Homolytic Addition Reaction of Vinylsulfonylfluorobenzene

The reaction of 3,6-bis(vinylsulfonyl)-1,2,4,5-tetrafluorobenzene with a large excess of tetrahydrofuran at 50-55°C gives the homolytic addition product 3,6-bis[2-(2-tetrahydrofuryl)ethylsulfonyl]-1,2,4,5-tetrafluorobenzene. The reaction is effected by peroxides radical process initiators obtained by the autooxidation of tetrahydrofuran.     

Radical Reactions of 1,4-Bis(vinylsulfonyl)tetrafluorobenzene with Tetrahydrofuran

Homolytic addition of tetrahydrofuran at the vinylsulfonyl groups of 1,4-bis(vinylsulfonyl)tetrafluorobenzene in the absence of radical initiator at 20 and 55°C leads to formation of 1,4-bis[2-(2-tetrahydrofuryl)ethylsulfonyl]tetrafluorobenzene in 16 and 42% yield, respectively, and a mixture of telomers. The latter are formed as a result of opening of the tetrahydrofuran ring in the adduct.     

Behavior of 3,6-Bis(vinylsulfonyl)-1,2,4,5-tetrafluorobenzene in Homolytic Addition of Dialkyl Phosphites

Reaction of 3,6-bis(vinylsulfonyl)-1,2,4,5-tetrafluorobenzene with dialkyl phosphites at thermal initiation (70°C) gives rise to 3,6-bis(dialkoxyphosphonoethylsulfonyl)-1,2,4,5-tetrafluorobenzenes in up to 45% yield. The formation of diethoxyphosphonyl radicals in the course of the reaction was observed with the use of ESR method applying spin trapping by 2-methyl-2-nitrosopropane. The use as initiator of the azo-bis-isobutyronitrile increased the yield of diadducts to 60%.     

Reactions of 1,2,4,5-Tetrafluoro-3,6-bis(vinylsulfonyl)benzene with Cyclic Amines

Reactions of 1,2,4,5-tetrafluoro-3,6-bis(vinylsulfonyl)benzene with pyrrolidine, piperidine, and morpholine lead to formation of different products, depending mainly on the reactant ratio. In the presence of 2 equiv of cyclic amine, adducts at both vinylsulfonyl groups are formed, while in reactions with 4 equiv of cyclic amine, the addition at the double bonds is accompanied by nucleophilic replacement of one or two fluorine atoms in the benzene ring.     

New heterocyclic system based on vinylsulfonylfluorobenzene and X-ray structural study of this compound

Oxidation of 1,2,4,5-tetrafluoro-3,6-bus (vinylthio)benzene (1) affords 1,2,4,5-tetra fluoro3,6-bis(vinylsulfonyl)benzene (2) in 65 % yield. The reaction of compound 2 with allylamine gives a new heterocyclic compound, 5,6-difluorobenzo-[a,d]-bis(3,3-dihydro-l,l-sulfonylallyl-4,4-perhydroazine) (3). This compound is the product of nucleophilic addition at the vinylsulfonyl group and intramolecular replacement of fluorine atoms of the benzene ring. The structure of compound 3 has been established by X-ray structural study.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 430–433, February, 1996.     

Heteroatomic derivatives of aziridine. 14. Reactions of 1-(carbomethoxyethyl)-, 1-[1,2-bis(carbethoxy)ethyl]-, and 1-[1,2-bis(carbomethoxy)vinyl]aziridine with thiols, 1,2-ethanedithiol,and thiolcarboxylic acids

The reactions of 1-(carbomethoxyethyl)-, 1-[1,2-bis(carbethoxy)-ethyl]-, and 1-[1,2-bis(carbomethoxy)vinyl]aziridine with thiols and thiolcarboxylic acids produce the corresponding sulfides and esters of S-substituted N-(2-mercaptoethyl) amino acids. The reaction of 1-[1,2-bis(carbethoxy)ethyl]aziridine with 1,2-ethane-dithiol results in the formation of {1,8-bis[1,2-bis(carbethoxy)-ethyl]amino}-3,6-dithiaoctane. Cyclization of the latter by condensation with phthaloyl chloride gives 9,10-benzo-8,11-dioxo-1,4-dithia-7,12-bis[1,2-bis(carbethoxy)ethyl]-7,12-diazacyclotetradec-9-ene.For report 13 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1340–1342, October, 1984.     

