N-[(6-Chloro-3-pyridinyl)methyl]-N′-cyano-N-methylethanimidamide

ChEBI: A carboxamidine that is acetamidine in which the amino hydrogens are substituted by a (6-chloropyridin-3-yl)methyl and a methyl group while the hydrogen attached to the imino nitrogen is replaced by a cyano group.

Preparation Method 1 Preparation of 2-chloro-5-aminomethylpyridine After mixing 23.5 g of dried hexamethylenetetramine, 200 mL of acetonitrile, and 27.4 g (90.2%) of 2-chloro-5-chloromethylpyridine. Heat and stir at reflux for 8h. Cool and filter to obtain 57.8 g of white solid. The resulting white solid was put into a 500 mL reaction bottle. Add 49mL water, 48mL hydrochloric acid. 120 mL of methanol was added with stirring. Heat to reflux for 1.5h. The reaction temperature was 61°C at the beginning of the reaction, and the reflux temperature was 50.5°C after 1 h. Methanol and dimethoxymethane were removed, and 80 mL of chloroform was added. 80g of 25% NaOH aqueous solution was added with stirring, the pH value was 8-9, the layers were separated, and the aqueous layer was extracted once with 80mL of chloroform. The chloroform layers were combined, the chloroform was removed under reduced pressure, and cooled to obtain 25.5 g of a pale yellow solid. The crude product was recrystallized once with methanol to obtain white crystals. The content is 97.3%, mp25～26℃. Preparation of N-cyano-N'-(2-chloro-5-pyridylmethyl)acetamidine In a 100mL reaction flask, put 15.89g (84.3%) of 2-chloro-5-aminomethylpyridine and 52.3mol of water . With stirring, 11.64 g (95%) of ethyl N-cyanoacetimidate was added dropwise at room temperature. Stir for 30 min after the drop. Add 18.5 mL of ethanol. When heated to 78°C, the light yellow solid dissolves and refluxes to full dissolution. Slowly cool, white crystals are precipitated and put in the refrigerator. Filter and dry to obtain 16.04g white crystals. The crude product was recrystallized with ethanol to obtain white crystals. The content is 98.5%, mp141～143℃. Synthesis of acetamiprid In a 250mL reaction flask, add 20.5g (85.27%) of N-cyano-N'-(2-chloro-5-pyridylmethyl)acetamidine, chloroform 54.5mL, methylbutyl ammonium bromide 0.11g. Under stirring, it was cooled to 15°C, and 11.6g of dimethyl sulfate and 8.4g of 50% NaOH aqueous solution were added dropwise at the same time, and the reaction was stirred at 15°C for 3h. Add 33.6 mL of water and 0.33 g of 40% dimethylamine aqueous solution, stir at room temperature for 1 h, separate the layers, extract the aqueous layer with chloroform, and combine the chloroform layers. Add 38 mL of water, and remove chloroform by atmospheric distillation. Cool, add methanol, and cool to 35°C. 37 mL of water was added dropwise to precipitate a solid. Cool to complete precipitation. Filtration yielded a light yellow solid, which was dried to obtain 17 g of product. The crude product was recrystallized from an aqueous methanol solution to obtain white needle-like crystals. mp101～103℃. The total yield of the above is 57% and the content is >85%. Other preparation methods acetamiprid is prepared by the reaction of N-cyano-N'-methylacetamidine and 2-chloro-5-chloromethylpyridine. Acetamiprid is prepared by reacting N-cyanoacetamidine with 2-chloro-5-chloromethylpyridine and then reacting with dimethyl sulfate in a methylation reaction. Acetamiprid can also be prepared by the reaction of N-cyanoethylimidate and N-methyl-2-chloro-5-pyridylmethylamine.

Insecticide.

Molecular Weight:222.67
XLogP3:1.4
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:3
Exact Mass:222.0672241
Monoisotopic Mass:222.0672241
Topological Polar Surface Area:52.3
Heavy Atom Count:15
Complexity:280
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes