Hydroxymethylphenylnaphthoie acid lactones

Reduction of 1-phenylnaphthalene-2,3-dicarboxylic anhydride (I) with zinc and acetic acid or lithium aluminium hydride yields a mixture of 1-phenyl-3-hydroxymethyl-2-naphthoie acid lactone (II) and 1-phonyl-2-hydroxymethyl-3-naphthoie acid lactone (III). Catalytic hydrogenation of (I) gave the tetrahydronaphthalene dicarboxylic anhydride (IV). Oxidation of the phenyldihydronaphthofuran (X), prepared by base-catalyzed cyclization of the ether (IX), also yielded lactones (II) and (III). The phenyltetrahydronaphthofuran (XII) was similarly prepared by cyclization of the phenylpropargyl cinnamyl ether (XI).     

A new intramolecular cyclisation reaction—I : Novel synthesis of benzo(k,1)thioxanthene-3,4-dicarboxylic anhydride and derived dyestuffs

A new direct synthesis of benzo(k,1)thioxanthene-3,4-dicarboxylic anhydride from 4-nitro-naphthalene-1,8-dicarboxylic anhydride and 2-aminobenzenethiol is reported; 4-(2-aminophenylthio) naphthalene-1,8-dicarboxylic anhydride and 4-phenylthionaphthalene-1,8-dicarboxylic anhydride are also formed. Similar reaction in presence of amyl nitrite or sodium nitrite results in formation of larger amounts of 4-phenylthionaphthalene-1,8-dicarboxylic anhydride, together with other products arising from the oxidation of 2-aminobenzenethiol; one such product is the new heterocycle 9,10-dithiaphenanthrene. 4-(2-Aminophenylthio)-naphthalene-1,8-dicarboxylic anhydride is rapidly converted by amyl nitrite or sodium nitrite in dimethylformamide into benzo(k,1)thioxanthene-3,4-dicarboxylic anhydride, constituting a novel one-stage intramolecular cyclisation reaction of greater convenience than the conventional two stage Pschorr cyclisation.     

Correlations between photoelectron and ultraviolet absorption spectra of polycyclic hydrocarbons. The perylene,coronene and bisanthene series

As in earlier work,¹ the p-bands in the optical spectra and the first bands in the PE spectra of polycyclic aromatic hydrocarbons are related to $\text{R}\text{4}$, where R is the Rydberg constant of the hydrogen atom. The α- and β -bands are related to 4.9 eV which is the IP of graphite. These regularities have been tested by means of the UV and PE data of 34 peri-condensed hydrocarbons belonging to the perylene-, 1,12-benzoperylene-, coronene- and bisanthene series.     

碳铂类似物的合成,表征及对大鼠W—256肉瘤的抑制作用

合成了十八种〔PtA_2X〕·yH_2O,其中A分别为NH_3、CH_3NH_2、1/2乙二胺和1/2(2,3-二甲基-2,3-丁二胺),X分别为1,1-环丙烷二羧酸根(CPrDCA)、2-甲-1,1-环丙烷二羧酸根(2-M-CPrDCA)、2-甲-1,1-环丁烷二羧酸根(2-M-CBDCA)、1,2-环戊烷二羧酸根(CPDCA)和1,1-环已烷二羧酸根(CHDCA),并进行了表征。测定了配合物抑制大鼠W-256肉瘤的活性,发现配合物〔Pt(NH_3)_2X〕系列按X不同有以下的活性次序:CPrDCA>2-M-CPrDCA>CPDCA>CBDCA(碳铂)≥2-M-CBDCA。     

Photochemistry of 1-methoxyphthalazine 3-oxide

Irradiation of 1-methoxyphthalazine 3-oxide in cyclohexane at 3500 Å resulted in the formation of phthalimide. On the other hand, irradiation in the presence of maleic anhydride resulted in the formation of 1-methoxynaphthalene-2,3-dicarboxylic acid anhydride. The similar cycloadduct was also observed by irradiation in the presence of benzoquinone. The formation of the cycloaddition products was also observed in acetic anhydride at 60°.     

LC-Polyimides. 22. Thermotropic Poly(Amide-Imide)s Derived from New Bisimide Spacers and Biphenyl-4,4′-dicarboxylic Acids

Abstract

A new class of diamine spacers was synthesized from α,ω-diaminoalkanes and 4-nitrophthalic anhydride. The resulting α,ω-bis(4-aminophthalimido)alkanes were polycondensed with terephthaloylchloride, 2-phenylthioterephthaloylchloride, naphthalene-2,6-dicarboxylic acid dichloride, and 4,4′-biphenyl dicarboxylic acid dichloride. Most poly(amide-imide)s proved to be semicrystalline, forming a smectic layer structure in the solid state. Yet only the poly(amide-imide)s derived from 4,4′-biphenyl dicarboxylic acid are thermotropic and form a smectic and a nematic LC-phase. Due to the high temperatures employed, the reversibility of the phase transitions suffers from thermal degradation.     