Synthesis and inverse electron demand Diels-Alder reactions of 3,6-bis(3,4-dimethoxybenzoyl)-1,2,4,5-tetrazine

The synthesis of 3,6-bis(3,4-dimethoxybenzoyl)-1,2,4,5-tetrazine (2) and the scope of its reactivity in inverse electron demand Diels-Alder reactions are disclosed representing the first systematic study of the [4 + 2] cycloaddition reactions of 3,6-diacyl-1,2,4,5-tetrazines.     

Polyfunctional macroheterocycles

The reaction of 1-[1,2-bis(carbomethoxy)ethyl]aziridine with ethane-1,2-dithiol leads to 1.8-bis[1,2-bis(carbomethoxy)ethylamino]-3,6-dithiaoctane. Condensation with phthalic and terephthalic acid dichloride gives 9,10-benzo-8, 11-dioxo-7,12-bis[1,2-bis(carbomethoxy)ethyl]-1,4-dithia-7,12-diazacyclotetradec-9-ene and 9,12-benzo-8,13-dioxo-7,14-bis[1,2-bis(carbomethoxy)ethyl]-1,4-dithia-7,14-diazacyclohexadeca-9,12-diene, respectively, while condensation with formaldehyde gives 7,9,18,20-tetrakis[1,2-bis(carbomethoxy)ethyl]-1,4,12,15-tetrathia-7,9,18.29-tetraazacyclodocosane. The corresponding disulfone is formed in the oxidation of 9,10-benzo-8,11-dioxo-7,12-bis[1,2-bis(carbomethoxy) ethyl]-1,4-dithia-7,12-diazacyclotetradec-9-ene with 30% hydrogen peroxide.See [1] for Communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1563–1565, November, 1988.     

新型亲水性共轭聚合物的制备及光催化制氢性能

制备了聚({4,8-双[(2,5,8,11,14,17,20-七氧二十二烷-22-基)氧基]苯并[1,2-b∶4,5-b']二噻吩}-交替-[2,5-二(噻唑-2-基)吡嗪])(P7O-2N-2N)和聚({4,8-双[(2,5,8,11,14,17,20-七氧二十二烷-22-基)氧基]苯并[1,2-b∶4,5-b']二噻吩}-交替-[3,6-双(5-溴-2-噻吩基)-1,2,4,5-四嗪])(P7O-4N)2个亲水性共轭聚合物, 通过调节主链含氮杂环上氮原子的位置, 系统研究了主链结构对材料吸收光谱、 能级、 氢结合自由能及光催化性能的影响. 研究发现, 与P7O-2N-2N相比, P7O-4N表现出更强的链间聚集、 更低的氢结合自由能及更好的光催化制氢性能.     

Crystal structures,optical properties and theoretical calculation of novel two-photon polymerization initiators

Three novel A–π–D–π–A type compounds 3,6-bis[2-(4-pyridyl)ethenyl]-9-ethylcarbazole (1), 3,6-bis[2-(2-pyridyl)ethenyl]-9-ethylcarbazole (2), 3,6-bis[2-(4-pyridyl)ethenyl]-9-ethylpyridylcarbazole (3) were conveniently synthesized by Pd-catalyzed Heck coupling methodology and characterized by single crystal X-ray diffraction determination. One-photon fluorescence, one-photon fluorescence quantum yields, one-photon fluorescence lifetime, and two-photon fluorescence have been investigated. The calculated two-photon absorption cross-sections for the three initiators by quantum chemical method are as high as 947, 943 and 815 × 10⁻⁵⁰ cm⁴ s photon⁻¹, respectively. Two-photon initiating polymerization microfabrication experiments have been carried out and the possible polymerization mechanism was also discussed. The results show that they are good two-photon absorbing chromophores and effective two-photon photopolymerization initiators.     

Facile Synthesis of Azahelicenes and Diaza[8]circulenes through the Intramolecular Scholl Reaction

Carbazole-based aza[7]helicenes and hetero[9]helicenes were successfully obtained via the intramolecular Scholl reaction of 3,6-bis(biphenyl-2-yl)carbazole congeners, while the reaction of 3,6-bis(naphthylphenyl)-appended carbazole gave a triple helicene via an unexpected simultaneous double aryl rearrangement. DFT calculations suggested that the rearrangement proceeded via an arenium cation intermediate. In addition, the reaction of methoxy-appended substrate gave an azahepta[8]circulene via the concurrent C−C bond formation. These helical dyes showed circularly polarized luminescence. The azahepta[8]circulene was further transformed into deeply saddle-distorted dibenzodiaza[8]circulenes as the first example of its solution-based synthesis and unambiguous structural determination.     

