P2P synthesis from BMK glycidate ethers

[caesare.robot]

SWIM started with [cas 5449-12-7] after 4h of heating got aqueous layer on top and oily bottom... what did wrong? too much acid?

 

[caesare.robot]

SWIM started with [cas 5449-12-7] after 4h of heating got aqueous layer on top and oily bottom... what did wrong? too much acid?

caesare.robotfurther attempts with cas 5449-12-7 and step 1 of described method gave proper and stable results!

 

[Evilcarrot2]

Can cas 77-83-8 be used?

 

[G.Patton]

Can cas 77-83-8 be used?

Evilcarrot2no, you won't get P2P

 

[Evilcarrot2]

no, you won't get P2P

G.PattonAs always thank you

 

[ossi]

Introduction​

Hydrolysis of BMK glycidate ethers is represented in this topic. The procedure is the same for ethyl (Et) [cas 41232-97-7] and methyl (Me) [cas 80532-66-7] esters of glycidic acid. In case of sodium (Na) salt of this acid [cas 5449-12-7], you can skip first stage of NaOH addition and start from acid hydrolysis. In addition, purification method of obtained P2P is described. This procedure have to be committed to get pure Phenylacetone (P2P) for further syntheses of methamphetamine or amphetamine.

Suppliers of BMK glycidate ethers can be found in BB Listing.

Difficulty rating: 2/10 View attachment 6617 ​

Equipment and glassware:

• 1000 mL Round bottom flask;
• Reflux condenser;
• Retort stand and clamp for securing apparatus;
• pH indicator paper;
• Vacuum source (optional);
• Rotovap machine (optional);
• Glass rod and spatula;
• 100 mL x2; 250 mL x2; 500 mL x2 Beakers;
• Magnet- oder Aufsatzrührer mit Heizplatte;
• Wasserbad;
• Trichter;
• 1000 ml Scheidetrichter;
• Einrichtung zur Vakuumdestillation (optional);

Reagenzien:​

• 100 g BMK-Glycidatether (cas 80532-66-7; cas 41232-97-7; cas 5449-12-7);
• ~20 g NaOH oder KOH;
• ~80 ml HCl (35 %) oder 100 ml H2SO4 (45 %);
• ~600 ml DCM oder Petrolether;
• ~100 g MgSO4 oder Na2SO4;
• ~500–600 ml destilliertes Wasser;
• ~ 50 g NaCl (optional);

View attachment 6616 ​

Hydrolyse von BMK-Glycidaten​

1. NaOH (oder KOH) 20 g werden in 250-300 ml destilliertem Wasser unter Rühren gelöst. Das Reaktionsgemisch (Rm) muss auf Raumtemperatur gekühlt werden. 100 g BMK-Glycidat (Methyl- oder Ethylester) werden zugegeben und vollständig gelöst. Ein Teil von BMK wird dabei hydrolysiert und schwimmt als Öl an der Oberfläche von Rm. Rm wird 1 h bei 75-80 °C mit einem Rückflusskühler gerührt .
2. Dann werden 200 ml HCl (35 %) oder 240 ml H2SO4 (45 %) in kleinen Portionen zu Rm gegeben und auf 80-90 °C erhitzt und 3 h gerührt. Rm müssen auf Raumtemperatur abgekühlt werden, der Niederschlag wird filtriert.
3. Die Reaktionslösung wird mit DCM oder Petrolether 3 x 100 ml extrahiert . Der Extrakt wird mehrmals mit Salzlösung auf einen neutralen pH-Wert von 7 gewaschen . Der Extrakt wird mit MgSO4 (oder Na2SO4) (optional) getrocknet und von Feststoffen filtriert.
4. Ein organisches Lösungsmittel (DCM oder Petrolether) wird abdestilliert, um 65 ml P2P zu ergeben.
​

P2P-Reinigung​

1. Das entstandene Phenylaceton (P2P) wird in einen Rundkolben mit destilliertem Wasser 1:1 (w/w) überführt und mit Wasserdampf unter Vakuum destilliert .
2. Gereinigtes P2P aus dem Auffangkolben wird aus einer Wassermischung mit DCM (oder Petrolether) 3 x 100 ml extrahiert. Der Extrakt wird mit MgSO4 (oder Na2SO4) getrocknet.
3. Die resultierende Lösung wird von den Feststoffen (Trockenmittel) filtriert und dann wird ein organisches Lösungsmittel abdestilliert.

