3-丙烯酰基-1,3-噁唑烷-2-酮的合成

3-α，β-不饱和酰基-1，3-噁唑烷-2-酮在烷基化及Diels-Alder等反应中在手性催化剂的存在下，产物都有较高的对映选择性。但3-丙烯酰基-3，3-噁唑烷-2-酮极易聚合，现有制备方法结果均不理想。本文将丙烯酸与丙烯酰氯在三乙胺的存在下生成酸酐，再在无水氯化锂的作用下与1，3-噁唑烷-2-酮在室温反应，反应结束后直接将反应混合物通过硅胶柱色谱进行层析分离得到3-丙烯酰基-1，3-噁唑烷-2-酮，产率达83％。合成路线如下：     

不饱和对称酮合成的新方法

最近等人首次采用Pd(acac)_2-PPh_3-Et_2AlOEt(1:3:2)络合催化剂可使N-丙基或N-丁基噁唑烷同过量丁二烯在甲苯溶剂里,于100℃反应15小时实现调聚反应,制得N-丙基-2,2-双(2,7-辛二烯)噁唑烷(Ⅰ)和N-丁基-2,2-双(2,7-辛二烯)噁唑烷(Ⅱ),产率分別为80和50％。反应中除生成化合物Ⅰ和Ⅱ外,每次实验还得到约10％的1,3,7-辛三烯。     

一种不含β-氢的苯并噁嗪的表征分析及催化固化研究

以邻烯丙基双酚A、多聚甲醛和烯丙基胺为原料，采用无溶剂的方法合成了一种不含β-氢的苯并噁嗪(2，2-二(3，8-二烯丙基-3，4-二氢-2H-1，3-苯并噁嗪)-丙烷(B—dbo)．GPC和元素分析结果表明，此噁嗪中间体主要是单量体和二聚体．用FTIR和^1H NMR对中间体结构进行了表征．结果表明，此苯并噁嗪的分子结构中存在三种反应官能团：噁嗪环、N-烯丙基、Ar-烯丙基．用DSC和FTIR研究三种反应基团在固化时的反应情况．将双酚A、邻烯丙基双酚A、TiCl4和PCl5作为催化剂按适量的比例加入B—dbo中，用DSC研究其固化行为，并对TiCl4催化试样在不同的固化温度下进行FTIR测试分析，提出在TiCl4催化下苯并噁嗪环副反应及开环固化机理．     

1,3,4-噁二唑键联二芳基乙烯化合物的合成及性质

将1,3,4-噁二唑基团引入二芳基乙烯分子中, 合成了2种新的二芳基乙烯类光致变色化合物1-氰基-2-(2H-5-苯基-1,3,4-噁二唑)-1,2-二(2,4,5-三甲基-3-噻吩)乙烯(3)和1,4-二{[1-氰基-2-(2H-5-苯基-1,3,4-噁二唑)-1,2-二(2,4,5-三甲基-3-噻吩)乙烯]-1,3,4-噁二唑}苯(4). 通过IR, NMR, MS和元素分析对化合物进行了结构表征, 并研究了其UV-Vis吸收、荧光发射、动力学特性和抗疲劳性质. 实验结果表明, 化合物[STHZ]3[STBZ]和[STHZ]4[STBZ]具有良好的光致变色性质, 光致变色闭环反应为零级反应, 开环反应为一级反应.     

1，2-二[3-（6，8-二叔丁基-3，4-二氢-1，3-苯并噁嗪）基]乙烷的合成及晶体结构

N-取代的3，4-二氢-1，3-苯并噁嗪具有生物活性，是潜在的安定剂和镇静剂，还是制备酚醛树脂的潜在中间体。一般以酚、伯胺和甲醛为原料，通过Mannish缩合反应来制备。本文通过2，4-二叔丁基苯酚、乙二胺和甲醛反应，合成了亚乙基桥联的双噁嗪，X-射线单晶衍射测定了它的晶体结构。     

3-(1-氢多氟烯基)-1-氧代-2，4，1-苯并噁嗪与双亲核试剂反应合成含氟杂环化合物

本文研究了3-(1-氢多氟烯基)-1-氧代-2，4，1-苯并噁嗪1与几种双亲核试剂的反应。化合物1与乙二胺反应生成7-氟烷基-1，4-二氮杂卓[1，2-d]喹唑啉-11-酮；在吡啶溶剂中与盐酸羟胺反应得到了2-氟烷基异噁唑[3,2-b]并喹唑啉-9-酮；与邻苯二胺反应得到2-氟烷基苯并咪唑类化合物。     

