An Investigation of the Structure of Copolymers of lsobutylene and Diene Prepared by Initiation with VCI4 in the Dark and with Visible Light

¹H-NMR spectra of copolymers of isobutylene and 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene were investigated in connection with the elucidation of the formation of soluble and insoluble copolymers. For copolymers soluble in heptane, benzene, and CCI₄ it was found that the incorporation of diene into the polymer chain proceeds by 1,4-addition in the case of copolymerizations conducted both in the dark and with visible light using VC1₄ as initiator. The formation of a soluble and an insoluble copolymer is attributed to a different type of initiation, either with radical-cations of isobutylene, if soluble copolymers are formed, or with radical-cations of diene, if the arising copolymers are insoluble.     

Reactive diene for synthesis of substituted catechols

(2R,3R)-2,3-Dimethoxy-2,3-dimethyl-5,6-dimethylene-1,4-dioxane has been synthesized and is a highly efficient diene in Diels-Alder reactions. Reaction with acetylenic dienophiles provides a simple route to substituted catechols. Reactions with some ethylenic dienophiles are also reported.     

Synthetic transformations of higher terpenoids: XVIII. Synthesis of optically active 9,10-anthraquinone derivatives

Retro-Diels-Alder decomposition of dodecahydro-endo-4b,12-ethenochrysene-1,4-diones obtained from a tricyclic diterpenoid, levopimaric acid, gave optically active 5-[2-(6-vinyl-2,6-dimethyl-2-carboxycyclohexyl) ethyl]-7-isopropyl-1,4-naphthoquinones which reacted with silyloxybutadienes to produce the corresponding 6- and 7-hydroxyanthraquinones, 5-furyl-7-hydroxytetrahydroanthraquinones, or 5-furyl-7-oxohexahydroanthraquinones. Condensation of the naphthoquinone derivatives with 5-isopropenyl-2,3-dihydrothiophene 1,1-dioxide resulted in the formation of 6,11-dioxodihydro- and 6,11-dioxohexahydroanthra[2,1-b]thiophene 3,3-dioxides. 6- and 7-Hydroxyanthraquinones were also obtained by reaction of dodecahydro-endo-4b,12-ethenochrysene-1,4-diones with Danishevsky diene, followed by cleavage of the polycyclic adducts. The cycloaddition of 5-[2-(-2-carboxy-2,6-dimethyl-6-vinylcyclohexyl)ethyl]-7-isopropyl-1,4-naphthoquinones in the presence of Lewis acids was characterized by increased regioselectivity.     

Desorption ionization by charge exchange (DICE) for sample analysis under ambient conditions by mass spectrometry

An ambient pressure ionization technique for mass spectrometric analysis of substances present on solid surfaces was developed. A nebulized spray containing molecular ions of a solvent such as toluene can be generated by passing the solvent through a stainless steel capillary held at a high voltage. When the stream of charged droplets produced in this way is directed onto a solid surface, the analytes present on the surface are desorbed and ionized by a charge exchange process. This technique was shown to desorb and generate positively charged molecular ions from compounds that are not readily ionized by some other ambient methods, under positive-ion generation mode. For example, intense signals representing radical cations of 1,4-hydroquinone, limonene, thymol, and several other compounds were observed when the analytes were deposited on a metal surface and exposed to a toluene spray nebulized from the metal capillary maintained at a potential of about +5 kV. In contrast, when the same samples were exposed to a spray of water/methanol/formic acid under customary DESI-like (positive-ion mode) conditions, no peaks representing the analytes were observed.     

4,4-Dimethyl-1,4-thiasilinane and Its S-Functional Derivatives

Synthetic approaches to 4,4-dimethyl-1,4-thiasilinane and its S-functional derivatives, 4,4-dimethyl-1,4-thiasilinane S-oxide, 4,4-dimethyl-1,4-thiasilinane S,S-dioxide, 4,4-dimethyl- 1-(phenylsulfonylimino)-1,4-thiasilinane, and 1,4,4-trimethyl-1,4-thiasilinan-1-ylium iodide, were studied. The S-functional derivatives of 4,4-dimethyl-4-thiasilinane, unlike 3,3-dimethyl-3-thiasilinane, are hydrolytically stable.     