Phenylaceton kann lange Zeit in einem verschlossenen Gefäß in einem Gefrierschrank gelagert werden. Es wird empfohlen, es vor weiteren Synthesen von Methamphetamin oder Amphetamin zu destillieren . Direkte Sonneneinstrahlung auf Phenylaceton und hohe Temperaturen vermeiden.​

G.Pattonmaybe this works with benzylcyanid?

 

[G.Patton]

maybe this works with benzylcyanid?

ossino

 

[Costa]

Introduction​

Hydrolysis of BMK glycidate ethers is represented in this topic. The procedure is the same for ethyl (Et) [cas 41232-97-7] and methyl (Me) [cas 80532-66-7] esters of glycidic acid. In case of sodium (Na) salt of this acid [cas 5449-12-7], you can skip first stage of NaOH addition and start from acid hydrolysis. In addition, purification method of obtained P2P is described. This procedure have to be committed to get pure Phenylacetone (P2P) for further syntheses of methamphetamine or amphetamine.

Suppliers of BMK glycidate ethers can be found in BB Listing.

Difficulty rating: 2/10 View attachment 6617 ​

Equipment and glassware:

• 1000 mL Round bottom flask;
• Reflux condenser;
• Retort stand and clamp for securing apparatus;
• pH indicator paper;
• Vacuum source (optional);
• Rotovap machine (optional);
• Glass rod and spatula;
• 100 mL x2; 250 mL x2; 500 mL x2 Beakers;
• Magnetic or top stirrer with a heating plate;
• Water bath;
• Funel;
• 1000 mL Separatory funnel;
• Vacuum distillation setup (optional);

Reagents:​

• 100 g BMK glycidate ethers (cas 80532-66-7; cas 41232-97-7; cas 5449-12-7);
• ~20 g NaOH or KOH;
• ~80 ml HCl (35%) or 100 ml H2SO4 (45%);
• ~600 mL DCM or Petroleum Ether;
• ~100 g MgSO4 or Na2SO4;
• ~500-600 mL Distilled water;
• ~ 50 g NaCl (optional);

View attachment 6616 ​

Hydrolysis of BMK glycidates​

1. NaOH (or KOH) 20g is dissolved in 250-300 ml distilled water with stirring. The reaction mixture (Rm) have to be cooled to room temperature. BMK glycidate 100 g (methyl or ethyl ester) is added and dissolved completely. Part of BMK is hydrolyzed during this procedure and floated as an oil in the surface of Rm. Rm is stired for 1 h at 75-80 °C with a reflux condenser.
2. Then, 200 ml HCl (35%) or 240 ml H2SO4 (45%) are added in small portions to Rm and heated to 80-90 °C and stired for 3 h. Rm have to be cooled to room temperature, the precipitate is filtered.
3. The reaction solution is extracted with DCM or petroleum ether 3 x 100 ml. Extract is washed with brine to neutral pH 7 several times. Extract is dried with MgSO4 (or Na2SO4) (optional) and filtered from solids.
4. An organic solvent (DCM or petroleum ether) is distilled off to give 65 ml of P2P.
​

P2P purification​

1. The resulting phenylacetone (P2P) is transferred to a round bottom flask with distilled water 1:1 (w/w) and distilled with steam under vacuum.
2. Purified P2P from receiver flask is extracted from water mixture with DCM (or petroleuum ether) 3 x 100 mL. Extract is dried with MgSO4 (or Na2SO4).
3. The resulting solution is filtered from the solids (drying agent) and then an organic solvent is distilled off.

