2－甲基－3－芳基－7－（5，5－二甲基－3－酮－1－环己烯－1－基）甲酸酯－4（3H）－喹唑啉酮的合成

以2－氨基对苯二甲酸（1）为起始原料，与乙酸酐缩合生成7－羧基乙酰苯邻 甲内酰胺（2）；2和芳胺缩合产生7－羧基－2－甲基－3－芳基－4（3H）－喹唑啉 酮（3）；3和N，N－双环己基碳双亚胺（DCC）加成得到中间体4，4在4－二甲氨基 吡啶（DMAP）催化下和5，5－二甲基－1，3－环己二酮（5）缩合得到目标产物2－ 甲基－3－芳基－7－（5，5－二甲基－3－酮－1－环己烯－1－基）甲酸酯－4（ 3H）－喹唑啉酮（6）。所得15个新型化合物的结构均经^1H NMR、元素分析确证， 部分化合物经IC／MSD确证。     

水中α,β-不饱和酮与3-甲基-1-苯基-2-吡唑啉-5-酮的加成反应

在水溶剂中有三乙基苄基氯化铵（TEBA）存在下，α,β-不饱和酮与3-甲基- 1-苯基-2-吡唑啉-5-酮发生迈克尔加成反应，以良好的产率生成相应的1,3-二芳基 -3-（3'-甲基-1'-苯基-5'-羟基-2'-吡唑啉-4'-基）-1-丙酮。     

水溶剂中芳醛与5，5－二甲基－1，3－环己二酮的反应

芳醛1与5，5－二甲基－1，3－环己二酮（2）在氯化三乙基苄基铵（TEBA）催 化下在水中生成2，2'－芳业甲基双（3－羟基－5，5－二甲基－2－环己烯－1－酮 ）（3），若在体系中有对甲苯磺酸存在时则生成3，3，6，6－四甲基－9－芳基－ 1，8－二氧代八氢化氧杂蒽（4）或3，3－二甲基－9－（3－羟基－5，5－二甲基 －2－环己烯－1－酮－2－基）－1－氧代四氢代氧杂蒽（6）而不是生成3，产率接 近定量。     

含三唑啉硫酮槟榔碱衍生物合成和生物活性

烟酸经酯化、肼解、与取代芳酸异硫氰酸酯缩合成1－（3－吡啶甲酰基）－4－芳基氨基硫脲（2），2经环合成生成2－（3－吡啶）－4－芳基－1，3，4－三唑啉－5－酮（3），接着用碘甲烷对吡啶环季铵化得相应的季铵盐4，4用硼氢化钠还原可得目标物2－（1－甲基－1，2，5，6－四氢吡啶－3－4）－4－芳基－1，2，4－三唑啉－5－硫酮（5），对所合成的目标化合物进行了舒张血管活性实验。     

双咪唑啉酮衍生物的有效合成

用烯基膦亚胺与二硫化碳、苄胺的串联aza—Wittig反应制取2-硫代-3-苄基-5-芳基亚甲基4-咪唑啉二酮（5）,5经S-烷基化反应合成了双2-烷硫基-3-苄基-5-芳基亚甲基-4H-咪唑啉-4-酮衍生物（6a-6d）。提出了可能的反应机理,探讨了5和6a-6d的反应条件和波谱性质。经^1H NMR,IR,MS和元素分析确证6a-6d均为新化合物。     

一锅法合成3-芳基-1，5-双（2-羟基芳基）-戊二酮-1，5

2-羟基苯乙酮、芳醛、氢氧化钾“一锅”反应合成了3-芳基-1，5-双（2-羟基芳基）-戊二酮-1，5。     

微波辐射一步法合成吡喃和吡喃[2, 3-c]吡唑衍生物

芳醛、丙二腈与5,5-二甲基-1,3-环己二酮或3-甲基-1-苯基-2-吡唑啉-5-酮在乙醇溶剂中用哌啶作催化剂,经微波辐射一步合成了2-氨基-3-氰基-4-芳基-7,7-二甲基-5-氧代-5,6,7,8-四氢苯并吡喃和6-氨基-5-氰基-4-芳基-1,4-二氢吡喃[2,3-c]吡唑,反应在2～12min内完成,产率53%～91%。     

