Synthesis of enamino ketones from <Emphasis Type="Italic">N</Emphasis>-(2-vinyloxyalkyl)-ethane-1,2-diamines

Condensation of N-(2-vinyloxyethyl)ethane-1,2-diamine with aromatic aldehydes gave mixtures of 2-aryl-1-(2-vinyloxyethyl)imidazolidines and N-arylmethylidene-N′-(2-vinyloxyethyl)ethane-1,2-diamines in an overall yield of 79–84%, while analogous condensation with cyclic and acyclic ketones resulted in the formation of only the corresponding Schiff bases (yield 53–83%).     

Condensation of <Emphasis Type="Italic">N</Emphasis>-(2-vinyloxyethyl)ethane-1,2-diamine with carbonyl compounds

Condensation of N-(2-vinyloxyethyl)ethane-1,2-diamine with aromatic aldehydes gave mixtures of 2-aryl-1-(2-vinyloxyethyl)imidazolidines and N-arylmethylidene-N′-(2-vinyloxyethyl)ethane-1,2-diamines in an overall yield of 79–84%, while analogous condensation with cyclic and acyclic ketones resulted in the formation of only the corresponding Schiff bases (yield 53–83%).     

Copolymers containing alternating sequences of nucleic acid–base pairs. I. Monomer synthesis

To provide suitable monomers for a study designed to synthesize copolymers containing alternating sequences of nucleic acid base pairs, the following electron-donor monomers were synthesized: 9-(2-vinyloxyethyl)adenine, 1-(2-vinyloxyethyl)thymine, and 1-(2-vinyloxyethyl)-cytosine. The following electron-acceptor monomers were also synthesized: 9-(2-maleimidoethyl)adenine, 1-(2-maleimidoethyl)thymine, and 1-(2-maleimidoethyl)cytosine. The methods of synthesis are described along with their characterization by the usual methods, and their physical properties are reported. A variety of novel compounds were required as intermediates in the above identified syntheses. This paper also includes characterization of these compounds and a report of their physical properties.     

Synthesis and spatial structure of 4-(2-hydroxyethyl)-5-(2-hydroxyphenyl)-2H-1,2,4-triazolo-3(4H)-thione

By reaction of 2-vinyloxyethyl isothiocyanate with salicylic acid hydrazide a synthesis of the corresponding thiosemicarbazide was performed. Alkaline hydrolysis of the latter led to an intramolecular heterocyclization into 1,2,4-triazole derivative. When cyclization was carried out in the water-alkali medium, 2-vinyloxyethyl fragment was shown to be hydrolyzed to form 4-(2-hydroxyethyl)-5-(2-hydroxyphenyl)-2H-1,2,4-triazolo-3(4H)-thione, whose spatial structure was established by XRD analysis.     

Synthesis and steric structure of [2-(3-pyridyl)piperidino](2-vinyloxyethylamino)methanethione

Thioureas derivatives were synthesized on the basis of anabasine, piperidine, and morpholine, and 2-vinyloxyethyl isothiocyanate. X-Ray diffraction was used to determine the steric structure of [2-(3-pyridyl)piperidino](2-vinyloxyethylamino)methanethione.     

First Representatives of O-(2-Vinyloxyethyl)oximes

Previously unknown ketone and acetaldehyde O-(2-vinyloxyethyl)oximes were synthesized in 22-88% by reaction of the corresponding oximes with 2-chloroethyl vinyl ether in the system KOH-DMSO.     

Anticorrosion properties of products of N-(2-Vinyloxyethyl)-1,2-ethylenediamine condensation with carbonyl compounds

N-(2-Vinyloxyethyl)-N′-cyclohexylidene-1,2-ethylenediamine and N,N′,N″-tris-[2-(2-vinyloxyethyl)-aminoethyl]hexahydro-1,3,5-triazine were synthesized by reactions of N-(2-vinyloxyethyl)-1,2-ethylenediamine with cyclohexanone and formaldehyde with yields of 91 and 90%, respectively. The IR and ¹H and ¹³C NMR spectral data and the results of studying their anticorrosion properties are given.     

Copolymers containing alternating sequences of nucleic acid base pairs. III. Spectroscopic studies

A study was conducted of the complementary base pair interactions between various pairs of electron-donor monomers, electron-acceptor monomers, homopolymers and alternating copolymers selected from the following group: ( 1 ) 9-(2-vinyloxyethyl)adenine; ( 2 ) 1-(2-vinyloxyethyl)thymine; ( 3 ) 1-(2-vinyloxyethyl)cytosine; ( 4 ) 9-(2-maleimidoethyl)adenine; ( 5 ) 6-chloro-9-(2-maleimidoethyl)purine; ( 6 ) 1-(2-maleimidoethyl)thymine; ( 7 ) 1-(2-maleimidoethyl)cytosine; ( 8 ) homopolymer of ( 4 ); ( 9 ) homopolymer of ( 6 ); ( 10 ) alternating copolymer of ( 2 ) and maleic anhydride; ( 11 ) alternating copolymer of ( 2 ) and ( 5 ); and ( 12 ) alternating copolymer of ( 2 ) and ( 4 ). By ¹H-NMR, in CDCL₃, the base pair interactions between ( 1 ) and ( 2 ) were shown to be hydrogen bonding, the extent of which was shown by a calculated binding constant, K = 61.81 L/mol. The nature of this interaction was conformed by IR. Neither monomer pairs ( 1 )/( 2 ) nor ( 4 )/( 6 ) exhibited hydrogen bonding in DMSO-d₆. However, hydrogen bonding interaction was observed for DMSO-d₆ solutions of homopolymers ( 8 ) and ( 9 ) and for alternating copolymer ( 12 ). On the basis of an upfield chemical shift of the 2- and 8-aromatic protons of ademine of ( 1 ) in D₂O, a partial overlap stacking interaction is proposed. No charge-transfer interactions could be observed by UV between donor-acceptor monomer pairs.     

