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Five π-complexes [M(HL)X2] (M = Pd2+, Pt2+; X = Cl−, Br−, I−) have been obtained by the reactions of [MCl4]2− with 1-allyl-3-(2-hydroxyethyl)thiourea (HL) in the presence of HCl and/or KBr/KI. (Br/I)-Containing chelated π-type complexes of this type are presented for the first time. A comprehensive structural and spectral characterization has revealed an identical atomic arrangement, with the Cl- and Br-bearing phases adopting the same triclinic structure (space group P), while [Pt(HL)I2] crystallizes in the monoclinic P21/n space group. The molecules of HL are coordinated in a bidentate manner with the formation of six-membered chelate metallocycles. The diagonal arrangement of “soft-hard” donor atoms (S–X, C–X) in the coordination sphere leads to Pearson's effect of “molecular antisymbiosis in the trans effect” that causes the interaction of M:L in a ratio of 1:1. The similarity of the structures of the synthesized complexes with that of cisplatin implies the same mechanism for their antitumor action, whilst different halide anions in the coordination sphere of the metal affects the cytotoxic activity of the complexes. Among the new cisplatin analogues, two of the platinum π-complexes are promising compounds, the action of which slows or completely stops cell division, causes a decrease in nucleus size and increases the proportion of heterochromatin in the structure of interphase nuclei, thus reducing the activity of transcriptional processes. A molecular docking study showed that the general mechanism of action for the complexes can be characterized by the formation of single and double-stranded breaks of DNA plasmid. The presence of the OH-group has a positive impact on the “ligand – DNA binding”.

Four novel Cu2+ coordination compounds with a (E)-N′-(2-hydroxybenzylidene)-2-phenylacetohydrazide (HBPAH, H2L) have been synthesized and characterized by single crystal X-ray diffraction method, IR, UV–Vis and EPR spectroscopy. In all obtained compounds the ligand is coordinated in typical O,N,O-tridentate chelate manner. It has been shown that synthesis conditions have a great influence on a structure of resulting complex compounds. Depending on starting Cu2+ compounds, concentration of reagents, pH and the presence of secondary ligands the HBPAH coordinates as a neutral molecule, mono- or dianion with formation of four different complexes: [Cu(HL)(H2L)]NO3 (I), [Cu(HL)Cl] (II), [Cu2(HL)2Cl2] (III) and [Cu2(L)2Py2] (IV). Complex I is interesting by the presence of two differently coordinated ligand molecules. Mononuclear complex compound II and its dimeric analogue III were obtained from the same reagents: CuCl2 and HBPAH but in different reaction conditions. In dimeric complex IV the HBPAH molecules are coordinated as dianions in imidol tautomeric form, the pyridine molecules act as secondary ligands complementing the coordination polyhedra of Cu2+ ions. Study of UV–Vis and EPR spectra of complex compounds I-IV in solutions showed that all the complexes undergo partial solvolysis upon dissolution.

N-acylhydrazones of salicylaldehyde is a well known class of ligands bearing O,N,O tridentate chelate coordination site. But up to now no structurally characterized Ag + complexes with O,N,O coordinated N-acylhydrazones of salicylaldehyde were known. Therefore three Ag + coordination compounds with functionally substituted N-acylhydrazones of salicylaldehyde were synthesized and characterized by X-ray diffraction, IR spectroscopy and thermogravimetric studies. In solutions the complexes were studied by 1 H NMR and UV–Vis spectroscopy. The influence of the presence and location of additional nitrogen donor atoms in N-acylhydrazones of salicylaldehyde on their coordination modes was investigated. Ligand N’-salicylidenephenylacetohydrazide (contains no additional donor atoms) coordinates to Ag + in classical O,N,O tridentate chelate manner. Ligand N′-salicylidene-3-pyridinecarbohydrazide (contains β-N additional donor atom in acyl moiety) involves mixed O,N,O + β-N coordination. Whereas N’-salicylidene-4-pyridinecarbohydrazide (contains γ-N additional donor atom) coordinates to Ag + in monodentate manner only via γ-N atom of heterocyclic substituent. All the complexes provide high coordination numbers of Ag + and irregular shapes of coordination polyhedra which are not consistent with classical concepts of Ag + coordination chemistry. However all the complexes are not thermally stable and easily undergo solvolysis upon dissolution.

