# Phenylacetone (P2P) synthesis from benzaldehyde with butanone



## William Dampier

*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.​


​*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.​


*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.​


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## Jack

Sci-Hub | The Synthesis and Investigation of Impurities found in Clandestine Laboratories: Baeyer-Villiger Route Part I; Synthesis of P2P from Benzaldehyde and Methyl Ethyl Ketone | 10.1016/j.forsciint.2016.03.034


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## cyb3r0

Thank you for the explanation. Please mention the required materials that you knew
benzaldehyde and Methyl Ethyl Ketone ( MEK ) 
Is this all that is required?
Thank you


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## MadHatter

Thank you so much for the easy and detailed synth description! 
How about the hydrogen peroxide, could that be substituted? It's a really controlled chemical nowadays, and a bitch to synthesize yourself. Its mainly there as a catalyst in the reaction between the glacial acetic acid and the 3-methyl-4-phenyl-3-buten-2-one, right? What could be a good substitute?


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## Jack

> Its mainly there as a catalyst in the reaction between the glacial acetic acid and the 3-methyl-4-phenyl-3-buten-2-one, right? What could be a good substitute?


It is not a catalyst it is an oxidant please read the link provided, search up baeyer villiger oxidation.


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## MadHatter

Jack said:


> It is not a catalyst it is an oxidant please read the link provided, search up baeyer villiger oxidation.



JackOk, good, an oxidant. And I see the reaction in the link. Thank you! In it they use sodium perborate for the BV- oxidation. That might be more accessible. I guess piranha solution could be used also? What other candidates are there?


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## MadHatter

After reading up a bit: how about sodium percarbonate? Would that suffice? Because if it would, this synthesis would become much more OTC. And definately worth the time to calculate the molar ratio.


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## William Dampier

Approximately 3kg percarbonate for this reaction+water. Find a concentrated peroxide is best choice.


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## MadHatter

That's perfectly doable. Of course it's second best, but hydrogen peroxide in concentrations above 3% is a strictly controlled substance nowadays in most of EU. 
One thought though: wont the carbonate ion react really vividly with the acetic acid? And maybe neutralize it?


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## William Dampier

maybe can buy ready peracetic acid, and use it for complete reaction without acetic acid and H2O2


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## Hans-Dietrich

William Dampier said:


> maybe can buy ready peracetic acid, and use it for complete reaction without acetic acid and H2O2



William Dampier
it would be logical to reflect this method in the initial post.


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## Jamroz

Is it necessarliy to make it under vacum destilation or normal pressure destilation will be enought ? Could you expand first step in the reaction hcl gas bubbled in mixture


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## William Dampier

Jamroz said:


> Is it necessarliy to make it under vacum destilation or normal pressure destilation will be enought ?



JamrozPossible


Jamroz said:


> Could you expand first step in the reaction hcl gas bubbled in mixture


here (click)


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## n00by Blitz

William Dampier said:


> 1. Product from Step 1, 10000 ml glacial acetic acid and 1300 g 50% H2O2 was stirring and heated at 55 *C for 23 hours.



William DampierJust to confirm. It is: 10 liters of glacial acetic acid. Am I correct?


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## William Dampier

yes, 10L of GAA


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## n00by Blitz

William Dampier said:


> yes, 10L of GAA



William DampierIs it OK to use a plastic drum or PVC pipe for this part?


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## a_king

is it possible to replace chloroform?


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## MadHatter

a_king said:


> is it possible to replace chloroform?



a_kingWhy would you want to replace chloroform? It's easy to synthesize yourself with acetone and bleach. Check youtube.
But if you really need to for some reason, dichloromethane and chloroform are usually interchangeable.


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## MadHatter

BTW, why such ENORMOUS quantities of GAA and H2O2? Is it possible to use less? What are their roles in this reaction?


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## MadHatter

I guess what I'm really wondering about is the stochiometry of this reaction. In other write-ups of the bayer-williger I can't seem to find this enormous amounts of GAA. Can somebody help me with the rationale? I'm really close to trying this one out, but the amount of GAA is problematic.


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## MadHatter

Even in a scaled-down version.


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## William Dampier

DocX said:


> I guess what I'm really wondering about is the stochiometry of this reaction. In other write-ups of the bayer-williger I can't seem to find this enormous amounts of GAA. Can somebody help me with the rationale? I'm really close to trying this one out, but the amount of GAA is problematic.



