ELECTRONIC EFFECTS OF POLYFLUORINATED SUBSTITUENTS ON THE POLYMERIZATION AND THE PROPERTIES OF POLYTHIOPHENES

Three series of polythiophenes containing fluoroalkoxy and fluoroether substituentswere prepared by electrochemical polymerization. The effect of substituents with fluoro-alkoxy or ether functional groups on the electrochemical polymerization of thiophene mono-mers and properties of the obtained polymers were analyzed. The introduction of a flu-oroether functional group at the 3-position of the thiophene ring leads to an increase ofthe oxidation potential of the monomer and to a decrease of the conductivity of the re-sulting polymers, even with the use of a CH_2 group as spacer. Conversely, the presenceof an oxygen atom directly at the 3-position of the thiophene ring, which offsets the nega-tive withdrawing effect of fluoroalkyl groups, facilitates the synthesis of highly conductingpolythiophenes.     

Synthesis and Anti-tumor Activity of Novel Amide Derivatives of Ursolic Acid

Ursolic acid was modified at C3 and C28 position to obtain fourteen derivatives including twelve novel compounds, and their chemical structures were characterized by IR, ^1H NMR and MS. Cell growth inhibitory effects of the derivatives against Hela cell were evaluated by MTT assay. All these derivatives were found to have stronger cell growth inhibitory than their parent compound, ursolic acid. The derivatives with a substituted acetyl group at C3 hydroxyl group show better activities than those with an unsubstituted hydroxyl group.     

Highly Chemical and Regio－selective Catalytic Oxidation with a Novel Manganese Catalyst

The chemical selectivity of a novel active manganese compound [Mn2^IVμ-O)3(TMTACN)2] (PF6)2 (1) in catalytic oxidation reactions depended on the structure of substrates and 1 was able to catalyze the oxidation of toluene into benzaldehyde and/or benzoic acid under very mild conditions. The following results were obtained: (1) The selectivity of the oxidation depended on the electronic density of double bonds. Reactivity was absent when strong electron-witherawing groups were conjugated with double bonds. (2) Allylic oxidation reactions mostly take place when double bond is present inside a ring system, whilst epoxiclarion reactions occur when the alkene moiety is part of linear chain. (3) In ring systems, the methylene group was more likely to be oxidized than the methyl group on ailylic position. As expected, the C--H bonds at the bridgeheads were unreactive.The secondary hydroxyl groups are more easily to be oxidized than the primary hydroxyl groups.     

Methylation of 5-Amino-3-methylthio-1H-pyrazole Derivatives and Two Related Crystal Structures

5-Amino-3-methylthio-1H-pyrazoles are very important building blocks from which a wide variety of pyrazole derivatives can be prepared. When substituted 5-amino-3-methylthio-1H-pyrazole was treated with CH3I, the methylation occurres at endocyclic two nitrogens at the same time. The ratio of isomers in products was depended upon the nature of 4-position substituent in the pyrazole ring. The products were characterized by X-ray diffraction analysis, and the ratios of isomer were explained by means of the results of ab inito calculation.     

Synthesis and characterization of hyperbranched polyurethane-benzyltetrazole

A series of hyperbranched polyurethane-benzyltetrazoles（H-PBTZs） with different linkage structures were synthesized via the polycondensation of hexamethylenediisocyanate as an A₂ type monomer with（4-（1H-tetrazol-5- yl）benzyl）-diethanolamine（TBDEA） as a BB’₂ type monomer in the absence of catalyst at different temperatures.The FTIR, and ¹³C and ¹H-NMR spectroscopy were used to characterize the molecular structures of TBDEA and H-PBTZs as well as the counterpart linear polyurethane-benzyltetrazole（L-PBTZ）.The molecular composition was determined by the reaction selectivity that the isocyanate group reacted with the hydroxyl group in diethanolamine segment or the active hydrogen atom on tetrazole ring.Raising reaction temperature was propitious to the reaction of isocyanate group with the active hydrogen atom on tetrazole ring.The degrees of branching（DB） for H-PBTZs obtained from the ¹H-NMR spectra increased with raising reaction temperature.The wider molecular weight distribution of 1.7-2.9 for H-PBTZs was obtained via GPC analysis.TGA results showed that H-PBTZs had high thermal stability compared with L-PBTZ.     

