Biologically active platinum complexes containing 8-thiotheophylline and 8-(methylthio)theophylline

Complexes [Pt(mu-N,S-8-TT)(PPh(3))(2)](2) (1), [Pt(mu-S,N-8-TT)(PTA)(2)](2) (2), [Pt(8-TTH)(terpy)]BF(4) (3), cis-[PtCl(8-MTT)(PPh(3))(2)] (4), cis-[Pt(8-MTT)(2)(PPh(3))(2)] (5), cis-[Pt(8-MTT)(8-TTH)(PPh(3))(2)] (6), cis-[PtCl(8-MTT)(PTA)(2)] (7), cis-[Pt(8-MTT)(2)(PTA)(2)] (8), and trans-[Pt(8-MTT)(2)(py)(2)] (9) (8-TTH(2) = 8-thiotheophylline; 8-MTTH = 8-(methylthio)theophylline; PTA = 1,3,5-triaza-7-phosphaadamantane) are presented and studied by IR and multinuclear ((1)H, (31)P[(1)H]) NMR spectroscopy. The solid-state structure of 4 and 9 has been authenticated by X-ray crystallography. Growth inhibition of the cancer cells T2 and SKOV3 induced by the above new thiopurine platinum complexes has been investigated. The activity shown by complexes 4 and 9 was comparable with cisplatin on T2. Remarkably, 4 and 9 displayed also a valuable activity on cisplatin-resistant SKOV3 cancer cells.     

4-Phosphoranylidene-5(4H)-oxazolones II. Reactions with alkylating agents

Summary When treated with alkyl halides at 20–90°C without solvent or in acetonitrile, 4-phosphoranylidene-5(4H)-oxazolones (1) give 4-C-alkylation products4 in good yields. Alkylation of1 with alkyl triflates in CH₂Cl₂ at room temperature results in O-alkylation products5. No O-to 4-C-alkylation rearrangement can be observed. The spectroscopic properties of the alkylation products are reported and discussed.

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4-Phosphoranyliden-5(4H)-oxazolone, 2. Mitt. Reaktionen mit Alkylierungsreagentien

Zusammenfassung Behandlung von 4-Phosphoranyliden-5(4H)-oxazolonen (1) mit Alkylhalogeniden bei 20–90°C ohne Lösungsmittel oder in Acetonitril liefert in guten Ausbeuten die 4-C-alkylierten Produkte4. Alkylierung von1 mit Alkyltriflaten in CH₂Cl₂ bei Raumtemperatur ergibt O-alkylierte Produkte (5). E6 wurde keine Umlagerung von O-alkylierten zu C-alkylierten Verbindungen beobachtet. Die spektroskopischen Eigenschaften der Alkylierungsprodukte werden berichtet und diskutiert.

     

Reactions of palladium (II) chloride with 1,4 - diphenyl - 2,3 - dimethyl - 1,4 - diazabutadiene and 1,4-DI(p-methoxyphenyl)-2,3-dimethyl- 1,4 - diazabutadiene

The reactions of palladium(II) chloride with 1,4 - diphenyl - 2,3 - dimethyl - 1,4 - diazabutadiene and 1,4 - di(p - methoxyphenyl) - 2,3 - dimethyl - 1,4 - diazabutadiene are described. With 1,4 - diphenyl - 2,3 - dimethyl - 1,4 - diazabutadiene diimine fission is produced, giving rise to a product identified by elemental analysis, IR and Raman spectra, and X-ray diffraction, as trans-dichlorobis(aniline) palladium(II). The complex is soluble in dimethylformamide and crystallizes with two molecules of solvent. The substance crystallizes in the monoclinic space group P2₁/n. The X-ray data were refined to R = 0.047 and R_w = 0.046. Final distances are PdN = 2.060(5)Åand PdC1 = 2.299(2)Å. There are two bifurcated intermolecular NH ... C1 and CH... C1 hydrogen bonds which, together with one more intermolecular hydrogen bond NH... O, are responsible for the packing of the molecules. However, when 1,4 - di(p - methoxyphenyl) - 2,3 - dimethyl - 1,4 - diazabutadiene was treated with palladium chloride under the same conditions cis - dichloro - 1,4 - di(p - methoxyphenyl) - 2,3 - dimethyl - 1,4 - diazabutadiene was formed, as deduced from elemental analysis, and IR and Raman spectra.     