DocXExcess acts as a solvent for the reaction. In terms of accessibility, try to use food vinegar concentrate. But with an excess of water, you need to think about an additional solvent.


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## MadHatter

No proble



William Dampier said:


> Excess acts as a solvent for the reaction. In terms of accessibility, try to use food vinegar concentrate.



William DampierNo problem finding 60% concentration in large amounts. Would that suffice, or would I need to dehydrate it first?


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## William Dampier

DocX said:


> No proble
> 
> No problem finding 60% concentration in large amounts. Would that suffice, or would I need to dehydrate it first?



DocXYes, rather an excess of water will make unstable acid, unless it works in situ, but it is unlikely to be in time. You can try distillation or extraction.


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## William Dampier

DocX said:


> I guess what I'm really wondering about is the stochiometry of this reaction. In other write-ups of the bayer-williger I can't seem to find this enormous amounts of GAA. Can somebody help me with the rationale? I'm really close to trying this one out, but the amount of GAA is problematic.



DocXThere is also an alternative route. Use hydrogen peroxide and soda ash (sodium carbonate, Na2CO3) for creating sodium percarbonate, a strong oxidizing agent, as is peracetic acid. The reaction will be different, but in the end with the same result.

Edit: rather, baking soda (NaHCO3) can be used to form an epoxide followed by hydrolysis (analog Weitz-Scheffer epoxidation reaction)


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## ASheSChem

so, you think we can do 2-Acetoxy-1-phenyl-1-propene with sodium percarbonate ? any idea for the recipe ?


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## William Dampier

ASheSChem said:


> so, you think we can do 2-Acetoxy-1-phenyl-1-propene with sodium percarbonate ? any idea for the recipe ?



ASheSChemNo, it will be a different route. Acetoxy only with a peracetic acid.


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## Mr.Blanks00

William Dampier said:


> View attachment 1386
> *Langkah 1. 3-metil-4-fenil-3-buten-2-satu.*
> 1. Campur 1000 g benzaldehida dan 1000 ml MEK, diaduk dan didinginkan pada 0 *C.
> 2. Gas HCl digelembungkan secara perlahan melalui campuran selama 1,5 jam.
> 3. Larutan diaduk selama 1,5 jam pada suhu kamar.
> 4. Ditambahkan air, dan larutan diekstraksi dengan kloroform, kemudian dicuci dengan larutan natrium bikarbonat dan dikeringkan (Na2SO4).
> 5. Pelarut dihilangkan di bawah vakum tinggi dan 3-metil-4-fenil-3-buten-2-satu didistilasi di bawah vakum (bp.76-78 *C). Hasil: 1000 gram.
> 
> View attachment 1387
> *Langkah 2. 2-Asetoksi-1-fenil-1-propena.*
> 1. Produk dari Langkah 1, 10.000 ml asam asetat glasial dan 1300 g 50% H2O2 diaduk dan dipanaskan pada suhu 55 *C selama 23 jam.
> 2. Setelah itu ditambahkan air 10000 ml air.
> 3. Diekstraksi dengan 5000 ml kloroform.
> 4. Pelarut dihilangkan di bawah vakum untuk menghasilkan 800 g 2-Asetoksi-1-fenil-1-propena.
> 
> 
> View attachment 1388
> *Langkah 3. 1-fenil-2-propanon.*
> 1. Produk untuk Langkah 2 dan 600 g natrium hidroksida dalam 2500 ml air diaduk pada 50 °C selama 12 jam.
> 2. Larutan diekstraksi dengan 1000 ml kloroform, dikeringkan (Na2SO4) dan pelarut dihilangkan di bawah vakum. Hasil: 650 gram.



William Dampierhalo, salam kenal, saya peserta baru di sini dari Indonesia, saya ingin bertanya kepada semua ahli kimia, saya membuat p2p dari asam penilasetat dan timbal dan asam glasial dalam botol stainless steel, saya mendapatkan hampir 100% minyak kuning dan merah dan air, saya ingin bertanya apakah minyak kuning itu penilaseton, dan bagaimana cara mencucinya dari kontaminan lain, terima kasih kepada semua ahli kimia yang mau menjawab pertanyaan saya.


