesizing step 2. If u already trying to synthesize Ill be happy to talk and stayin contact with u

 

[gmo]

Are you already in try or just asking? I'm almost trying that recipe just Williams guiding and directing me. I think I've done obtaining first intermediate I'had 3butane2one now I'm on acetoxy synthesizing step 2. If u already trying to synthesize Ill be happy to talk and stayin contact with u

mckennaiI tried unsuccessfully once, now I want to start again with the mentioned combined method and the opinions of friends and some simple initiatives. I will be happy to cooperate with you

 

[lalalander]

Everyone says this method has flaws. Has anyone ever really gotten significant yields with this method?

 

[Ortist]

Everyone says this method has flaws. Has anyone ever really gotten significant yields with this method?

lalalanderI used this method many times. Modified a bit. The best results I got was 30ml of P2P from 100ml of benzaldehyde. Also I know a few people who researched this reaction alot; their best results were around 35ml of P2P.

Working method:

1. Methyl-phenyl-butenone prepared as follows: 500ml of benzaldehyde is mixed with 1000ml of MEK. Mixture is cooled in a bucked filled with ice to around +5 degrees.
2. To this is added aqueous HCL, 35-37%, (you have to add 100g of pure HCL which corresponds to about 286ml of 37%HCL)
3. Mix and keep it in a bucket with ice overnight, let the ice melt.
4. Wait 24 hours more
5. Put it in a separatory funnel, discard lower layer.
6. Wash the dark brown-red mixture with 500ml of water, discard water.
7. Distill everything that boils below 150 degrees at atmosferic pressure and discard
8. Distill the rest in vacuum to get a yellow oil

This oil will darken on standing within a week.


Bayer-Villiger:
1. 100ml of above prepared oil add to mixture of 300ml of glacial acetic acid and 100ml of 50% hydrogen peroxide.
2. Heat & stir it at 55 degrees.
3. When reaction starts temperature will go up above 55..60 (about 1..2 hours) : this is the indication to turn OFF heating. If temperaturfe climbs to 70 then cool your flask under running water a bit.
4. Stir until temperature falls back to 50..55 degrees, then turn heating ON again
5. Stir & heat for 6 hours
7. Pour mixture to 1L of water, extract 3 times with 100+100+100ml of DCM
8. Distill DCM off


Saponification:
1. Put Bayer-Villiger product from the step above in a flask with stirring. Slowly add
NaOH solution (30g NaOH, 250ml water, 250ml ethanol). Slowly means dropwise, about 3..5 drops a second. Mixture becomes reddish-orange

2. At the end of addition pH should be above 12
3. To the mixture add acetic acid (any percentage) until neutral pH. Mixture will turn yellow
4. Pour this to 1L of water and extract 3 times with 100+100+100ml of DCM
5. Distill DCM & traces of ethanol off at atmospheric pressure
6. Distill your P2P under vacuum.
7. There will be alot of tar left in a flask

 

[gmo]

I used this method many times. Modified a bit. The best results I got was 30ml of P2P from 100ml of benzaldehyde. Also I know a few people who researched this reaction alot; their best results were around 35ml of P2P.

Working method:

1. Methyl-phenyl-butenone prepared as follows: 500ml of benzaldehyde is mixed with 1000ml of MEK. Mixture is cooled in a bucked filled with ice to around +5 degrees.
2. To this is added aqueous HCL, 35-37%, (you have to add 100g of pure HCL which corresponds to about 286ml of 37%HCL)
3. Mix and keep it in a bucket with ice overnight, let the ice melt.
4. Wait 24 hours more
5. Put it in a separatory funnel, discard lower layer.
6. Wash the dark brown-red mixture with 500ml of water, discard water.
7. Distill everything that boils below 150 degrees at atmosferic pressure and discard
8. Distill the rest in vacuum to get a yellow oil

This oil will darken on standing within a week.


