Acetic Acid Ammonia Oxygen Radicals Salicylaldehyde Schiff Base Reaction With Organic Tin Compounds

Organotin complexes of Schiff bases have extentively bioactivity activities,especially anti–tumour activity, so its synthesis, reaction, properties and applicationshave recently increased attention, and have made gratifying achievements.The presentstudy such as more amine kind, amino acid and acylating hydrazone schiff,o-alkyhydroxylamine schiff also has amine variety of coordination model and strongcoordination ability, but very little. By α-aminoxyacetic acid as raw materials,therefore we design schiff base ligand through salicylaldehyde，with organic tinchloride reaction to generate a series of novel organotin complexes,for organotincomplexes application to provide experimental support and theoretical basis. It mainlyincludes the following contents:1. Synthesis of α-Aminoxyacetic Acid Hemihydrochlorideα-Aminoxyaeetic acid hemihydrochloride is one kind of important applicationvalue of fine chemicals and chemical intermediate,because the price is high,and itssynthetic route is complex,and very few investigations have been reported so far inthe domestic.In this paper, we mainly use the cheap chloroactic acid instead ofexpensive bromine acetic acid, and use the same cheap two kinds of different rawmaterial(acetone or2-butanoneoxime) of α-aminoxyacetic acid hemihydrochloride,toreduce the cost and improve production rate.Using acetone as the raw material for the synthesis of α-aminoxyacetic acidhemihydrochloride:solution in toluene, acetone oxime and sodium metal directreaction of acetone oxime sodium, with sixteen alkyl ammonium bromide as phasetransfer catalyst, and chloroacetic acid sodium generating acetone carboxy-methoxime.At last，we can get α-aminoxyaeetic acid hemihydrochloride after acidhydrolysis., m.p.154-155C, total yield is42.4%.Using2-butanoneox as the raw material for the synthesis of α-aminoxyaceticacid hemihydrochloride:solution in toluene,2-butanoneox oxime and sodium metaldirect reaction of2-butanoneox oxime sodium, with sixteen alkyl ammonium bromideas phase transfer catalyst, and chloroacetic acid sodium generating acetone carboxy-methoxime.At last，we can get α-aminoxyaeetic acid hemihydrochloride after acidhydrolysis.,m.p.153-154℃,totalyield is47.3%;Another process,excess2-butanon-eoxime latter and sodium hydroxide react directly to get rid of water.After completing the reaction,adding chloroactic acid in toluene solution,2-butanonecarboxymethoxime was acided and hydrolyzed to gave α-aminoxyaeetic acidhemihydrochloride, m.p.153-154℃, total yield is45.6%.2. Synthesis of schiff base ligand derived from α-aminoxyacetic acid andsalicylaldehyde, with organo-tin compound.In this paper,we synthesize a new type of α-aminoxyacetic acid schiff base,selecting potassium hydroxide,α-aminoxyaeetic acid hemihydrochloride and salicylicaldehyde as as starting material, under reflux in toluene3h, reaction ratio is1.5:1.0:1.0, in the condition without oxygen and water.The structure was characterizedby UV,IR,1~H NMR,(13)~C NMR and etc.,and was determined phenolic imide structurecontaining Intramolecular hydrogen bond.And then their organotin compands were synthesized with ligand and diphenyltindichloride, the molar ratio is1:1, in no water, no oxygen, alkaline conditions,getingtwo novel organotin complexes: A~1and A~2.The structure of A~1was characterized byUV,IR,1~H NMR,(13)~C NMR and etc. It’s structure which heart tin atom attached to twooxygen atoms, a nitrogen atom and two butyl,and coupled with the ligand structure,was identified it as a five coordination complex of six yuan double ring structure; Thestructure of A~2was characterized by UV,IR,1~H NMR and etc.It’s structure which hearttin atom attached to one oxygen atom, a chlorine atom and two butyl, forming a fourcoordination without ring structure.And then their organotin compands were synthesized with ligand and dibutyltindichloride, the molar ratio is1:1, in no water, no oxygen, alkaline conditions.Thestructure was characterized by UV,IR,1~H NMR. and etc.It’s structure which heart tinatom attached to two oxygen atoms, a nitrogen atom and two phenyl,and coupled withthe ligand structure, was identified it as a five coordination complex of six yuandouble ring structure.And then their organotin compands were synthesized with ligand andtri-p-tolychlorotion,the molar ratio is1:1, in no water, no oxygen, alkaline conditions.The structures were characterized by UV, IR,1~H NMR and etc. We determine its forma kind of ester base tin by characterizing the structure.