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## Mr.Blanks00

hello, nice to meet you, I'm a new participant here from Indonesia, I want to ask all chemists, I made p2p from penylacetic acid and lead and glacial acid in a stainless steel bottle, I got almost 100% yellow and red oil and water, I want to ask if the yellow oil is penylacetone, and how to wash it from other contaminants, thank you to all chemists who want to answer my question.


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## cokemuffin

What would you suggest using if chloroform is not available?


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## Jamroz

I will prepare hcl gas from sulfuric acid and hydrochloric acid, can anyone tell me what amount I need hcl and h2so4? when i know i have added enough gas?


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## UWe9o12jkied91d

cokemuffin said:


> What would you suggest using if chloroform is not available?



cokemuffinI would say DCM, but I might be wrong
You also easily make chloroform by reacting cold 0* C bleach with acetone in stoechiometric amounts with a small 10% ish molar excess of bleach.Nilered has a video.


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## cokemuffin

UWe9o12jkied91d said:


> I would say DCM, but I might be wrong
> You also easily make chloroform by reacting cold 0* C bleach with acetone in stoechiometric amounts with a small 10% ish molar excess of bleach.Nilered has a video.



UWe9o12jkied91dI saw the video, but i'm mainly interested in large scale manufacture, getting 6l chloroform that way is not really cheap and efficient. I'll probably try to further chlorinate DCM to chloroform.


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## TotalSynthesis

Did anybody try this with caro's acid instead of GAA? 
It should get a much better yield, at least i guess i read that somewhere but cant find any paper.

In the Peracetic way, GAA will also be the solvent but when using Caro's acid, i guess our precursor wont be soluble in the H2SO4 H2O2 mixture. Any idea which solvent could be used with Caro's ?


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## MadHatter

I would be a bit weary mixing a ketone with caros acid ...


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## Drogan39

William Dampier said:


> View attachment 1386
> *Step 1. 3-methyl-4-phenyl-3-buten-2-one.*
> 1. Mixed 1000 g benzaldehyde and 1000 ml MEK, stirring and chilled at 0 *C.
> 2. HCl gas was bubbled slowly through a mixture 1.5 hours.
> 3. The solution was stirred for 1.5 hours at room temperature.
> 4. Water was added, and the solution extracted with chloroform, then washed with sodium bicarbonate solution and dried (Na2SO4).
> 5. Solvent was removed under high vacuum and 3-methyl-4-phenyl-3-buten-2-one was distilled under vacuum (bp.76-78 *C). Yield: 1000 g.
> 
> View attachment 1387
> 
> 
> 
> William Dampier said:
> 
> 
> 
> View attachment 1386
> *Step 1. 3-methyl-4-phenyl-3-buten-2-one.*
> 1. Mixed 1000 g benzaldehyde and 1000 ml MEK, stirring and chilled at 0 *C.
> 2. HCl gas was bubbled slowly through a mixture 1.5 hours.
> 3. The solution was stirred for 1.5 hours at room temperature.
> 4. Water was added, and the solution extracted with chloroform, then washed with sodium bicarbonate solution and dried (Na2SO4).
> 5. Solvent was removed under high vacuum and 3-methyl-4-phenyl-3-buten-2-one was distilled under vacuum (bp.76-78 *C). Yield: 1000 g.
> 
> View attachment 1387
> *Step 2. 2-Acetoxy-1-phenyl-1-propene.*
> 1. Product from Step 1, 10000 ml glacial acetic acid and 1300 g 50% H2O2 was stirring and heated at 55 *C for 23 hours.
> 2. After this time water added 10000 ml water.
> 3. Extracted with 5000 ml chloroform.
> 4. Solvent removed under vaccum to yield 800 g of 2-Acetoxy-1-phenyl-1-propene.
> 
> 
> View attachment 1388
> *Step 3. 1-phenyl-2-propanone.*
> 1. Product for Step 2 and 600 g sodium hydroxide in 2500 ml water was stirred at 50 °C 12 hours.
> 2. Solution extracted with 1000 ml chloroform, dried (Na2SO4) and the solvent removed under vacuum. Yield: 650 g.
> 
> 
> 
> 
> William Dampier
> tic acid and 1300 g 50% H2O2 was stirring and heated at 55 *C for 23 hours.
> 2. After this time water added 10000 ml water.
> 3. Extracted with 5000 ml chloroform.
> 4. Solvent removed under vaccum to yield 800 g of 2-Acetoxy-1-phenyl-1-propene.
> 
> 
> View attachment 1388
> *Step 3. 1-phenyl-2-propanone.*
> 1. Product for Step 2 and 600 g sodium hydroxide in 2500 ml water was stirred at 50 °C 12 hours.
> 2. Solution extracted with 1000 ml chloroform, dried (Na2SO4) and the solvent removed under vacuum. Yield: 650 g.
Click to expand...