超声辐射下一步法合成2-氨基-3-氰基-4-芳基-7，7-二甲基-5-氧代-5，6，7，8-四氢-4H-苯并[b]吡喃

芳醛、丙二腈和5，5-二甲基-1，3-环己二酮在乙二醇中不加任何催化剂经超 声辐射5-7min得2-氨基-3-氰基-4-芳基-7，7-二甲基-5-氧代-4H-5，6，7，8-四氢 苯并[b]吡喃，产率88％—96％．     

无外加催化剂条件下邻取代芳香醛与5, 5-二甲基-1, 3-环己二 酮的反应研究

在DMF溶剂中,不外加催化剂使邻取代芳香醛(1)与5,5-二甲基-1,3-环己二酮(2)发生缩合和加成反应生成3,3,6,6-四甲基-4a-羟基-9-芳基-1,8-二氧代-2,3,4,4a,5,6,7,8,9,9a-十氢化-1H-氧杂蒽(3a-3d)。在同样条件下,邻羟基芳香醛与5,5-二甲基-1,3-环己二酮则发生缩合、加成和脱水反应生成3,3-二甲基-9-(5,5-二甲基-3-羟基-2-环己烯-1-酮-2-基)-1-氧代-2,3,4,9-四氢化-1-氧杂蒽(4a-4b)。用单晶X-射线分析法确定了产物3a和4a的晶体结构。     

聚醚酮醚酮酮/含萘环聚醚酮醚酮酮无规共聚物的合成与性能

在无水AlCl3及N－甲基吡咯烷酮（NMP）存在下，以4,4′-二（α－萘氧基）二苯酮（DNBP）作为第三单体，将其与4，4′－二苯氧基二苯酮（DPBP）和对苯二甲酰氯（TPC）在1，2－二氯乙烷（DCE）中进行低温溶液共缩聚反应，合成了一系列聚醚酮醚酮酮／含萘环聚醚酮酮醚酮酮无规共聚物，用IR、DSC、TG及WAXD等方法对其结构和性能进行了表征与测试。研究结果表明共聚物的玻璃化转变温度（Tg)要比纯PEKEKK的高，而其熔融温度（Tm)和结晶度（Xc)则随共聚物中含萘环PEKEKK结构单元含量的增加而逐渐降低。共聚物具有优异的耐热性能及抗腐蚀性能。     

无外加催化剂条件下芳香醛与活性亚甲基化合物的缩合反应和迈克尔加成反应

在DMF溶剂中，不外加催化剂使芳香醛(1)与2,2-二甲基-1,3-二氧六环-4,6-二酮(2)发生缩合反应生成2,2-二甲基-5-芳亚甲基-1,3-二氧六环-4,6-二酮(3a～f)。在同样条件下，芳香醛与5,5-二甲基-1,3-环己二酮(4)则发生缩合和迈克尔加成反应生成2,2'-芳亚甲基双(3-羟基5,5-二甲基-2-环己烯-1-酮)(5a～h)。用单晶X-射线分析法确定了产物5b的晶体结构。     

Fluorinated 2-benzoylcyclohexane-1,3-diones and their vinylogous acyl chlorides in the reactions with primary and secondary amines

The reaction of 5,5-dimethyl-2-[(3-fluoro- and 4-fluoro)benzoyl]cyclohexane-1,3-diones with primary and secondary amines affords their exocyclic enamine derivatives. Under similar conditions 5,5-dimethyl-2-(2-fluorobenzoyl)]cyclohexane-1,3-dione undergoes dehydrofluorination and intramolecular cyclization to give 3,3-dimethyl-2,3,4,9-tetrahydro-1H-xanthene-1,9-dione. The reaction of vinylogous substitution of the enol derivatives of the fluorinated 5,5-dimethyl-2-benzoylcyclohexane-1,3-diones (vinylogous acyl chlorides) with amines results in the formation of the endocyclic enaminoderivatives.     