Phenylacetone can be stored long time in a sealed vessel in a freezer. It is recommended to distill it before further syntheses of methamphetamine or amphetamine. Avoid direct sunlight onto phenylacetone and exposure to high temperatures.​

G.PattonHi, could you answer some doubts?

3.- What is the pH in this stage after wahsing with DCM? The wash with brine is mandatory? If yes, what is the concentration of NaCl solution?
4.- This is simple distilation at DCM boling point (around 40ºC) rigth?

P2P Purification is worthy in yield terms to reach amphetamine? If yes, do you know how much does it increase?

1.- What is the point of mixing with water (65 ml), and distill again to separete from water? or could we have some unwanted components?
What is the pressure and the temperature in this stage for the vacuum distilation?
Is possible simple distilation without vacuum? Around water boiling point (100ºC)

​

 

[G.Patton]

Hi, could you answer some doubts?

3.- What is the pH in this stage after wahsing with DCM? The wash with brine is mandatory? If yes, what is the concentration of NaCl solution?
4.- This is simple distilation at DCM boling point (around 40ºC) rigth?

P2P Purification is worthy in yield terms to reach amphetamine? If yes, do you know how much does it increase?

1.- What is the point of mixing with water (65 ml), and distill again to separete from water? or could we have some unwanted components?
What is the pressure and the temperature in this stage for the vacuum distilation?
Is possible simple distilation without vacuum? Around water boiling point (100ºC)

​

Costa>3

Extract is washed with brine to neutral pH 7 several times.

25% NaCl aq is okay and yes. It is necessary.
>4
Yes, you are right. You can use rotovap.
>P2P Purification is worthy in yield terms to reach amphetamine? If yes, do you know how much does it increase?
yes, it is necessary. I can't say for sure. The difference can vary greatly.
>1.- What is the point of mixing with water (65 ml), and distill again to separete from water?
read about steam distillation in Lab FAQ section
>What is the pressure and the temperature in this stage for the vacuum distilation?
Is possible simple distilation without vacuum? Around water boiling point (100ºC)

Depends on vacuum, I can't answer you. I think it is impossible, you'll spoil your p2p with height temperature (probably).

 

[Costa]

>3

25% NaCl aq is okay and yes. It is necessary.
>4
Yes, you are right. You can use rotovap.
>P2P Purification is worthy in yield terms to reach amphetamine? If yes, do you know how much does it increase?
yes, it is necessary. I can't say for sure. The difference can vary greatly.
>1.- What is the point of mixing with water (65 ml), and distill again to separete from water?
read about steam distillation in Lab FAQ section
>What is the pressure and the temperature in this stage for the vacuum distilation?
Is possible simple distilation without vacuum? Around water boiling point (100ºC)

Depends on vacuum, I can't answer you. I think it is impossible, you'll spoil your p2p with height temperature (probably).

G.PattonTanks so much for your quick reply!

 

[Costa]

>3

25% NaCl aq is okay and yes. It is necessary.
>4
Yes, you are right. You can use rotovap.
>P2P Purification is worthy in yield terms to reach amphetamine? If yes, do you know how much does it increase?
yes, it is necessary. I can't say for sure. The difference can vary greatly.
>1.- What is the point of mixing with water (65 ml), and distill again to separete from water?
read about steam distillation in Lab FAQ section
>What is the pressure and the temperature in this stage for the vacuum distilation?
Is possible simple distilation without vacuum? Around water boiling point (100ºC)

Depends on vacuum, I can't answer you. I think it is impossible, you'll spoil your p2p with height temperature (probably).

