Synthesis and Properties of New-type Troponoid Dithio-Crown Ethers

Troponoiddithio-crownethersareakindofnovelcomPounds.Takeshitaetall-'havereportedthesynthesisandmercurophilicpropertiesofthiskindofcompounds.lnthereportedcomPounds,thetWosulfuratomsareattached,partorall,tothetroponeringdirectly.Whetherthedithio-crownethersstillhaveselectiveandreversiblemercurysaltcaptUringabi1itywhenthetWosulfuratomslinktothebenZylic-mpepositionoftroponeringarousedourinterest.Herein,wewishtoreportthatfromthereactionof3,7-dichloromethyl-5-isopropyl-2-methoxytropone4withbis(mer…     

Synthesis of novel poly(aryl ether amide)s containing the phthalazinone moiety

Two novel heterocyclic diamine monomers: 1,2-dihydro-2-(4-aminophenyl)-4-[ 4-( 4-aminophenoxy) phenyl ]-(2H )-phtha-lazin-1-one and 1, 2-dihydro-2-( 4-aminophenyl )-4-[ 4-( 4-aminophenoxy) -3, 5-dimethylphenyl ] - (2H) -phthalazin-1-one were successfully synthesized using readily available heterocyclic bisphenol-like monomers through two steps in high yield. A series of novel poly( aryl ether amide)s containing the phthalazinone moiety with inherent viscosities of 1.16-1.67 dL/g were prepared by the direct polymerization of the novel diamines and aromatic dicarboxylic acids using triphenyl phosphite and pyridine as condensing agents. The polymers were readily soluble in a variety of solvents such as N, N-dimethyl-formamide (DMF), N,N-dimethylacetamide (DMAc), dimethylsulfoxide ( DMSO ), N-methyl-2-pyrrolidinone (NMP), and pyridine. The polymers had high glass transition temperatures (Tg) in the 291-329℃ range.     

浆态床中合成气制二甲醚宏观动力学的研究(英文)

以液体石蜡为介质,在合成甲醇催化剂与甲醇脱水催化剂比例为5、催化剂浓度为10 g/300 mL液体石蜡,温度为250℃~280℃,压力为3 MPa~5 MPa,气体空速为4 000 mL/(g(h)~7 000 mL/(g(h)的条件下,建立了浆态床合成气制二甲醚宏观动力学模型。甲醇合成反应和甲醇脱水反应的活化能分别为14.06 kJ/mol和23.53 kJ/mol。甲醇当量生成速率和二甲醚生成速率的计算值与实验值的相对误差在10%和20%以内。     

含环己烯、二氮杂萘结构的新型聚醚酮的合成及表征

合成了一种新型单体１－甲基－４,５－二（４－氯代苯甲酰基）环己烯,该单体与４－（４－羟基苯基）－２,３－二氯苯萘－１－酮单体经亲核取代反应,成功地合成了含环己烯结构的杂环联苯型醚酮聚合物。用ＦＴ－ＩＲ、＾１Ｈ－ＮＭＲ、ＤＳＣ、Ｘ－射线衍线等方法对该聚合物进行了表征,并研究了它的溶解性能。结果表明,这种可溶性无规共聚物,有较高的玻璃化温度,并且结构中有不饱和和双键,是一种反应性高分子。     

Two-fragment α-adrenolytics

A method for the synthesis of hypotensive alkyl(phenyl)[ω-(N-phenylpiperazino)alkyl]-phosphine oxides by reacting alkyl(ω-haloalkyl)phenylphosphine oxides withN-phenylpiperazine was elaborated. Phenyl[γ-(N-phenylpiperazino)propyl]propylphosphine oxide reacts with alkyl halides to give [γ-(N-alkyl-N′-phenylpiperazinio)propyl]phenyl(propyl)oxophosphine halides. For Part 1 see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 488–492, March, 2000.     

Thermal Decomposition of Trialkyl/Arylphosphine Gold(I) Cyanide Complexes

Combined TG/DTA techniques have been used to study the thermal decomposition of R₃PAuCN (where Ris ethyl, cyclohexyl, o-tolyl, m-tolyl, p-tolyl, allyl, cyanoethyl,1-naphthyl and phenyl) complexes. It was observed that all of these complexes underwant decomposition cum redox reactions in the range of 200–600oC with evolution of both transligands, which are phosphine and cyanide, leaving metallic gold as a residue. The thermal decomposition of o-Tol₃PAuCN has revealed that this is a stepwise process. In the first step decomposition takes place with evolution of phosphine and generation of AuCN, which in second step undergoes a redox reaction to produce metallic gold. The DTA curves have also confirmed these results. This revised version was published online in July 2006 with corrections to the Cover Date.     

冠醚取代蒽醌超分子体系的设计与合成及分子内能量转移的研究

大环冠醚由于其自组装性能及分子识别能力而引起人们广泛的重视.近来,冠醚又成为在超分子体系中用于建构主体分子的一种重要的建造单元^[1~4].Costa^[5]等曾报道苯并冠醚与被识别的稀土离子铕(Ⅲ)与铽(Ⅲ)之间的能量传递过程,选择性激发冠醚主体观察到稀土离子的发光.由于二氮杂冠醚与稀土离子能形成更稳定的配合物^[6].我们利用了冠醚分子的分子识别能力及蒽醌分子的光敏性,设计合成了一种新的氮杂冠醚取代蒽醌分子(图1)(以下文中用代号AQ-CW表示),并以该分子作为主体分子,以稀土离子作为客体构成超分子体系,研究超分子体系内的能量转移过程.     

老化反应对高碱度烷基水杨酸钙胶体结构及抗磨性的影响

采用冷冻蚀刻电镜（ＦＥ－ＥＭ）,傅立叶红外光谱（ＦＴ－ＩＲ）及钙分布测定等研究了高碱度烷基水杨酸钙的老化过程,并探讨了老化机理,老化反应高碱度烷基水杨酸钙胶体粒子变小,胶体中氢氧化钙的相对含量增加,粘度降低,总碱值（ＴＢＮ）升高;老化后样品的清净性及抗磨性明显提高;水、甲醇及氢氧化钙等影响老化效果。     

烷基多苷的分析测定

ＧＣ、＾１Ｈ－ＮＭＲ和＾１３Ｃ－ＮＭＲ核磁共振技术都能准确地测量出烷基多苷的平均聚合度,可判断出烷基多苷中主要苷类的出峰位置。     

CX_2(X=H,F,Cl)与甲基异丙基醚C-H键插入反应的理论研究

用从头计算方法在MP2 /6 31G(d)水平上研究了CX2 (X =H ,F ,Cl)与甲基异丙基醚的C -H键插入反应。CCl2 与甲基异丙基醚两个不同的α C的C -H键插入势垒分别为 117.2kJ/mol (甲基 )和 2 0 .6kJ/mol (异丙基 )。CF2 与异丙基α C的C -H键上插入势垒为 12 0 .0kJ/mol,在插入甲基上C -H键时会引起C -O键的断裂。CH2 的插入反应则不需要势垒。对CX2 与二甲醚、甲乙醚、甲基异丙基醚、甲基苄基醚上各种不同的C -H键插入势垒进行了比较 ,甲基和苯基都促使其毗邻的C -H键更容易被CX2 所插入