Syntheses of vinyl polymers containing a large π-electron cloud in the side chain

Several novel vinyl polymers containing five fused benzene rings in side chains were synthesized either by polymerization of the appropriate vinyl monomers or by chemical modification of the appropriate polymer. Thus, 3-(α-acryloyloxy)ethylperylene was prepared from perylene by Friedel-Crafts acylation with acetyl chloride and subsequent hydrogenation, followed by the reaction of the resulting alcohol with acryloyl chloride. 3-Acrylamido- or methacrylaminoperylene was prepared by the nitration of perylene, reduction of the resulting 3-nitroperylene, and the reaction with acryloyl or methacryloyl chloride. p-Vinylbenzal-3-acetylperylene was prepared by the condensation and dehydration reaction between p-vinylbenzaldehyde and 3-acetylperylene under alkaline medium, and, in the same manner, p-vinylbenzal-3-aminoperylene was prepared from p-vinyl benzaldehyde and 3-aminoperylene. All these monomers were polymerized with α,α′-azobisisobutyronitrile as catalyst in solution to afford the corresponding vinyl polymers. A vinyl polymer containing perylene-3-acetyl side chain was also prepared by the acetalization of poly(vinyl alcohol) with 3-formylperylene.     

Preparation of polymers containing sugar residues

The synthesis of five different polymers containing sugar residues on side chain is described. 1-O-Methacryloyltetra-O-acetyl-D -glucose, 1-O-methacryloyltetra-O-acetyl-D -galactose, and 6-O-methacryloyltetra-O-acetyl-D -glucose were prepared and polymerized. The polymethacrylates obtained were converted into water-soluble polymers by removing the acetyl protective group with sodium methoxide. 6-O-Methacryloyldiisopropylidene-D -galactose was also prepared and polymerized. The isopropylidene protective group was removed by acid hydrolysis. Poly (N-methacryloylglucosamine) was prepared directly by the polymerization of N-methacryloyl-D -glucosamine without the use of any protective group.     

Novel heterocycles. 2. Synthesis of the 1,3,2-benzodiazaphosphorin ring system

A series of 1,3-disubstituted-2,3-dihydro-1,3,2-benzodiazaphosphorin-4(1H)one 2-oxides was prepared by a method involving the treatment of an appropriate anthranilamide with phosphorus trichloride. Tricyclic diazaphosphorins 24 and 28 were also prepared. Some spectral data of the products are also discussed.     

AB5型多元贮氢合金的化学制备及其性能研究

LaNi5贮氢合金在传统的贮氢应用中得到利用而被充分的研究，但LaNi5用作电池的电极太贵，不稳定，对腐蚀太敏感，而且吸放氢过程中晶胞过度膨胀和收缩，吸放氢前后体积变化率大，从而导致合金严重粉化。为了克服这些缺点，人们采用添加辅助元素部分取代基本元素的方法。即用混     

Synthesis and antibacterial activity of 2-phenyl-4H-benzo[b]thiopyran-4-ones (Thioflavones) and related compounds

A number of 2-phenyl-4H-benzo[b]thiopyran-4-ones (thioflavones) and related compounds have been prepared to test their antibacterial activity. The flavone derivatives were also prepared to compare with their antibacterial activity. It was found that hydroxythioflavones were easily prepared by demethylation of methoxythioflavones with aluminium chloride. In the test of antimicrobial activity, methoxy- or hydroxythioflavones were found to be inactive. It is suggested that the sulfone or sulfoxide of thioflavone is required for antimicrobial activities against yeast funguses and molds. These thioflavone derivatives exhibit low acute toxicity.     

Zur Darstellung sechsgliedriger Cyclosilane mit einem Heteroatom

In the nearly unknown class of cyclosilanes with one heteroatom, decaphenyl-oxa-cyclohexasilane was prepared for the first time by removing of water. The diol was prepared by hydrolysis of the corresponding 1,5-dichlorocompound. Cyclisation was not successful with 1,5-Di(ethylamine)decaphenylpentasilane, which was prepared also for the first time. Spectroscopic data were determined of all synthesized compounds.

Herrn Prof. Dr.G. Zigeuner zum 60. Geburtstag gewidmet.     