L'importance de la presence de l'oxygene en position-7 dans les reactions des alkylmagnesiens secondaires avec les anhydrides tricycliques pontes.

The reaction of secondary alkylmagnesium bromides with endo and exo bicyclo-[2.2.1]hept-5-ene-2,3-dicarboxylic anhydrides lead at the corresponding ketoacids whereas with the 7-oxa exo bicyclo[2.2.1]hept-5-ene-2,3 dicarboxylic anhydride produced only the monosubstituted lactones.     

Novel polybenzoxazinones with tricyclic fused-rings

A series of polybenzoxazinones containing phenoxathiin and phenoxaphosphine units were prepared from tricyclic diacid chlorides and 4,4′-diaminobiphenyl-3,3′-dicarboxylic acid and 4,4′-diamino-3,3′-diphenylmethane dicarboxylic acid. The low temperature solution polymerization technique afforded polyamic acid which subsequently underwent cyclization along the polymer chain in a solvent mixture of refluxing N,N′-dimethylacetamide, acetic anhydride, and pyridine to give polybenzoxazinones in moderate yields. The polymers thus obtained had inherent viscosities in the range of 0.15–0.23 dL/g, were sparingly soluble in N-methyl-2-pyrrolidone, and were found to be thermally more stable than the corresponding open-chain polymer with diphenylether linkage.     

Pyrolysis of cyclo-aromatic diesters

Studies on the pyrolysis of cyclo-aromatic diesters derivatives of 3-phenylprop-2-en-1-ol are presented. The diesters are obtained during catalyzed esterification process of a stoichiometric ratio of 3-phenylprop-2-en-1-ol with suitable cycloaliphatic or aromatic acid anhydride in the solvent-free medium. As an acid anhydrides cyclohexane-1,2-dicarboxylic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic anhydride, and phthalic anhydride were applied. The thermal properties of obtained compounds under inert atmosphere were tested by means of differential scanning calorimetry and thermogravimetry coupled with FTIR analysis. The pyrolysis products were determined and the probable mechanism of their decomposition was proposed.     

Efficient MW‐Assisted Synthesis of Some New Isoquinolinone Derivatives With In Vitro Antitumor Activity

An efficient and convenient synthesis of novel [1,3]oxazino[3,2‐b]isoquinoline‐5,12‐dione derivative 4 was achieved by the reaction of anthranilic acid with homophthalic anhydride under microwave irradiation, followed by cyclization with acetic anhydride. Some new isoquinolinone and fused isoquinolinone derivatives were prepared via reaction of compound 4 with different nitrogen nucleophiles by using reflux and a focused microwave reactor. Microwave irradiation favored the formation of the desired products with improved yields and shortened reaction times. This is a simple and green method for the synthesis of isoquinolinone derivatives. The structures of the prepared compounds were elucidated by IR, ¹H‐NMR, and mass spectroscopy. Some of the newly prepared compounds were tested in vitro against a panel of three human tumor cell lines, namely, hepatocellular carcinoma (liver) HepG2, colon cancer HCT‐116, and mammary gland breast MCF‐7. Almost all of the tested compounds showed satisfactory activity.     

Spectral characterisation of new organic fluorescent dyes with an alkoxysilane moiety and their utilisation for the labelling of layered silicates

New fluorescence dyes with an alkoxysilane moiety were synthesised by the condensation of 3-(triethoxysilyl)-1-propanamine (3-aminopropyltriethoxysilane) with 4,10-benzothioxanthene-3,1′-dicarboxylic acid anhydride (BTXA) and N,N-dimethylaminonaphthalene-1,8-dicarboxylic acid anhydride (DMANA), which was accompanied by the formation of an imidic bridge. The compounds N-(3-(triethoxysilyl)propyl)-thioxantheno[2,1,9-dej]isoquinoline-1,3-dione (BTX-S) and 4-(N′, N′-dimethyl)-N-(triethoxysilyl)propyl-1,8-naphthalene dicarboxylic acid imide (DMAN-S) were characterised by steady-state and time-resolved fluorescence spectroscopy in chloroform and ethanol. Both conjugates (BTX-S and DMAN-S) exhibited absorption and emission bands in the same region as the un-substituted BTXA and DMANA. An important Stokes shift was observed for DMAN-S in ethanol. A high fluorescence quantum yield was observed for BTX-S in both solvents and for DMAN-S in chloroform. In addition, the newly developed fluorescent silane dyes were covalently attached to the microscopic particles of layered silicates and on the surface of SiO₂ wafers as a proof of concept for fluorescence particle (surface) visualisation. The surface wafer modification was precisely characterised by X-ray photoelectron spectroscopy (XPS). Successful covalent linkage onto the particles of layered silicates was proved by confocal laser scanning microscopy technique.     