Synthesis, basicity, structural characterization, and biochemical properties of two [(3-hydroxy-4-pyron-2-yl)methyl]amine derivatives showing antineoplastic features

The N,N'-bis[(3-hydroxy-4-pyron-2-yl)methyl]-N,N'-dimethylethylendiamine (malten) and 4,10-bis[(3-hydroxy-4-pyron-2-yl)methyl]-1,7-dimethyl-1,4,7,10-tetraazacyclododecane (maltonis) were synthesized and characterized. The acid-base behavior, structural characterizations, and biochemical studies in aqueous solution were reported. Each compound contains two 3-hydroxy-2-methyl-4-pyrone units (maltol) symmetrically spaced by a polyamine fragment, the 1,4-dimethylethylendiamine (malten), or the 1,7-dimethyl-1,4,7,10-tetraazacyclododecane (maltonis). They are present at physiological pH 7.4 in the form of differently charged species: neutral but in a zwitterion form for malten and monopositive with an internal separation of charges for maltonis. Malten and maltonis are both able to alter the chromatin structure inducing the covalent binding of genomic DNA with proteins, a feature consistent with the known antiproliferative activity exerted by this class of molecules. Solid-state results and MD simulations in water show that malten, because of its molecular topology, should be more prone than maltonis to act as a donor of H-bonds in intermolecular contacts, thus it should give a better noncovalent approach with the negatively charged DNA. Crystal structures of [H(2)malten](2+) and [H(2)maltonis](2+) cations were also reported.     

Polymer reactions—X thermal pyrolysis of poly(isoprene)

Poly(isoprene) (97% cis-1,4 and 3% 3,4) has been pyrolysed in a carrier stream of helium from 315 to 384°. The products were online identified and quantitatively analysed by an interfaced pyrolysis GC peak identification system. The first order rate constant for pyrolysis is 1.1 × 10^?2 sec^?1 at 384° with an overall activation energy of 41 kcal mol^?1. The main products are isoprene and 1-methyl-4-isopropenyl cyclohexene. The dominant initiation process has been shown to be β chain scission leading to two allylic radicals. The former product is derived from an unzipping reaction, the latter together with 1.5-dimethyl-5-vinylcyclohexene are the main C₁₀ products from the allylic radicals. All the other minor products can be account for by simple chain propagation reactions with or without intramolecular hydrogen transfers.     

Asymmetric synthesis of rubiginones A(2) and C(2) and their 11-methoxy regioisomers

Convergent enantioselective syntheses of angucyclinone-type natural products rubiginones A(2) (2) and C(2) (1) and their 11-methoxy regioisomers 3 a and 3 b have been achieved by using two domino processes from a common enantiomerically pure 1-vinylcyclohexene 4. Key steps in the synthesis of this diene were the stereoselective conjugate addition of AlMe(3) on (SS)-[(p-tolylsulfinyl)methyl]-p-quinol (9) and the elimination of the beta-hydroxy sulfoxide fragment, after oxidation to sulfone, to recover a carbonyl group. The first domino sequence comprised Diels-Alder reaction with a sulfinyl naphthoquinone followed by sulfoxide elimination. An efficient opposite regioselection in the cycloaddition step was achieved in the convergent construction of the tetracyclic skeleton using a sulfoxide at C-2 or C-3 of the dienophiles 5 or 6, derived from 5-methoxy-1,4-naphthoquinone. The second domino process, triggered by oxygen and sunlight, allowed the transformation of the initial tetracyclic adducts into the final products after B ring aromatization, silyl deprotection and C-1 oxidation.     