Amino Trans-position through the Chiral Aziridine

Aziridines are valuable synthetic reagents and intermediates.[1～3] The highly strained three membered ring readily opens with excellent stereo- and regio-control to afford a wide variety of more stable ring opened chiral amines. (1 S, 2S)-1-Phenyl-2-amino-1,3-propanediol (1) is sulphonated at amino group and the hydroxyl group. Obtainning two kinds of sulphonated 1. Then it reacts in the conditions of Mitsunobu reagents (DEAD/PPh3) and alkaline, get α-phenyl-1-p-toluensulfonyl-aziridinemethanol (4). The chiral aziridine intermediate can aza-payne rearrange and ring opened with the reagent of LiAlH4 to get the N-tosyl-norephedrine (5) and 3-sulphurylamino-1aryl-propanol (7). The structure of these products was detected by IR, 1H NMR and MS spectra.     

Solid state reactions of nitrogenous heterocyclic compounds(Ⅰ)——Solid state reactions of 3-methyl-l-phenyl-5-pyrazolone with carbonyl compounds

The solid state reaction of 3-methyl-1-phenyl-5-pyrazolone (MPP) with aromatic aldehydes and ke-tones benzil derivatives and imides,and the solid state Michael addition reaction of MPP with 4-arylidene-3-methyl-1-phenyl-5-pyrnzolone 2 were investigated.Some new solid state reactions between the reactants were found,from which a series of new compounds were obtained The structures of the products were identified by IR,1H NMR,MS,elemental analyses and also by X-ray crystal analysis,and the reaction mechanism of MPP with aromatic aldehydes and ketones was proposed     

Synthesis, Crystal Structure, Physical Properties, and Application of a Series of Functional Dibenzo[d,f][1,3]dioxepine Derivatives

The twisted aromatics, functional dibenzo[d,f][1,3]dioxepine derivatives were synthesized in high yields from reactions of 5,5＇-dibromo-2,2＇-biphenol with corresponding ketal or ketone compounds under acid catalysis. The structures of these compounds were characterized by ^1H NMR, elemental analysis, UV-Vis absorption spectrum and X-ray diffraction analysis. The conformation of O--C--O bridged biphenyl derivatives with varied substitute groups on 6,6＇-position was studied by X-ray crystallography and force-field simulation. The result of calculations by UNIVERSAL 1.02 force field in Cerius2 package（4.6） indicates that dibenzo[d,f][1,3]dioxepine derivatives show twisted conformations and the twisted angle between the phenyl rings is about 40°, which is accordant with the result from crystal structure determination, though the obtained angles in the crystal of dibenzo[d,f][1,3]dioxepine derivatives with the varied substitute groups on 6,6＇-position are shown to be slightly shifted to 40° owing to intermolecular interactions in crystal stacking. DSC studies exhibit that the substitute groups on 6,6＇-position can induce a large variation of endothermic peaks ranging from 80 to 135 ℃. The conjugated polymers based on dibenzo[d,f][1,3]dioxepine derivatives, which have ultraviolet emitting with a quantum efficiency of 10%, were obtained by Yamamoto coupling.     