G.PattonHi!
I made this process, and after this step:
"2. Then, 200 ml HCl (35%) or 240 ml H2SO4 (45%) are added in small portions to Rm and heated to 80-90 °C and stired for 3 h. Rm have to be cooled to room temperature, the precipitate is filtered."
This is what I have obtained (see the picture below). Is this the expected aspect of the reaction? and my question is: is this top layer already P2P? should I put aside this layer (and keep it) and add DCM to the rest (bottom layer) in order to extract the remaining P2P from there?

Many thanks in advance!

 

[G.Patton]

Hi!
I made this process, and after this step:
"2. Then, 200 ml HCl (35%) or 240 ml H2SO4 (45%) are added in small portions to Rm and heated to 80-90 °C and stired for 3 h. Rm have to be cooled to room temperature, the precipitate is filtered."
This is what I have obtained (see the picture below). Is this the expected aspect of the reaction? and my question is: is this top layer already P2P? should I put aside this layer (and keep it) and add DCM to the rest (bottom layer) in order to extract the remaining P2P from there?

Many thanks in advance!


View attachment 8635

CostaHello, yes, it is P2P oil. You have to separate layers and then extract water (bottom) layer by DCM. Next, combine p2p oil with DCM extracts and follow instructions (wash with brine and so on).

 

[Costa]

Hello, yes, it is P2P oil. You have to separate layers and then extract water (bottom) layer by DCM. Next, combine p2p oil with DCM extracts and follow instructions (wash with brine and so on).

G.PattonIs the washing of the extract (P2P oil) with brine made the same way as the washing with DCM? I mean, when adding brine to the p2p will I get two layers? In that case which one do I have to keep?

 

[G.Patton]

Is the washing of the extract (P2P oil) with brine made the same way as the washing with DCM? I mean, when adding brine to the p2p will I get two layers? In that case which one do I have to keep?

CostaYes, pour brine solution into separatory funnel with DCM and P2P, shake it couple minutes and decant. You need organic layer. Check pH of brine after washing. It has to be around 7 pH.

 

[Costa]

Yes, pour brine solution into separatory funnel with DCM and P2P, shake it couple minutes and decant. You need organic layer. Check pH of brine after washing. It has to be around 7 pH.

G.PattonHi, I followed the procedure step by step as mentioned in the instructions and it didn't work. I made several extractions of the "water" (bottom layer) using DCM and once I combined them (pouring over the P2P layer), there was some kind of reaction because lot of solids appeared. Anyway, I continued with the procedure, just in case; so I add the brine (NaCl + water) and it was even worst...
In your last message you told I should add DMC and brine at the same time, so today I will try following this method.

You told I have to check the pH of the brine; what is "brine" refers to? is it the layer with NaCl (the remaining layer once I separate the oily layer with P2P)? the addition of the NaCl is just to rise the pH? why is NaCl used instead if NaOH for this objective?

 

[G.Patton]

Hi, I followed the procedure step by step as mentioned in the instructions and it didn't work. I made several extractions of the "water" (bottom layer) using DCM and once I combined them (pouring over the P2P layer), there was some kind of reaction because lot of solids appeared. Anyway, I continued with the procedure, just in case; so I add the brine (NaCl + water) and it was even worst...
In your last message you told I should add DMC and brine at the same time, so today I will try following this method.

You told I have to check the pH of the brine; what is "brine" refers to? is it the layer with NaCl (the remaining layer once I separate the oily layer with P2P)? the addition of the NaCl is just to rise the pH? why is NaCl used instead if NaOH for this objective?

CostaHi.

>>>there was some kind of reaction because lot of solids appeared.

I have no idea what is it, have you checked your precursor? What are you use for this synthesis?

>>>In your last message you told I should add DMC and brine at the same time

I wrote that you have to add them in one separatory funnel, there is no difference of addition sequence.

>>>You told I have to check the pH of the brine; what is "brine" refers to? is it the layer with NaCl (the remaining layer once I separate the oily layer with P2P)? the addition of the NaCl is just to rise the pH? why is NaCl used instead if NaOH for this objective?