Two complexes of Ag(I) with the N-allylmorpholine-4-carbothioamide (HL) with general formula ([Ag(HL)NO3]·3H2O)n (1) and [Ag(HL)NO3]n (2) were synthesized and isolated in crystalline state. X-ray diffraction study of compounds showed that both complexes are coordination polymers which differ by coordination manners of nitrate anions and presence of cocrystallized water molecules. In solid state in both complexes the ligand molecules are coordinated in bridging mode by μ2-S atom and the C C double bond of the allyl moiety with formation of stable six-membered chelate metallocycles and 1D Ag–S–Ag polymeric chains. However dissolution of the complexes in DMSO leads to cleavage of polymeric chains as well as Ag-(C C) π-coordination bonds, as evidenced by the 1H and 13C NMR spectroscopy data. Crystallographic data have also revealed so-called “additional” coordination of Ag+ ions, which complements the “usual” coordination polyhedra of Ag+ expanding its coordination numbers from 3 to 5 and 6, leading to stabilization of such compounds in solid state. Results of DFT calculation of IR spectra were compared with experimental data and fragmentation of complexes was investigated by MALDI-TOF mass spectrometry and TPD MS methods.

Anti- and syn-isomers of 2-(2-aminothiazole-4-yl)-2-hydroxyiminoacetic acid (anti-A and syn-A respectively) were used as potential biologically active polydentate complexing agent for Co2+, Ni2+, Cu2+ and Pd2+ ions for the synthesis of novel complex compounds with directed angiogenesis-correcting action. It shown that the location of functional groups in ligand molecules, the electronic structure of metal as complexing agent and the synthesis conditions affect the localization of coordination bonds and the structure of formed complexes. The interaction of ethanol solutions of metal salts with anti-A and syn-A in an acidic medium at the component ratios M:L = 1:1 and 1:2 leads to the formation of complexes [Co(anti-A)(H2O)3SO4] (1); [Ni(anti-A)(H2O)3SO4] (2); [Cu(anti-A)2Cl2] (3); [Pd(anti-A)2Cl2] (4); [Cu(syn-A)2Cl2] (5); [Pd(syn-A)Cl2] (6) with different coordination of ligands. Coordination mode of ligands identified by IR, UV–Vis, XPS and 1H (13C) NMR spectra. The structures of salt of the anti-A and complexes 1, 2, 6 were determined by X-ray diffraction study. Anti-A is coordinated to metal ions in a chelate manner by the nitrogen atom of the hydroxylimino group and the oxygen atom of the deprotonated carboxyl group. In this case, the 2-aminothiazole fragment does not involve in complexation. Syn-A is coordinated to the central metal ion in neutral form through the nitrogen atoms of hydroxyimino group and thiazole ring. All synthesized complex compounds form stable solutions in neutral medium, which makes it possible to use them as potential biologically active substances. Investigation of biological effects for syn-A shows mitogenic and antiapoptotic activity against endotheliocytes, while anti-A causes inhibition of proliferation almost in the entire concentration range. Complex compounds of Cu2+ and Pd2+ with anti-A and syn-A (3–6) cause an increase of antiproliferative activity of endothelial cells compared with baseline complexing agents. In this case, the activity of complexes with syn-A is superior to activity of analogues with anti-A. The results of cytotoxicity tests revealed a pronounced cytotoxic action for complexes 3 and 4, cytotoxic and proapoptotic activity for 6 and cytostatic effect for 5. For all compounds investigated, a checkpoint from S to G2 has been established, which may indicate DNA replication disturbance or dysregulation in the endogenous signals of the cell cycle of endotheliocytes.