Sorry dir the Noob question i am Not a chemist.....
From *Step 2. 2-Acetoxy-1-phenyl-1-propene.

It is possible to do a electro oxidation?*
Like this?
*


https://erowid.org/archive/rhodium/chemistry/isosafrole.electro.html





Electrochemical Reduction of Nitroalkenes to Oximes and Amines - [www.rhodium.ws]


*


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## ASheSChem

William Dampier said:


> HCl gas is bubbled slowly through the mixture for a 1.5 h.



William Dampierwe need to obtain a certain PH or something ? 
if we doing the method in a lower quantities, it's 1.5h too?


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## G.Patton

ASheSChem said:


> we need to obtain a certain PH or something ?



ASheSChemHCl works here as catalyst. You don't need to reach pH.


ASheSChem said:


> if we doing the method in a lower quantities, it's 1.5h too?


yes


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## Mo0odi

Methyl ethyl ketone is there an alternative 

thank you all


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## Fenster

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?


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## Phoneix73

Solvent evaporated, can normal vacuum be used or what is the method?


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## Fenster

Phoneix73 said:


> Solvent evaporated, can normal vacuum be used or what is the method?



Phoneix73270C is very high to distil without glassware.


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## Phoneix73

distilled or evaporated under vacuum, at what temperature is it heated, evaporated or distilled? and how many hours will it be distilled


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## Fenster

The reference is 270C as the boiling point. I do wonder if the solvent can be removed and just use it as is in step 2.


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## Fenster

I need help!

100g of both Benzaldehyde and MEK were added to a 500ml RBF and chilled to zero. The mixture was put on mag Stir and HCL was bubbled through the solution, quickly at first and then slow and steady once the HCl generator was fine tuned. (HCl over Conc. Sulphuric Acid). The solution turned yellow, then red, followed by very dark red. After 1.5 Hours, gas was removed and let stir at room temperature for 1.5 hours. Added 200ml of distilled water, instantly two layers formed. A dark layer (organic bottom) and a aqueous layer clear yellow. 40ml of DCM was added to the solution. 

Here is my problem. The DCM appears to have merged with the organic layer. It's a lovely smelling camphur solution, actually it's a beautiful smell. However I cannot see the DCM layer in the sep funnel. Damn, how the fuck to resolve this?


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## Fenster

So I separated and did a DCM extraction on the Aqueous phase. Nothing was left after evaporation of DCM. I'm thinking I'm going to have to distill everything in the organic phase and see whats left over as a solid. 

This is a real pain, has anyone done this synth successfully? Can anyone tell me if DCM is the issue. I don't want to make Chloroform or buy it


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## Fenster

@William Dampier have you run this synth?

Any help would be much appreciated.


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## Fenster

Unfortunately my glass thermometer broke, so I couldn't read off the fractions. Managed to pull a clear layer of what smells like DCM and HCL. I changed over to an oil bath and got over smoke temp of veg oil around 220, switched on vacuum and pulled a pale yellow oil over. It's an effort without short path to bring the column up to such a high temp. I figure I was pulling over around 200. 

I don't think the oil is going to crystallise so I think next step will be DCM extract on the distillate.


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## Fenster

So that was a complete failure. DCM dissolves straight into the yellow distillate.

Now I imagine Chloroform would behave the same way. This is really annoying.


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## Fenster

Aldol Condensation.

The directions for this are in Organic Reactions



> 200 gms of Benzaldehyde and 300 gms of Methyl Ethyl Ketone are mixed in a 1 litre beaker and cooled below 5°C. HCl gas is bubbled through until 40gms has been added. The mixture goes from a clear solution to a red colour and becomes turbid so that you can't see through it. The mixture is kept over night and becomes a brown colour. It is washed with water and then 10% NaOH solution, the organic layer seperated and distilled. At 240°C a yellow oil comes accross and the temperature gradually rises to 260°C.