含1，3，4-噁二唑取代的酰基硫脲的合成及杀菌活性

大量文献报道了1，3，4-噁二唑的合成及广泛的生物活性，酰基硫脲类化合物也因其广谱的生物活性引起了人们浓厚的研究兴趣。根据活性因子叠加的原理，本文将一系列1，3，4-噁二唑引入到酰基硫脲中，从对氯苯氧乙酸出发，得到的酰基异硫氰酸酯再与一系列2-氨基-5-芳基-1，3，4-噁二唑反应，合成了10个酰基硫脲类化合物。所有化合物均经元素分析、红外光谱、核磁共振谱和质谱确认。同时对所有化合物进行了生物活性测试。合成路线如下。     

“受阻路易斯酸碱对”催化的2,3-二取代2H-1,4-苯并噁嗪氢化反应机理研究

在受阻路易斯酸碱对（FLPs）催化的2，3-二取代2H-1，4-苯并噁嗪氢化反应中，3号位取代基不同会导致反应效率极大改变，因此我们选取反应活性具有较大差别的三种底物作为模型化合物对其反应机理进行了研究，建立了氢化反应势能面.发现当B（C₆F₅）₃与2，3-二苯基2H-1，4-苯并噁嗪或2-甲基-3-苯基2H-1，4-苯并噁嗪混合后，会形成FLPs与路易斯酸碱加合物的混合物.而将B（C₆F₅）₃与2，3-二甲基2H-1，4-苯并噁嗪混合后主要形成没有催化活性的路易斯酸碱加合物，因其能量低于FLPs，在催化体系中不容易转化为FLPs，这导致三种模型化合物在FLPs催化的氢化反应中效率不同.进一步的取代基电子效应及位阻效应计算表明：B（C₆F₅）₃与2-甲基-3-取代2H-1，4-苯并噁嗪混合后形成的路易斯酸碱加合物和FLPs化合物之间稳定性差别源于3位取代基空间位阻不同.     

醋酸铜催化“一锅法”合成5-(1-苯基-3-苯基丙基-2-炔基)-2,2-二甲基-1,3-二噁烷-4,6-二酮衍生物

在醋酸铜催化作用下,以抗坏血酸钠为还原剂,以醛、2,2-二甲基-1,3-二噁烷-4,6-二酮和苯乙炔为原料,通过包含Knoevenagel缩合与Conjugate加成反应的多组分反应,有效地合成了10种5-(1-苯基-3-苯基丙基-2-炔基)-2,2-二甲基-1,3-二噁烷-4,6-二酮衍生物.该工艺具有收率高(63%～86%)、反应温和、操作简单及环境友好等优点,为合成5-(3-苯基-1-苯基丙基-2-炔基)-2,2-二甲基-1,3-二噁烷-4,6-二酮衍生物提供了一种有效的方法.     

1-[3′-(4"-甲氧基苯基)-5′-甲基异噁唑-4′-甲酰基]-4-芳基氨基硫脲及其衍生物的合成

以3,5-二取代异噁唑-4-甲酰肼为基本原料制备关键中间体1-(3-对甲氧基苯基-5-甲基异噁唑-4-基)-4-芳基氨基硫脲(3a～3c);3在不同条件下经关环反应制得含有3,5-二取代异噁唑的2-芳氨基噻二唑(4a～4c),2-芳氨基噁二唑(5a～5c)和3-[3′-(4"-甲氧基苯基)-5′-甲基-异噁唑4′-基)-4-芳基-1,2,4-三唑-5-硫酮(6a～6c);6与碘甲(乙)烷反应合成了4-芳基-5-[3′-(4″-甲氧基苯基)-5′-甲基异噁唑-4′-基]-3-甲(乙)硫基-1,2,4-三唑(7a～8c),其结构经1H NMR,IR,MS和元素分析表征,其中4,5,7和8未见文献报道.     

