Question Acetoacetanilide to APAAN

[haze2000]

Do you guys think that the conversion of Acetoacetanilide [102-01-2] to APAAN [4468-48-8] is possible? I ask this because in a paper from 2018 there is mentioned that 102-01-2 was seized way back in 2013 in holland and that this can be readily converted to apaan. I will attach link and relevant text below.

[ In 2013 a pre-pre-precursor was discovered in the Netherlands 3-oxo-N-phenylbutanamide [102-01-2] which can be readily converted into APAAN ]

https://www.sciencedirect.com/science/article/abs/pii/S0379073818301166

 

[WalterFan]

Yes, if you start from 102-01-2, the most advanced way to make the final product takes 3 weeks

 

[lalalander]

Do you know anything about how exactly this can be done?

 

[yuiopjkl]

In the reference cited, 3-oxo-N-phenylbutanamide is not mentioned, but the substance that is mentioned is 3-oxo-2-phenylbutanamide (cas: 4433-77-6, alpha-phenylacetoacetamide)

 

[WalterFan]

Then why don’t you try it instead?

 

[ancelotti]

Sombody got the synthesis from 4468-48-8 to p2p ?

 

[yuiopjkl]

BMK (benzylmethylketone) synthesis from APAAN (a-phenylacetoacetonitrile). Large scale

 

[yuiopjkl]

APAAN conversation with sulfuric acid:
350 ml of concentrated sulfuric acid is placed in a 3000ml flask and cooled to -10°C. The total first crop of moist alpha-phenylacetoacetonitrile obtained according to the procedure above (corresponding to 188-206g or 1.2-1.3 moles of dry product) is added slowly, with shaking, the temp being kept below 20°C (If pure dry alpha-phenylacetoacetonitrile is used, half its weight of water should be added to the sulfuric acid or charring will take place on the steam bath). After all is added the flask is warmed on the steam bath until solution is complete and then for five minutes longer. The solution is cooled to 0°C, 1750ml of water added rapidly, and the flask placed on a vigorously boiling water bath and heated for two hours, with occasional shaking. The ketone forms a layer and, after cooling, is separated and the acid layer extracted with 600ml of ether. The oil and ether layers are washed successively with 100ml of water, the ether combined with the oil and dried over 20g of anhydrous sodium sulfate. The sodium sulfate is collected on a filter, washed with ether, and discarded. The ether is removed from the filtrates, and the residue distilled from a modified Claisen flask with a 25 cm fractionating side arm. The fraction boiling at 110-112°C at 24 mmHg is collected; it weighs 125-150g (77-86% of the theoretical amount).