Nitroso Compounds by Reaction of Organomercurials with Nitrosyl Chloride

By the reaction of RHgX (X = Cl, Br, OAc) with NOC1, mercury is eliminated as CIHgX and, if R is aromatic, nitroso compounds are obtained, i.e., nitrosobenzene, 1-nitrosonaphthalene, 4-nitroso-lV^V- dimethylaniline, 2-nitrosophenol, 4-nitrosophenol and methyl 3-ni- trososalicylate. If R is aliphatic or alicyclic, with RHgX to NOC1 1 : 3, gem-chloronitroso compounds are obtained that have not been described previously, i.e., 2-chloro-2-nitrosocyclohexanol, l-acetoxy-2- chloro-2-nitrosocyclohexane, l-chloro-2-methoxy-l-nitrosocyclopentane, methyl 2-chloro-2-nitroso-3-methoxypropionate, 1-chloro-l-nitroso- ethane and 2-chloro-2-nitrosoethanol. All products have been characterized by chemical and IR spectral analysis

Intramolecular Cyclization Reactions in Haloalkyl-Cobalt Complexes with Macrocyclic Equatorial Ligands

Organocobalt complexes containing axial haloalkyl groups afford metallacycles of different size by N or O alkylation of the macrocyclic equatorial ligands. The reaction mechanism involves the intra-molecular nucleophilic attack of a negatively charged atom of the equatorial ligand on the axial XCH2 haloalkyl group with simultaneous detachment of a halide ion, X−. In imino/oxime and amino/oxime derivatives, the generation of the negatively charged nitrogen requires the abstraction of a proton and the reaction occurs only in alkaline medium. In bis(dimethylglioximato) and Schiff base complexes, a negatively charged oxygen is present in the equatorial ligand and the reaction occurs even in neutral medium. Three-, six- and seven- membered metallacycles are obtained, with the common feature that the Co–C bond is shorter and more resistant toward homolysis than in parent complexes or in closely related derivatives. Keywords

Synthesis of Two Molybdenum(VI) Complexes Coordinated by Schiff Base Derivatives: N-Phenyl-2-hidroxy-1-naphthaldimine and N-Benzyl-2-hidroxy-1-naphthaldimine. Molecular and Crystal Structure of [MoO2(C5H7O2)(OCH3)(2-OC10H6CH=NHC6H5)]

The synthesis of two monomeric molybdenum(VI) Schiff base complexes derived from N-phenyl-2-hidroxy-1-naphthaldimine and N-benzyl-2-hidroxy-1-naphthaldimine: [MoO2(C5H7O2)(OCH3)(2-OC10H6CH=NHC6H5)] (I) and [MoO2(C5H7O2)(OCH3)(2-OC10H6CH=NHCH2C6H5)] (II) described in this paper are the first examples in which potentially bidentate Schiff bases are monodentately bonded to molybdenum as zwitterionic ligands. The structure of complex I was determined by X-ray analysis. Within the same ligand, the hydrogen atom attached to nitrogen forms an intramolecular hydrogen bond of 2.548(2) Å with the oxygen atom coordinated to molybdenum. The octahedral coordination of molybdenum is completed by two oxo-oxygens, two acetylacetonato oxygens and one methoxy oxygen. The compounds were characterized by chemical analysis, IR spectroscopy and single crystal structure determination

Synthesis and Characterizationof New Molybdenum(VI) Oxalate Complexes. CrystalStructure of Tetramethylammonium Salt of μ-Oxo-diaquadioxalatotetraoxodimolybdenum(VI)

In the reaction of molybdenum(VI) oxide with oxalic acid and RCl(R = pyH and -picH), new dinuclear complexes of molybdenum(VI)R2 Mo2O5(C2O4)2(H2O)2 have been prepared. When molybdenum(VI)oxide was treated with aqueous solution of tetramethylammoniumoxalate complex, (CH3)4N 2 MoO3(C2O4) H2O was isolated. Theunknown crystal structure of (CH3)4N 2 Mo2O5(C2O4)2(H2O)2 wasdetermined from single crystal diffractometer data and refined to thefinal R value of 0.0317. When irradiated, this class of compoundsshows considerable photochromic properties. The photochemicalprocess is of the redox type: molybdenum(VI) centers are reduced tomolybdenum(V) moieties. The presence of molybdenum(V) specieswas confirmed by the ESR spectra