Cation binding properties of poly(crown ethers) with photodimerizable groups

Polymers that have crown ether groups as cation binding sites and cinnamic acid ester groups as photodimerizable groups were prepared by the cationic polymerizations of 2-vinyloxyethyl 4′-(2,3-benzo-1,4,7,10,13-pentaoxa-2-cyclopentadecene)acrylate and 2-vinyloxyethyl 4′-(2,3-benzo-1,4,7,10,13,16-hexaoxa-2-cyclooctadecene)acrylate. When irradiated with ultraviolet (UV) light the cinnamic acid ester groups of the polymers caused dimerization in dilute solution without the formation of insoluble materials. The irradiation was carried out in a dioxane solution and an aqueous solution in the presence and absence of salts. The effect of phototransformation of polymers on the cation binding properties was investigated by a method of picrate salts extraction. The binding ability of the phototransformed polymers for alkali and alkaline earth metal cations was higher than that of the native polymer. Furthermore the cation binding ability of the phototransformed polymers was less sensitive to temperature than that of the native polymer. The effect of the degree of photodimerization of the polymers and the concentration of KCl that exists during irradiation on the cation binding ability was also investigated.     

Synthesis of N-substituted phenoxazine polymers bearing vinyl backbone

Vinyl monomers bearing N-substituted phenoxazine or 2,8-dimethylphenoxazine units were synthesized starting with the corresponding phenoxazines. N-substituents were 2-vinylbenzyl-oxycarbonylethyl group prepared via 2-carboxyethyl group, 3-methacrylamido-, 3-acrylamido-, or 3-(4-styrenesulfonamido)-propyl group prepared via 3-aminopropyl group, vinylbenzyl, or 2-vinyloxyethyl group attached by the displacements of sodium salts of the phenoxazines to the chlorides, and 2-methacryloyl- or 2-acryloyl-oxyethyl group prepared via 2-hydroxyethyl group. Free-radical polymerixations of these novel monomers proceeded smoothly, except those with 2-vinyloxyethyl group, which were susceptible to BF₃-etherate. Changes of the visible absorption spectrum of iodine in THF with addition of the monomers and polymers were considerable, with the appearance of new absorption peaks or shoulders in major cases.     

Reaction of 2-Chloro-5-(chloromethyl)thiophene with Monoethanolamine Vinyl Ether

At the alkylation of monoethanolamine vinyl ether with 2-chloro-5-(chloromethyl)thiophene in ethyl alcohol (60-70°C) a product of disubstitution and transvinylation, viz. N,N-bis(5-chloro-2-thienylmethyl)-N-(2-hydroxyethyl)ammonium chloride is formed. The analogous reaction in the absence of solvent proceeds with the formation of N-(5-chloro-2-thienylmethyl)-N-(2-vinyloxyethyl)amine.     

Preparation and properties of photocrosslinkable poly(2-vinyloxyethyl cinnamate)

Photocrosslinkable poly(2-vinyloxyethyl cinnamate)'s with substituents in para position of cinnamoyl moieties were prepared cationically. Polymerizability of the monomers was markedly governed by the substituent and the glass transition temperatures of the polymers varied in the range of about 0 to 72°C. The photocrosslinking mechanism in relation to the photosensitivity of the polymers is discussed on the basis of spectroscopical studies.     

Functional Methacryloyloxy Acetals: V. Electrophilic Addition of Carboxylic Acids to 2-Vinyloxyethyl Methacrylate

Mono- and dicarboxylic acids (acetic, methacrylic, E-crotonic, and malonic) quantitatively add to 2-vinyloxyethyl methacrylate under mild conditions (1 wt % CF₃COOH, 20–60°C, 1–4 h) according to the Markownikoff rule to give the corresponding mono- and bis-adducts with high regio- and chemoselectivity. The products may be regarded as a new family of functionalized methacrylates.     