> The oil can be crystalized by cooling in the freezer overnight. This in itself does not induce crystalization but if you also put a spoon in the freezer and then dip it in and out of the cool mixture you get some seed crystals that induce crystalization. The mass turns from an orange oil to sulfur coloured crystals, mp 38°C, 180 gms (Methyl Phenyl Butenone.



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.


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## Fenster

I put the distillete in the freezer over night, nothing happened, I dipped a frozen spoon into the mix and it instantly crystalized. Quite extraordinary. I'll move onto step 2.


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## Fenster

> 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 %


Why is the first two reactants quoted in MLS, and the H2O2 is quoted in grams. Another point if confusion in this write up.


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## Fenster

> 3. The reaction mixture is extracted with chloroform 5 L and dried over magnesium sulphate (Na2SO4).


Can someone please explain, how extraction with Chloroform works when the product is not in the Aqueous phase. Your Chloroform will merge with the organic layer, and you will have 1 phase. 

What this should read-



> Rx is washed with distilled water X3 then washed 3x with Sodium Bicarbonate. The organic layer is put into simple short path distillation an collected between 220 and 260. The distillete will be a yellow coloured oil. The oil is put into the freezer with a cold stainless spoon and frozen overnight. To initiate crystalization the spoon is dipped into the solution until crystalization begins.


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## Fenster

> 2.2.5. 2-Acetoxy-1-phenyl-1-propene 4 (Baeyer–Villiger reaction
> using SARD-Oxy plus)
> SARD-oxy plus (3 g, 2–6 mmol of sodium percarbonate) was
> added portion-wise over 6 h to a mixture of 3-methyl-4-phenyl-3-
> buten-2-one 3 (0.5 g, 3 mmol), glacial acetic acid (7 mL, 0.122 mol),
> at 55 8C. The solution was heated under reflux at 55 8C for a total of
> 24 h. Upon cooling to room temperature, brine was added followed
> by extraction with chloroform, which was then washed with brine.
> The organic solution was dried (Na2SO4) and the solvent removed
> under vacuum. Yield 43% based on 1
> H NMR.2


This may prove useful to some for step 2.

Using a common OTC laundry oxidation powder resulted in the baeyer villager reaction success with a yield of 43%.


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## Fenster

> 1-Phenyl-1-penten-3-one 8
> NaOH solution (10 mL, 2 M) was added to a mixture of
> benzaldehyde (4 g, 39 mmol) and MEK (2.8 g, 39 mmol) and the
> resulting solution stirred at room temperature overnight. The
> solution was extracted with chloroform, dried (Na2SO4) and the
> solvent removed under vacuum. The residue was purified by
> distillation (90 8C, 0.1 mmHg) with the resulting oil solidifying
> after one day (m.p. 40–41 8C). Yield 50%.


Variation to step 1. 

If you are having trouble generating stable dry HCL it seems you can just use NaOH and stir overnight. Yields are lower but your not dealing with the hassle of generating HCL gas.


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## Phoneix73

Fenster said:


> Variation to step 1.
> 
> If you are having trouble generating stable dry HCL it seems you can just use NaOH and stir overnight. Yields are lower but your not dealing with the hassle of generating HCL gas.



Fensterso how many degrees do we distill in the last step


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## Fenster

C



Phoneix73 said:


> so how many degrees do we distill in the last step



Phoneix73Can you be specific?

The thermometer was broken, but to distill:
1-methyl-4-fenyl-3-Buten-2-one It was very hot. Without short path distillation and only a 40cm fractional column. It is such a pain to get that to come over even with a vacuum. an oil bath with vegetable oil at smoke temp cleared a clear liquid that was very HCl saturated, and also the DCM that failed to separate. I turned on vacuum and pulled a thin yellow oil above 200. The distillation flask becomes very thick before you can pull it all over. You can read about xtal formation in my earlier posts. 