Background: One of the most promising strategies to develop multi-targeted anticancer therapeutics is to introduce to the structure of a potential drug two or more pharmacophores (functional groups or structural fragments), which have antiproliferative, proapoptotic or antimetastatic properties acting via different mechanisms. Objective: To design, synthesize and perform screening of a novel hybrid anticancer compound. Method: A novel hybrid compound 4-[(E)-2-phenylethenesulfonamido]-N-hydroxybutanamide, combining butanehydroxamate and styrenesulfonamide moieties, was designed, synthesized and investigated as a potent antimetastatic and antiproliferative agent. The structure and purity of the synthesized compound were confirmed by 1H NMR, 13C NMR, LC/MS spectroscopy and elemental analysis. The compound was screened for the anticancer activity in vitro against HeLa and in vivo against Lewis lung carcinoma tumor, using an antitumor metalloenzyme inhibitor GM6001 (Ilomastat, Galardin) and Pifithrin-μ as control anticancer agents. Results: It was found that the application of our compound resulted in a high fraction of apoptotic cells in the cell population, along with disruption in the cell cycle profile manifested as arrest of proliferative phases. Furthermore, changes of the morphological properties (i.e., an enhancement of adhesive properties and reduction of the nuclear-to-cytoplasm ratio) were found. The in vivo screening revealed that the compound significantly inhibited the metastasizing process that was manifested by a reduction in the number and volume of metastases. Conclusions: The obtained results demonstrate that our compound can serve as a base for further structure optimization in order to design new highly-effective antimetastatic and antitumor agents.

Novel Cu(II), Fe(III), Co(III) and Ni(II) coordination compounds with a 2-[(2-hydroxyphenyl)methylene]hydrazine-N-(2-propenyl)carbothioamide have been synthesized and characterized by single crystal X-ray diffraction, IR, UV–Vis, 1 H, ( 13 C) NMR and X-ray photoelectron spectroscopy. The optimal conditions for the complexation reactions have been determined. Depending on synthesis conditions the ligand coordinates to the metal ion as a neutral molecule, monoanion or bianion mode forming complexes with composition [Cu(H 2 L)Cl] ( I ), [Fe(H 2 L) 2 ]NO 3 ( II ), [Co(H 2 L) 2 ]Cl ( III ) and [Ni(HL)Py] ( IV ). The stability constants for the compounds I − III have been calculated. It has been found that the ligand molecules are coordinated in a tridentate manner by the sulfur, azomethine nitrogen and phenol oxygen in both thione (complexes I − III ) or thiolic (complex IV ) tautomeric forms.