Kinetic regularities of the reaction of dimethyldioxirane with cyclic acetals

Kinetic regularities of the reactions of dimethyldioxirane (1) with 1,3-dioxolane, 2-propyl-1,3-dioxolane, 2-i-propyl-1,3-dioxolane, 2-phenyl-1,3-dioxolane, and 2,2-pentame-thylene-1,3-dioxolane (RH) in acetone have been studied spectrophotometrically in the temperature range from 15 to 48°C. The reaction rate d[1] /dt=k[1]·[RH] does not depend on the oxygen concentration in the reaction mixture. The activation parameters in the reaction with 1,3-dioxolane have been determined: lgk=(5.13±0.6)−(10.07±0.82)/Q, where Q=2,303 RT kcal/mol.     

Preparation and radical ring-opening polymerization of 2-substituted-4-methylene-1,3-dioxolanes

2-Methyl-2-phenyl-4-methylene-1,3-dioxolane ( IIa ), 2-ethyl-2-phenyl-4-methylene-1,3-dioxolane ( IIb ), 2-phenyl-2-(n-propyl)-4-methylene-1,3-dioxolane ( IIc ), 2-phenyl-2-(i-propyl)-4-methylene-1,3-dioxolane ( IId ), 2-(n-heptyl)-2-phenyl-4-methylene-1,3-dioxolane ( IIe ), 2-methyl-2-(2-naphthyl)-4-methylene-1,3-dioxolane ( IIf ), and 2,2-diphenyl-4-methylene-1,3-dioxolane ( IIg ) were prepared and polymerized in the presence of a radical initiator. IIa–IIf were found to undergo vinyl polymerization with ring-opening reaction accompanying the elimination of ketone groups in bulk. IIg was found to undergo the quantitative ring-opening reaction accompanying the elimination of benzophenone in solution to obtain polyketone without any side reaction.     

Synthesis of 1-Bromo-3-butyn-2-one and 1,3-Dibromo-3-buten-2-one

Synthetic procedures for the preparation of 1-bromo-3-butyn-2-one and 1,3-dibromo-3-buten-2-one are given. These compounds are prepared from 2-bromomethyl-2-vinyl-1,3-dioxolane, which can readily be prepared from 2-ethyl- 2-methyl-1,3-dioxolane. The synthetic routes are as follows: 2-bromomethyl-2-vinyl-1,3-dioxolane is converted to 2-(1,2-dibromoethyl)-2-bromomethyl-1,3-dioxolane. Double dehydrobromination with ^tBuOK affords 2-ethynyl-2-bromomethyl-1,3-dioxolane. Formolysis with formic acid gives 1-bromo-3-butyn-2-one. Deacetalized 2-bromoethyl-2-vinyl-1,3-dioxolane was treated with Br₂ and Li₂CO₃/12-crown-4 in tetrahydrofuran to give 1,3-dibrom-3-buten-2-one in moderate yield.     

Fluorinated dioxolanes. 3. Nucleophilic reactions of perfluoro-4-methyl-1,3-dioxolanes

Conclusions Perfluoro-2,4-dimethyl-2-fluorocarbonyl-1,3-dioxolane reacts with sodium carbonate to give perfluoro-2-methylene-2-methyl-1,3-dioxolane. Under the reaction conditions, the latter dimerizes to perfluoro-2-(2,4-dimethyl-1,3-dioxolan-2-ylmethylene)-4-methyl-1,3-dioxolane, and on treatment with CsF is converted into perfluoromethyl-(1,3-dioxolany-2-yl)ketone.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 938–942, April, 1989.     

New Chiral Diamines of the Dioxolane Series: (+)-(4S,5S)-2,2-Dimethyl-4,5-bis(diphenylaminomethyl)- 1,3-dioxolane and (+)-(4S,5S)-2,2-Dimethyl-4,5-bis(methyl- aminomethyl)-1,3-dioxolane

The reaction of sodium diphenylamide with 2,2-dimethyl-4,5-bis(tosyloxymethyl)-1,3-dioxolane gave (+)-(4S,5S)-2,2-dimethyl-4,5-bis(diphenylaminomethyl)-1,3-dioxolane, which was brought into complex formation with cobalt chloride. Treatment of 2,2-dimethyl-4,5-bis(tosyloxymethyl)-1,3-dioxolane with sodium N-methylanilide resulted in cleavage of the SÄO bond in the p-toluenesulfonate moiety with formation of N-methyl-N-phenyl-p-toluenesulfonamide and 4,5-bis(hydroxymethyl)-2,2-dimethyl-1,3-dioxolane disodium salt. Diethyl (4R,5R)-2,2-dimethyl-1,3-dioxolane-4,5-dicarboxylate reacted with methylamine to give the corresponding dicarboxamide which was reduced with lithium aluminum hydride to (4S,5S)-2,2-dimethyl-4,5-bis(methylaminomethyl)-1,3-dioxolane having chiral carbon and nitrogen atoms.     