Synthesis of Covalently-Linked Linear Donor-Acceptor Copolymers Containing Porphyrins and Oligothiophenes

5,15-Di-bithienyl porphyrin (1) and its Cu(Ⅱ), Zn (Ⅱ) complexes (2 and 3)[1] were polymerized according to Scheme 1 by chemical oxidation using FeCl3 as oxidant for making organic conductor, and the linear porphyrin-thiophene copolymers were obtained. The structures of the copolymers were identified by elemental analysis and IR spectra. The conductivity of poly 5,15-di-bithienyl porphyrin (4) doped with FeCl3 was measured to reach over 10-6 S/cm, which was in the range of semiconductor and higher than that of other porphyrin-thiophene copolymers prepared by Shimidzu. The higher conductivity may be due to the better conjugation between the thienyl group and the porphyrin ring. The thienylporphyrins 7 and 8 could not be polymerized under the similar conditions, but could be polymerized by electrochemical oxidation (working electrode: gold-plate electrode; counter electrode: platinum; reference: standard calomel electrode SEC; solvent: 0.1 mol·dm-3 n-Bu4NClO4 in dry MeCN).     

蒂巴茵衍生物的合成研究

The reaction of 7α-acetyl-6,14-endoethano-6,7,8,14-tetrahydrothebaine with 2-（thien-2-yl）ethylmagnesium bromide was investigated. The tertiary alcohol derivative 7α-[R-l-hydroxyl-l-methyl-3-（thien-2-yl）propyl]）-6,14- endoethano-6,7,8,14-tetrahydrothebaine （3） and a by-product 4 were isolated. The structure of 4 was elucidated by X-ray analysis. The Grignard reaction shows high degree of stereoselectivity according with Cram rule. The crystal structure of 4 indicates that dihydrofuran ring was opened to form a phenolic hydroxyl group and a three-membered ring structure. It maintains the main rigid structure of morphine and contains a C（6）-C（14） enthano bridge. The 1-hydroxyl-1-methyl-3-（thien-2-yl）propyl group at C（7） position adopted S-configuration.     

红紫素-18酰亚胺衍生物的合成及其可见光谱的研究

选择脱镁叶绿酸 a甲酯为原料进行 3 位化学修饰和E环改造 .经 3 乙烯基的溴化氢加成和与联苯酚的亲核取代反应 ,完成了 3 位联苯氧基的引入 ;在碱性条件下 ,通过空气氧化将E环转变为环己二羧酸酐形成红紫素 18甲酯衍生物 ;所得氧化产物进而和盐酸羟胺反应 ,经胺解开环和再缩合成环构成N 羟基红紫素 18酰亚胺衍生物 ;对其羟基进行烷基化和酰基化 ,合成出N 取代红紫素 18酰亚胺衍生物 .同时讨论了化学结构变化对分子可见光谱的影响 .所合成新化合物的结构均经UV ,IR ,1 HNMR光谱和元素分析予以确认     

红紫素-18酰亚胺衍生物的化学修饰

以脱镁叶绿酸-a甲酯为原料, 通过对其3-位乙烯基的氧化, 得到了3-甲酰基脱镁叶绿酸甲酯, 利用Wittig反应合成了对应的3-(2-取代的乙烯基)脱镁叶绿酸甲酯. 结合E环的改造, 将其转变成酸酐环进而转变成N-取代的酰亚胺环. 目标化合物具有亲水区和疏水区两部分, 吸收波长明显向红位移. 合成得到的红紫素-18酰亚胺衍生物有可能成为光动力疗癌的理想光敏剂. 合成的新化合物均由核磁共振、红外光谱、元素分析和质谱予以证实.     

C(3)-乙烯基的化学修饰与含氧基团取代的叶绿素-a衍生物的合成

以焦脱镁叶绿酸-a甲酯为起始原料, 通过加成和氧化反应将其3-位上的乙烯基转化为羟乙基、溴乙基、二羟乙基、二溴乙基和溴羟乙基, 再经过二甲亚砜/乙酸酐或者高钌酸四丙基铵(TPAP)/N-甲基吗啉-N-氧化物所组成的混合氧化剂的氧化反应, 得到多种C(3)-多酮基取代的二氢卟吩衍生物. 其单羟基作为离去基团与不同的活泼亚甲基化合物经过重排过程, 得到相应的酮基取代的二氢卟吩衍生物. 所得新叶绿素衍生物的化学结构均经UV, IR, ¹H NMR及元素分析得以证实, 并对相应的反应提出可能的反应机理.     