Intramolecular Cyclization Reactions in Haloalkyl-Cobalt Complexes with Macrocyclic Equatorial Ligands

Organocobalt complexes containing axial haloalkyl groups afford metallacycles of different size by N or O alkylation of the macrocyclic equatorial ligands. The reaction mechanism involves the intra-molecular nucleophilic attack of a negatively charged atom of the equatorial ligand on the axial XCH2 haloalkyl group with simultaneous detachment of a halide ion, X−. In imino/oxime and amino/oxime derivatives, the generation of the negatively charged nitrogen requires the abstraction of a proton and the reaction occurs only in alkaline medium. In bis(dimethylglioximato) and Schiff base complexes, a negatively charged oxygen is present in the equatorial ligand and the reaction occurs even in neutral medium. Three-, six- and seven- membered metallacycles are obtained, with the common feature that the Co–C bond is shorter and more resistant toward homolysis than in parent complexes or in closely related derivatives. Keywords

Synthesis and Structure of Two Isomeric Enaminones

The reaction of ethyl 2-hydroxy-4-(4-hydroxy-6-methyl-2H-pyran-2-on-3-yl)-4-oxo-2-butenoate (1) and 1-naphthylamine in ethanol affords two isomeric enaminones: ethyl 4-hydroxy-3-[3-(1-naphthyl-amino)-2-butenoyl]-2H-pyran-2-on-6-carboxylate (2) and ethyl 4-(4-hydroxy-6-methyl-2H-pyran-2-on-3-yl)-2-(1-naphthylamino)-4-oxo-2-butenoate (3). The structures of both compounds were determined by the single crystal X-ray diffraction. Tautomerism may be involved in two parts of a molecule, in the cyclic part (pyrone ring) and in the side chain, to give a variety of possible tautomeric forms. Attention has been turned to the endo-enol enamine and exo-enol enamine tautomeric equilibrium, since both tautomers were found in the crystals of compounds with similar structures. The NMR spectroscopic data and X-ray structural analysis confirmed that both compounds exist in the endo-enol enamine form in the solution and in the crystalline state. The molecules are characterized by strong, intramolecular hydrogen bonds of N−H⋅⋅⋅0 and O−H⋅⋅⋅O type reinforced by π-delocalization. The molecules as a whole are not planar, exhibiting planarity only in the Central heteroconjugated moiety, while naphthyl rings are almost perpendicular to the Central part

CLINICAL RECOMMENDATIONS FOR DIAGNOSING, TREATMENT AND MONITORING OF PATIENTS WITH UTERINE CERVICAL CANCER – CROATIAN ONCOLOGY SOCIETY AND CROATIAN SOCIETY FOR GYNECOLOGY AND OBSTETRICS AS CROATIAN MEDICAL ASSOCIATION UNITS AND CROATIAN SOCIETY OF GYNECOLOGICAL ONCOLOGY

Rak vrata maternice, u odnosu na malignome drugih ginekoloških sijela, jest bolest mlađih žena koja se može redovitim kontrolama i zdravstvenim odgojem prevenirati, a u slučaju pojave bolesti učinkovito liječiti. Metode liječenja uključuju kirurgiju, radioterapiju i kemoterapiju, ovisno o stadiju bolesti i općem stanju bolesnica. Odluku o liječenju donosi multidisciplinarni tim. S obzirom na važnost ove bolesti, potrebno je definirati i provoditi standardizirani pristup u dijagnostici, liječenju i praćenju ovih bolesnica. U tekstu koji slijedi iznesene su kliničke smjernice s ciljem implementacije standardiziranih postupaka u radu s bolesnicama s rakom vrata maternice u Republici Hrvatskoj.Cervical cancer, in comparison with other gynecological malignancies, mainly affects younger women. It can be prevented trough educational programs, screening and early detection. It also can be efficiently treated when it appears. Treatment modalities include surgery, chemotherapy and radiotherapy, according to the stage of the disease and patient condition. Treatment decisions should be made after multidisciplinary team discussion. Due to the significance of this disease it is important to define and implement standardized approach for diagnostic, treatment and monitoring algorithm as well. The following text presents the clinical guidelines in order to standardize the procedures and criteria for the diagnosis, management, treatment and monitoring of patients with uterine cervical cancer in the Republic of Croatia