Research on polyfunctional oxides

N,N-Diethylcarbamoyl-4,5-epoxy-2-hexenoic acid reacts with ketones in the presence of anhydrous FeCl₃ to give 2,2,4-trialkyl-5-[2-N,N-diethylcarbamoyl(vinylene)]-1,3-dioxolane. 2,2,4-Trimethyl-5-(1-propenyl-3-hydroxy)-1,3-dioxolane is formed in the reduction of 2,2,4-trimethyl-5-[2-carbethoxy(vinylene)]-1,3-dioxolane withlithium aluminum hydride.     

Acetalation and Ketalation Catalyzed by SO42-/TiO2-MoO3

The catalytic activities of SO42-/TiO2-MoO3 in synthesizing cyclohexanone ethylene ketal,cyclohexanone 1,2-propanediol ketal, 2-propyl-1,3-dioxolane, 4-methyl-2-isopropyl-1,3-dioxolane,2-isopropyl-1,3-dioxolane, 4-methyl-2-isopropyl-1,3-dioxolane, butanone ethy-lene ketal and butanone 1,2-propanediol ketal were reported. It has been demonstrated that SO42-/TiO2-MoO3 is an excellent catalyst. Various factors concerned in this reaction have been investigated. The optimum conditions have been found, that is, the molar ratio of aldehyde/ketone to alcohol was 1:1.5 or 1:1.3,the mass ratio of the catalyst used to the reactants was 0.25～1.5%, and the reaction time was 45～60 min. Under this conditions, the yield of cyclohexanone ethylene ketal is 82.7%, cyclohexanone 1,2-propanediol ketal is 83.4%, the yield of 2-propyl-1,3-dioxolane is 68.1%,4-methyl-2-isopropyl-1,3-dioxolane is 87.5%, the yield of 2-isopropyl-1,3-dioxolane is 70.7%,4-methyl-2-isopropyl-1,3-dioxolane is 82.5%, the yield of butanone ethylene ketal is 74.1%, and butanone 1,2-propanediol ketal is 94.9%.Some equation and experiment results concerned of the synthetic acetals or ketals were listed as follows.     

Oxidation of 1,3-Dioxacyclanes with Oxone and Potassium Persulfate Catalyzed by 2,2,5,5-Tetramethyl-4-Phenyl-3-Imidazoline-3-Oxide-1-Oxyl

The catalytic effect of 2,2,5,5-tetramethyl-4-phenyl-3-imidazoline-3-oxide-1-oxyl on the oxidation of 2-isopropyl-1,3-dioxolane, 2-phenyl-1,3-dioxolane, 2-phenyl-4-chlormethyl-1,3-dioxolane, 2-isopropyl-1,3-dioxane, 2-isopropyl-4-methyl-1,3-dioxane, 2-phenyl-1,3-dioxane, 2-phenyl-4-methyl-1,3-dioxane with oxone and potassium persulfate is reported. The corresponding glycol monoesters were obtained with yields of 90-100%.     

Cyclic acetal-photosensitized polymerization. VII. Photopolymerization of 2-vinyl-4-hydroxymethyl-1,3-dioxolane

In order to assess the effect of the methylol group at the 4-position of 1,3-dioxolane on polymerization, the photopolymerization of 2-vinyl-4-hydroxymethyl-1,3-dioxolane (VHDO) was carried out in benzene at 40°C. The reaction scheme of VHDO was considered to be the same as that of 2-vinyl-1,3-dioxolane (VDO). The rate of polymerization and the molecular weight of polymer were small because of the degradative chain transfer by allylidene group. Moreover, the rate of polymerization of VHDO was greater than that of VDO, whereas the molecular weight of polymer of VHDO was less than that of VDO.     

Polymerization by crystallization of trioxane from cyclohexane solutions in presence of 1,3-dioxolane

Trioxane–1,3-dioxolane copolymers of high molecular weights and good thermal stability are obtained with high yields by a crystallization-polymerization method. The feed consists of concentrated solutions of trioxane in cyclohexane in the presence of dissolved 1,3-dioxolane. The 1,3-dioxolane/trioxane molar ratio in the feed lies in the range 2 to 10%. The results are compared with those obtained from isothermal copolymerizations.