7-氧杂双环[2.2.1]庚-2,3-二甲酸衍生物的合成及其抗HIV活性

以呋喃和顺丁烯二酸酐为原料,经环化反应制得7-氧杂双环[2.2.1]庚-5-烯-2,3-二甲酸酐(3);打开3的酸酐五元环,选择性地进行单酯化反应,合成了一系列7-氧杂双环[2.2.1]庚-3-烷氧羰基-2-甲酸(4a～4d),其结构经1H NMR和MS表征.初步探讨了4的抗HIV构效关系,其中4a的治疗指数与其先导化合物去甲基斑蝥素相当,毒性较之降低.     

A study of novel heat-resistant polymers: Preparation of photosensitive fluorinated polybenzoxazole precursors and physical properties of polybenzoxazoles derived from the precursors

A series of novel photosensitive polybenzoxazole precursors were prepared from polycondensation of 2,2-bis(3,3′-amino-4,4′-hydroxyphenyl)hexafluoropropane with photosensitive dicarboxylic acid chlorides such as p-phenylenediacryloyl chloride and benzophenone-4,4′-dicarboxylic chloride. The precursors are soluble in common organic solvents owing to the presence of perfluoromethyl groups in the chain structure, and insolubilized in the solvents on irradiation with the light. Polybenzoxazole patterns with high resolution as well as high aspect ratio were reproduced by baking the precursor patterns at 300°C. The pattern shrinkage on the conversion to polybenzoxazole was slight. The polybenzoxazole films offered good heat-resistance up to 400°C in addition to good electrical properties.     

外式双环[2.2.1]庚烷(庚-5-烯)-2,3-二甲酸酐膦二肽衍生物的合成

选择有机磷基团对斑蝥素的结构骨架进行修饰改造,以外式双环[2.2.1]庚-5-烯-2,3-二甲酸酐为原料,设计合成了一系列斑蝥素类似物。化合物的结构经1HNMR,MS及元素分析确证。     

Synthesis of Mixed Bisamides of Cyclic ortho-Dicarboxylic Acids

A procedure was developed for preparation of bisamides of cyclic ortho-dicarboxylic acids byacylation of m- or p-phenylenediamine in acetone solution at room temperature simultaneously with twodifferent anhydrides of cyclic or aromatic ortho-dicarboxylic acids; another process consisted in treating ananhydride of aromatic or cyclic dicarboxylic acid with monoamide of cis-4-cyclohexene-1'2-dicarboxylicacid in dimethylformamide at room temperature.     

The Non-planarity of the Bicyclo[2.2.1]hept-2-ene Double bond. Crystal Structures of Bicyclo[2.2.2]oct-2-ene,Bicyclo[2.2.1]hept-2-ene,and Bicyclo[2.1.1]hex-2-ene Systems

The crystal structures of (1R,4R,5S,8S)-9,10-dimethylidentricyclo[6.2.1.0^2,7]undec2(7)-ene-4,5-dicarboxylic anhydride ( 3 ), (1R,4R,5S,8S)11-isopropylidene-9,10-dimethylidenetricyclo[6.2.1.m^2,7]undec-2(7)-ene-4,5-dicarboxylic anhydride ( 6 ), (1R,4R,5S8S)-9,10-dimethylidenetricyclo[6.2.2.0^2,7]dodec-2(7)-ene-4,5-dicarboxylic anhydride ( 9 ), (1R4R5S8S)-TRICYCLO[6.2.2.0^2,7]dodeca-2(7), 9-diene-4,5-dicarboxylic anhydride ( 12 ) and (4R,5S)-tricyclo[6.1.1.0^2.7]dec-2(7)-ene-4,5-dicarboxylic acid ( 16 ) were established by X-ray diffraction. The alkyl substituents onto the endocyclic bicyclo[2.2.1]hept-2-ene double bond deviate from the C(1), C(2), C(3), C(4), plane by 13.5°4 in 3 and by 13.9° in 6 , leaning toward the endo-face. No such out-of-plane deformations were observed with the bicyclo[2.2.2]oct-2-ene derivatives 9 and 12 . The exocyclic s-cis-butadiene moieties in 3, 6 and 9 do not deviate significantly from planarity. The deviation from planarity of the double bond n bicyclo[2.2.1]hept-2-ene derivatives and planarity in bicyclo[2.2.2]oct-2-ene analogues is shown to be general by analysis of all known structures in the Cambridge Crystallographic Data File. The non-planarity of the bicyclo[2.2.1]hept-2-ene double bond cannot be attributed only to bond-angle deformations which would favour rehybridizatoin of the olefinic C-atoms since the double bond in the more strained bicyclo[2.1.1]hex-2-ene drivative 16 deviates from planarity by less than 4°.     

