硫酮

We have had the extensive studies on theα-acetyl-α-carbamoyl ketene--acetals and its further applications, for example, their adols condensations with aldehydes giveα-alkenoyl-α-carbamoyl ketene--acetals which can be utilized as the 1,5-bielectronic five-carbon components to react with various binucleophlilic species in a [5+1] annulation.

我们小组在以前的工作中对α-乙酰基-α-胺甲酰基二硫缩烯酮在合成中的应用进行了深入的研究，如与醛缩合生成α-烯酰基-α-胺甲酰基二硫缩烯酮，将其作为1，5-双亲电五碳合成子的[5+1]成环策略等。

Generally speaking, the reaction types involvingα-oxoketene--acetals mainly include the regioselective addition-aromatization with organometallic reagents, conjugate addition-cyclization with nitrogen nucleophilicspecies, nucleophilic reactions ofα-carbon, acting as odorless dithiol equivalentsin thioacetalization, Michael additions and [5+1] annulation, as well as the synthetic applications based on the above reactions.

一般来说，基于α-羰基二硫缩烯酮化学的反应主要为：与金属有机试剂的选择性加成反应，与氮亲核体的共轭加成反应，α-碳原子的亲核性及相关反应，烷硫基作为硫醇的替代试剂的应用，α-羰基二硫缩烯酮在碳环、杂环化合物合成中的应用等。

Ophenyl phenol,ophenyl phenol sodium salt tetrahydrate,7ADCA,2ethyl phenyl hydrazine hydrochloride,2,3dihydrofuran,7ethyl3(2hydroxy ethyl)indole,methyl ester of etodolac; 1,8diethyl1,3,4,9tetrahydropyrano[3.4b] indole1acetic acid methyl ester,5chloro2methoxy benzoic acid,4(2aminoethyl)benzene sulfonamide,5cyano phthalide,phthalhydrazide,9thioxanthenone,n[(1,4benzodioxane2yl)carboxyl]piperazine HCL,2chloro4amino6,7dimethoxyquinazoline,2chloro benzimidazole,1(4fluorobenzyl)2chlorobenzimidazole,2methylthio4pyrimidone,5amino4imidazole carboxamide HCL,6chloro2hexanone,11oxo6.11hydrodibenzothiepin,6,11dihydrodibenzooxepin11one,10,11dihydrodibenzocyclohepten5one;dibenzosuberone,dibenzo cyclohepten5one;dibenzosuberenone,3,5dihydroxy benzoic acid,3,5dihydroxy benzyl alcohol,2mercapto benzimidazole,3,4dihydroxy benzaldehyde,3,4dihydroxy benzonitrile,2amino5chloro benzonitrile,2(4chlorophenoxy)ethyl chloride,2(4chloro phenoxy)tert,butane,ditrimethylol propane;DTMP,2,2bis(4hydroxyphenyl)butane; bisphenol B,1,1'bis(4hydroxyphenyl)cyclohexane;bisphenol Z,tetrabromobisphenolS,3,5ditertbutyl salicylic acid,3,4,5trihydroxy benzoic acid stearyl ester,1,2,4trimethoxybenzene.

华业公司产品：邻苯基苯酚，邻苯基苯酚钠盐，7氨基3去乙酰氧基头孢烷酸，邻乙基苯肼盐酸盐，2，3二氢呋喃，7乙基色氨醇，依托度酸甲酯，5氯2甲氧基苯甲酸，4(2氨乙基)苯磺酰胺，5氰基苯酞，双酮酞嗪，9噻吨酮，N〔(1，4苯并二恶烷2基)羰基〕哌嗪盐酸盐，2氯4氨基6，7一二甲氧基喹唑啉，2氯苯并咪唑，1(4氟苄基)2氯苯并咪唑，2甲硫基4嘧啶酮，5氨基咪唑4 甲酰胺盐酸盐，6氯2已酮，11氧6.11二氢苯并〔b.c〕虑平，11氧代6，11二氢二苯并氧杂卓，10，11二氢二苯并环庚烯5酮，二苯并环庚烯5酮，3，5二羟基苯甲酸，3，5二羟基苯甲醇，2巯基苯并咪唑，3，4二羟基苯甲醛，3，4二羟基苯腈，2氨基5氯苯腈，2(4氯苯氧基)1氯乙烷，2(4氯苯氧基)叔丁烷，双丙烷，2，2二(4羟基苯基)丁烷；双酚B，1，1'双(4羟基苯基)环己烷；双酚Z，2[3，5二溴4(2，3二溴丙氧基)]苯砜，3，5二叔丁基水杨酸，3，4，5三羟基苯甲酸十八烷基脂，1，2，4三甲基氧基苯。

Among the variousα-oxo ketene dithioacetals,α-alkenoyl ketene dithioacetals are easier to prepare and bear much more functionalities.