Homolytic telomerization of vinyltrimethylsilane with 5,5-dimethyl-1,3-dioxane

The homolytic telomerization of vinyltrimethylsilane by 5,5-dimethyl-1,3-dioxane follows three principal routes, with the formation of 2- and 4-substituted 5,5-dimethyl-1, 3-dioxanes and a formate ester. The rings in the reaction products (2-trimethylsilylethyl- and 4-trimethylsilylethyl-5,5-dimethyl-1,3-dioxane) exist in the chair conformation. The substituants in the 2- and 4-positions of the dioxane ring occupy equatorial positions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1031–1035, August, 1986.     

Reaction of 5,5-dimethyl-4-cyanomethylene-1,3-oxathiolan-2-one with amines and ammonia

A simple method for the synthesis of 5,5-dimethyl-4-cyanomethylene-2-cyanomethyl-2-[1-methyl-1-(carbamoyloxy)ethyl]-1,3-dithiolanes was developed on the basis of the reaction of 5,5-dimethyl-4-cyanomethylene-1,3-oxathiolan-2-one with amines (primary and secondary) and ammonia.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 335–338, March, 1992.     

KF-Al2O3催化下3-芳基-3-(5，5-二甲基-3-羟基-2-环己烯-1-酮-2-基)丙酰胺衍生物的合成

芳醛、5，5—二甲基—1，3—环己二酮、丙二酸亚异丙酯、芳胺在KF-Al2O3催 化下，在DMF中反应生成3—芳基—3—(5，5—二甲基—3—羟基—2—环己烯—1— 酮—2—基)丙酰胺衍生物，产率良好。     

The Use of 4-(Bromomethylene)-5,5-dimethyl-1,3-dioxolan-2-one as “Masked” α-Bromo-α'-Hydroxy Ketone in the Synthesis of Heterocyclic Systems

4-(Bromomethylene)-5,5-dimethyl-1,3-dioxolan-2-one was obtained on the basis of the readily obtainable 4-methylene-5,5-dimethyl-1,3-dioxolan-2-one. It forms 2-imidazo[1,2-a]pyridin-2-yl-2-propanol with 2-aminopyridine, 11a-hydroxy-1,1-dimethyl-3-oxo-1,5,11,11a-tetrahydro[1,3]oxazolo[3,4-a]pyrido[1,2-d]-10-pyrazinium bromide with 2-(aminomethyl)pyridine, and the corresponding derivative of 4-hydroxyoxazolidin-2-one with 2-(3,4-dimethoxyphenyl)ethylamine. The last product was converted by intramolecular amidoalkylation without isolation into 10b-(bromomethyl)-8,9-dimethoxy-1,1-dimethyl-1,5,6,10b-tetrahydro[1,3]oxazolo[3,4-a]isoquinolin-3-one.     

A Convenient Synthesis of 3-Aryl-3-(5,5-dimethyl-3-hydroxy-2-cyclohexene-1-one-2-yl) Propanic Esters Catalyzed by KF-Alumina

A series of 3-aryl-3-(5,5-dimethyl-3-hydroxy-2-cyclohexene-1-one-2-yl) propanic esters were synthesized by reaction of aromatic aldehydes, 5,5-dimethyl-1,3-cyclohexanedione and isopropylidene malonate in alcohols catalyzed by KF-Al₂O₃. The structure of 4a was determined by X-ray analysis.     

