4 - (2 - Aminoethoxy) Methyl Benzophenone Synthesis And Properties

Benzophenone derivatives, which have good photochemistryproperties, are commonly applied in the area of photoinitiators,Ultra-violet absorbers, electronic and medicinal industry and so on.Starting from 4-methylbenzophenone and 4-(bromomethyl)benzoate respectivly, three routes were designed to synthesize a newbenzophenone-containingcompound 4-((2-aminoethoxy)methyl)benzophenone(AMBP), which can be used as a kind of crosslinkers of DNAstrands, water-soluble photosensitives and to synthesize molecular probesand so on. The results indicated that: an important organic intermediate4-hydroxymethylbenzophenone(3) was synthesized by halogenation andhydrolyzation trader phase transfer catalyted conditions using4-methylbenzophenone as starting material, the metal salt of 3 failed toreact with methyl (2-chloroethyl)carbamate (ClCH₂CH₂NHCOOCH₃) togive methyl 2-(4-benzoylbenzyloxy)ethyl carbamate(4), which is animportant intermediate to synthesize AMBP in the first route; In thesecond route, 4-methylbenzophenone firstly reacting withN-bromosuccinimide(NBS) to give 4-bromethylbenzophenone, then4-bromethylbenzophenone directly reacting with NaOCH₂CH₂NH₂ canaffords the title compound AMBP reactions with the total yield 12.3％,which was two-steps in all, but the resulting mixture consisted mainly ofthe side-products 4-(2-hydroxyethylami-no)methylbenzophenone(9),2-((4-((2aminoethoxy)methyl)phenyl)(phenyl)methyleneamino)ethanol(10) and 2-((4-((2-hydroxyethylamino)methyl)phenyl)(phenyl)methyleneamino)ethanol (11); With amino-protected NaOCH₂CH₂NHBoc and4-bromomethylbenzop-henone as starting materials the title compoundwas successfully obtained via 4-(((2-Carboxyamino)ethoxy)methylbenzo-phenone(13) followed by a hydrolysis process with the total yield 59.7％,which was three-steps in all; In addition, AMBP can be successfullyobtained with the total yield 48.1％in the presence of Lewis acid,benzene and 4-((2-aminoethoxy)methyl)benzoyl chloride(15) which come from (2-(4-(Methoxycarbonyl)benzyloxy)ethyl)carbamic acid(14)which was synthesized using the reaction of NaOCHCHNHBoc andmethyl 4-(bromemethyl)benzoate, which was four-steps in all. AMBP andthe intermediates 9, 10, 11, 13, 14, and 15 were not reported by references.The structure of the compounds were characterized by infrared spectrum(IR), Ultra-violet spectrum (UV), proton nuclear magnetic resonance (¹HNMR), mass spectrum(MS) and elemental analysis.The photosensitive properties of AMBP was investigated, and thecuring rate of Acrylated epoxy oligomer(AEO) in the presence ofdifferent AMBP/tertiary amines systems were measured. The resultsindicated that the curing rate of AEO in the presence of AMBP was slow,the curing time was 30s, but fast in the AMBP/triethanolamine system,curing time 4s.The biological activities of compounds 9, 10, 11, 13, and AMBP wereinvestigated as well. The results indicated that 10 and 11 had goodacaricidal activities, both 13 and AMBP had a little fungicidal activitiesand still AMBP had phytocidal activitives.