After the oxidation there was no more need for Distillation but you need to make a separation plan early. Even on a <50g scale there is a lot of liquid to extract from. The DCM in this step works really well as you can decant most of the liquid off and then use a sep funnel to get the DCM layer. Unfortunately my vacuum pump broke  so I had to try evap the solvent without vacuum. It's possible but I don't recommend. The volatiles coming off with the DCM are not nice at all. I ended up pouring the last if the DCM into a Pyrex tray and let evap over night. So that adds a whole day into an already 3 day process.


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## Phoneix73

Fenster said:


> C
> 
> Can you be specific?
> 
> The thermometer was broken, but to distill:
> 1-methyl-4-fenyl-3-Buten-2-one It was very hot. Without short path distillation and only a 40cm fractional column. It is such a pain to get that to come over even with a vacuum. an oil bath with vegetable oil at smoke temp cleared a clear liquid that was very HCl saturated, and also the DCM that failed to separate. I turned on vacuum and pulled a thin yellow oil above 200. The distillation flask becomes very thick before you can pull it all over. You can read about xtal formation in my earlier posts.
> 
> After the oxidation there was no more need for Distillation but you need to make a separation plan early. Even on a <50g scale there is a lot of liquid to extract from. The DCM in this step works really well as you can decant most of the liquid off and then use a sep funnel to get the DCM layer. Unfortunately my vacuum pump broke  so I had to try evap the solvent without vacuum. It's possible but I don't recommend. The volatiles coming off with the DCM are not nice at all. I ended up pouring the last if the DCM into a Pyrex tray and let evap over night. So that adds a whole day into an already 3 day process.



Fenster*



use this kind of stud thermometer
*


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## Phoneix73

i also had a thermometer, so it was divided in half, it was very funny


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## Fenster

Are you using Distillation glassware or just jars?


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## Fenster

Ok, step 3 - I added NaOH solution heated to 50c and put into mag Stir after 6 hours a thick almost solid creamy mess was in my rbf. I added DCM and two layers appeared. At first, I was very happy!!! As the creamy thick layer sat on the bottom and I thought the clearer layer was the DCM extracted goodies was on top. No no no..... The Milky thick layer was the DCM. I know for a fact that when I remove the DCM I'm not going to have a yellow clear oil aka p2p. 


@HEISENBERG 

Have you team reviewed this process before publishing. Seems the experts have gone silent on this proceedures. Would be nice to get some support on a method your team published. 

Ok, so I'll attempt Distillation on the creamy mess and see what comes over.


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## G.Patton

Fenster said:


> I added DCM and two layers appeared.



FensterYou ask about method review but you don't follow the method and complaining that something went wrong 


> *2. *Reaction solution is extracted with chloroform


DCM is non-polar solvent, chloroform is polar solvent.


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## Fenster

D



G.Patton said:


> You ask about method review but you don't follow the method and complaining that something went wrong
> 
> DCM is non-polar solvent, chloroform is polar solvent.



G.PattonDCM has a dipole moment. It is polar albeit slightly. 

Are you sure your a chemist? I don't mean to be rude but DCM is not an NPS in the traditional sense. 

Can I ask, have you or your team performed this method in totality?


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## Fenster

What I need help with is the step 2.

I have 50% H2O2 and GAA. The amounts in the write up are 10L of GAA and 1300g of H2O2.

Are they expecting me to weigh the 50% H2O2 or am I supposed to accept it as a typo and use 1300ml?

The other write up is using sodium percarbonate directly and this write up here is generating it in situ. With GAA and H202.

I just need to confirm the amounts listed.


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## Fenster

50% H2O2 = 1.197g/ml

1300g h202 (50%) = 1086ml

10:1 GAA to H2O2 to make acid in situ. 

Is this the amount or is it a typo?

This process is being completed with lab grade reagents and glassware so if I follow it directly I should get the same results. However this write up needs work. Let's get this corrected and published as it should be.


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## Fenster

> 2.2.4. 2-Acetoxy-1-phenyl-1-propene 4
> Sodium perborate (5 g, 32 mmol) was added portion-wise over
> 6 h to a mixture of 3-methyl-4-phenyl-3-buten-2-one 3 (2 g,14 mmol), glacial acetic acid (7 mL, 0.122 mol), and acetone (4 mL)
> at 55 8C. The solution was heated under reflux at 55 8C for a total of 24 h. Upon cooling to room temperature, water (20 mL) was added
> followed by extraction with chloroform. The organic solution was dried (Na2SO4) and the solvent removed under vacuum. 4 was used
> in the subsequent hydrolysis without any further purification,
> crude yield 80%.1



Here is the original forensics work up from the twodogs proceedures. Obviously it varies a little from the OP here as the method here makes sodium perborate in situ. I'm just trying to make sense of the ratios.