Development of biobased polyurethane‐imides from maleinized cottonseed oil and castor oil

An eco‐friendly coating system, which is largely biobased, has been developed from castor and cottonseed oil. Cottonseed oil was functionalized with maleic anhydride by “ene” reaction to give maleinized cottonseed oil (MACSO); the anhydride groups were reacted with isocyanates to yield –NCO terminated polyurethane prepolymer. The prepolymer was further chain extended with hydroxyl groups of castor oil to give polyurethane‐imides (PUIs). The cross‐linked films thus obtained had good mechanical properties, and the imide groups in the backbone improved the corrosion resistance of PUIs as revealed by potentiodynamic polarization study. With increasing content of MACSO, thermal stability, glass transition temperatures (T_g), tensile strength, and corrosion resistance of resulting PUIs significantly increased.     

Analogs of 3-(1-phenyl-3-oxobutyl)-4-hydroxycoumarin (warfarin) prepared from substituted salicylic acids

Some derivatives of salicylic acid containing substituents meta to the carboxyl group were used to prepare analogs of the anticoagulant drug warfarin, 3-(1-phenyl-3-oxobutyl)-4-hydroxycoumarin, containing substituents in either the 6-or 8-position of the courmarin ring. When the substituent was the hydroxyl group, the resulting products are previously identified metabolites of warfarin. The substituted salicylic acid is first acetylated with acetic anhydride, then either converted to the acid chloride and condensed with diethyl malonate in the presence of sodium hydroxide or converted to the mixed anhydride with formic acid and condensed with ethoxymagnesium diethyl malonate to yield, in either case, the corresponding 3-carbethoxy-4-hydroxycoumarin substituted in the 6- or 8-position of the coumarin ring. These compounds readily condense with benzalacetone to form the corresponding substituted warfarin in the presence of 5 mole % tertiary amine catalyst. This method offers an improved route for the synthesis of 8-hydroxywarfarin.     

Synthese von Makrocyclen durch Ringerweiterung von 14gliedrigen cyclischen Imiden

Synthesis of Macrocyles by Ring Enlargement of 14-Membered Cyclic Imides In the presence of a base, cyclododecanone derivative 2 , activated in α-position by an allyloxycarbonyl group, underwent ring enlargement with isocyanates to give 14-membered imides (Schemes 1–3). Cleavage of the activating group gave new 14-membered imides which could be transformed by further ring-enlargement reactions into new macrocyclic compounds.     

Biotransformation of benzaldehyde-type and acetophenone-type derivatives by Pharbitis nil hairy roots

The glucosylation of some coumarin and flavone derivatives on incubation with the hairy roots of morning glory (Pharbitis nil) was previously reported. We further studied the biotransformation of benzaldehyde- and acetophenone-type derivatives. Vanillin and isovanillin were reduced to alcoholic derivatives and glucosylated at the phenolic and the alcoholic hydroxyl groups. In the case of 3,4-dihydroxybenzaldehyde, the formyl group was reduced and the 3-hydroxyl or 4-hydroxyl groups were glucosylated to give monoglucosides. The 3-hydroxyl group was predominantly glucosylated to the 4-hydroxyl group. 4-beta-D-Glucopyranosyloxy-3-methoxybenzylalcohol was obtained in low yield. In time-course experiments with vanillin, it was found that the high-level reduction of the formyl group and glucosylation of the phenolic hydroxyl group occurred, and finally 4-O-beta-D-glucopyranosylvanillylalcohol was obtained as the main product. In the case of 3,4-dimethoxybenzaldehyde, 3,4,5-trimethoxybenzaldehyde, and salicylaldehyde, the formyl groups were reduced, and then the hydroxyl groups at the benyl position were glucosylated to give alcoholic glucosides in relatively high yields. In 4-hydroxy-3-methoxyacetophenone, the 4-hydroxyl group was glucosylated and two dimerized glucosides, biphenyl and biphenylether types, were obtained in low yields. In acetophenone, 1-beta-D-glucopyranosyloxy-1-phenylethane and 2-beta-D-glucopyranosyloxyacetophenone were obtained. As mentioned above P. nil hairy roots showed various biotransformative activities including glucosylation of phenolic and benzylic hydroxyl groups, reduction of the formyl group near the benzene ring, and phenol oxidation dimerization. The glucosylation reaction was especially interesting for the production of valuable glucosides.     

