硫酰

In this thesis, a convenient and efficient synthesis of highly functionalizeddihydropyrido[2,3-d]pyrimidines via a double [5 + 1] annulation strategy startingfrom easily available α-alkenoyl-α-carbamoyl ketene--acetals 1 and cheapreagents (NH4OAc, DMF, and POCl3) has been developed.

本论文探索了一种简便有效的合成高度官能化的二氢吡啶并[2，3-d]嘧啶的方法，此方法由易得的α-乙酰基-α-氨基乙酰基二硫缩烯酮1和便宜的试剂(醋酸铵，二甲基甲酰胺和三氯氧磷)通过两步[5 + 1]加成而实现。

In chapter three, the activating agents of ytterbium have been examined. Barbier-type reaction promoted by ytterbium metal was examined. The experimental results shown that the yield of Barbier reaction of imines with allylic bromide promoted by ytterbium is higher than that of aldehydes and ketones with allylic bromide under the same reaction conditions. In this chapter, the reductive cleavage of Se-Se and S-S bond induced by ytterbium metal was also studied.

首先研究了金属镱的活化剂以及活化方法，接着考察了金属镱促进的Barbier反应及其在合成高烯丙基胺和高烯丙基醇中的应用，以及影响该反应的主要因素；究了金属镱促进的二硫醚和二硒醚的S—S键和Se—Se键的还原断裂，继而与氯代烃，胺基甲酰氯反应生成相应的硫醚，硒醚，胺基甲酸硫代酯和硒代酯。

Methods 4-Hydroxy- benzonitrile was treated with sodium hydrogen sulfide and anhydrous magnesium chloride in dimethyl formamide to give thioamide, which was then directly cyclized with ethyl 2-chloroacetoacetate without separation to give ethyl 2-(4-hydroxyphenyl)-4-methylthiazole-5-carboxylate(2) in one-pot; then 2 was formylated with Duff reaction adopting hexamethylenetetramine in trifluoroacetic acid to give ethyl 2-(3-formyl-4-hydroxyphenyl)-4-methylthiazole-5-carboxylate(3); finally, the target compound was obtained by the treatment of 3 with hydroxylamine hydrochloride and sodium formate in formic acid.

采用"一勺烩"方法，以4-羟基苯甲腈为起始原料，首先与硫氢化钠和无水氯化镁在N，N-二甲基甲酰胺中反应，所得中间体不经分离，直接加入2-氯乙酰乙酸乙酯进行环合反应，得到2-(4-羟基)苯基-4-甲基-5-噻唑甲酸乙酯（2）；然后通过六亚甲基四胺/三氟乙酸进行Duff反应，得到2-(3-甲酰基-4-羟基)苯基-4-甲基-5-噻唑甲酸乙酯（3）；再经盐酸羟胺/甲酸/甲酸钠体系脱水得到目标化合物。

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。

Development period of the parasitoid pupa from the 5th instar larva fed on MSB was significantly longer. Length of cocoon of MSB treatment was significantly shorter than the control. However, no obvious differences were detected in the development periods of egg to larva, cocoon mass size, wasp emergence rate, sex ratio, longevity and forewing length of wasp between KMD1 and the control. 3. Amino acid content in the haemolymph of SSB after fed with transgenic rice Although there were no changes on the components of amino acids in the haemolymph of SSB after fed with two transgenic rice lines, there were some changes on relative contents of amino acids.

取食KMD1 36h后0天，20种氨基酸中除天门冬酰胺、丝氨酸、苏氨酸和甲硫氨酸外，其它16种氨基酸的含量都高于对照，其中组氨酸、甘氨酸、苯丙氨酸、异亮氨酸、赖氨酸差异达显著水平，谷氨酰胺、脯氨酸差异达极显著水平，与氨基酸总量表现一致的变化趋势；取食KMD1后1天，除天门冬酰胺、谷氨酰胺和赖氨酸高于对照外，其它17种氨基酸均较对照低，但仅丝氨酸、苏氨酸和色氨酸与对照差异显著；取食KMD1后3天，绝大多数氨基酸含量的变化与取食KMD1后0天的趋势一致，除丙氨酸和色氨酸比对照稍低，其它18种氨基酸均高于对照，其中精氨酸、缬氨酸差异显著，丝氨酸差异达极显著。

And then methanesufonic acid which is colorless and oderless is obtained by the hydrolysis of methane sulfonyl chloride at 70～90℃.