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## G.Patton

Fenster said:


> Are you sure your a chemist? I don't mean to be rude but DCM is not an NPS in the traditional sense.



FensterIt sounds rude. Do you know forum rules? You are right, i was wrong about DCM, I thought it vice versa. And yes, I am chemist actually but don't want to answer you any more.

solvent and relative polarity:
hexane 0.009
chloroform 0.259
methylene chloride 0.309 
acetic acid 0.648








Solvent Polarity Table - Miller's Home


Miller's Home




sites.google.com


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## Fenster

G.Patton said:


> It sounds rude. Do you know forum rules? You are right, i was wrong about DCM, I thought it vice versa. And yes, I am chemist actually but don't want to answer you any more.
> 
> solvent and relative polarity:
> hexane 0.009
> chloroform 0.259
> methylene chloride 0.309
> acetic acid 0.648
> 
> 
> 
> 
> 
> 
> 
> 
> Solvent Polarity Table - Miller's Home
> 
> 
> Miller's Home
> 
> 
> 
> 
> sites.google.com



G.PattonOk, thanks. 

Do we have a definitive answer though. Has this been tested and developed in house or is this method scraped from somewhere else?


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## TotalSynthesis

@Fenster actually i dont even understand your problem but it seems you dont even understand what will be "generated in situ"

what you need is peracetic acid and this can be generated in situ by adding sodiumperborate to acetic acid, 

second way is by mixing h2o2 with acetic acid and a tiny little bit h2so4. this is best to let it sit for a few days.

this method works, i tried it myself. Dont ask me for my exact h2o2:GAA ratio because mine again was a bit different and i only used 35%h2o2

only because of varied quantities of whatever it does not mean that one way does not work but the other does. 
if you understand what's happening, then you'll be able to do small adjustments but if you dont understand whats happening then better do not claim a method to be bullshit


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## Fenster

Sodium Perborate is insanely cheap and easy to acquire so why use Peroxide at all?


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## Felix34-73

2) The solvent is evaporated under vacuum. 2-Acetoxy-1-phenyl-1-propene (cas 24175-87-9) 800 g how many degrees and how many mm hg pressure here
-------------------------------------------------
3) evaporated under vacuum. 1-Phenyl-2-propanone yield 650 g. how many degrees is this how many mm hg pressure


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## Fenster

Felix34-73 said:


> 2) The solvent is evaporated under vacuum. 2-Acetoxy-1-phenyl-1-propene (cas 24175-87-9) 800 g how many degrees and how many mm hg pressure here
> -------------------------------------------------
> 3) evaporated under vacuum. 1-Phenyl-2-propanone yield 650 g. how many degrees is this how many mm hg pressure



Felix34-73
2) There isn't much information about this compound. I got a yellow oil after the DCM stopped coming over. 

3) there is a lot of tar as a side product. I couldn't concentrate the vapour enough to get enough vapour to distill even under vacuum. I'm going to run this through on a larger scale then I did (I ran 100g of Benzaldehyde through) if I still have trouble getting the P2P to come over I'm going to steam distill everything including the DCM, the p2p should come over with the h20 and dissolve straight into the DCM where it can be separated. Like a an essential oil Distillation.


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## jokerr

Will you do the synthesis video of the formula?


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## Felix34-73

For the pH neutral process, I will use sodium carbonate + how many Gr, I will make the pH in the separating funnel neutral, I can make the scarbonate and water mixture directly in the solution and bring it to pH 7 level.


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## jokerr

hello masters,
I started from the first stage.
I added 100 g of benzaldehyde and 100 ml of mek, cooled it to 0 degrees and gassed for 1.5 hours.
then I stirred it for another 1.5 hours at room temperature and it will rest overnight.
continue operations tomorrow.


