α，α－二乙酰基烯酮二硫代缩酮的碱分解反应及缩酮基的稳定性研究

通过α，α-二乙酰基烯酮二硫代缩酮在乙硫醇钾作用下的分解作用制备了乙酰基烯酮二硫代缩酮．找出了最佳反应条件，探讨了缩酮在反应条件下的稳定性．

α,α-双酰基烯酮二硫代半缩酮的合成

以碳酸钾为碱，β－二酮或β－酮酯和二硫化碳、溴乙醇反应。

α-氧代烯酮环二硫代缩酮化学——Grignard试剂与α-肉桂酰基烯酮环二硫代缩酮的区域选择性加成反应

乙基、丙基、丁基、苯基和苄基卤化镁等Grignard试剂与具有三亲电中心的肉桂酰基烯酮环二硫代缩酮类化合物2反应,生成选择性共轭加成产物3,为合成含复杂烃基的a-氧代烯酮环二硫代缩酮提供了一条新的途径.该反应体现了2中的环二硫缩酮基对反应的调控作用.

α-溴代-α-乙酰基二硫缩烯酮与芳醛缩合反应的研究

从α-溴代-α-乙酰基二硫缩烯酮出发,与多种不同芳醛反应合成了γ-位的醛缩合产物α-溴代-α-烯酰基二硫缩烯酮.探讨了在不同碱、溶剂、反应温度和原料配比等反应条件下该缩合的反应情况及其产率,并对各化合物的结构进行了表征.结果表明,在以氢氧化钠为碱,叔丁醇为溶剂,常温条件下可以较高产率地获得目标产物.

α-氧代烯酮环二硫代缩酮化学(XXXI)──α-肉桂酰基乙烯酮缩1,3-丙二硫醇与Grignard试剂的共轭加成反应

缩酮基为六元环、具三亲电中心的α-肉桂酰基烯酮-１，３-亚丙二硫基缩酮（２），与乙基、丙基、丁基、苯基及苄基卤化镁等的反应均得到β＇-碳上的共轭加成产物（３）．该反应证实了（２）中环二硫缩酮基对这一加成反应的调控作用．

α-乙酰基二硫缩烯酮的新合成方法

The α-acetyl ketene dithioacetals 2, which bear various alkylthio groups, are a kind of important intermediates in organic synthesis. In this paper, dithioacetals 2 were prepared in very high yields (90%—100%) via the deacetylation reaction of the corresponding α,α-diacetyl ketene dithioacetals 1 in the presence of concentrated sulfuric acid. This reaction involves an %in-situ% electrophilic addition-deacetylation mechanism and shows the nucleophilicity of the α-carbon atom in α-oxo ketenedithioacetals. Meanwhile, when the reaction time was prolonged to 22—25 h, the β-keto thiolesters 3a and 3c were produced in good yields.

α,α-二乙酰基二硫缩烯酮和芳醛的缩合反应研究

在碱性条件下 ,α,α-二乙酰基二硫缩烯酮和芳醛的缩合反应受烷硫基的影响 .α,α-二乙酰基二苄硫缩烯酮 1和芳醛 3缩合生成单面缩合脱乙酰基产物α-肉桂酰基二苄硫缩烯酮 4 ;α,α-二乙酰基环二硫缩烯酮 2和芳醛 3缩合生成双面缩合产物α,α-二肉桂酰基环二硫缩烯酮 5 .

α-乙酰基二硫缩烯酮α碳原子的酰化反应

As a kind of versatile synthons, α-oxoketene dithioacetals have found their wide utilizations in organic synthesis. Owing to the interaction between two electron donating groups(RS) and an electron withdrawing group in the α position, the α-carbon atom of α-EWG ketene S,S-acetals shows a high nucleophilicity. In this paper, the reactions of α-acetyl cyclic ketendithioacetals with a series of acyl chlorides were performed and a new route to the C～C bond formation reaction at the α-carbon atom of α-oxoketene dithioacetals was described. By the above reactions, α-acetyl-α-acyl ketendithioacetals were prepared with good to high yields(55%～82%) via the acylation of α-acetyl cyclic ketendithioacetals at the α-carbon atom of α-acetyl ketendithioacetals mediated by titanium tetrachloride in dry dichloromethane at reflux temperature. The mechanism of the acylation between compound 1 and acyl chloride was proposed, which belongs to nucleophilic addition-elimination reaction.