以硫、硫化钠、硫酸二甲酯为起始原料制备了二甲基二硫，然后用氯气氧化二甲基二硫得甲烷磺酰氯，经水解合成了甲烷磺酸，产品无色无味。

In this thesis,the AM1,MNDO,MINDO/3(mainly AM1)and INDO/S-CI semiempirical MO methods were used toinvestigate the excited-state intramolecular protontransfer reactions of salicylic acid derivatives—salicylic acid,methyl salicylate,salicylaldehyde,o-hydroxyaceto-phenone,salicylamide and 3-hydroxy-picolinamide (6 conformers and 2-3 anion species);2-(2'-hydroxy-5' methylphenyl) benzotriazole(4 conformers),2-(2' hydroxyphenyl) benzimidazole (3 conformers and 3anion species),Bis-2,5-(2-benzoxazolyl)hydroquinone(3 conformers),2-(2'-hydroxyphenyl)benzothiazole(2conformers) and 7-azaindole dimer (2 conformers).Theinvestigations were described as follows.Geometry optimization,relative stability andhydrogen bonding energy First,for sylicylic acid derivative molecules,the AM1,MNDO and MINDO/3 methods were used toinvestigate ground-state geometry optimization,energies,relative stabilities and hydrogen-bondingenergies on the five kinds of the molecules(designing 6 conformers and 2-3 anion species).Comparing with experimental data,the optimizedgeometry,the order of stability,the hydrogen-bonding energies and the distances between O-O in O-H..O hydrogen bonds by AM1 method were in agreementwith the experimental data,however,the C-C bondlengths optimized by MNDO and MINDO/3 were longer,C-O and O-H bond lengths were shorter;for C-N bondlengths,the results opitimized by MNDO method werethe same as those by AM1 method,nevertheless the C-Nbond lengths given by MINDO/3 method were muchshorter.For some sylicylic acid derivatives(e.g.methyl salicylate,salicylamide),the order ofstabilities on the conformers given by MNDO andMINDO/3 methods were not in agreement with theexisting conformers deduced by experimental methods,and the hydrogen bonding energies calculated by MNDO.and MINDO/3 methods were smaller.Second,the studyon the other systems found that the optimizedgeometry of the proton-transfered product with INDOmethod could not be obtained,only could theoptimized geometry of reactant be obtained,and thecalculated hydrogen bonding energies were greater.Many results of calculation indicated that the studyon the excited-state intramolecular proton transferreaction system using AM1 method was suitable andreliable.

本论文用AM1、MNDO、MINDO/3（主要是AM1）和INDO/S-CI半经验分子轨道方法对水杨酸衍生物系列——水杨酸、水杨酸甲酯、水杨醛、O-羟基乙酰苯酮、水杨酰胺和3-羟基吡啶酰胺（6种异构体和2-3种阴离子）；2-（2'-羟基-5'-甲基苯基）苯并三〓唑（4种异构体）；2-（2'-羟基苯基）苯并咪唑（3种异构体和3种阴离子）；2，5-二间氮杂氧茚氢醌（3种异构体）；2-（2'-羟基苯基）间〓杂硫茚（2种异构体）和7-〓吲哚二体（2种异构体）的激发态分子内质子转移反应在以下几个方面进行了较系统的理论研究：几何构型优化和相对稳定性及氢键能首先以水杨酸衍生物系列分子为例，用AM1、MNDO和MINDO/3方法考察了5种分子（每种分子设计6种异构体和2-3种阴离子）的基态几何构型优化，能量、相对稳定性和氢键能计算，通过和实验数据进行比较，AM1方法给出的优化几何构型、稳定性次序、氢键能和O—H。。。O氢键的0—0距离与实验数据吻合最好，MNDO和MINDO/3方法优化的C-C键长偏长，C-O键和O-H键长偏短；对于C-N键长，MNDO和AM1优化结果差别不大，而MINDO/3给出了过短的C-N键长，MNDO和MINDO/3方法给出的有些水杨酸衍生物分子（如水杨酸甲酯和水杨酰胺）异构体的稳定性次序和实验上推测的可存在异构体结果不一致，MNDO和MINDO/3方法给出的氢键能偏低，对其他体系的研究发现INDO方法常常不能得到质子转移产物的优化几何构型，只能得到反应物的优化构型，并且估算的氢键能偏高，大量的计算结果表明AM1方法对本论文研究的激发态分子内质子转移反应体系是适宜和可靠的。