Reactions of π-benzeneruthenium(II) complexes with alkylating reagents

The compounds (π-C₆H₆)Ru(R)Cl(PPh₃) (RCH₃, C₆H₅), (π-C₆H₆)RuCl(π-C₃H₅) and [(π-C₆H₆)Ru(π-C₅H₅)]Cl are described. The ³¹P NMR spectra of a series of tertiary phosphine complexes of the π-benzeneruthenium system are also reported.     

Synthesis of 3-(6-alkylaminopurin-9-yl)-2,3-dideoxy-D-thero-pentopyranoses and their reduction to 3-(6-alkylaminopurin-9-yl)-2,3-dideoxy-D-thero-pentitols

3-(6-Alkylaminopurin-9-yl)-2,3-dideoxy-D-threo-pentopyranoses 3 were prepared by condensation of unprotected 2-deoxy-D-ribose (2) with N⁶-alkyladenines 1 in a phosphorus pentoxide reagent mixture. Reduction of the pentoses 3 gave the corresponding 3-(6-alkylaminopurin-9-yl)-2,3-dideoxy-D-threo-pentitols 4. The structures of 3 and 4 were determined by ¹³C nmr, ¹H nmr and 2D ¹H nmr (COSY).     

Reactions of 4-nitro-1,2,3-triazole with alkylating agents and compounds with activated multiple bonds

When 4-nitro-1,2,3-triazole is alkylated, a mixture of N₁- and N₂-isomers is formed, with the latter usually predominating. The same behavior is also observed in addition reactions of 4-nitrotriazole to activated multiple bonds.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 932–935, July, 1986.     

Reactions of (2,3-dimethylenetetramethylene)bis(dipropylborane) with carbonyl compounds

(2,3-Dimethylenetetramethylene)bis(dipropylborane) (1) prepared by borylation of 2,3-dimethylbutadienediyl dipotassium reacts with ketones to form symmetrical diols in a yield of 46–73%. [4+2]-Cycloaddition reactions of diborane1 with 1,2-dicarbonyl compounds proceed highly stereospecifically, affording onlycis-isomers of 4,5-dimethylenecyclohexane1, 2-diols.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 155–159, January, 1993.     

Synthesis of 6-Amino-5-R2-7-(6-R1-4-oxo-3,4-dihydro-2-quinazolyl)-5H-pyrrolo[2,3-b]pyrazine-2,3-dicarbonitriles

It has been found that malonodinitrile and 2-(6-R¹-oxo-3,4-dihydro-2-quinazolyl)acetonitrile in the presence of triethylamine undergo hetarylation by 5,6-dichloro-2,3-pyrazinedicarbonitrile at the active methylene group to give the triethylammonium salt of 2-(3-chloro-5,6-dicyano-2-pyrazinyl)malononitrile or 5-chloro-6-cyano(6-R¹-4-oxo-1,2,3,4-tetrahydro-2-quinazolylidene)methyl-2,3-pyrazinedicarbonitriles. Reaction of these with primary amines leads to annelation of the pyrrole ring at the pyrazine [b] edge to give 6-amino-5-R-5H-pyrrolo[2,3-b]pyrazine-2,3,7-tricarbonitriles and 6-amino-5-R²-7-(6-R¹-4-oxo-3,4-dihydro-2-quinazolyl)-5H-pyrrolo[2,3-b]pyrazine-2,3-dicarbonitriles respectively.     

Some Reactions with 3-(2-Chloro-7-Methylquinolinyl) Chalcone Derivatives

The preparation of some new 3-quinolinylchalcone derivatives was described. Their reaction with hydrazines, hydroxylamine hydrochloride, malononitrile and ethyl cyanoacetate gave the corresponding pyrazoline, isoxazoline, cyanopyridine and cyanopyridone derivatives, respectively. The biological activity of some of the products was evaluated.     

Reactions of mercapto amino acids Communication 7. Reactions of N-acyl-2,3-dihaloalanines, (acyloxy)pyruvic acids

Russian Chemical Bulletin -     

Reactions of 6-(Dimethylamino)fulvene with diazoazoles and arene- and azolediazonium salts

6-(Dimethylamino)fulvene reacted with 3- and 4-substituted 5-diazoazoles, as well as with 4-substituted benzene- and pyrazole-5-diazonium salts, in an aprotic solvent with high regioselectivity at an extremely high rate to give acyclic coupling products at the α-carbon atom of the cyclopenta-1,3-diene fragment. The nature of the diazo component did not affect the reaction direction, rate, or yield. Hydrolysis of the azo compounds obtained from arenediazonium salts involved elimination of the dimethylamino group with formation of aldehydes, and their reaction with pyrrolidine resulted in replacement of the dimethylamino group by pyrrolidine ring.