Polymerization of acetylenic derivatives. XXVII. Synthesis and properties of isomeric poly-N-ethynylcarbazole

Poly-N-ethynylcarbazole (PEC) was prepared thermally, by using Ziegler-Natta catalysts, and also by using TiCl₄ and phosphine complexes for initiation. The spectral data (infrared, NMR, x-ray diffraction, and ultraviolet) were best interpreted based on a cis-transoidal/cis-cisoidal stereoblock structure for (both soluble and insoluble) polymers prepared by Ziegler-Natta catalysts and on a trans-cisoidal structure for the polymers prepared with the other catalysts. The cis-transoidal/cis-cisoidal stereoblock structure isomerized thermally into a trans-cisoidal structure, at temperatures which were dependent on the type of initiation.     

Some fatty acids having an o-heterocycle in their terminal positions. IV. (2-Methyl-2H-chromen-2-yl)acetic acids

(2-Methyl-2H-chromen-2-yl)acetic acid 2a was prepared by condensations of salicylaldehyde with diethyl isopropylidenemalonate followed by hydrolyses. Similarly three methoxy derivatives 2c, 2d , and 2e were also prepared from the corresponding salicylaldehyde.     

Synthesis of polyurethanes from fluorinated diisocyanates

A number of polyurethanes based on fluorinated aliphatic diisocyanates, perfluorinated aromatic diisocyanates, and chlorinated aromatic diisocyanates have been prepared. The polyurethane prepared from perfluorotrimethylene diisocyanate and hexafluoropentanediol was a rubbery solid which hydrolyzed readily in air to a liquid or sticky solid but was stable if protected from moisture. The products of hydrolysis were isolated and identified. Polyurethanes based on hexafluoropentamethylene diisocyanate were synthesized by reaction of hexafluoropentanediamine with hexafluoropentamethylene bischloroformate and with tetrafluoro-p-phenylene bischloroformate. Polyurethanes were synthesized by reaction of tetrafluoro-p-phenylene diisocyanate with hexafluoropentanediol and pentanediol. Other perfluoroaryl diisocyanate-based polyurethanes were synthesized by reaction of tetrafluoro-m-phenylene diisocyanate with hexafluoropentanediol and with tetrafluoro-p-hydroquinone. Polyurethanes were also synthesized by reaction of tetrachloro-p-phenylene diisocyanate and 2,3,5,6-tetrachloro-p-xylylene-α,α′-diisocyanate with hexafluoropentanediol.     

Design and synthesis of novel fused heterocycles using 4-chromanone as synthon

A new series of heterocyclic systems, including azole, azolopyrimidine, and pyridopyrimidine derivatives, attached to 2H-chromene scaffold, was prepared by a convenient procedure through the reactions of (E)-2-dimethylamino-methylene chromanone with different nitrogen binucleophiles. Various substituted chromeno[4,3-b]pyridine derivatives were also prepared through the reactions of (E)-2-dimethylaminomethylene chromanone with a series of active methylene compounds.

     

Sensitive determination of yohimbine in plasma by micropipette tip-based poly(methacrylic acid-co-ethylene glycol dimethacrylate) monolith SPME coupled with HPLC method

A simple, miniaturized micropipette tip-based poly(MAA-co-EGDMA) monolith was prepared by in situ polymerization for sensitive micro-extraction of yohimbine in aqueous and plasma samples. Several parameters for monolith preparation were systematically optimized to obtain monolith with better permeability and absorption property. Methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) were selected as monomer and crosslinker and the ratio of MAA and EGDMA was 1:6. Methanol containing 30% dimethyl sulfoxide was selected as porogens. The prepared micropipette tip-based poly (MAA-co-EGDMA) monolith could be easily connected with a syringe infusion pump for loading solutions. Several factors such as washing solvents, flow rate of sampling, sample volume, and pH of sample solutions which affect enrichment efficiency of yohimbine were also evaluated in this work. Under optimized conditions, good enrichment capacity and stability of poly(MAA-co-EGDMA) monolith were obtained. Finally, the prepared micropipette tip-based poly(MAA-co-EGDMA) monolith solid phase micro-extraction combined with high-performance liquid chromatography was also used to analyze yohimbine in plasma samples. The developed method exhibited good sensitivity with limit of detection as low as 0.5?ng/mL, and also showed wide linearity in the range of 1.0–2000 ng/mL with R²?≥?0.998, excellent reproducibility with relative standard deviation (RSD) ≤?2.5%, and good recoveries in the range of 97.9–103.8% of yohimbine in human plasma.     