Firstly, polyacrylamide with 26 million molecular weight was compounded in lab through establishing optimum compounding initiator proportionality of 1:1. 3 and mass concentration of 170 mgL^(-1), temperature of 10 ℃, acrylamide mass percentage of 25%, electrical conductivity of 3.6 μSm^(-1) and pH value of 6.57. The salt-resistance, thermal endurance and shear-resistance of polyacrylamide could be enhanced b introducing sulfonic acid group or styrene sulfonate group or drawing the two groups above at the same time. Secondly, chelator HEDP, bactericide isoquinoline ketone and oxygen scavenger thiourea were optimized to improve the compatibility of polyacrylamide and formation water.

在由室内试验确定了复合引发剂最佳比值1：1.3和质量浓度170 mgL^(-1)、合成最佳温度10℃、丙烯酰胺单体质量分数25%、电导率3.6μSm^(-1)和pH值6.57后，合成出相对分子质量高于2.6×10^7的聚丙烯酰胺，同时通过丙烯酰胺单体复配引入磺酸基团、苯乙烯磺酸基团或同时引入此两种基团，提高了聚合物的抗盐、抗温、抗剪切性能；后针对聚丙烯酰胺与地层水配伍性差的问题，优选出HEDP螯合剂、异噻唑烷酮杀菌剂和除氧剂硫脲，对聚合物稳定效果明显。

As CAAX-mimetics, 1, 3-dihydro-5-phenyl-2-H-1, 4-benzodiazepin-2-one was modified by linking carboxyl groups with various carbon through N-1 and C-3, 3-(imidazol-4-yl) propion amido group with different substituents was connected at C-7; In the synthesis of bisubstrate analogues, thiocarbamido compounds was alkylated by alkyl iodide and then hydrolyzed to give alkylthiol benzoate compounds.

1，4-苯并二氮杂草-2-酮类化合物的合成过程中分别对其1、3、4和7位进行了基团变化，在1和3位连接不同长度含羧基或酯基的侧链，在7位连接不同取代的咪唑丙酰氨基。在苯甲酸硫醇酯化合物合成过程中，建立了一种硫原子连有不同长度碳链的苯甲酸硫醇酯的合成方法。

Research result indicated that the cooperative effect between swell and precursor is main factor for the nanoparticle loaded in Nafion, and moreover, polarity of solvent and water content in Nafion also affects the load largely. To improve away the surface concentration of CdS nanocrystal on two side of membrane for general preparation, thioacetamide was first used as a precursor instead of inorganic sulfur source(H2S and Na2S) in synthesis of CdS nanocrystal. The assembly mechanism for several sulfur source had been studied, and CdS/Nafion with the character of homogeneous disperse had been prepared, which is fit for mass transmission in photocatalitic reaction. Following the investigation of several crystallizing way, simple and reliable hydrothermal-crystallizing was found. According to this way, maximal TiO2 load in Nafion achieved 43%. Activity of TiO2/Nafion or CdS/Nafion as a photocatalyst was explored initially for disintegrating liquid contamination. Maximal decompose rate achieved 86% under condition of this research.

研究结果表明：Nafion膜对纳米粒子负载量的主要影响因素是溶胀作用与前驱体协同效应，同时溶剂极性和薄膜含水量对负载量也影响相当大；本课题首次使用硫代乙酰胺代替传统无机硫源（H2S、Na2S）合成CdS纳晶，研究了各种硫源的组装机理，克服了常规技术存在的CdS纳晶趋于膜表面富集的缺点，得到了有利于光催化传质需要的体相均匀分布CdS/Nafion；研究了多种Nafion膜内纳米粒子晶化途径，找到了简单可靠的水热晶化法，TiO2纳晶最高负载量达43％；初步探索了TiO2/Nafion、CdS/Nafion作为光催化剂降解水中模拟污染物的活性，在本实验条件下最高降解率达86％。

They weren't aggressive, but I yelled and threw a rock in their direction to get them off the trail and away from me, just in case.

他们没有侵略性，但我大喊，并在他们的方向扔石头让他们过的线索，远离我，以防万一。

In slot 2 in your bag put wrapping paper, quantity does not matter in this case.

在你的书包里槽2把包装纸、数量无关紧要。