Synthesis of some new pyrimidine selanyl derivatives

The targeted synthesis of 2-(methylsulfanyl)-6-(furan-2-yl)-4(3H)-selenoxo -pyrimidine-5-carbonitrile failed due to the formation 1-methyl-2-methylsulfanyl-6-oxo -4-(furan-2-yl)-1,6-dihydropyrimidine-5-carbonitrile. A new series of 5,6,7,8-tetrahydro-1-benzo thieno[2,3-d]pyrimidine-4-yl substituted selanyl derivatives were prepared by the reaction of sodium diselenide with 4-chloro-5,6,7,8-tetrahydro-1-benzothieno[2,3-d]pyrimidine followed by the reaction with chloroacetic acid derivatives such as ethyl chloroacetate, chloroacetamide or chloroacetonitrile. Hydrazinolysis of ethyl (5,6,7,8-tetrahydro-1-benzothieno[2,3-d]pyrimidine- 4-ylselanyl)acetate with hydrazine hydrate gave the corresponding hydrazino derivative. The latter reacted with ethyl acetoacetate, acetylacetone, diethyl malonate, ethoxymethylenemalononitrile or ethyl 2-cyano-3-ethoxyacetate to afford 5-methyl-2-[2-(5,6,7,8-tetrahydro-1-benzothieno [2,3-d]pyrimidine-4-ylselanyl)acetyl]-2,4-dihydropyrazol-3-one, 1-(3,5-dimethylpyrazol-1-yl)-2- (5,6,7,8-tetrahydro-1-benzothieno[2,3-d]pyrimidin-4-ylselanyl)ethanone, 1-[2-(5,6,7,8-tetrahydro -1-benzothieno[2,3-d]pyrimidine-4-ylselanyl)acetyl]-2,4-dihydropyrazolidine-3,5-dione and 5-Amino-1-[2-(5,6,7,8-tetrahydro-1-benzothieno[2,3-d]pyrimidin-4-ylselanyl)acetyl]-1H-pyrazol -4-yl substituted carbonitrile or ethyl carboxylate, respectively. The structure of the novel compounds was confirmed by spectroscopic tools (IR, ¹H NMR ¹³C NMR and mass spectra) and elemental analysis.     

Synthesis of some ethyleneimine derivatives of pyrimidine

It has been shown that 2, 6-dichloto-4-methylpyrimidine reacts with ethyleneimine in benzene solution in the presence of triethylamine or in an aqueous alkaline medium with the formation of 6-chloro-2-ethyleneimino-4-methylpyrimidine. The condensation of 2, 6-di-chloro-4-methyl-5-nitropyrimidine with an excess of ethyleneimine and in benzene solution in the presence of triethylamine has given 2, 6-diethyleneimino-4-methyl-5-nitropyrimidine.     

Structure and dynamics of some macrocyclic pyrimidine derivatives

The conformation of macrocycles consisting of the uracil and two thiopyrimidine moieties linked by polymethylene spacers depends on the spacer length, intramolecular hydrogen bonds, and the solvent nature. In CDCl₃ the intramolecular hydrogen bond (NH) appreciably stabilizes the “skew” conformation but only for the macrocycles with methylene spacers consisting of five carbon atoms. Protonation leads to the cleavage of intramolecular hydrogen bonds, destabilization of the “skew” conformation, and self-association due to the strong intermolecular hydrogen bond involving the acid counterion, and the intermolecular bond is cleaved in a polar solvent.     

The synthesis of oxides of sulfolene and some of its methyl derivatives

The synthesis of the oxides of 3-sulfolene, 2-methyl-3-sulfolene, and 3-methyl-3-sulfolene by the reaction of the corresponding 3-sulfolenes with peracetic acid has been described.     

Protonation of 4-hydroxypyrazolo[3,4-d]pyrimidine and its methyl derivatives

The ability of 4-hydroxypyrazolo[3,4-d]pyrimidine and its methyl derivatives to form mono- and dications was shown by UV and PMR spectroscopy; an assumption regarding the structures is expressed on the basis of the data obtained.     

