ω,ω′-Urea- and -dithioacetal-derivatives of hypericin

An ω,ω′-disubstituted hypericin derivative bearing two dicyclohexylurea moieties separated by propionyl chains from the chromophore and an ω,ω′-dithioacetal of hypericin were prepared. Both showed excellent production of oxidizing species comparable to hypericin when irradiated with appropriate light as shown by the photodestruction of bilirubin IXα.     

ω,ω′-Urea- and -dithioacetal-derivatives of hypericin

An ω,ω′-disubstituted hypericin derivative bearing two dicyclohexylurea moieties separated by propionyl chains from the chromophore and an ω,ω′-dithioacetal of hypericin were prepared. Both showed excellent production of oxidizing species comparable to hypericin when irradiated with appropriate light as shown by the photodestruction of bilirubin IXα.     

New α,ω-diamido and α,ω-diamino mono-and bi-bridged acridine dimers

A novel set of dimers derived from 9-amino acridine was prepared and characterized by¹H and¹³CNMR. These derivatives are bridged at several different positions of the heterocyclic moieties, by the way of ,-diamido or ,-diamino side-chains. Additionally the preparation of some bi-bridged compounds was achieved.

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Neue ,-Dimaido- und ,-Diamino-Mono- und Bi-überbrückte Acridin-Dimere

Zusammenfassung Es wurde eine neue Reihe von Dimeren des 9-Aminoacridins hergestellt und mittels¹H und¹³C-NMR charakterisiert. Diese Derivate sind an verschiedenen Positionen des Heterocyclus mit ,-Diamido- oder ,-Diamino-Seitenketten überbrückt. Zusätzlich wurden auch einige zweifachüberbrückte Verbindungen hergestellt.

     

ω,ω′-imino dicarboxylic acids and some of their derivatives

Summary Starting from the corresponding-chloro carboxylic acids we prepared, -imino dicarboxylic acids and their N- and O- derivatives; the products had the following structures:     

Synthesis and characterization of α,ω-dichloro-polymethylphenylsilane

The synthesis of a functional polysilane, α,ω-dichloro-polymethylphenylsilane (α,ω-dichloro-PMPS), based on the Wurtz-type reductive coupling, has been considered. A study of some reaction parameters shows that both yield and molecular weight distribution of α,ω-dichloro-PMPS can be greatly influenced by the work-up conditions, reaction time, monomer concentration and temperature during the initiation of the polymerization. By varying the synthesis conditions, different ratios of high and low molecular weight fractions were obtained. Samples of different molecular weight were isolated by fractional precipitation of the crude polymers. The chlorine-end functionalization was confirmed by ²⁹Si NMR spectroscopy and the concentration of end-groups was quantitatively determined by elemental analysis of chlorine.     

Synthesis of symmetrical acetylenic hydrocarbons and their α,ω-di-derivatives from α,α,α-trichloro- and α,α,α,ω-tetrachloro-alkanes

Summary By the action of sodium in xylene on polychloro hydrocarbons containing -CCl₂-CCl₂- or- CC1=CC1-, groupings the corresponding symmetrical acetylenic hydrocarbons containing 10,14, and 18 carbon atoms in the molecule were obtained. From ,-disubstituted tetrachloroalkanes by the same method 1,10-diethoxy-5-decyne, 1,14-diethoxy-7-tetradecyne, and 1,14-bisdiethylamino-7-tetradecyne were obtained.The spectra were determined in the Optical Laboratory of the Institute of Heteroorganic Compounds of the USSR by N. A. Chumaevskii, who we thank.     

Synthesis and Characterization of Monodisperse α,ω-Divinylpolydimethylsiloxane and ω-Vinylpolydimethylsiloxane

Abstract

ω-Vinylpolydimethylsiloxanes (ω-PDMS) and α,ω-divynilpolydimethylsiloxanes (α,ω-PDMS) have been synthesized by anionic polymerization of hexamethylcyclotrisiloxane (D3). The reactions were carried out in n-hexane and tetrahydrofuran (THF), respectively. The initiator was n-butyl-lithium (n-BuLi); tetrahydrofuran was used as an electron donor compound to promote the polymerization of D3. The synthesized polymers have been characterized by infrared (FTIR), proton nuclear magnetic resonance spectroscopy (NMR), light scattering (LALLS), and gel permeation chromatography (GPC). Molecular weights ranging from 20,000 to 100,000 were obtained with relatively narrow molecular weight distributions; Mw/Mn < 1.25.     

Synthesis and characterization of α-N,N-dihydroxyethylaminopropyl-ω-butylpolydimethylsiloxanes

A series of α-N,N-dihydroxyethylaminopropyl-ω-butylpolydimethylsiloxanes with different molecular weight were synthesized. The preparation included five steps which were hydroxyl protection, alkylation, anionic ring-opening polymerization, hydrosilylation and deprotection. The structure of reaction products was characterized by FT-IR, GC, 1H NMR. 2007 Qing Si Zhang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.     

α,ω-Bis-N-aziridinoalkanes

By reactions of ,-diamines with 1,2-dihaloethanes there were synthesized ,-bis-N-aziridinoalkanes (la-g) and bis-N-aziridinoethyl ether (II). From 1,3-diaminopropane and dichloroethane bis-aziridine (III) was isolated in addition to (Ia). NMR spectra of the products were studied.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 882–885, April, 1991.     

ω,ω′-Appended nucleo-base derivatives of hypericin

ω,ω′-Disubstituted hypericin derivatives with the nucleo-bases thymine, cytosine, and adenine in these positions were prepared starting from tri-O-methyl-ω-bromoemodin. The most promising derivative proved to be that with a thymine moiety. It displayed the best solubility of the three products together with a potency to produce singlet oxygen and/or reactive oxygen species comparable to the parent compound hypericin. In addition, although no specific interaction with DNA or poly(2′-deoxyadenylic acid) could be detected, it proved to be significantly better accumulating in the nucleus of prostatic cancer LNCaP cells than hypericin making it a promising candidate for a second-generation photodynamic hypericin agent.     

ω,ω′-Appended nucleo-base derivatives of hypericin

ω,ω′-Disubstituted hypericin derivatives with the nucleo-bases thymine, cytosine, and adenine in these positions were prepared starting from tri-O-methyl-ω-bromoemodin. The most promising derivative proved to be that with a thymine moiety. It displayed the best solubility of the three products together with a potency to produce singlet oxygen and/or reactive oxygen species comparable to the parent compound hypericin. In addition, although no specific interaction with DNA or poly(2′-deoxyadenylic acid) could be detected, it proved to be significantly better accumulating in the nucleus of prostatic cancer LNCaP cells than hypericin making it a promising candidate for a second-generation photodynamic hypericin agent.     

Analysis of {α,ω-Dichloroalkane or α,ω-Dibromoalkane] + Benzene and α,ω-Dichloroalkane + Tetrachloromethane} Mixtures in Terms of Group Contributions

Abstract

Molar excess enthalpies, H ^E _m, at 298.15K and atmospheric pressure have been determined for three binary liquid mixtures [x{1,3-dichloropropane or 1,4-dichlorobutane and 1,6-dichlorohexane} + (1 - x) tetrachloromethane]. These experimental results along with the data available in the literature on molar excess Gibbs energies, G ^E _m, activity coefficients at infinite dilution, In γ^∞ _i , and molar excess enthalpies, H ^E _m, for α,ω-dihaloalkanes + benzene or + tetrachloromethane mixtures are examined on the basis of the DISQUAC group contribution model.