Fluorobenzo-1,4-thiazine oxides from bis-(vinylsulfinyl)-and bis(vinylsulfonyl)-fluorobenzenes and 2-aminoethanol

It has been established that 1, 2, 4, 5-tetrafluoro-3, 6-bis (vinylsulfinyl)- and 1, 2, 4, 5-tetrafluoro-3, 6bis(vinylsulfonyl)benzenes react with 2-aminoethanol by nucleophilic addition at the activated double bond with replacement of fluorine atoms on the benzene ring by the amino group of 2-aminoethanol to give 4, 9-bis(2 hydroxyethyl)-5,10-difluoro-1, 2, 3, 4, 6, 7, 8, 9-octahydrobenzo[1, 2-b; 5, 4-b]di-1, 4-thiazine 1,6-dioxide and 1, 1, 6, 6-tetraoxide respectively.Irkutsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences (SO RAN), Irkutsk 664033. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1195–1198, September, 1996. Original article submitted June 5, 1996.Deceased     

V形咔唑衍生物的合成及荧光性质

以N-烷基咔唑作为电子给体和共轭桥中心, 二米基硼作为端基电子受体, 合成了两个V形A-π-D-π-A型新化合物: 3,6-二{[(E)-2-(5-二米基硼)噻吩]乙烯基}-N-丁基-咔唑 {N-butyl-3,6-bis{(E)-2-[5-(dimesitylboryl)thiophen-2-yl]-vinyl}-carbazole, BBTC}和3,6-二[(E)-(4-二米基硼)苯乙烯基]-N-己基-咔唑, {N-hexyl-3,6-bis[(E)-4-(dimesitylboryl)-styryl]-carbazole, BBSC}. 这两个化合物在蓝绿光波段都有较强的荧光发射. 光谱数据表明, 扩大共轭体系并在端基引入含硼基团导致吸收谱和发射谱显著红移, 并增大分子内电荷转移.     

Complex-forming and ion-selective properties of bis(2-diphenylphosphorylalkyl)phenyl ethers of ethylene glycols. Crystal structures of cadmium complexes

New complexes of cadmium iodide with 1,3-bis[2-(diphenylphosphoryl)phenoxy]propane [CdL⁰I₂], 1,2-bis[2-(diphenylphosphorylethyl)phenoxy]ethane [CdL^{1, 2}I₂], and 1,8-bis[2-(diphenylphosphorylethyl) phenoxy]-3,6-dioxaoctane [CdL^{3, 2}I₂] are synthesized and their IR spectra and crystal structures are studied. Electroanalytical characteristics of membranes of ion-selective electrodes based on L⁰, L^{1, 2}, L^{3, 2}, and known crown ethers are compared for cations of alkali, alkaline-earth, and transition metals. Ligand L^{3, 2} is the first podand with terminal diphenylphosphoryl fragments to exhibit selectivity with respect to the cadmium cation.     

Synthesis of 1-(pyridylalkyl)-1-aza-3,6-diphosphacycloheptanes

Reactions of 1,2-bis[(hydroxymethyl)(phenyl)phosphino]ethane with primary pyridylalkylamines gave earlier unknown 1-aza-3,6-diphosphacycloheptanes containing the pyridyl group in the exocyclic substituent. The reactions were found to be stereoselective, preferentially yielding the racemate with the RR/SS-configuration of the P atoms. A mixture of diastereomers of 3,6-diphenyl-1-[2-(2-pyridyl)ethyl]-1-aza-3,6-diphosphacycloheptane reacted with dichloro(cycloocta-1,5-diene)platinum(II) to give cis-P,P-chelate complexes from the meso-isomer and bridged oligomeric complexes from the racemate.     

α-Thioureidoalkylation of 4-alkyl- and 4-phenylthiosemicarbazides

Previously unknown 1,3-dialkyl-4,5-bis[4-alkyl(phenyl)thiosemicarbazido]imidazolidine-2-thiones and 4,5,7-trialkylperhydroimidazo[4,5-e]-1,2,4-triazine-3,6-dithiones have been synthesized by the α-thio-ureidoalkylation of 4-alkyl(phenyl)thiosemicarbazides using 1,3-dialkyl-4,5-dihydroxyimidazolidine-2-thiones.     

Stereoselective [4+2] cycloadditions of tetrazines to 3-oxo- and 3-arylimino-4′-methylenedihydro-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furans]

Stereoselective inverse-demand [4+2] cycloadditions of 3,6-bis(pyridin-2-yl)-1,2,4,5-tetrazine and dimethyl 1,2,4,5-tetrazine-3,6-dicarboxylate to 4′-methylenedihydro-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furans] and 4′-methylene-1′-(4-nitrophenyl)spiro[bicyclo[2.2.1]heptane-3,2′-pyrrolidine] were studied. Cycloadditions took place stereoselectively at the exocyclic CC double bonds to give novel 11:14-isopropylidene-14-methyl-2,3-diaza-8-oxadispiro[5.1.5.2]pentadecane and 11:14-isopropylidene-11-methyl-2,3,8-triazadispiro[5.1.5.2]pentadecane derivatives in 50–98% de. The structures of the novel dispiro compounds were determined by NMR techniques, NOESY spectroscopy and X-ray diffraction.     