You can use distilled water for washing of your extract. Brine (NaCl aq solution) is used in order to rinse acid trace from your P2P extract. It's easy, cheap and safe. Also, it is more convenient to separate layers with brine. You have to wash the organic extract by brine until neutral pH 7.

 

[Costa]

Hi.

I have no idea what is it, have you checked your precursor? What are you use for this synthesis?


I wrote that you have to add them in one separatory funnel, there is no difference of addition sequence.


You can use distilled water for washing of your extract. Brine (NaCl aq solution) is used in order to rinse acid trace from your P2P extract. It's easy, cheap and safe. Also, it is more convenient to separate layers with brine. You have to wash the organic extract by brine until neutral pH 7.

G.Pattongreat, thanks! I will make the extraction combining DCM and brine. Just one question, I have to make 3 extractions with 100ml DCM + brine; but, how much brine on each extraction? it doesn't matter?

 

[G.Patton]

great, thanks! I will make the extraction combining DCM and brine. Just one question, I have to make 3 extractions with 100ml DCM + brine; but, how much brine on each extraction? it doesn't matter?

CostaYou have to carry out extraction by DCM and then wash your DCM extract with brine. It is important. Read manual carefully and try to understand the sense of each step. In opposite case you will extract water by brine.

 

[Costa]

I have no idea what is it, have you checked your precursor? What are you use for this synthesis?

i used: cas 5449-12-7. I took off the P2P layer and with the rest, I made the extractions with DCM. Each extraction (the oily layer obtained when adding DCM), I combined them with the P2P. It was then when the precipitate appeared.

Today I will not combine the P2P with the extractions, just in case... I will made the extractions with DCM and each extract, I will wash them with brine, as you told. Lets see what happens.

thanks

 

[G.Patton]

I have no idea what is it, have you checked your precursor? What are you use for this synthesis?

i used: cas 5449-12-7. I took off the P2P layer and with the rest, I made the extractions with DCM. Each extraction (the oily layer obtained when adding DCM), I combined them with the P2P. It was then when the precipitate appeared.

Today I will not combine the P2P with the extractions, just in case... I will made the extractions with DCM and each extract, I will wash them with brine, as you told. Lets see what happens.

thanks

Costa>>>the oily layer obtained when adding DCM
not oily, you'll get DCM with dissolved P2P there.

 

[Costa]

Hi, as said, I repeated the process following the instructions of the document (and your comments) step by step. I got exactly the same product on this step:

I took the oily layer (top layer, which has P2P) and once it cooled down after 10 minutes it has this aspect:

.

Then I added DCM over the other layer (the "water") in order to make the first extraction, however, this was the aspect of the mixture:

as you can see, there was some kind of white precipitate on the bottom, there were not two layers, just the white solids and the rest.
What did I do wrong? The document is not very clear...
Many thanks in advance and sorry for that many questions, but this process it is being a headache...

 

[G.Patton]

Hi, as said, I repeated the process following the instructions of the document (and your comments) step by step. I got exactly the same product on this step: View attachment 8916 I took the oily layer (top layer, which has P2P) and once it cooled down after 10 minutes it has this aspect: View attachment 8917 .

Then I added DCM over the other layer (the "water") in order to make the first extraction, however, this was the aspect of the mixture:
View attachment 8918 View attachment 8919 View attachment 8920 as you can see, there was some kind of white precipitate on the bottom, there were not two layers, just the white solids and the rest.
What did I do wrong? The document is not very clear...
Many thanks in advance and sorry for that many questions, but this process it is being a headache...

CostaIt is quite strange. Check cas 5449-12-7 mp. Also, you can take the solid orange "p2p oil" from your beaker (take couple grams) and dissolve in water at room temperature or with slight heating (about 30 deg C). I think that this solid is water soluble salt. If you'll get oily layer on the top, I am right.