α,α′-二氧代烯酮环二硫代缩酮的特征红外光谱(Ⅱ)

本文在前文［１］的基础上继续研究了α，α′－二氧代烯酮环二硫代缩酮的其他一些特征红外光谱，指出了它们随化学结构而变化的规律。

α,α-二乙酰基二苄硫缩烯酮的碱催化脱乙酰基反应及缩合反应机理研究

The behavior of α,α-diacetyl ketene dibenzylthioacetal 1a under basic conditions was studied. Catalyzed by steric hindered base as t-BuONa(in t-BuOH), α-acetyl ketene dibenzylthioacetal 2a could be obtained in 98% yield within 3 min via deacylation of 1a. Assisted by t-BuONa(in t-BuOH), α-cinnamoyl ketene dibenzylthioacetals were produced in high yields by reacting both 1a and 2a with arylaldehydes; whereas, under the same conditions, the corresponding α,α-dicinnamoyl ketene dibenzylthioacetals 4 were formed when furan-2-carbaldehyde and thiophene-2-carbaldehyde were used as the electrophiles. These evidences support the proposed mechanism that, catalyzed by t-BuONa (in t-BuOH), the reaction of 1a with arylaldehydes may normally proceed via a sequential deacylation-condensation process and the formation of double condensation products 4 may be due to the higher activity of furan-2-carbaldehyde and thiophene-2-carbaldehyde under the selected reaction conditions.

α,α′-二氧代烯酮环二硫(氮)代缩酮的紫外光谱

本文研究了α，α′－二氧代烯酮环二硫（氮）代缩酮的紫外光谱，指出了它们随化学结构而变化的一些特征。

α,α’-二氧代烯酮环二硫代缩酮类化合物的谱学研究

研究了 5种含有苯环取代基的α ,α’ 二氧代烯酮环二硫代缩酮类化合物的红外光谱的特征吸收规律 ,指出了这类化合物分子结构对红外吸收谱带的影响 ;对1HNMR ,13 CNMR共振谱带做了全面的归属 ,并且讨论了分子结构对1HNMR ,13 CNMR共振谱带化学位移的影响 ,其变化规律与红外光谱一致 。

α,α′-二氧代烯酮环二硫代缩酮类化合物的特征红外光谱(Ⅲ)

研究了 5种α ,α′ 二氧代烯酮环二硫代缩酮类化合物的羰基、碳碳双键、碳硫等一些特征红外光谱 ,尤其着重研究了在共轭体系下的各种特征谱带随化学结构而变化的规律。

α-氧代烯酮环二硫代缩酮化学(XXV)──经由取代-环合芳构化反应合成羟乙基芳基硫醚

以巯基乙醇为亲核体，经由β，β－１，３－亚丙二硫基－α，β－不饱和酮１与２－甲基烯丙基氯比镁的加成产物２的取代－环合芳构化反应，以适中产率得到羟乙基芳基硫醚３．首次发现２在酸催化下生成α，β－不饱和环已酮４的新反应途径．

α,α′-二氧代烯酮环二硫代缩酮的NMR研究

报道标题化合物的ＮＭＲ谱，利用１Ｈ，１３ＣＮＭＲ和ＤＥＰＴ等技术确定新化合物的化学结构。

α,α′-二氧代烯酮环二硫代缩酮类化合物的紫外光谱研究

在两种不同溶剂条件下 ,研究了 5种α ,α′ 二氧代烯酮环二硫代缩酮类化合物的紫外光谱特性。在同一种溶剂条件下 ,比较含氮化合物与含硫化合物的紫外光谱特性 。

α,α'-二氧代烯酮环二硫代缩酮类化合物的晶体结构研究

The crystals of α,α’-dioxoketene cyclic dithioacetals were prepared and their crystal structures were determined by X-ray crystallography.The influence of bond lengths,bond angles,dihedral angles and the molecular conformation on different substituted cyclic dithionacetals aldehyde ketone was discussed.Compound A is Monoclinic form,P21/c Space group,Unit cell dimensions,a=0.78337（6）nm,b=O54937（4）nm,c=2.8243（2）nm,α=90°,β=90.7740（10）°,γ=90°,V=1.215（4）nm3,Z=4,Dc=1.445g/cm3,F（000）=552.Compound B is Orthorhombic form,P212121 Space group,Unit cell dimensions,a=0.5665（5）nm,b=0.7980（7）nm,c=2.924（3）nm,α=90°,β=90°,γ=90°,V=1.322（2）nm3,Z=4,Dc=1.399g/cm3,F（000）=584.

用卡尔曼滤波-分光光度法分析α-羰基烯酮环二硫代缩酮化合物

本文将卡尔曼滤波－分光光度法用于α－羰基烯酮环二硫代缩酮化合物的分析。通过对卡尔曼滤波新息序列和滤波过程中浓度变化趋势的考察。

α-乙酰基-α-苯甲酰基二硫缩烯酮与吡啶甲醛的缩合

报道了α-乙酰基-α-苯甲酰基二硫缩烯酮与吡啶甲醛在碱性条件下的缩合反应,并对所合成的化合物进行了表征.

1,3-双芳氧乙酰基-1,3,2-二氮磷杂环戊烷-2-硫(硒)代化合物的合成及除草活性研究

利用 P( NEt2 ) 3 与双酰胺类化合物在干馏条件下的环缩合反应合成了一系列含双芳氧乙酰基的新型五元磷杂环 ,对所合成的化合物进行了元素分析和谱学表征 .初步生物活性测定表明 ,部分化合物具有优良的选择性除草活性 .合成中首次发现此类磷杂环的 P Se与 P—Se的转化现象 ,通过 X射线单晶衍射确证了产物的结构 。