Bayer-Villiger:
1. 100ml of above prepared oil add to mixture of 300ml of glacial acetic acid and 100ml of 50% hydrogen peroxide.
2. Heat & stir it at 55 degrees.
3. When reaction starts temperature will go up above 55..60 (about 1..2 hours) : this is the indication to turn OFF heating. If temperaturfe climbs to 70 then cool your flask under running water a bit.
4. Stir until temperature falls back to 50..55 degrees, then turn heating ON again
5. Stir & heat for 6 hours
7. Pour mixture to 1L of water, extract 3 times with 100+100+100ml of DCM
8. Distill DCM off


Saponification:
1. Put Bayer-Villiger product from the step above in a flask with stirring. Slowly add
NaOH solution (30g NaOH, 250ml water, 250ml ethanol). Slowly means dropwise, about 3..5 drops a second. Mixture becomes reddish-orange

2. At the end of addition pH should be above 12
3. To the mixture add acetic acid (any percentage) until neutral pH. Mixture will turn yellow
4. Pour this to 1L of water and extract 3 times with 100+100+100ml of DCM
5. Distill DCM & traces of ethanol off at atmospheric pressure
6. Distill your P2P under vacuum.
7. There will be alot of tar left in a flask

OrtistCan I use chloroform in Saponification step 4 extracted?

 

[Cbison]

I used this method many times. Modified a bit. The best results I got was 30ml of P2P from 100ml of benzaldehyde. Also I know a few people who researched this reaction alot; their best results were around 35ml of P2P.

Working method:

1. Methyl-phenyl-butenone prepared as follows: 500ml of benzaldehyde is mixed with 1000ml of MEK. Mixture is cooled in a bucked filled with ice to around +5 degrees.
2. To this is added aqueous HCL, 35-37%, (you have to add 100g of pure HCL which corresponds to about 286ml of 37%HCL)
3. Mix and keep it in a bucket with ice overnight, let the ice melt.
4. Wait 24 hours more
5. Put it in a separatory funnel, discard lower layer.
6. Wash the dark brown-red mixture with 500ml of water, discard water.
7. Distill everything that boils below 150 degrees at atmosferic pressure and discard
8. Distill the rest in vacuum to get a yellow oil

This oil will darken on standing within a week.


Bayer-Villiger:
1. 100ml of above prepared oil add to mixture of 300ml of glacial acetic acid and 100ml of 50% hydrogen peroxide.
2. Heat & stir it at 55 degrees.
3. When reaction starts temperature will go up above 55..60 (about 1..2 hours) : this is the indication to turn OFF heating. If temperaturfe climbs to 70 then cool your flask under running water a bit.
4. Stir until temperature falls back to 50..55 degrees, then turn heating ON again
5. Stir & heat for 6 hours
7. Pour mixture to 1L of water, extract 3 times with 100+100+100ml of DCM
8. Distill DCM off


Saponification:
1. Put Bayer-Villiger product from the step above in a flask with stirring. Slowly add
NaOH solution (30g NaOH, 250ml water, 250ml ethanol). Slowly means dropwise, about 3..5 drops a second. Mixture becomes reddish-orange

2. At the end of addition pH should be above 12
3. To the mixture add acetic acid (any percentage) until neutral pH. Mixture will turn yellow
4. Pour this to 1L of water and extract 3 times with 100+100+100ml of DCM
5. Distill DCM & traces of ethanol off at atmospheric pressure
6. Distill your P2P under vacuum.
7. There will be alot of tar left in a flask

OrtistIs the alkaline wash of MPB necessary? I noticed you didn’t do that but distilled after the water wash

 

[Ortist]

Everyone says this method has flaws. Has anyone ever really gotten significant yields with this method?

lalalanderYou can also distill P2P with water, but it is very slow. However you MUST distill methyl-phenyl-nutenone under vacuum because there is significant amount of crap and MPB will not distill with water

 

[gmo]

1. Borohydride or Al/Hg depending on the amount of P2P. Al/Hg doesn't require dry conditions but it is a messy workup (Al sludge) and loading more than 20..25g of P2P are hard to handle (too exotermic). Can do many Al/Hg flasks in parallel. Borohydride is cleaner procedure but water can hurt yeld alot

2. Around 70% molar. Roughly you will get 1g from 1g

3. I only make racemic and it is a good stuff. More euphoretic, more energy. Racemic could be converted to D-meth but you will loose roughly 50%. L-meth could be turned into racemate again but it is a different story

OrtistThank you very much,how L-meth can be turned into racemate?and why in Mexico can use al/hg method in large scale?

 

[Xiao hua]

even hcl has bubbled 1.5h.Why not add Hcl liquid? Why. Can someone explain me. Thanks

 

[Ortist]

even hcl has bubbled 1.5h.Why not add Hcl liquid? Why. Can someone explain me. Thanks

Xiao huaYou can use aqueous HCl. Just use 1 liter of benzaldehyde to 2 liters of MEK and calculated amount of 35..37% hydrochloric acid. You need 20g of PURE HCl per each 100g of benzaldehyde. So 1L of benzaldehyde will require 200g of PURE HCl. Now calculate how much aqueous acid do you need.