在众多的α-羰基二硫缩烯酮类化合物中，α-烯酰基二硫缩烯酮具有易于制备，官能团多等特点。

Benzyloxy benzoyldimethylsulfoxide was prepared by the reaction of ethyl 4-benzyloxybenzoate and dimethyl sulfoxide in the presence of sodium hydride, followed by Pummerer reaction with concentrated hydrochloric acid to afford eo-hydroxy-co-thio-methyl-(4/-benzyloxy) acetophenone, which reacted with urea, thiosemicarbazide, semicarbazide hydrochloride and o-phenylenediamine to give imidazolidine-2,4-dione, l,2,4-triazine-3- one and quinoxaline derivatives, respectively.

本文用4-苄氧基苯甲酸乙酯和二甲亚砜为原料，在氢化钠存在下反应，合成了(4′-苄氧基)-苯甲酰基-二甲亚砜。研究了该亚砜在浓盐酸的存在下发生的Pummerer重排反应，用重排产物ω-羟基-ω-甲硫基-(4′-苄氧基)-苯乙酮分别与尿素、氨基脲、氨基硫脲和邻苯二胺反应合成了2，4-咪唑啉-二酮、1，2，4-三嗪-3-酮、喹喔啉等含氮杂环化合物。

The chapter two was focused on the samarium diiodide promoted organic reactions and their applications in organic synthesis, firstly, a new synthesis of highly substituted cyclopentadienes from a,β-alkynone promoted by samarium diiodide was investigated and the highly substituted cyclopentadienes were prepared in moderate to good yields under mild conditions. Secondly, the Michael addition and Michael-aldol tandem reaction of diorganyl diselenides or diorganyl disulfides with α,β-alkynones mediated by samarium diiodide were studied and a series of alkenylsulfides and alkenylselenides were prepared in good yields. Then the highly regioselecfive nucleophilic addition of the allylsamarium bromide to α,β-alkynones were explored. We found that the allylsamarium bromide reacts with α,β-alkynones to afford regiospecificly 1. 2-nucleophilic addition products in good yields under mild condition. At last we studied the coupling reaction of aryl halides promoted by NiCl〓/PPh〓/Sm〓.

第二章 研究了二碘化钐、金属钐促进的有机反应：1、二碘化钐促进下α，β-炔基酮的偶联环化反应，提供了一种制备多取代环戊二烯的新方法；2、二碘化钐促进下的二硫醚、二硒醚与α，β-炔基酮的Michael加成反应，为高产率地制备多取代的烯基硫或烯基硒化合物提供了方便可靠的新方法；3、二碘化钐促进下的二硫醚、二硒醚与α，β-炔基酮和醛、酮的Michael—aldol串联反应，提供了一种一锅法高产率地制备多取代的含硫的烯丙基醇或含硒的烯丙基醇类化合物的方便可靠的原子经济性的新方法；4、烯丙基溴化钐与α，β-炔基酮的高度区域选择性的1，2-亲核加成反应；5、NiCl〓/PPh〓/Sm〓促进的卤代芳烃的偶联反应-一种从各种卤代芳烃制备联苯类化合物的有效方法。

Generally, these compounds are derived from accessible α–oxoketen dithioacetals and the common methods of preparation involve regioselective sodium borohydride 1,2-reduce of α–oxoketen dithioacetals, 1,2-nucleophilic addition of organomatals such as organomagnesium, organolithium, Reformatsky regent to α–oxoketen dithioacetals, Baylis-Hillman reaction between polarized ketene dithioacetals and aldehydes.

主要方法包括：使用硼氢化钠1，2-选择性还原α-羰基二硫缩烯酮；利用有机金属化合物（如有机镁试剂，有机锂试剂，Reformatsky试剂等）对α-羰基二硫缩烯酮进行1，2-亲核加成；通过α-羰基二硫缩烯酮与芳醛进行Baylis-Hillman反应等获得。

N-substituded thioacridones with five different structures were synthesized via a route involving Ull-man reaction, cyclization, N-alkylation and sulfurization. The structures of each thioacridone were identified with IR and MS. The results from UV-spectrophotometry show that the five N-alkythioacridones all have stronger absorption in the visible light region.