o-Acetylaminophenylglyoxylic Acid Anil and Its Derivatives

1-Acetyl- and 1-benzoyl-2- and -3-phenyliminooxoindolines were synthesized. o-(Acetylamino)phenylglyoxylic acid anil was prepared from 1-acetyl-3-phenylimino-2-oxoindoline. More stable o-(acetylamino)phenylglyoxylanilide anil can be prepared not only from o-(acetylamino)phenylglyoxylanilide but also from an ester or chloride of o-(acetylamino)phenylglyoxylic acid anil. o-(Acetylamino)phenylglyoxylothiosemicarbazide was prepared from o-(acetylamino)phenylglyoxylic acid anil and from the corresponding anilide.     

Synthesis and Polymerization of a New Class of Oligosaccharide-and Polyamide-Macromers Having a Styrene End-Group

As an approach to synthesis of oligo- and polysaccharide-containing polymers, two types of polystyrenes having pendant carbohydrate groups were prepared. Their functions, especially amphiphilic behaviors in water, were revealed.

A new polyamide macromer having a vinylbenzyl group (M_n 3000-3800) was prepared by the anionic polymerization of bicyclic oxalactam followed by the reaction with p-vinylbenzylamine. Another polyamide macromer telechelated with amino groups (M_n, 1400 and 4100) was also prepared by the similar method.     

3-Deazaguanine N7- and N9-(2′-Deoxy-β-D-ribofuranosides): Building Blocks for Solid-Phase Synthesis and Incorporation into Oligodeoxyribonucleotides

Oligonucleotides continuing 3-deaza-2′-deoxyguanosine ( I ) or its N⁷-regioisomer 2 were prepared by solid-phase synthesis using P¹¹¹ chemistry. Protection of ¹ or ² with N,N V-dimethylformamide diethyl acetal followed by 4,4′-dimethoxytritylation afforded imidazo[4,5-c]pyridines 10b and 11b , respectively. The latter were converted into the 3′-phosphonates 10c or lie, respectively; the cyanoethyl N,N-diisopropylphosphoramidite 10d was also prepared. The oligonucleotide building blocks were employed in automated solid-phase synthesis. 1 he self-complementary oligomers 13 , 15 , and 17 were prepared and characterized by enzymatic hydrolysis with snake-venom phosphodiesterase followed by alkaline phosphatase. There CD spectra exhibited the general structure of a B-DNA.     

Water-Soluble imide-amide copolymers. III. Preparation and characterization of poly (acrylamide-co-N,N-diallylaniline) and poly (acrylamide-co-sodium N,N-diallylsulfanilate)

N,N-diallylaniline monomer was prepared in good yields, for use in preparation of homopolymer and for copolymerization with acrylamide. Functionalized N,N-diallylaniline monomer, as sodium N,N-diallylsulfanilate, was also prepared in good yields for copolymerization with acrylamide. Both monomers were fully characterized by elemental analysis, IR, and NMR. Poly (N,N-diallylaniline) was obtained by polymerization of a strongly acidic aqueous solution of N,N-diallylaniline initiated with hydrogen peroxide. Spectroscopic data from this homopolymer was used to facilitate spectral assignments of the new copolymers. Copolymers of acrylamide with N,N-diallylamine were prepared at monomer feed ratios of 10, 20, and 30 mol % amine and gave 3.5, 7.4, and 8.9 mol % incorporation, respectively. Similar diallyl monomer incorporation rates were obtained for the copolymerization of sodium N,N-diallylsulfanilate with acrylamide. With 10, 30, and 50 mol % of the sodium salt relative to acrylamide, 3.9, 8.4, and 19.2 mol % incorporation of the diallyl monomer was obtained.     