Синтезовано ряд гідроксаматних та гідроксиматних комплексів Ru(III), Rh(III) і Pd(II) із 4-аміно-N-гідроксибензамідом (АГБА) та досліджено їх ІЧ, ЕСП та ЯМР 1Н спектральні характеристики. Встановлено, що АГБА взаємодіє з іонами металів головним чином за типом O,O’-координації, причому будова комплексів значною мірою залежить від рН середовища. В кислому та слабокислому середовищах АГБА утворює переважно гідроксаматні комплекси з координацією гідроксамової кислоти в нейтральній або монодепротонованій формах. В ЯМР 1Н спектрах гідроксаматних комплексів синглет NH протона зсувається в сильне поле, що пов’язано з утворенням металохелатних циклів. В лужному або близькому до нейтрального середовищах АГБА взаємодіє як діаніон, що приводить до утворення гідроксиматних комплексів аніонного типу. В ЯМР 1Н спектрах таких комплексів синглети NH та ОН протонів відсутні. В залежності від природи металу центральний іон формує координаційний вузол у формі плоского квадрата [комплекси Pd(II)] або октаедра [комплекси Ru(III) і Rh(III)], що підтверджується наявністю d-d переходів в електронних спектрах поглинання. В ІЧ-спектрах комплексів найбільш характеристичними є смуги поглинання валентних коливань зв’язку N–O оксимної групи, які зазнають низькочастотного зміщення на Dν = -(24–44) см-1. Отримані результати, а також аналіз літературних даних показують, що в реакціях комплексоутворення гідроксамових кислот з іонами перехідних металів підвищення рН середовища сприяє бідентатній координації АГБА з утворенням п’ятичленних металоциклів хелатного типу., A series of hydroxamate and hydroximate complexes of Ru(III), Rh(III) and Pd(II) with 4-amino-N-hydroxybenzamide (AHBA) has been synthesized, and their IR, UV-Vis and NMR 1H spectral characteristics have been studied.It has been found that AHBA interacts with metal ions mainly by the type of O,O’-coordination, wherein the structure of the complexes is largely dependent on the pH of medium. In acidic and weakly acidic media AHBA predominantly forms hydroxamate complexes with coordination of hydroxamic acid in neutral or mono deprotonated states. In NMR 1H spectra of hydroxamate complexes a singlet of NH protones is shifted upfield, which is associated with formation of cyclic metal chelates. In alkaline or near neutral media AHBA reacts as dianion to form anionic type hydroxamate complexes. In NMR 1H spectra of such complexes the singlets of NH and OH are absent. Depending on the nature of the metal, the central ion forms a square-planar [complexes of Pd(II)] or octahedral [complexes of Ru(III)] coordination unit, and it confirms the presence of d-d transition in electronic absorption spectra. The most characteristic of absorption bands in IR-spectra of the complexes are oxime group N–O of stretching vibrations that undergo low frequency offset by Dν = -(24–44) cm-1. The results obtained, as well as analysis of the published data show that increase of pH in the complexation reactions of hydroxamic acids leads to bidentate coordination of AHBA with formation of five-membered metallocycles., Синтезирован ряд гидроксаматных и гидроксиматных комплексов Ru(III), Rh(III) и Pd(II) с 4-амино-N-гидроксибензамидом (АГБА) и изучены их ИК, ЭСП и ЯМР 1Н спектральные характеристики. Установлено, что АГБА взаимодействует с ионами металлов главным образом по типу O,O’-координации, причем строение комплексов в значительной степени зависит от рН среды. В кислой и слабокислой средах АГБА образует преимущественно гидроксаматные комплексы с координацией гидроксамовой кислоты в нейтральной или монодепротонированной формах. В ЯМР 1Н спектрах гидроксаматных комплексов синглет NH протона смещается в сильное поле, что связано с образованием металлохелатных циклов.В щелочной или близкой к нейтральной средах АГБА взаимодействует как дианион, что приводит к образованию гидроксиматных комплексов анионного типа. В ЯМР 1Н спектрах таких комплексов синглеты NH и OH протонов отсутствуют. В зависимости от природы металла центральный ион формирует координационный узел в форме плоского квадрата [комплексы Pd(II)] или октаэдра [комплексы Ru(III) и Rh(III)], что подтверждает наличие d-d переходов в электронных спектрах поглощения. В ИК-спектрах комплексов наиболее характеристическими являются полосы поглощения валентных колебаний связи N–O оксимной группы, которые претерпевают низкочастотное смещение на Dν = -(24–44) см-1. Полученные результаты, а также анализ литературных данных показывают, что в реакциях комплексообразования гидроксамовых кислот с ионами переходных металлов повышение рН среды способствует бидентатной координации АГБА с образованием пятичленных металлоциклов хелатного типа.

The syntheses and spectral (IR, UV-VIS, XPS, and 1H and 13C NMR) characteristics of the rhodium(III), palladium(II), and platinum(II) complexes with 2-(2-hydroxybenzoyl)-N-methylhydrazinecarbothioamide (HBMHCTA) are described. The coordination of HBMHCTA to the central metal ion and its intraligand rearrangement in the complex formation of rhodium(III) ions are studied. The structure of the mixed-ligand complex [Pd(H2L)PPh3] is determined by X-ray diffraction analysis.