Cyanoacetylene and Its Derivatives: XXVIII. Reactions of 2-Mercaptobenzothiazole with Nitriles of αα,ββ-Acetylene γγ-Hydroxyacids and with 3-Phenyl-2-propynonitrile

Nucleophilic addition of 2-mercaptobenzothiazole to 4-alkyl-4-hydroxy-2-alkynonitriles at 1:1 ratio in the presence of 4-6 wt% of Et₃N occurs regio- and stereospecifically to afford (Z)-4-alkyl-3-(benzothiazolyl-2-thio)-4-hydroxy-2-alkenonitriles (yield 40-51%). In the presence of 1.3 wt% of Dabco the thiazole and 4-hydroxy-4-methyl-2-pentynonitrile (1:1) give rise to a mixture of 2-alkenonitrile and 2-(3,3,6,6-tetramethyl-2-cyanomethyl-5-cyanomethylene-1,4-oxathian-2-yl)thiobenzothiazole. At the use of 4-6 wt% of LiOH arises an intractable mixture containing 1,4-oxathiane, benzothiazol-2-one, 2-[1-(5,5-dimethyl-2-cyanomethyl)-4-cyanomethylene-1,3-oxathiolan-2-yl)-1-methylethyl]thiobenzothiazole, bis(2,2,5,5-tetramethyl-6-cyanomethyl-3-cyanomethylene-1,4-oxathian-6-yl) disulfide, bis[1-(5,5-dimethyl-2-cyanomethyl-4-cyanomethylene-1,3-oxathiolan-2-yl)-1-methylethyl] disulfide, and 3-[1-(5,5-dimethyl-2-cyanomethyl-4-cyanomethylene-1,3-oxathiolan-2-yl)-1-methylethyl]benzothiazol-2-one (according to ¹H and ¹³C NMR data). 2-mercaptobenzothiazole adds to 3-phenyl-2-propynonitrile in the presence of 7 wt% of KOH with regio- and stereospecific formation of (Z)-3-(benzothiazolyl-2-thio)-3-phenyl-2-propenonitrile (88%).     

Mononuclear, five-coordinate lanthanide amido and aryloxide complexes bearing tetradentate (N2O2) Schiff bases

Two monomeric, five-coordinate lanthanide complexes, [bis-5,5'-(1,3-propanediyldiimino)-2,2-dimethyl-4-hexene-3-onato]samarium[2,6-bis(tert-butyl)-4-methylphenoxide] and [bis-5,5'-(1,3-propanediyldiimino)-2,2-dimethyl-4-hexene-3-onato]erbium[2,6-bis(tert-butyl)-4-methylphenoxide], were isolated from the reactions of 2,6-bis(tert-butyl)-4-methylphenol with [bis-5,5'-(1,3-propanediyldiimino)-2,2-dimethyl-4-hexene-3-onato]lanthanide[bis(trimethylsilyl)amido] (lanthanide = Er(3+) and Sm(3+)). The purified phenoxides were recovered in excellent yields and analytical purity, and the reactions proceeded cleanly without Schiff-base degradation or cluster formation. Analogously, [bis-3,3'-(1,3-propanediyldiimino)-1-phenyl-2-butene-1-onato]erbium[bis(trimethylsilyl)amido] was also directly converted to [bis-3,3'-(1,3-propanediyldiimino)-1-phenyl-2-butene-1-onato]erbium[2,6-bis(tert-butyl)-4-methylphenoxide]; however, a less sterically demanding alcohol (i.e., ethanol) yielded a neutral trinuclear oxo alkoxide species with each dianionic Schiff base asymmetrically bridging through micro-oxo interactions. In this polynuclear cluster, each symmetry-related, seven-coordinate erbium(III) ion exhibits monocapped trigonal prismatic geometry, which assembles by sharing triangular capped faces. Single-crystal X-ray diffraction revealed square-pyramidal metal coordination in each five-coordinate lanthanide ion with varied S(4) ruffling of the "square base" donor atoms and the six-membered propylene diamine chelate ring adopting the boat conformation. To contrast the effect of subtle ligand changes, we also report the synthesis and characterization of [bis-5,5'-(2,2-dimethyl-1,3-propanediyldiimino)-2,2-dimethyl-4-hexene-3-onato]samarium[bis(trimethylsilyl)amido], having gem-dimethyl substituents appended to the propylene bridge central carbon. The six-membered diamine chelate ring in this compound adopts the chair conformation without metal-hydrocarbon interaction. Also presented are qualitative activity observations and polymerization data for the polymerization of rac-lactide and epsilon-caprolactone using the five-coordinate lanthanide amidos and phenoxides.