Unusual amino acids. 5. Synthesis of 3,5-dioxopyrazolidine derivatives

Monohydrazides of 2-R-4-methyl-4-cyclohexene-1,1-dicarboxylic acids react with trifluoroacetic acid anhydride to give 4-substituted 3,5-dioxopyrazolidines, with phosphorus trichloride to give 4-(2-R-5-chloro-4-methylcyclohexane)-3,5-dioxopyrazolidines, and with acetic anhydride to give 4-(2-R-4-methyl-4-cyclohexene)-3,5-diacetoxypryazoles.For Communication 4, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 903–907, July, 2000.     

Controlling silica surfaces using responsive coupling agents

The surface chemistry of silica was modified using coupling agents capable of participating in oxidation or in the Diels-Alder (and retro Diels-Alder) reactions. The synthesis of the latter coupling agents, using trialkoxysilane groups linked to a cyclopentadiene structure, was achieved by the condensation of sodium cyclopentadienolide with 1-chlorodimethylsilyl-3-triethoxysilylpropane to give 1-cyclopentadienyldimethylsilyl-3-trialkoxysilylpropane. The cyclopentadiene ring in this structure was shown to undergo normal Diels-Alder chemistry with maleimides or maleic anhydride to give 7-(dimethylsilylpropyltrialkoxysilane)-5-norbornene-2,3-dicarboxylic acid anhydride. The retro Diels-Alder reaction of 7-(dimethylsilylpropyltrialkoxysilane)-5-norbornene-2,3-dicarboxylic acid anhydride in solution was not very efficient: the adduct is very stable and only undergoes the retro Diels-Alder reaction at temperatures in excess of 200 °C. Once grafted to the surface, however, the retro Diels-Alder reaction was achieved at a level greater than 90% by use of thermolysis in the presence of free cyclopentadiene. In addition, a polyene-based coupling agent derived from squalene was prepared by hydrosilylation using HMe₂SiOSiMe₂CH₂CH₂Si(OEt)₃. Once grafted to the surface, oxidation by ozone led to ozonides that could be reduced to ketone/aldehyde groups. These in turn could be trapped by functional groups such as hydrazines to make surface-bound hydrazones. With both types of coupling agents, the surface energy and nature of the functional groups bound to the surface could be changed on demand in response to an external stimulus.     

超支化聚(酯-酰胺)的合成与流变改性研究

近十几年来 ,超支化聚合物因具有独特的结构和特殊的性能而受到普遍关注[1] .超支化聚合物具有低的熔体粘度 ,与线性聚合物共混可显著改善其加工流变性 ,具有商业应用潜力 .关于超支化聚合物在流变改性方面的应用已有文献报道[2～ 6] ,但目前文献中的大多数单体合成较繁琐且收率不高 ,这已成为制约超支化聚合物应用的瓶颈 ,如何以简便的途径合成超支化聚合物已成为当前研究的重点 .本文设计一条新的合成路线 ,即以 1 ,2 ,4 苯三酸酐、乙醇胺及乙酸酐为原料 ,以高的收率得到了单体N ( 2 乙酰氧基乙基 ) N ( 2′ ,4′ 二羧基苯甲酰基 )胺 (…     

Synthesis and properties of organosoluble poly(amide imide imide)s based on tetraimide dicarboxylic acid condensed from 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 4,4′‐oxydianiline,and trimellitic anhydride and various aromatic diamines

A novel tetraimide dicarboxylic acid was synthesized with the ring‐opening addition of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 4,4′‐oxydianiline, and trimellitic anhydride in a 1/2/2 molar ratio in N‐methyl‐2‐pyrrolidone followed by azeotropic condensation to tetraimide dicarboxylic acid. A series of poly(amide imide imide)s (PAIIs) with inherent viscosities of 0.8–1.1 dL/g were prepared from tetraimide dicarboxylic acid with various aromatic diamines by direct polycondensation. Most of the PAIIs were readily soluble in a variety of amide polar solvents and even in less polar m‐cresol and pyridine. Solvent‐cast films had tensile strengths ranging from 99 to 106 MPa, elongations at break ranging from 8 to 13%, and initial moduli ranging from 2.0 to 2.3 GPa. The glass‐transition temperatures of these PAIIs were recorded at 244–276 °C. They had 10% weight losses at temperatures above 520 °C in air or nitrogen atmospheres. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1092–1102, 2002