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## Fenster

Im running the same process at the same stage. Don't expectuch help from the team here. They seem to have abandoned this write up. I think a lot of write ups are just copy pasted.





jokerr said:


> hello masters,
> I started from the first stage.
> I added 100 g of benzaldehyde and 100 ml of mek, cooled it to 0 degrees and gassed for 1.5 hours.
> then I stirred it for another 1.5 hours at room temperature and it will rest overnight.
> continue operations tomorrow.



jokerr
Consider, that MEK and Benzaldehyde have different molecular weight and density. Therefore 100ml of MEK is not 100g. This only an issue later when you go to add 100g of h202(50%)

There are several measures in this write up where one side of the reaction is stated in grams and the other in MLS. H2O2 I stated in grams of a 50/50 mixture. So you have to account for the water and the peroxide when calculating the MLS from weight. Unless your going to start weighing liquids.

Let me know how you go, when I did .1M reaction I ended up with such poor yields that i couldn't extract the p2p from the tar crap. This write up doesn't really inform you much along the way of what to expect. You can the impression of just extract and distill.

Let me know how you go extracting the MPB tomorrow. Did your Rx mixture go bright red?


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## Fenster

There is the possibility of steam distillation of the product. You will see what I mean by tar when you get to the extraction. Are you using chloroform or DCM?


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## jokerr

hello master.
@G.Patton 
The solution is extracted with chloroform (CHCl3) 800 ml x2, then the extract is washed with sodium bicarbonate solution (NaHCO3) to neutral pH

Are there two different operations in order of what I need to do in this section?

liquid / liquid extraction
acid /base extraction.

do i understand right? .


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## jokerr

Fenster said:


> There is the possibility of steam distillation of the product. You will see what I mean by tar when you get to the extraction. Are you using chloroform or DCM?



FensterHello ,
I use chloroform.
I got a dark yellow form.


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## jokerr

Fenster said:


> There is the possibility of steam distillation of the product. You will see what I mean by tar when you get to the extraction. Are you using chloroform or DCM?



Fenstermy calculation is like this, where am i doing wrong? can you please explain.

100ml benzaldehyde 100ml methyl ethyl ketone
hcl 40gr salt and 15ml sulfuric acid
200ml pure water
chlorform 80+80

sodium bicarbonate 10%- water 90%


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## jokerr

Fenster said:


> Im running the same process at the same stage. Don't expectuch help from the team here. They seem to have abandoned this write up. I think a lot of write ups are just copy pasted.
> 
> 
> 
> 
> Consider, that MEK and Benzaldehyde have different molecular weight and density. Therefore 100ml of MEK is not 100g. This only an issue later when you go to add 100g of h202(50%)
> 
> There are several measures in this write up where one side of the reaction is stated in grams and the other in MLS. H2O2 I stated in grams of a 50/50 mixture. So you have to account for the water and the peroxide when calculating the MLS from weight. Unless your going to start weighing liquids.
> 
> Let me know how you go, when I did .1M reaction I ended up with such poor yields that i couldn't extract the p2p from the tar crap. This write up doesn't really inform you much along the way of what to expect. You can the impression of just extract and distill.
> 
> Let me know how you go extracting the MPB tomorrow. Did your Rx mixture go bright red?



FensterI realized my mistake.
thanks a lot by faster


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## Fenster

jokerr said:


> I realized my mistake.
> thanks a lot by faster



jokerrI ended up with a very very dark organic layer with DCM. I then distilled this under vacuum which removed the DCM and then a yellow oil came over. This was frozen overnight and the first time needed to be manipulated to crystal, second time was 60g solid xtal mass sulfur coloured and smelling of camphor.


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## Fenster

@jokerr I don't think gpatton is interested. I asked for soooo much help and they seemed to just wait until I got frustrated and then disarming language by accusing me of not following procedure. I've have DM the op and no response. 

I have the original forensics write up. Might shed some light. This write up is honestly dog shit here.


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## G.Patton

jokerr said:


> The solution is extracted with chloroform (CHCl3) 800 ml x2, then the extract is washed with sodium bicarbonate solution (NaHCO3) to neutral pH
> 
> Are there two different operations in order of what I need to do in this section?



jokerrHi. It means that you have to combine extracts, add aqueous NaHCO3 solution and extract it (yes liquid / liquid extraction), then separate layers. You have to check pH of organic solution after this procedure. It have to be neutral (pH 6.5-7.5).


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