The reaction of trichlorosilyltetracarbonyliron hydride (HFe(CO)4SiCl3) with conjugated dienes

Isoprene, 1,3-butadiene and 2,3-dimethyl-1,3-butadiene react with HFe(CO)₄SiCl₃ by addition of the Fe---H function to the diene. Isoprene appears to add predominantly 1,4 and 2,3-dimethyl-1,3-butadiene appears to add 1,2, while 1,3-butadiene may add both ways. In the case of isoprene and 1,3-butadiene loss of CO from the addition compound gives a stable π-allyl- Fe(Co)₃SiCl₃ product. Either cis- or trans-1,3-pentadiene is reduced to pentene by HFe(CO)₄SiCl₃.     

Molecular level model for the agonist/antagonist selectivity of the 1,4-dihydropyridine calcium channel receptor

Summary Crystal structures of the 1,4-dihydropyridine (1,4-DHP) calcium channel activators Bay K 8643 [methyl 1,4-dihydro-2,6-dimethyl-3-nitro-4-(3-nitrophenyl)-pyridine-5-carboxylate], Bay O 8495 [methyl 1,4-dihydro-2,6-dimethyl-3-nitro-4-(3-trifluoromethylphenyl)-pyridine-5-carboxylate], and Bay O 9507 [methyl 1,4-dihydro-2,6-dimethyl-3-nitro-4-(4-nitrophenyl)-pyridine-5-carboxylate] were determined. The conformations of the 1,4-DHP rings of these activator analogues of Bay K 8644 [methyl 1,4-dihydro-2,6-dimethyl-3-nitro-4-(2-trifluoromethylphenyl)-pyridine-5- carboxylate] do not suggest that their activator properties are as strongly correlated with the degree of 1,4-DHP ring flattening as was indicated for members of the corresponding antagonist series. The solid state hydrogen bonding of the N(1)-H groups of the activators is not, unlike that of their antagonist counterparts, to acceptors that are directly in line with the donor. Rather, acceptor groups are positioned within ± 60 degrees of the N(1)-H bond in the vertical plane of the 1,4-DHP ring. Previously determined structure-activity relationships have indicated the importance of this N(1)-H group to the activity of the 1,4-DHP antagonists. Based on these observations, a model is advanced to describe the 1,4-DHP binding site of the voltage-gated Ca²⁺ channel and its ability to accommodate both antagonist and activator ligands.     

Oxidative dihydroxylation of alicyclic unsaturated hydrocarbons with vinyl- and norbornene fragments in pseudohomogenic system

Oxidation of alicyclic unsaturated hydrocarbons (4-vinylcyclohexene, 5-vinylnorbornene, 5-cyclohexenylnorbornene, and 5-vinylbicyclooctene) with 30% hydrogen peroxide solutions and percarbamide is studied. Reaction was carried out at 40–70°C in the presence of heterogenized peroxocomplex compounds of molybdenum and tungsten formed “in situ” in the reaction of metal oxohalides with H₃PO₄, nano-dimensional particles of carbon material, and hydrogen peroxide. Main oxidation products of alicyclic diene hydro-carbons are the corresponding unsaturated epoxides and diols. Depending on the reaction condition their ratio varies in a wide range.     

Asymmetric hydrovinylation of 1-vinylcycloalkenes. Reagent control of regio- and stereoselectivity

1-Vinylcycloalkenes undergo highly regio- and enantioselective (>98% ee) 1,4-hydrovinylation (HV) when treated with ethylene (1 atm) at room temperature in the presence of [(S,S)-2,4-bis-diphenylphosphinopentane (BDPP)]CoCl(2) (0.05 equiv) and methylaluminoxane. The minor 1,2-HV products, seen only in 1-vinylcyclohexene (~15%) and 1-vinylcycloheptene (2%), are formed as racemic mixtures. The corresponding Ni(II)-catalyzed HV reactions of these substrates give mostly the 1,2-adducts. Racemic 4-tert-butyl-1-vinylcyclohexene, when treated with Co[(S,S)-(BDPP)]Cl(2) and ethylene, undergoes a rare enantiodivergent reaction giving two diastereomers each in >98% ee.     