Four novel Pd2+ and Pt2+ mononuclear π-coordination compounds with general formula [M(HL)1,2Cl2], M=Pd2+, Pt2+ have been synthesized by reaction of [PdCl4]2-, [PtCl4]2- anions with N-allyl-4-morpholinethiocarboxamide (HL1) and N-Allyl-N'-tert-butylthiourea (HL2). All complexes have been characterized by single-crystal X-ray diffraction study and 1H, 13C NMR spectroscopy. Cytotoxic, cytostatic and proapoptotic activities of compounds have been determined in vitro on HeLa cell line and compared with cisplatin as etalon drug. All complex compounds possessed pronounced cytotoxic activity with IC50 indexes in range of 2·10-6-1.5·10-4М (IC50 of cisplatin is 5.7∙10-5М) and showed proapoptotic, cytostatic and antisyntetic influence higher or comparable with cisplatin. The comparative influence of cisplatin and synthesized metal complexes on pTZ19R* plasmid DNA was monitored by agarose gel electrophoresis. All compounds showed high affinity to DNA that correlates with observed cytostatic and proapoptotic levels. In general Pd(II) compounds showed higher activity than Pt(II) ones.

A series of novel zinc(II), nickel(II) and palladium(II) complexes with a thiourea derivative (N-(2-pyridinyl)morpholine-4-carbothioamide) (HL) and its oxidation product (N-(2-pyridinyl)morpholine-4-carboxamide) (HL′) have been synthesized and characterized by single crystal X-ray diffraction study, IR, UV–Vis, 1H and 13C NMR spectroscopy. It has been shown that under synthesis conditions, HL coordinates in a thiol tautomeric form leading to formation of mononuclear complexes cis-[ML2], where two ligand molecules are coordinated to metal ions via pyridinyl nitrogen and imidothiolic sulfur in a bidentate manner with the formation of six-membered chelate metallocycles. It has been found that utilizing different conditions nickel complexes are able to crystallize in two polymorphic modifications, which differ solely in the mode of intermolecular interactions. It has been shown that a mixed-ligand complex Ni(C10H13N3O2)2(C2H5SO4)2 can be obtained by reaction of Ni(NO3)2 with reaction by-products (pyridine-containing carboxamide and monoethyl sulfate) formed in selected synthesis conditions.

Novel mono- and binuclear complexes of Zn(II) with thiourea derivatives (H2L) (N-2-propenyl-N′-2-pyridinylthiourea) and thiosemicarbazide, H3L (2-[(2-hydroxyphenyl)methylene]hydrazine-N-(2-propenyl)carbothioamide, (2-[(2-hydroxyphenyl)methylene]hydrazine-N-phenylcarbothioamide) have been synthesized. The possibility of mono- or tridentate coordination to the central metal ion of these ligands both in neutral and in monodeprotonated thionic tautomeric form with the stoichiometric ratios Zn:L = 1:1 and 1:2 has been shown. The synthesized complexes Zn(CH3COO)2(H2L)2 (I), Zn2(CH3COO)2(H2L)2·Zn2(CH3COO)(H2O)(H2L)2 (II), Zn(H2L)2 (III), Zn2(CH3COO)2(H2L)2 (IV) have been studied by IR, UV–Vis, 1H, 13C NMR spectroscopy and single crystal X-ray diffraction (I, II, IV). It has been established that in compound (I) the central Zn atom forms a strongly distorted tetrahedral ZnS2O2 coordination, while in (II) and (IV) it forms a square-pyramidal ZnSNO3 environment. In the case of complex (II) the asymmetric unit contains two molecules of binuclear complex compounds, which are slightly differ by coordination in vertex direction of Zn polyhedron. The square-pyramidal geometry of Zn(II) ions from the first molecule completed by two acetate anions, which is similar to compound (IV). In the second molecule, the Zn(II) coordination polyhedrons are completed by one acetate anion and one water molecule.