Reactivity of fluorinated sulfur-containing heterocycles towards nucleophilic and oxidizing reagents

The reaction of 5,5-bis(trifluoromethyl)-6-thia-bicyclo[2.2.1]hept-2-ene, 5,5-bis(trifluoromethyl)-6-thia-bicyclo[2.2.2]oct-2-ene and 2,2-bis(trifluoromethyl)-3,6-dihydro-4,5-dimethyl-2H-thiopyran with i-C₃H₇MgCl leads to the formation of ring opening products as the result of nucleophilic attack of the Grignard reagent on the sulfur atom. According to DFT calculations the reactivity of the sulphur-containing substrate correlates with the strain energy of the heterocycle. The oxidation of 3-thia-4,4-bis(trifluoromethyl)tricyclo[5.2.1.0^2,5]non-7-ene by hydrogen peroxide in hexafluoro-iso-propanol solvent resulted in formation of the corresponding sulfoxide however, the reaction with m-chloroperoxybenzoic acid produced the product of exhaustive oxidation of sulfur and the double bond. In sharp contrast, the oxidation of 5,5-bis(trifluoromethyl)-6-thia-bicyclo[2.2.1]hept-2-ene and 5,5-bis(trifluoromethyl)-6-thia-bicyclo[2.2.2]oct-2-ene by MCPBA (2d, 25 °C) proceeds with the preservation of the double bond, leading to the selective formation of the corresponding sulfones.     

Nucleosides. Part LIX. The 2-(4-nitrophenyl)ethylsulfonyl (Npes) Group: A New Type of Protection in Nucleoside Chemistry

The 2-(4-nitrophenyl)ethylsulfonyl (npes) group is developed as a new sugar OH-blocking group in the ribonucleoside series. Its cleavage can be performed in a β-eliminating process under aprotic conditions using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as the most effective base. Since sulfonates do not show acyl migration, partial protection of 1,2-cis-diol moieties is possible leading to new types of oligonucleotide building blocks. A series of Markiewicz-protected ribonucleosides 1–10 is converted into their 2′-O-[2-(4-nitrophenyl)ethylsulfonyl] derivatives 29–38 in which the 5′-O? Si bond can be cleaved by acid hydrolysis forming 39–45 . Subsequent monomethoxytritylation leads to 46–50 , and desilylation affords the 5′-O-(monomethoxytrityl)-2′-O-[2-(4-nitrophenyl)ethylsulfonyl]ribonucleosides 51–55 . Acid treatment to remove trityl groups do also not harm the npes group (→ 56–58 ). Unambiguous syntheses of fully blocked 2′-O-[2-(4-nitrophenyl)ethylsulfonyl]ribonucleosides 96–102 are achieved from the corresponding 3′-O-(tert-butyl)dimethylsilyl derivatives. Furthermore, various base-protected 5′-O-(monomethoxytrityl)- and 5′-O-(dimethoxytrityl)ribonucleosides, i.e. 59–77 , are treated directly with 2-(4-nitrophenyl)ethylsulfonyl chloride forming in all cases a mixture of the 2′,3′-di-O- and the two possible 2′- and 3′-O-monosulfonates 107–148 which can be separated into the pure components by chromatographic methods. The npes group is more labile towards DBU cleavage than the corresponding base-protecting 2-(4-nitrophenyl)ethyl (npe) and 2-(4-nitrophenyl)ethoxycarbonyl (npeoc) groups allowing selective deblocking which is of great synthetic potential.     

Reactions of vinylthiohalobenzenes with glykols and 1,5-diaminopentane

Reactions of 3,6-bis(vinylthio)-l,2,4,5-tetrafluoro- and 3-vinylthio-l,2,4,5-tetrafluoro-6-chlorobenzenes with glycols in dimethylformamide give rise to compounds mixture, mainly mono- and disubstituted, and the products of theortfo-cyclization, and in reaction with 1,5-diaminopentane even at a double excess of the latter is replaced only one fluorine of benzene ring resulting in l,5-bis[3,6-bis(vinylthio)-2,4,5-trifluoroanilino] pentane. The study was carried out under financial support of the Russian Foundation for Basic research (grant no. 96-03-33264).