Synthesis Of N-substituted-2-aminomethyl Phenol And Their Application In The Synthesis Of Benzoxazine

N-alkylation is regarded as an important type of organic synthesis reaction, which attracts more and more attention. The products of N-alkylation have found widely application in the pharmaceutical, agricultural chemicals, optoelectronics and other fields. The paper mainly studied the N-alkylation reaction conditions of the 2-aminomethyl phenol and N-aryl-2-chloroacetamide, and obtained an optimized conditions. Under this optimized conditions, eight novel N-aryl-2-(2-hydroxybenzylamino) acetamides 40a~40h were synthesized. Furthermore, 1,3-benzoxazines 41a~41c was synthesized using 40 c as raw material. The structures of the synthesized compounds were characterized by 1H NMR,13 C NMR and IR.(1) The reaction of 2-aminomethyl phenol and N-(2-methylphenyl)-2-chloroacetamide was selected as the model reaction to optimize the N-alkylation reaction process. It was mainly investigated the effect of reaction time, bases, the amount of the base, the ratio of the reactants and temperature on the yields of the reaction, and obtained an optimized conditions: reaction time 7 h, anhydrous Na2CO3(100% mol), n(2-aminomethyl phenol) : n(N-(2-methylphenyl)-2-chloroacetamide) = 1.2 : 1.0, temperature 85 ?, solvent DMF/THF(v:v = 1:1).(2) Under the above optimized process conditions, eight novel N-aryl-2-(2-hydroxy-benzylamino) acetamide 40a~40h were synthesized in yields of 38.4~57.5%. It was found that the benzene ring containing no substituent or an electron withdrawing group gave higher yield than that containing electron donating groups.(3) 2-Aryl-3-amidyl-1,3-benzoxazine 41a~41c were synthesized by reaction of N-aryl-2-(2-hydroxybenzylamino) acetamide 40 c with nitrobenzeneformaldehyde in the presence of La(OTf)3(5.0% mol).(4) The fungicidal activities of the synthesized compounds were evaluated. At concentration of 50 ?g/m L, the inhibition activity of compound 40 d against Sclerotinia sclerotiorum is 87.7%. The inhibition activity of compound 40 c against Botrytis cinerea is 73.8%, and 64.3% for compound 40 d, 61.9% for compound 40 a. Compound 40 d exhibits a broad spectrum of fungicidal activity.