New Pd(II) complexes with 1-allyl-3-(2-pyridyl)thiourea (APTU) of the formulas [Pd(C9H11N3S)Cl2] (I) and [Pd(C9H11N3S)2]Cl2 (II) were obtained and examined by UV-Vis, IR, and 1H NMR spectroscopy. The conditions for the complexation reactions were optimized. The instability constants and molar absorption coefficients of these complexes were calculated. Comparison of the characteristic bands in the UV-Vis and IR spectra of the complexes and free APTU revealed that the ligand in both complexes is coordinated to the metal atom in the thione form in the bidentate chelating mode through the S atom of the thiourea group and the pyridine N atom. In the UV-Vis spectra of the complexes, the charge transfer bands (π → π* Py) and n → π* (C=NPy), (C=S) experience hypsochromic shifts by 450–470 cm−1 caused by the coordination of APTU to the metal ion, which gives rise to ligand-metal charge-transfer bands (C=NPy → Pd, n → π* (C=S)) and (SPd). The protons in the 6-, 4-, and 3-positions of the pyridine ring and the thiourea NH proton in the chelate ring are most sensitive to the complexation.

Cyclization of 2-(2-{4-[allylamino(thioxo)methyl]piperazin-1-yl}ethyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione by the action of iodine, bromine, or sulfuryl chloride gave 2-(2-{4-[4,5-dihydro-5-(halomethyl)-thiazol-2-yl]piperazin-1-yl}ethyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione hydrohalides which were converted into 2-{2-[4-(5-methylthiazol-2-yl)piperazin-1-yl]ethyl}-1H-benzo[de]isoquinoline-1,3(2H)-dione.

The present paper describes the synthesis and spectral properties of Rh(III) and Pd(II) coordination compounds with N-(pyridine-2-yl)morpholine-4-carbothioamide (PMCTA). The compounds have the general composition [RhL2Cl2]Cl · C2H5OH (1), [PdL2]Cl2 (2), [PdL2](ClO4)2 · 2C3H6O (2a), [PdLCl2] · 2H2O (3). All complexes were characterized by elemental analysis, IR, 1H NMR, 13C NMR, XPS and UV–Vis spectra. It has been shown that PMCTA behaves as a bidentate (N,S)-ligand, forming six membered metallocycles and coordinating to the metal ion through the carbothioamide sulfur atom and the pyridine nitrogen atom. The UV–Vis spectra suggest that the Pd(II) complexes are square planar, while the Rh(III) complex has an octahedral geometry. The molecular structure of the Pd(II) complex with PMCTA (M:L = 1:2) was determined by single-crystal X-ray diffraction.

Cyclization of N-hetaryl-N′-(prop-2-en-1-yl)thioureas by the action of sulfuryl chloride leads to the formation of the corresponding 2-hetarylimino-5-chloromethylthiazolidine hydrochlorides which are converted into the free bases by treatment with aqueous sodium sulfite.