On the mechanism of the nickel-catalysed regioselective cyclodimerization of isoprene

A study of various Ni-ligand catalysed oligomerizations of isoprene has shown that with π-acidic P ligands the selectivity to cyclodimers amount to 97%. A new type of ligand is introduced, viz. fluoroalkyl phosphites having π-acceptor properties comparable to those of, e.g. PCl₃. With tris(hexafluoroisopropyl) phosphite the main product is 1,4-dimethy1-4-vinylcyclohexene. A detailed explanation based on a two-step mechanism is given. As to the first step, for a series of ligands having similar steric properties the changes in product distribution as a function of the electronic ligand parameter are explained in terms of a gradual change in HOMO-LUMO interactions between Ni and the olefins, with strong π-acidic ligands promoting the head-to-head coupling of the isoprene molecules. The second step, involving reductive elimination of a cyclodimer from the metal, shows an increasing selectivity towards substituted cyclohexenes for the head-to-head and tail-to-tail intermediates with increasing π-acidity of the ligand. The qualitative orbital treatment presented as an explanation is also applicable to reactions found for other metallacyclopentanes.     

Gas Phase Reaction of Tetrachlorogermane with Conjugated Dienes in the Presence of Hexachlorodisilane Initiator

Studies of the reaction of GeCl₄ with acyclic conjugated dienes (1,3-butadiene, 2-methyl-1,3- butadiene, 2,3-dimethyl-1,3-butadiene) and cyclopentadiene in the presence of Si₂Cl₆ initiator were carried out. With acyclic dienes, corresponding 1,1-dichloro-1-germacyclo-3-pentenes and 1,1-dichloro-1-silacyclo-3- pentenes are preferrably formed. With cyclopentadiene the main reaction products are cyclopentenyltrichlorogermanes and cyclopentenyltrichlorosilanes formed respectively by hydrogermylation and hydrosilylation of the starting diene. The explanation of the established rule is offered.     

A novel positively charged asymmetry membranes from poly(2,6-dimethyl-1,4-phenylene oxide) by benzyl bromination and in situ amination: Part II: Effect of charged group species on membrane performance and morphologies

Positively charged membrane with various charged groups were prepared by in situ amination and phase inversion in which the amine-organic solution and bromomethylated poly(2,6-dimethyl-1,4-phenylene oxide) (BPPO) was cast and immerged into an ethanol coagulation bath. The separation performance and morphologies were examined to investigate the effect of hydrophilicity of charged groups on the selective properties and the structure formation of the membranes. Positively charged groups introduced in the membranes were trimethylbenzylammonium, triethylbenzylammonium, tri-n-propylbenzylammonium and tri-n-butylbenzylammonium, in order of increasing hydrophobicity. Pure water flux and rejection to gelatin of the membranes at three pH values changed remarkably with increasing chain length of alkyl groups. The tendency of the change was mainly explained by coagulation value of the casting solution. The streaming potential and ion exchange capacity of the membranes were determined and the results showed that the membranes were all positively charged. Furthermore, water content, pore size distribution and SEM images of the membranes were examined as well.     

Effect of acyl chain length and branching on the enantioselectivity of Candida rugosa lipase in the kinetic resolution of 4-(2-difluoromethoxyphenyl)-substituted 1,4-dihydropyridine 3,5-diesters.

Since 2,6-dimethyl-4-aryl-1,4-dihydropyridine 3,5-diesters themselves are not hydrolyzed by commercially available hydrolases, derivatives with spacers containing a hydrolyzable group were prepared. Seven acyloxymethyl esters of 5-methyl- and 5-(2-propoxyethyl) 4-[2-(difluoromethoxy)phenyl]-2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylate were synthesized and subjected to Candida rugosa lipase (CRL) catalyzed hydrolysis in wet diisopropyl ether. A methyl ester at the 5-position and a long or branched acyl chain at C3 gave the highest enantiomeric ratio (E values). The most stereoselective reaction (E = 21) was obtained with 3-[(isobutyryloxy)methyl] 5-methyl 4-(2-difluoromethoxyphenyl)-2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate, and this compound was used to prepare both enantiomers of 3-methyl 5-(2-propoxyethyl) 4-[2-(difluoromethoxy)phenyl]-2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylate. The absolute configuration of the enzymatically produced carboxylic acid was established to be 4R by X-ray crystallographic analysis of its 1-(R)-phenylethyl amide.     

