Synthesis, Crystal Structure And Antitumor Activity Of Three Dihydropyrimidinone Methanesulfonic Acids And Their Coordination Polymers

In this paper, three dihydropyrimidinones have been synthesized through methanal(acetaldehyde or benzaldehyde), acetylacetic ester and urea catalyzed by sulfamic acid in solventethanol. The sulfonation reaction of the dihydropyrimidinones with chlorosulfonic acid in1,4-dioxane produced three corresponding dihydropyrimidinone methanesulfonic acids, namely:(5-ethoxycarbonyl-1,6-dihydropyrimidin-2-one-4-yl)methanesulfonic acid(HLA),(5-ethoxycarbonyl-6-methyl-1,6-dihydropyrimidin-2-one-4-yl)methanesulfonic acid(HLB) and(5-ethoxycarbonyl-6-phenyl-1,6-dihydropyrimidin-2-one-4-yl)methanesulfonic acid(HLC). Thestructure of three dihydropyrimidinone methanesulfonic acids was characterized through XRD andIR. The coordination reactions of dihydropyrimidinone methanesulfonic acids with metal ionsobtain seven dihydropyrimidinone coordination polymers, namely:[KLA·H2O]n(1),[NaLB(H2O)1.5]n(2),[K2(LB)2(H2O)2]n(3),{[NaLC(H2O)3]·(H2O)}n(4),[K2(LC)2]n(5),[Zn(LC)2(H2O)2]n(6),[Mg(LC)2(H2O)2]n(7). Their crystal structures were determined by XRD. Theantitumor activity of related compounds has been tested.K+ion in [KLA·H2O]n(1) is located in a eight coordination environment which are fiveoxygens of three sulfonic groups in different HLAligand, one oxygen of keto-carbonyl in HLAandtwo oxygens of two coordinated water molecules.HLBligand is used to synthesize complex2and complex3. In [NaLB(H2O)1.5]n(2), Na+coordinated by two oxygen atoms of two sulfonic groups in two ligands, two oxygen atoms of twoketo-carbonyl groups in HLBand two oxygen atoms of two coordinated water molecules andshows a six-coordinated octahedral geometries. In complex3[K2(LB)2(H2O)2]n, K+ions displaytwo coordination forms of seven-coordination of K1and six-coordination of K2. Five oxygenatoms of three sulfonic groups in different HLBligand, one oxygen atom of a keto-carbonyl inHLBand one coordinated water molecule coordinate to K1ions to form pentagonal bipyramidgeometries. K2ion coordinates with three oxygen atoms of three sulfonic groups, one oxygenatom of a keto-carbonyl in ester group in HLBand one oxygen atom of a coordinated watermolecule. Complex3is expanded into3D supramolecular construction via hydrogen bond.Four compounds about complex4to complex7are obtained by using HLCligand. Thesecomplexes are all stacked to two-dimensional layered structure through π-π effects betweenaromatic rings in HLCligand. Besides, each of metal ions of these complexes possesses sixcoordination atoms. The six coordination positions of Na+ion of {[NaLC(H2O)3]·(H2O)}n(4) areone oxygen atom of sulfonic group in HLC, one oxygen atom of a keto-carbonyl in HLCand four water molecules. K+ion of [K2(LC)2]n(5) coordinates with three oxygen atoms of two sulfonicgroups, two oxygen atoms of two keto-carbonyl groups and one water molecule. Metal ions of[Zn(LC)2(H2O)2]n(6) and [Mg(LC)2(H2O)2]n(7) have the same coordinate pattern and thecoordinated atoms are two oxygen atoms of two sulfonic groups, two oxygen atoms of twoketo-carbonyl groups and two coordinated water molecules.Antitumor activity of compound1,3,4and5showed that: these compounds have someantitumor activity and their antitumor activity is poorer than positive drug5-fluorouracil.