Synthesis of APAAN (a-phenylacetoacetonitrile) with sodium amide (1kg scale)

[WillD]

Reaction scheme:

Synthesis:
1. 1000 g of benzyl cyanide, 1300 ml of ethyl acetate added to the reactor and stirring mixture.
2. Added 500 g sodium amide, in small portions, to control the boil mixture.
3. The reaction mixture was reflux two hours and left for 12 hours at room temperature.
4. After 12 hours, the mixture was diluted with 8 liters of water and stirred until the solid sludge was completely dissolved.
5. Added 4 liters of crushed ice and stirring.
6. Extracted with 3 liters of benzene (toluene, DCM, ether, etc) and the extracts discarded.
7. The separated aqueous phase was acidified with a solution of glacial acetic acid (600 ml) in water (2000 ml).
8. The precipitate was filtered and used without further purification for the preparation of benzyl methyl ketone.

 

[pdwshopnl]

I hear about this synth. Have you orginal patent from literature?
I Have only this but I can't find IT on internet:

Bodroux, Compt, rend. 151, 234 (1910)
Bull. soc. chim. (4) 7, 848 (1910)

Can you tel more abou the synthesis conditions, that is, do they have to be strictly anhydrous, as in the case of the reaction with sodium ethoxide?
Or analytical grade (purest) reagents sufficient?

 

[pdwshopnl]

Your links go to made apaan with sodium ethoxide.
This Road known all, also in my opinion is very difficult becouse must keept anhydrous condition all time.

This topic tell about very very Old Road make apaan (in literature write about IT in 1910 year). Its been prepared by the condensation of ethyl acetate with the sodium derivative of benzyl cyanide prepared from benzyl cyanide and sodium amide.
I search more information about this synth for many many Times... belive me.
And only what I find in literature is in this two article from 1910 year:

Bodroux, Compt, rend. 151, 234 (1910)
Bull. soc. chim. (4) 7, 848 (1910)

But IT is too Old and I dont get IT.

In my opinion this Road to get apaan is only sense way to succes.

 

[Sabatier]

I see. I do apologize.

 

[WillD]

Your links go to made apaan with sodium ethoxide.

pdwshopnlIn fact, this is the best variant of this synthesis, using sodium (or potassium) methylate, ehtylate, etc

 

[pdwshopnl]

I mean links who add other user (from organic synthesis sites about make apaan with sodium ethoxide) - its delete now. Your patent of course is not with sodium ethoxide.

 

[KokosDreams]

What's the yield in g (APAAN) for this method?

 

[melk]

With apaan
you had no loss or maybe a little of nothing

What's the yield in g (APAAN) for this method?

KokosDreams

 

[melk]

In 2010 you had legal apaan for 20€ / kg pure this was progress lol

 

[cokemuffin]

Any idea of how to aquire the KCN for the benzyl cyanide, thought about adding h2so4 to potassium hexacyanoferrate(III) and lead the resulting HCN gas into a solution of KOH?

 

[cokemuffin]

Any idea of how to aquire the KCN for the benzyl cyanide, thought about adding h2so4 to potassium hexacyanoferrate(III) and lead the resulting HCN gas into a solution of KOH?

cokemuffinIf that ain't an option what about potassium hexacyanoferrate(III) to Potassium ferrocyanide via KOH and then pyrolysis?
4KOH + 4K3[Fe(CN)6] → 2H2O + O2 + 4K4[Fe(CN)6] | K4[Fe(CN)6] → 4 KCN + FeC2 + N2

 

[ossi]

Reaction scheme:
View attachment 1414

Synthesis:
1. 1000 g of benzyl cyanide, 1300 ml of ethyl acetate added to the reactor and stirring mixture.
2. Added 500 g sodium amide, in small portions, to control the boil mixture.
3. The reaction mixture was reflux two hours and left for 12 hours at room temperature.
4. After 12 hours, the mixture was diluted with 8 liters of water and stirred until the solid sludge was completely dissolved.
5. Added 4 liters of crushed ice and stirring.
6. Extracted with 3 liters of benzene (toluene, DCM, ether, etc) and the extracts discarded.
7. The separated aqueous phase was acidified with a solution of glacial acetic acid (600 ml) in water (2000 ml).
8. The precipitate was filtered and used without further purification for the preparation of benzyl methyl ketone.

William Dampieri have pure sodium, not sodium amid.
how should i work?
please @G.Patton

 

[CryoThio]

Can you tell us if sodium methoxide will replace sodium amide without changes to the procedure? Sodium methoxide is supposed to work, and afaik is cheaper.