Reactions of 4-dicyanomethylenepyrans with hindered primary amines

The reaction of 2,6-dimethyl- and 2,6-diphenyl-4-dicyanomethylene-4H-pyran with hindered primary amines such as isopropylamine and cyclohexylamine gave 1-alkyl-2-amino-3-cyano-6-rnethyl(or phenyl)-4-acetonylidene (or phenacylidene)-1,4-dihydropyridine derivatives. The 6-methyl-4-acetonylidene examples underwent a facile thermal rearrangement to give 1-alkyl-2,6-dimethyl-4-dicy anomethy lene-1,4-dihydropy ridines. Several reactions of the acylidene derivatives are described.     

Extension of the voltammetric theory to inert,permeable thin-film coated rotating disc electrodes: Part II. Behaviour of ferrocene-ferricinium ion and quinone-hydroquinone systems on polymer-coated electrodes

The voltammetric behaviour of ferrocene-ferricinium ion and quinone-hydroquinone systems is investigated on electrochemically thin film polymer coated electrodes. Ferrocene oxidation is studied in 0.1 M NBu₄ ClO₄-nitromethane on rotating disc platinum electrodes coated with poly(2-hydroxymethyl-1,4-phenylene) oxide (I), poly-(2,6-dimethyl-1,4-phenylene) oxide (II), and poly[4-(2-aminoethyl)-1,2-phenylene] oxide (III) films. The quinone-hydroquinone system is investigated in aqueous medium (1 M HClO₄) with (I), (II) and poly-(2-cyano-1,4-phenylene) oxide films. Experimental results are in good agreement with the previously calculated voltammetric curves in steady-state mass transfer conditions. The charge transfer and diffusion parameters on these polymer-coated electrodes are calculated The quinone-hydroquinone system is rendered reversible by coating a platinum electrode with I.     

Multiply-charged negative clusters of adenosine-5′-monophosphate in the gas phase

Multiply-charged noncovalent cluster anions of adenosine-5'-monophosphate (AMP) were formed by electrospray ionization (ESI). Ions in higher charge states were observed when the ions were accumulated in an ion trap with helium buffer gas before detection. We determined the smallest size (n(a)) or appearance size as a function of charge state (q), i.e., n(a) = 4 for q = 2, n(a) = 8 for q = 3, and n(a) = 13 for q = 4. The relation between n(a) and q can be described by a charged droplet model. When the size is larger than n(a) for a given q, the fragmentation pathway of an anion cluster is dominated by loss of neutral fragments. In contrast, when the size approaches the appearance size, only charged fragments are formed.     

Study of diketone/metal ion complexes by electrospray ionization mass spectrometry: Influence of Keto-Enol tautomerism and chelation

The formation and collisionally activated dissociation (CAD) behavior of a series of complexes containing cyclic or linear diketone ligands and alkali, alkaline earth, or transition metal ions are investigated. Electrospray ionization (ESI) is utilized for introduction of the metal ion complexes into a quadrupole ion trap mass spectrometer. The proximity of the carbonyl groups is crucial for formation and detection of ion complexes by ESI. For example, no metal ion complexes are observed for 1,4-cyclohexanedione, but they are readily detected for the isomers, 1,2-and 1,3-cyclohexanedione. Although the diketones form stable doubly charged complexes, the formation of singly charged alkaline earth complexes of the type (nL + M²⁺ ? H⁺)⁺ where L = 1,3-cyclohexanedione or 2,4-pentanedione is the first evidence of charge reduction. CAD investigations provide further evidence of charge reduction processes occurring in the gas-phase complexes. The CAD studies indicate that an intramolecular proton transfer between two diketone ligands attached to a doubly charged metal ion, followed by elimination of the resulting protonated ligand, produces the charge reduced complex. For transition metal complexation, the preference for formation of doubly charged versus singly charged complexes correlates with the keto-enol distribution of the diketones in solution.