With gaseous HCl you'll get a bit better yeld and a bit less sideproducts. But in my opinion it doesn't worth it especially on big scale. Also with aqueous HCL you have to use more MEK otherwise your HCl will separate on the bottom too early.

"Gas for 1.5 hour" is WRONG. You have to gas until you get 20g of gas into each 100g of benzaldehyde. How long it can take nobody knows.

 

[Ortist]

hcl aqeuos in our country are cheap. Can you tell me all these ways? We will talk on Facebook

Xiao huaSee post #121 above on this page

 

[Xiao hua]

See post #121 above on this page

OrtistHow bro. in this page no have 121

 

[Xiao hua]

You can use aqueous HCl. Just use 1 liter of benzaldehyde to 2 liters of MEK and calculated amount of 35..37% hydrochloric acid. You need 20g of PURE HCl per each 100g of benzaldehyde. So 1L of benzaldehyde will require 200g of PURE HCl. Now calculate how much aqueous acid do you need.

With gaseous HCl you'll get a bit better yeld and a bit less sideproducts. But in my opinion it doesn't worth it especially on big scale. Also with aqueous HCL you have to use more MEK otherwise your HCl will separate on the bottom too early.

"Gas for 1.5 hour" is WRONG. You have to gas until you get 20g of gas into each 100g of benzaldehyde. How long it can take nobody knows.

OrtistBro what can instead of chloroform in step one?

 

[Ortist]

How bro. in this page no have 121

Xiao hua

Phenylacetone (P2P) synthesis from benzaldehyde with butanone

Everyone says this method has flaws. Has anyone ever really gotten significant yields with this method? I used this method many times. Modified a bit. The best results I got was 30ml of P2P from 100ml of benzaldehyde. Also I know a few people who researched this reaction alot; their best...

bbgate.com

 

[Xiao hua]

Phenylacetone (P2P) synthesis from benzaldehyde with butanone

Everyone says this method has flaws. Has anyone ever really gotten significant yields with this method? I used this method many times. Modified a bit. The best results I got was 30ml of P2P from 100ml of benzaldehyde. Also I know a few people who researched this reaction alot; their best...

bbgate.com

OrtistBro how to separate isomers of amphetamine and meths

 

[mckennai]

Can we correct something??? You saying magnesium sulphate anhydrous and giving Na2SO4 and one of the steps u saying mgso4 for it again.. Can you be clear for exact item and with exact values?? For usage and for buying.. We need to know amount that we need to get and use.. U didnt give any value for how much amount of that mgso4 or na2so4 we need... Thanks

 

[mckennai]

Reagents:​

• Benzaldehyde 1000 g;​
• Methyl ethyl ketone (MEK) 1000 ml;​
• Distilled water 14.5 L;​
• Chloroform (CHCl3) 7.6 L;​
• Sodium bicarbonate solution (NaHCO3);​
• Magnesium sulphate (Na2SO4) anhydrous;​
• Glacial acetic acid 10 L;​
• Hydrogen peroxide (H2O2) 1300 g 50 %;​
• Sodium hydroxide (NaOH) 600 g;​

Equipment and glassware:​

• 5 and 10 L Round bottom flasks;​
• Water bath;​
• HCl gas source;​
• 25-30 L Batch reactor with reflux condenser and heating system;​
• Vacuum source;​
• Glass rod and spatula;​
• Rotovap machine (optional);​
• pH indicator paper;​
• Laboratory scale (1-1000 g is suitable);
• Measuring cylinders 1000 mL;
• 1000 mL x3; 2000 mL x3; 5000 mL x3 Beakers;
• Several buckets;

Step 1. 3-Methyl-4-phenyl-3-buten-2-one synthesis (cas 1901-26-4).
1. Benzaldehyde 1000 g and methyl ethyl ketone (MEK) 1000 ml are mixed in 5 L flask, stirred and chilled at 0 °C.
2. HCl gas is bubbled slowly through the mixture for a 1.5 h.
3. The solution is stirred for addition 1.5 h at room temperature.
4. Distilled water 2 L is added. The solution is extracted with chloroform (CHCl3) 800 ml x2, then the extract is washed with sodium bicarbonate solution (NaHCO3) to neutral pH and dried over magnesium sulphate (MgSO4).
5. Solvent is evaporated under vacuum and 3-methyl-4-phenyl-3-buten-2-one (cas 1901-26-4) is distilled under vacuum (b.p. 269.6±9.0 °C at 760 mm Hg). Reaction yield is 1000 g.​

View attachment 1386
​

Step 2. 2-Acetoxy-1-phenyl-1-propene (cas 24175-87-9) synthesis.