Efficient access to some new pyrimidine derivatives and their antimicrobial evaluation

1-[4-(3-Hydroxyphenyl)-6-methyl-2-thioxo-1,2,3,4-tetrahydropyrimidin-5-yl]ethanone ( 1 ) was used as a precursor for heterocyclic synthesis. Condensation of compound 1 with monochloroacetic acid and benzaldehyde gave thiazolopyrimidine 2 which in turn underwent cyclization with malononitrile dimmer to afford malononitrile derivative 3 . Also, the reaction of compound 1 with benzaldehyde under a basic condition produced chalcone 4 . Chalcone 4 can be used as a key intermediate for further preparation of heterocyclic compounds. In addition, compound 1 was allowed to react with malononitrile dimmer and/or ethyl chloroacetate to give pyrimidines 8 and 9 , respectively. Alkylation of compound 8 with ethyl chloroacetate afforded S-alkylated product 10 which was treated with hydrazine hydrate to yield the hydrazino derivative 11 . Alternative synthesis of compound 10 was taken place through reaction of compound 9 with malononitrile dimmer. The biological activity of the synthesized compounds was investigated. Compounds 1 , 4 , 5 , and 8 recorded high activities against Gram positive bacteria (S. aureus). Structures of the new synthesized compounds were elucidated by elemental analysis and spectral data.     

The microdetermination of certain pyrimidine derivatives

N-Bromosuccinimide has been used in a new titrimetric method for the microdetermination of uracil, thymine, and sulfadiazine. The reaction between these compounds and N-bromosuccinimide in dilute aqueous solutions is discussed. The determination is carried out within the limits of 10 mg to 100 μg where the experimental error did not exceed ±2%.     

Synthesis and properties of some pyrimido[5,4-d]pyrimidine derivatives

A method for the preparation of 2,4,8-trioxo-6-methyl derivatives of pyrimido[5,4-d]pyrimidine with various alkyl residues in the 7 position is described. It is shown that the chlorine in the 4 position of the 2,4-dichloro derivative of pyrimido[5,4-d]pyrimidine is the most labile in nucleophilic substitution reactions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 517–520, April, 1977.     

Synthesis and structure of some thienopyrimidine derivatives

A series of substituted thieno[2,3-d]pyrimidines was synthesized starting from ethyl-2-amino-4-isopropylthiophene-3-carboxlate. Reaction of 2-hydrazino-5-isopropyl-thieno[2,3-d]pyrimidin-4(3H)-one and its 3-methyl analogue with different reagents afforded thieno[2,3-d]triazolo[4,3-a]pyrimidines and thieno[3,2-e]triazolo[4,3-a]pyrimidines, beside open chain derivatives. Correspondence: Atef A. Hamed, Department of Chemistry, Faculty of Science, Menoufia University, Shebin El Koam, Egypt.     

Effect of some pyrimidine thiol derivatives on the vulcanization of various elastomers

Some pyrimidine thiol derivatives were synthesized and tested in rubber formulations. They were incorporated in natural rubber, styrene butadiene rubber and polychloroprene mixes. It was found that their influence on the vulcanization reaction increases as the inductive effect of substituents attached to the nitrogen atom increases. The activity of investigated compounds falls in the same order according to their chemical structure for the different types of rubber.     

Synthesis of some new pyrimidine derivatives and evaluation of their anticancer and antibacterial activities

Starting from the reaction of ethyl cyanoacetate with thiourea and the appropriate aldehydes, a series of new pyrimidine derivatives were prepared. Ten selected pyrimidine derivatives were subjected to a screening system for the investigation of their antitumor potency against liver (HEPG2) cell line. The antitumor activity results indicated that most of the selected pyrimidine derivatives showed moderate growth inhibition activity against the tested cell line, but with varying intensities in comparison to the known anticancer drugs: 5-fluorouracil and doxorubicin. Some of the synthesized compounds were also tested for their antimicrobial activity against bacteria as well as fungal isolates.     

Mass-spectrometric investigation of some 2,6-dimethyloxazolo[4,5-d]pyrimidine derivatives

The fragmentation of the molecular ions of 4-chloro- and 4-alkylamino -2,6-dimethyloxazolo[4,5-d]pyrimidines involves splitting out or fragmentation of the substituent in the 4 position or cleavage of the oxazole ring. The compositions of the fragment ions were determined on the basis of the high-resolution mass spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1255–1258, September, 1982.     