An unexpected reaction of 2-vinyloxyethyl isothiocyanate with halocarboxylic acids

Reactions of 2-vinyloxyethyl isothiocyanate with aliphatic halocarboxylic acids give rise to their 1-(2-isothiocyanatoethoxy)ethyl esters in quantitative yields. An unusual rearrangement of 1-(2-isothiocyanatoethoxy)ethyl chloro(bromo)acetate and 3-bromopropanoate to 5-aza-7-chloro(bromo)-4-oxo-3-thiaheptanoic and to 6-aza-8-bromo-5-oxo-4-thiaoctanoic acids, respectively, was observed. Monohalocarboxylic acids and their esters were shown to readily alkylate l,3-oxazolidine-2-thione to form the same thiaheptanoic and thiaoctanoic acids and their esters.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 350–354, February, 1993.     

Hydrazine bisalane is a potential compound for chemical hydrogen storage. A theoretical study

Electronic structure calculations suggest that hydrazine bisalane (AlH(3)NH(2)NH(2)AlH(3), alhyzal) is a promising compound for chemical hydrogen storage (CHS). Calculations are carried out using the coupled-cluster theory CCSD(T) with the aug-cc-pVTZ basis set. Potential energy surfaces are constructed to probe the formation of, and hydrogen release from, hydrazine bisalane which is initially formed from the reaction of hydrazine with dialane. Molecular and electronic characteristics of both gauche and trans alhyzal are determined for the first time. The gauche hydrazine bisalane is formed from starting reactants hydrazine + dialane following a movement of an AlH(3) group from AlH(3)AlH(3)NH(2)NH(2) rather than by a direct attachment of a separate AlH(3) group, generated by predissociation of dialane, to AlH(3)NH(2)NH(2). The energy barriers for dehydrogenation processes from gauche and transalhyzal are in the range of 21-28 kcal mol(-1), which are substantially smaller than those of ca. 40 kcal mol(-1) previously determined for the isovalent hydrazine bisborane (bhyzb) system. H(2) release from hydrazine bisalane is thus more favored over that from hydrazine bisborane, making the Al derivative an alternative candidate for CHS.     

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and nuclear magnetic resonance analyses of end-functionalized saccharidic polymers: an example of a useful analytical technique combination

The living cationic polymerization of a saccharidic monomer (1,2:3,4-di-O-isopropylidene-6-O-(2-vinyloxyethyl)-D-galactopyranose, GVE) gives rise to aldehyde end-capped polymers (PGVE--CHO) of low molar masses (<10 000 Da) and low molar mass distribution (<1.2). These polymers were derivatized by selective introduction of either hexamethylenediamine (PGVE-NH2) or 9-fluorenylmethyl carbazate (PGVE-Fmoc) end groups. The resulting polymers were fully characterized by complementary use of nuclear magnetic resonance (1H NMR) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). The expected structure according to the polymerization mechanism, the occurrence of side reactions and the success of the post-functionalization reactions were confirmed.     

N,N′-bis(2-Vinyloxyethyl)carbodiimide

Previously unreported N,N-bis(2-vlnyloxyethyl)carbodiimide was synthesized by the reaction of N,N -bis(2-vinyloxyethyl)thiourea with yellow mercuric oxide in CH₂Cl₂ at room temperature.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1897–1898, August, 1990.     

Unexpected result of the reaction of 2-vinyloxyethyl isothiocyanate with bromoacetic acid

2- [1-(Bromoacetoxy)ethoxy]ethyl isothiocyanate (II) (BrCH₂CO₂CH(CH₃)OCH₂CH₂. N-C-S) was found to be an adduct of 2-vinyloxyethyl isothiocyanate (I) with bromoacetic acid. Upon storage, (II) rearranges to previously unreported 1-bromo-3-aza-4-oxo-5-thiaheptanoic acid (III) (BrCH₂CH₂NHC(O)CH₂C0₂H).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2370–2372, October, 1991.     

DAR青成色剂的合成

以1-羟基-N-[4-(2,4-二特戊基-苯氧基-丁基)-2-萘甲酰胺为母体,以2,5-二巯基-1,3,4-噻二唑为吸附基团,分别以1-甲酰基-2-(4-氨基)苯肼,1-乙酰基-2-(4-氨基)苯肼和1-三氟乙酰基-2-(4-氨基)苯肼为增强基团合成了3种DAR青成色剂。结构经IR、^1H NMR、MS及元素分析等检测确证。     

Determination of hydrazine in biofluids by capillary gas chromatography with nitrogen-sensitive or mass spectrometric detection.

Plasma and liver levels of hydrazine were determined at 10, 30, 90 and 270 min in rats given 0.09, 0.27, 0.84 and 2.53 mmol of hydrazine per kg body weight orally by capillary gas chromatography-mass spectrometry of its pentafluorobenzaldehyde adduct (DFBA, m/z 388) using selected ion monitoring with 15N2-labelled hydrazine as the internal standard (adduct, m/z 390). The mean half-life for hydrazine in the plasma was approximately 2 h but varied with dose. Urinary excretion (0-24 h) of hydrazine and its metabolite acetylhydrazine were determined employing nitrogen-phosphorus detection of the adducts utilising a novel internal standard, pentafluorophenylhydrazine, the adduct of which structurally resembles DFBA. The fraction of the original dose excreted as hydrazine (and acetylhydrazine) declined with increasing dose.