采用乌尔曼反应、酸催化环化、N-烷基化和硫代化四步反应路线合成了5种不同结构的N-取代硫代吖啶酮，利用IR和MS分析手段表征了其结构，UV分光光度计的测定结果表明5种硫代吖啶酮在可见光区都有较强的吸收。

Two series of polyurethane acrylate grafted acrylic resins (Acr-g-TPU-PETA and Acr-gPPU-PETA) self-emulsifying systems are obtained by grafting -NCO group modified polyurethane acrylates with acrylic copolymer prepared from n-butyl acrylate, styrene,βhydroxyethyl methacrylate and acrylic acid The self-emulsifying systems showed Newtonian fluidity with viscosity closed to that of water, the solid contents were around 30% The T〓 of 15～4℃ for dried film before photocuring favored film formation at room temperature DSC and DMA results showed that PU-PETA is compatible with acrylic resin in the grafted resin The TG and dTG curves for Acr-g-PU-PETA samples were substantially different from the corresponding blends, and the brodened dTG peaks for photocured grafted resin suggest that there might be multiple interactions among chain segments The photocued film of the grafted resins self-emulsifying system exhibited good overall properties with polyurethane acrylate grafts ranging from 30% to 50%, and Acr-g-TPU-PETA series showed better properties than Acr-gPPU-PETA series The adhesion of the photocured film was 1～2 grade, impact strength was 50kg-cm and flexibility was 1mm The Shore hardness and the adhesion of the film decreased markedly if PETA was replaced by HEMA as photoactive group due to the lower C=C double bond content in the grafted resin The polyhydroxy amine-linked thioxanthones photoinitiators can be evenly dispersed in self-emulsifying system without color spot appearing in the dried film The films photocured with IV〓～IV〓 generally exhibited higher Shore hardness, gloss and solventresistance than that cured with Irgacure 2959 and did not induce the rusting of the iron substrate Pigmenting with titanium oxide had no effect on the photocuring The polyhydroxy amine-linked thioxanthone IV〓 and IV〓 can be new candidates for the formulation of titanium oxide pigmented photocurable water-borne coatings for their pale-yellow appearance and slight interference with the color of the coatings WB 4759 with high water-solubility coalesced and separated from the dried resin film, and even induced the rusting of iron substrate.

以丙烯酸丁酯，甲基丙烯酸-β-羟乙酯，丙烯酸及苯乙烯合成厂丙烯酸共聚树脂，并与含-NCO端基的聚氨酯丙烯酸酯接枝反应，经水性化后，得到两个系列（Acr-g-TPU-PETA和Acr-g-PPU-PETA）各5个不同配比的丙烯酸树脂接枝聚氨酯丙烯酸酯自乳化体系，粘度与水相近，为牛顿流体，固含量30％左右。光固化前干燥涂膜的玻璃化转变温度在-15℃～4℃之间，有利于室温下成膜。DSC及DMA谱表明两种树脂基本相容。Acr-g-PU-PETA的热失重行为明显不同于共混材料，接枝样dTG峰明显宽化，表明接枝样中链段之间的相互作刚有多重性，丙烯酸树脂与聚氨酯之间有一定的相容性。接枝树脂自乳化体系光固化涂层的综合性能以聚氨酯丙烯酸酯成分为50％～30％者相对较好，且以Acr-g-TPU-PETA系列更理想。光固化膜的附着力为1～2级，冲击强度为50kg·cm，柔软性多为1mm。以HEMA代替PETA作为接枝树脂的活性基团，碳—碳双键密度太低，光固化膜交联点太少，硬度和附着力均较差。多羟基胺连硫杂蒽酮光引发剂能均匀分散于树脂自乳化体系和接枝树脂干膜中，不出现色斑，光固化膜肖氏硬度一般高于以Irgacure 2959为光引发剂的光固化膜，光泽度及耐丁酮溶剂性能均有所提高，不会诱导铁基生锈，钛白着色对光固化结果几乎没有影响。本论文所合成的多羟基胺连硫杂蒽酮光引发剂IV〓与IV〓为浅黄色，对光固化涂层的颜色干扰较小，为配制钛白着色光固化水性涂料提供了新的光引发剂。水溶性太强的WB 4759在干膜中易聚结析出，且对所附着的铁基有诱导锈蚀作用。

By the bio-assay directed fractionation of the volative constituents.dimethyl disulfide,allyl methyl trisulfide,allyl methyl sulfide and diallyl disulfide were found to increase the beating rate and beating amplitude in a standard medium,but the compund 2-pentanone without sulfide did not affect either of them.

从具有生物活性的挥发性提取物中分离得到的二甲基二硫、烯丙基甲基三硫、烯丙基甲基硫醚和二烯丙基二硫对培养心肌细胞心率和振幅均有不同程度的增强作用，而不含硫的2-戊酮则没有作用。

I can not make it blossom and suits me

我不能让树为我开花

When temperatures are above approximately 80 °C discolouration of the raceways or rolling elements is a frequent feature.

当温度高于 80 °C 左右时，滚道或滚动元件褪色是很常见的特征。