红紫素-18酰亚胺衍生物的合成

以脱镁叶绿酸甲酯为原料, 通过对其3-位乙烯基的氧化, 得到3-(2,2-二甲氧基乙基)-3-去乙烯基脱镁叶绿酸甲酯, 经过甲酸处理得到3-(2-氧代乙基)-3-去乙烯基脱镁叶绿酸甲酯, 选择适当的条件, 通过Grignard 反应合成了对应的3-(2-羟基烷基)-3-去乙烯基脱镁叶绿酸甲酯. 实验结果表明: 3-(2-氧代乙基)-3-去乙烯基脱美叶绿酸甲酯和Grignard试剂的反应, 只要反应条件控制得当, 13²-位的甲氧甲酰基不会脱去. 结合E环的改造, 将其转变成酸酐环进而转变成N-取代的酰亚胺环. 目标化合物的合成也可以将3-(2,2-二甲氧基乙基)-去乙烯基脱镁叶绿酸甲酯转变成N-取代的酰亚胺后, 再和Grignard试剂反应, 完成目标化合物的合成. 合成的一系列化合物具有长波长的紫外吸收. 化合物的结构变化对紫外吸收的影响作了相应的讨论. 合成的新化合物均由核磁共振、红外光谱、元素分析予以证实.     

Derivate des 5, 6-Dihydro-p-dithiin-2, 3-dicarbonsäure-anhydrids,I: Imide

5. 6-Dihydro-p-dithiin-2. 3-dicarboxylic anhydride reacts with primary amines quite readily to form the substituted imides. The imide formation occurs much more easily than with maleic or phthalic anhydride. The imide and all N-substituted imides have a fairly strong, bright yellow colour. Their absorption spectra differ considerably from those of the anhydride, ester and dinitrile. Electron-attracting substituents on the imide nitrogen increase the absorption maximum somewhat, while strongly electron-releasing groups decrease it, and may even shift it to a shorter wave-length. It is therefore concluded that the imide nitrogen is part of the election acceptor group of the chromorphoric system.     

焦脱镁叶绿酸-a甲酯衍生物的合成及其结构与光谱性能关系研究

以焦脱镁叶绿酸-a甲酯(MPP-a, 1)为起始原料,通过乙二醇对E-环羰基进行保护,选用四氧化锇和高碘酸钠将3-位碳碳双键氧化,生成131-二氧环戊基-131-去氧焦脱镁叶绿酸-d甲酯(2),经Grignard反应将3-甲酰基转换成羟烷基得仲醇3,再通过高钌酸四乙基胺和N-甲基吗啡啉N-氧化物将其氧化成酮4,脱去保护基生成3-烷酰基3-去乙烯基焦脱镁叶绿酸-a甲酯(6).焦脱镁叶绿酸-d (MPP-d)7与过量重氮甲烷发生加成和重排反应,生成6a及3-烷酰甲基3-去乙烯焦脱镁叶绿酸甲酯衍生物8和9,7的3-位醛基经过Wittig和氧化反应得到3-苯乙二酰基焦脱镁叶绿酸甲酯11.所合成的新卟吩衍生物均经UV,IR,¹H NMR及元素分析证明其结构,并且讨论了周边取代羰基对核磁共振光谱和最大可见光吸收的影响.