No, it will be a different route. Acetoxy only with a peracetic acid.
Phenylacetone (P2P) synthesis from benzaldehyde with butanone
- Thread starter William D.
- Start date
Im going to try this synth with dichloro-methane (DCM). I don't see this being an issue only that it will be heavier then water. Any reason to not use readily available DCM and synth Chloroform?
Aldol Condensation.
The directions for this are in Organic Reactions
This write up seems to be more inline with what I am seeing. Has anyone actually tried to extract with solvent from the organic layer. Using chloroform won't work, as it's miscible with the organic layer. Unless I'm missing something the write up needs to be tested and modified.
Anyone tried this synth before.
The directions for this are in Organic Reactions
This write up seems to be more inline with what I am seeing. Has anyone actually tried to extract with solvent from the organic layer. Using chloroform won't work, as it's miscible with the organic layer. Unless I'm missing something the write up needs to be tested and modified.
Anyone tried this synth before.
- By TheNut22
OK. Just heat the benz-hyde and MEK with hydrochloric acid about 3-5 hours. Temp: 90-110 C.
Just thank me.
Just thank me.
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Everyone says this method has flaws. Has anyone ever really gotten significant yields with this method?
- By Ortist
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
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
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I just wanted to point out that there are new studies done about this. The more MEK that is used the less byproducts that are formed. In the study I read they used a ratio of 1 to 6 (1 benzaldehyde to 6 MEK) but when they increased this amount to 8 times and 10 times all byproducts disappeared
10 g benzaldehyde + 24 g MEK + 28 g hydroc.acid (~20%) = 28 g of crystals, dried in pyrex dish = 13 g of crystals.
Just keep it simple. When you are done heating, extract the brown organic layer. Wash with 40 ml of water. Extract again. Put 20 ml:s of 10% KOH-solution in. Get rid of the water. Check pH. If too acidic, or too basic, put it to 7. Get rid of the water again. Put it in freezer, because you can then, when frozen, pour the oily shit away, and get almost white crystals. Put the crystals in pyrex dish, or something and dryi it. It can liquify, but no problem. Just heat, freeze, heat, freeze, you dry those crystals, but they cannot be crispy dry. Don't know why. Maybe they are just like that.
Just keep it simple. When you are done heating, extract the brown organic layer. Wash with 40 ml of water. Extract again. Put 20 ml:s of 10% KOH-solution in. Get rid of the water. Check pH. If too acidic, or too basic, put it to 7. Get rid of the water again. Put it in freezer, because you can then, when frozen, pour the oily shit away, and get almost white crystals. Put the crystals in pyrex dish, or something and dryi it. It can liquify, but no problem. Just heat, freeze, heat, freeze, you dry those crystals, but they cannot be crispy dry. Don't know why. Maybe they are just like that.
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- By chema12
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Can 3-methyl-4-phenyl-3-buten-2-one be distilled without vacuum?
- By waltjr5858
Lol it turned to some bad stuff without vac... I went on to the next step the next time with some minor cleaning and no distillation....I didn't clean up till the end with steam distillation... works fine... yield still plenty good enough. I hate the way that stuff vac distilled......
- By waltjr5858
Yup so it wasn't just me... thought I screwed something up but it's pretty easy at that point HA. I've now gotten through the entire thing and just doing a steam distillation at the end and it turns out perfectly every time. Although it took some tries to get there.
Too much GAA use maybe 1.6lish
Hydrolysis is too long in my exp
1.25eq base and 2hrs worked best for me
you didnt get 50% peroxide and attempt this
will d scale up no testing time again
Purification via methylphenylbutanones bisulfite adduct is so much superior (same with p2p) both for not having to make chloroforms sake and end purity
huge excess of mek? Intentional? also amino acids r a better cat than hcl for the aldol and id use perborate for the villiger as thats higher yielding in my exp than H2O2. Percarbonate is less good getting maybe 35% but much easier and not watched at all
Hydrolysis is too long in my exp
1.25eq base and 2hrs worked best for me
you didnt get 50% peroxide and attempt this
will d scale up no testing time againPurification via methylphenylbutanones bisulfite adduct is so much superior (same with p2p) both for not having to make chloroforms sake and end purity
huge excess of mek? Intentional? also amino acids r a better cat than hcl for the aldol and id use perborate for the villiger as thats higher yielding in my exp than H2O2. Percarbonate is less good getting maybe 35% but much easier and not watched at all
- By lalalander
I'm considering purifying P2P using bisulfite, but I've read many times that the recovery is low. What is the yield after re-liberating it from the bisulfite adduct?
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- By mewnmewamine
80s and 90s just try not to have much water in solution as bisulfite adducts are annoyingly slightly soluble in them :3
- By lalalander
Does MPB form a bisulfite adduct? No matter how many times I tried, I wasn’t successful. I tried with water, and with a methanol-water mixture. It just doesn’t work.
- By lalalander
The suspected P2P adduct was left to dry on the filter. Right now, its texture is indistinguishable from that of a mica-based eyeshadow — it looks exactly like it. Like phenylacetic acid. Is this normal?
is this route can be scaled down ?
- By mewnmewamine
Things essentially always work scaled down its scaling up where things go wrong you should be good :3