Досліджені реакції комплексоутворення N-заміщених похідних тіосечовини з PdCl2. Встановлено, що функціонально заміщені похідні тіосечовини є ефективними хелатуючими агентами, при цьому природа замісників суттєво впливає на склад і будову комплексних сполук. Так, (N-піридин-2-іл)тіосечовини при взаємодії з PdCl2 утворюють два типи комплексів у співвідношенні M:L 1:1 та 1:2, до складу яких ці реагенти входять як S,N-донорні бідентатні ліганди, координуючись до іона паладію атомом сірки тіонної групи та атомом азоту піридинового ядра. Реакція N-алілтіосечовин із PdCl2 при еквімолярному співвідношенні реагентів приводить до утворення π-комплексів, в яких координація здійснюється за участю атома сірки тіонної групи та С=С подвійного зв’язку алільного фрагмента. Розроблені препаративні методи синтезу такого типу комплексних сполук. Склад синтезованих речовин та спосіб координації лігандів встановлені методами елементного аналізу та 1H ЯМР спектроскопії. Окрім того, будова комплексів 4, 5 доведена рентгеноструктурним методом. Медико-біологічними дослідженнями встановлено, що комплексні сполуки 5 і 6 in vitro проявляють цитостатичну та цитотоксичну дію на пухлинні клітини лінії HeLa., The complexation reactions of N-substituted thiourea derivatives with PdCl2 have been investigated in the present work. The functionally substituted thiourea derivatives are found to be effective chelating agents, in which the nature of substituents has a significant impact to the compositions and structures of complexes. Thus, (N-pyridine-2-yl)thioureas in the interaction with PdCl2 form two types of complexes in the molar ratio of M:L 1:1 and 1:2, in which they act as S,N-bidentate ligands coordinated to the palladium ion by thione sulphur and the nitrogen atom of the pyridine ring. The reaction of N-allylthioureas with PdCl2 in the equimolar ratio results in formation of the π-complexes where the ligands are coordinated by the thione sulphur and the C=C double bond of the allylic moiety. The preparative methods for the synthesis of this type of complexes have been developed. The composition of the products synthesized and the ligands coordination mode have been determined by elemental analysis and 1H NMR spectroscopy. Furthermore, the structure of compounds 4, 5 has been confirmed by the X-ray diffraction study. The biomedical studies have proven that the complex compounds 5 and 6 in vitro have the cytostatic and cytotoxic activity against tumour HeLa cells., Исследованы реакции комплексообразования N-замещенных производных тиомочевины с PdCl2. Установлено, что функционально замещенные производные тиомочевины являются эффективными хелатирующими агентами, при этом природа заместителей существенно влияет на состав и строение комплексных соединений. Так, (N-пиридин-2-ил)тиомочевины при взаимодействии с PdCl2 образуют два типа комплексов в соотношении M:L 1:1 и 1:2, в состав которых эти реагенты входят как S,N-донорные бидентатные лиганды, координируясь к иону палладия атомом серы тионной группы и атомом азота пиридинового ядра. Реакция N-аллилтиомочевин с PdCl2 при эквимолярном соотношении реагентов приводит к образованию π-комплексов, в которых координация осуществляется с участием атома серы тионной группы и С=С двойной связи аллильного фрагмента. Разработаны препаративные методы синтеза этого типа комплексных соединений. Состав синтезированных веществ и способ координации лигандов установлены элементным анализом и методом 1H ЯМР спектроскопии. Кроме того, строение комплексов 4, 5 доказано рентгеноструктурным методом. Медико-биологическими исследованиями установлено, что комплексные соединения 5 и 6 in vitro оказывают цитостатическое и цитотоксическое действие на опухолевые клетки линии HeLa.

Interaction of potassium salts of quinazolin-2-thiol-4-one with γ-substituted allyl halides gave thiazoloquinazolinones with linear or angular structures depending on the structure of the carbonyl radical. S-Allyl substituted quinazolin-2-thiol-4-one reacted with halogens to give iminium salts of thiazinoquinazolinone with an angular structure. The conversion of these salts to the corresponding bases and thiazoloquinazolinones has been studied.

Cyclization of piperazine derivative (III), which contains a fragment intrinsic to antitumor drugs by the action of bromine, iodine, or sulfuryl chloride affords the corresponding hydrohalides.

Cyclization of N-hetaryl-N′-(prop-2-en-1-yl)thioureas by the action of sulfuryl chloride leads to the formation of the corresponding 2-hetarylimino-5-chloromethylthiazolidine hydrochlorides which are converted into the free bases by treatment with aqueous sodium sulfite.

Reaction of the potassium salt of 2-thioquinazolin-4-one with propargyl halides leads to formation of 2-propargylthioquinazolin-4-one derivatives, which undergo heterocyclization when they are treated with electrophilic or nucleophilic reagents and, depending on the nature of the cyclization agent, leads to formation of tricyclic systems with angular or linear structure.

Interaction of potassium salts of quinazolin-2-thiol-4-one with γ-substituted allyl halides gave thiazoloquinazolinones with linear or angular structures depending on the structure of the carbonyl radical. S-Allyl substituted quinazolin-2-thiol-4-one reacted with halogens to give iminium salts of thiazinoquinazolinone with an angular structure. The conversion of these salts to the corresponding bases and thiazoloquinazolinones has been studied.