Synthesis of novel photodegradable poly(o-nitrobenzaldehyde acetal) polymers

The synthesis of novel photodegradable poly(o-nitrobenzaldehyde acetals) is described. The polymers were prepared by condensing o-nitrobenzaldehyde with a series of glycols. Polyesteracetals can also be prepared by first preparing the o-nitrobenzaldehyde glycol acetal or polyacetal prepolymer and subsequent reaction with a diacid chloride. These polymers, although light sensitive, appear to be thermally stable since they were prepared in part by melt condensation techniques. The polymers are useful as positive working photodegradable polymers.     

Preparation and characterization of a polystyrene/bovine serum albumin nanoparticle‐coated capillary for chiral separation using open‐tubular capillary electrochromatography

Polystyrene (PS) nanoparticles coated by BSA, hereafter denoted as PS/BSA, were prepared and chemically immobilized for the first time onto a capillary inner wall for open‐tubular CEC (OTCEC). EOF and scanning electron micrography were used to characterize the prepared nanoparticle‐coated capillaries. To investigate the performance of the prepared columns in OTCEC, chiral separation of d ,l ‐tryptophan (dl ‐Trp) was performed in monolayer BSA‐modified capillary and PS/BSA nanoparticle‐coated columns. The results indicated that the nanoparticle‐modified column afforded a higher resolution compared with the monolayer type. Rapid enantioseparation of dl ‐Trp (within 3 min) was achieved with the PS/BSA‐immobilized column using an electroosmotic pump‐assisted CEC. Enantiomer separations of other compounds like dl ‐tyrosine and warfarin were also achieved with the column. Besides, run‐to‐run and column‐to‐column repeatabilities of the PS/BSA‐coated column in the chiral separation were systematically introduced.     

Synthèse d'analogues azotés d'esters chrysanthémiques et pyréthriques

3,3-Dimethyl-2-vinyl-l-ethoxycarbonylaziridines were prepared from 2-acylaziridines and phosphoranes, phosphonate or silyl anions. A 3,3-di-methyl-2-ethoxycarbonyl N-vinylaziridine was also prepared. These compounds constitute some analogues of chrysanthemic and pyrethric acid esters.     

Effect of temperature and solvents on stereospecific polymerization of vinyl alkyl ethers catalyzed by aluminum sulfate–sulfuric acid complex

The effect of polymerization temperature and solvents was determined on the crystallinity of polymers of vinyl isobutyl ether and of vinyl n-butyl ether prepared with aluminum sulfate–sulfuric acid complex catalyst. Principally, the methyl ethyl ketone (MEK)-insoluble fractions of these polymers were used for characterization. Density, per cent crystallinity by x-ray diffraction, infrared ratio, and dilatometric volume contraction of these polymer fractions were used as criteria of crystallinity. The MEK-insoluble fractions of poly(vinyl n-butyl ethers) prepared in carbon disulfide in the temperature range of ?30 to +25°C did not show any significant difference in the values of the above crystallinity parameters. The polymer obtained at 50°C. was less crystalline than the rest of the polymers. The MEK-insoluble fractions of poly(vinyl isobutyl ethers) prepared at 0–50°C. in carbon disulfide and n-heptane solvents also did not significantly differ in their degree of crystallinity. They were, however, decidedly less crystalline than the MEK-insoluble fractions of the corresponding polymers obtained at ?20°C. These data a indicate that on increasing the temperature of polymerization the crystallinity of the polymers was either unchanged or decreased slightly. The polymerizations of vinyl n-butyl ether and vinyl isobutyl ethers were also carried out in binary mixtures of carbon disulfide with n-heptane, chlorobenzene, and MEK. Generally, increasing the concentration of carbon disulfide increased the inherent viscosities of polymers as well as the weight percentage of their MEK-insoluble fractions. The MEK-insoluble fraction of poly(vinyl isobutyl ether) prepared in carbon disulfide-MEK mixture (volume ratio 2:1) was isotactic and highly crystalline. Likewise, the MEK-insoluble fractions of two polymers of vinyl n-butyl ether prepared in MEK itself were also isotactic and highly crystalline. Compared to poly(tetramethylene oxide), these latter fractions exhibited less dependence of rate of crystallization upon temperature. Consequently, at low degrees of supercooling they crystallize much more rapidly than does poly(tetramethylene oxide).