Methylation of pyrimidine derivatives

A mixture of isomers that differ with respect to the position of the methyl group is formed in the methylation of 5,5-diethyl-6-imino-5,6-dihydro[1H, 3H]pyrimidine-2,4-dione with excess methyl iodide in the presence of ethoxide. Isomerization of the Dimroth-rearrangement type was observed. The mass spectra of the isomers are examined, and the IR spectra of the tautomeric forms are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 823–826, June, 1978.     

Simple synthesis of some pentafluoropropenyl derivatives of pyrimidine and purine based on addition-elimination reaction

Various pentafluoropropenyl derivatives of pyrimidine and purine bases have been obtained in good to high yield. The procedure involves the reaction of appropriate lithium derivatives prepared from both electron-rich and electron-poor pyrimidines, with the hexafluoropropene at a low temperature, via an addition-elimination process. Organolithiums of pyrimidine and purine bases give addition-elimination products as E/Z mixtures, whereas the products of the reaction of lithium amide of protected inosine with hexafluoropropene contain traces of an addition product as well as the stable perfluoroenamine. The methodology proposed allows a series of perfluorovinyl nucleobases to be obtained quickly and conveniently.     

Dynamics and structure of some tricarbonylferrole-iron tricarbonyl derivatives

A series of compounds of the formula Fe₂(CO)_6-x(PR₃)_x(R′C₂R″)₂ (x = 0, R′ and R″ = Ph, R′ and R″ = H, R′ = Ph and R″ = H; x = 1, K = Ph or n-Bu, and R′ and R″ = Ph) were studied by ¹³C NMR to observe their solution properties. The tricarbonylferrole unit was found to be static from ?125 to +95° C, while the π-Fe(CO)₃ group appeared to be fluxional over the same temperature range. Definite assignments of the carbonyl carbon and ferrole ring carbon resonances have been made. A low temperature single crystal X-ray study of Fe₂(CO)₅PPh₃(PhC₂Ph)₂ demonstrated that the phosphine ligand was attached to the ferrole iron contrary to previous belief based on chemical evidence.     

The mass spectra of some benzyl esters and thioethers

The electron impact mass spectra of a large number of benzyl esters of carboxylic acids are reported. The fragmentation behaviour is discussed and the esters are divided into groups according to structure and fragmentation. For most esters benzylic cleavage with H transfer competes with simple cleavage.     

Stationary nutations and CIDEP of benzyl radicals during photolysis of methyl benzyl ketone

Transient benzyl radicals are generated by photolysis of methyl benzyl ketone in toluene solution. Modulation of the rate of radical initiation at 86 kHz causes stationary nutations of the magnetization. They are detected by ESR spectroscopy and used to evaluate the relaxation times as well as the chemically induced dynamic electron polarization of the spin system.     

IR spectra of pyrimidine carboxylic acids and some problems involving their structure

The IR spectra of solid pyrimidinecarboxylic acids and of solutions of them in dioxane and chloroform were obtained. It is demonstrated that the frequencies of the stretching vibrations of the carboxyl C=O groups of acids that are not capable of tautomerism correlate linearly with their acidity constants.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 833–835, June, 1972.     

Synthesis,characterization, antioxidant properties and DFT calculation of some new pyrimidine derivatives

Abstract

In this study, 5-benzoyl-4-(4-(methylthio)phenyl)-6-phenyl-1,2,3,4-tetrahydro-2-thioxo (1), oxo (2) and imino (3) pyrimidine derivatives were prepared via Multicomponent Cyclocondensation Reactions (MCRs). The compounds thiazolo[3,2-a]pyrimidin-3(5H)-one (4) and thiazin-4(6H)-one (5) were obtained via the reaction of compound 1 with bromoacetic acid and 3-bromopropionic acid, respectively. Structures were determined by using FT-IR, ¹H/¹³C NMR and elemental analyses. Also the compounds 4 and 5 were analyzed by X-ray single crystal analysis. All compounds were investigated as corrosion inhibitors using density functional theory (DFT) at the level of B3LYP/6-31G (d, p). According to the calculations, the compound 3 appears to be a good inhibitor for corrosion. On the other hand, total antioxidant properties were measured in vitro by DPPH^?, ABTS^?+ test, hemolysis of phenylhydrazine erythrocytes and metal chelating effect. The results were compared with standard antioxidants such as trolox and α-tocopherol. These data revealed that compounds 1, 2 and 5 are more active with respect to 3 and 4 in scavenging the radicals.