1. 3-Methyl-4-phenyl-3-buten-2-one (cas 1901-26-4) 1 kg from Step 1, glacial acetic acid 10 L and hydrogen peroxide (H2O2) 1300 g 50 % are poured into a 25-30 L batch reactor with reflux condenser, stirred and at 55 °C for 23 h.
2. Next, distilled water 10 L is added.
3. The reaction mixture is extracted with chloroform 5 L and dried over magnesium sulphate (Na2SO4).
4. Solvent is evaporated under vacuum. 2-Acetoxy-1-phenyl-1-propene (cas 24175-87-9) yield is 800 g.​

View attachment 1387​

Step 3. 1-Phenyl-2-propanone (P2P; cas 103-79-7).

1. 2-Acetoxy-1-phenyl-1-propene (cas 24175-87-9) 800 g from Step 2 and sodium hydroxide (NaOH) 600 g in distilled water 2500 ml is stirred at 50 °C for 12 h in 10 L flask with reflux condenser.
2. Reaction solution is extracted with chloroform 1000 ml, dried over magnesium sulphate (Na2SO4) and the solvent is evaporated under vacuum. 1-Phenyl-2-propanone yield is 650 g.​

View attachment 1388​

William DampierCan we correct something??? You saying magnesium sulphate anhydrous and didnt give the exact values how much we need to get.. And second one u saying "na2so4" in brickets but one of the writings in your steps somewhere u saying "mgso4". Actually magnesium sulphate mgso4 but na2so4 sodium sulphate.. Please can you give exact item with net-clear values for usage

 

[gmo]

Thank you very much,how L-meth can be turned into racemate?

 

[WillD]

Thank you very much,how L-meth can be turned into racemate?

gmoMaybe with some temperature exposure this is possible. But we don't know for sure.

 

[mckennai]

Im doing this one with two different way. 1. Williams method qnd lalalander's experienced topic. . 2. Sci hub.. im wondering about thread.. 1 waiting times 2, different reagents.. 3, totally differenr tactis..

Can somebody give a right and fastest way for p2p obtaining from benzaldehyde and mek?? Which way should i follow? Ive hcl and h2so4 for making hcl gas bubling but didnt used glasswares for dripping hcl over sulphuric acid with atmohsperic pressure glass setup, i just bought dosage pump and setted up for dripping selected amount of ml in hour over sulphuric acid.. is it ok anyway??. Or please write a route for me i couldnt do well that glassware setups for hcl gassing nd vacumming. Ill fix it for vacumming but i dont have any idea for doing right things for hcl gassing

 

[WillD]

Bunsen flask with silicone hose and syringe with hcl

 

[OrgUnikum]

Bunsen flask with silicone hose and syringe with hcl

William DampierMake this PE, polyethylene tubing (there should be no high temperature so no problem). Or PTFE tubing if you have too much money. Silicone tubing will disintegrate on contact with MEK, Benzaldehyde or Acetone. Instantly.

Source: Any chemical resistance chart and personal experience

 

[mckennai]

I really need your answer in pm williams it's very important for me today I hope u see and answer early as possible as you can :"(

 

[bigbadbear]

​

Step 2. 2-Acetoxy-1-phenyl-1-propene (cas 24175-87-9) synthesis.

1. 3-Methyl-4-phenyl-3-buten-2-one (cas 1901-26-4) 1 kg from Step 1, glacial acetic acid 10 L and hydrogen peroxide (H2O2) 1300 g 50 % are poured into a 25-30 L batch reactor with reflux condenser, stirred and at 55 °C for 23 h.
2. Next, distilled water 10 L is added.
3. The reaction mixture is extracted with chloroform 5 L and dried over magnesium sulphate (Na2SO4).
4. Solvent is evaporated under vacuum. 2-Acetoxy-1-phenyl-1-propene (cas 24175-87-9) yield is 800 g.​

View attachment 1387​

For the second step, can I use a 15-liter flask ? and carry out the extraction process in a 50-liter plastic barrel?

William Dampier

 

[bigbadbear]

For the second step, can I use a 15-liter flask ? and carry out the extraction process in a 50-liter plastic barrel?