CLINICAL RECOMMENDATIONS FOR DIAGNOSING, TREATMENT AND MONITORING OF PATIENTS WITH OVARIAN CANCER – CROATIAN ONCOLOGY SOCIETY AND CROATIAN SOCIETY FOR GYNECOLOGY AND OBSTETRICS AS CROATIAN MEDICAL ASSOCIATION UNITS AND CROATIAN SOCIETY OF GYNECOLOGICAL ONCOLOGY

Rak jajnika i jajovoda po učestalosti je peta zloćudna bolest žena u Hrvatskoj. Histološki je rak jajnika najčešće epitelnog podrijetla, i to seroznog podtipa. Rjeđi su različiti neepitelni malignomi jajnika, a posebnu skupinu čine epitelni karcinomi niskoga zloćudnog potencijala karakterizirani neinvazivnošću, klinički indolentnim tijekom i dobrom prognozom te primarni rak potrbušnice i rak jajovoda. Klinički su ovi zloćudni tumori u ranim stadijima razvoja uglavnom asimptomatski, zbog čega se najčešće dijagnosticiraju u kasnijim stadijima bolesti. Dijagnoza se potvrđuje patohistološkim nalazom, a iznimno citološkim nalazom nakon provedene dijagnostičke obrade. O liječenju odlučuje multidisciplinarni tim uzimajući u obzir dob, opće stanje i komorbiditete bolesnice, kao i obilježja samog tumora uključujući stadij bolesti, histološki tip i gradus tumora. Principi liječenja primarnog raka potrbušnice i jajovoda temelje se na principima liječenja epitelnog raka jajnika koji obuhvaćaju primjenu kirurških zahvata, kemoterapije, imunoterapije i hormonske terapije, kao i suportivno-simptomatskih mjera tijekom cijelog liječenja. Razlikuje se terapijski pristup rjeđim, neepitelnim histološkim tipovima tumora koji se češće dijagnosticiraju u ranim stadijima bolesti, imaju indolentniji tijek pa se kod ovih bolesnica češće primjenjuju poštedni kirurški zahvati s ciljem očuvanja plodnosti. U tekstu koji slijedi predstavljene su kliničke upute s ciljem standardizacije postupaka i kriterija postavljanja dijagnoze, liječenja te praćenja bolesnica s rakom jajnika, jajovoda i potrbušnice u Republici Hrvatskoj.Ovarian cancer together with fallopian tube represents the fifth most common female cancer in the Republic of Croatia. Epithelial ovarian cancer, serous subtype, encompasses most of malignant ovarian neoplasms. Less common are various non-epithelial ovarian malignancies. A special group consists of epithelial carcinomas of low malignant potential with clinically indolent flow, good prognosis and no invasion, and primary cancer of the peritoneum and fallopian tube cancer. Clinically, these malignant tumors are generally asymptomatic in early stages, and usually diagnosed in advanced stages. The diagnosis is confirmed by pathological examination, and occasionally, cytological findings after completing diagnostic procedures. Multidisciplinary team makes treatment decisions, taking into account age, general condition and comorbidities of the patient and characteristics of the tumor itself, including disease stage, histological type and grade of the tumor. The principles of treatment of primary peritoneal and fallopian tube cancer are based on the principles of treatment of epithelial ovarian cancer involving surgery, chemotherapy, immune and hormone therapy, and symptomatic-supportive care throughout the treatment. Less common histological types have a different treatment approach being more frequently diagnosed in the early stages of the disease, have more indolent flow, so in these patients conservative surgeries with the goal of preserving fertility are more often employed. The following text presents the clinical guidelines in order to standardize the procedures and criteria for the diagnosis, management, treatment and monitoring of patients with ovarian carcinoma, fallopian tube and primary peritoneal cancer in the Republic of Croatia