固相配位化学反应研究XXXIX. 四氰合镍酸钾与固体有机酸在室 温下的固相反应

本文用红外、紫外可见漫反射、X射线粉末衍射和四极质谱等实验手段,研究了四氰合镍酸钾一水合物与草酸、丙二酸、反丁烯二酸、丁二酸、己二酸的固相反应,发现K~2[Ni(CN)~4].H~2O与一些固体酸在室温下就发生反应,生成Ni(CN)~2.xH~2O,并放出HCN气体。由产物与反应物相对含量大小,得到固体有机酸的酸性强弱顺序为:草酸二水合物>丙二酸>反丁烯二酸>丁二酸>己二酸。讨论了可能的反应机制。     

固相配位化学反应研究——ⅩⅩⅩⅨ.四氰合镍酸钾与固体有机酸在室温下的固相反应

本文用红外、紫外可见漫反射、X 射线粉末衍射和四极质谱等实验手段,研究了四氰合镍酸钾一水合物与草酸、丙二酸、反丁烯二酸、丁二酸、己二酸的固相反应,发现 K_2[Ni(CN)_4]·H_2O 与一些固体酸在室温下就发生反应,生成 Ni(CN)_2·xH_2O,并放出 HCN 气体.由产物与反应物相对含量大小,得到固体有机酸的酸性强弱顺序为:草酸二水合物>丙二酸>反丁烯二酸>丁二酸>己二酸。讨论了可能的反应机制.     

固相配位化学反应研究XXXIV. 室温下六氰合铁(II)及(III)酸钾 的固相酸碱反 应

本文研究了室温时K~3Fe(CN)~6,K~4Fe(CN)~6在酸碱条件下发生的固相配位化学反应。结果表明:K~3Fe(CN)~6与NaBH~4固相混合物室温下不反应,但加入固体氢氧化钠后,K~3Fe(CN)~6与NaBH~4的固相氧化还原反应在室温下很容易进行。K~4Fe(CN)~6与K~2S~2O~8的固相氧化还原反应在室温下能顺利进行,但当固体KOH存在时,反应明显受到抑制。K~3Fe(CN)~6与K~2C~2O~4.H~2O室温下无反应,但与H~2C~2O~4.2H~2O在室温时即发生固相取代反应。     

固相配位化学反应研究XXXIV. 室温下六氰合铁(II)及(III)酸钾 的固相酸碱反 应

本文研究了室温时K~3Fe(CN)~6,K~4Fe(CN)~6在酸碱条件下发生的固相配位化学反应。结果表明:K~3Fe(CN)~6与NaBH~4固相混合物室温下不反应,但加入固体氢氧化钠后,K~3Fe(CN)~6与NaBH~4的固相氧化还原反应在室温下很容易进行。K~4Fe(CN)~6与K~2S~2O~8的固相氧化还原反应在室温下能顺利进行,但当固体KOH存在时,反应明显受到抑制。K~3Fe(CN)~6与K~2C~2O~4.H~2O室温下无反应,但与H~2C~2O~4.2H~2O在室温时即发生固相取代反应。     

固体酸ZrO2-Ce2O3/SO2-4催化合成丙二酸二丁酯

以含铈固体超强酸ZrO2-Ce2O3/SO4 2-为催化剂,丙二酸和正丁醇为原料合成了丙二酸二丁酯.最佳反应条件为:催化剂活化温度500℃,丙二酸100mmol,n(酸):n(醇)=1.0:2.5,催化剂用量1g,反应时间2h,酯化率达95.8%.结果表明,加入铈有助于提高固体超强酸的使用寿命.     

固相配位化学反应研究 ⅩⅩⅩⅣ.室温下六氰合铁(Ⅱ)及(Ⅲ)酸钾的固相酸碱反应

本文研究了室温时K_3Fe(CN)_6,K_4Fe(CN)_6在酸碱条件下发生的固相配位化学反应.结果表明:K_3Fe(CN)_6与NaBH_4固相混合物室温下不反应,但加入固体氢氧化钠后,K_3Fe(CN)_6与NaBH_4的固相氧化还原反应在室温下很容易进行.K_4Fe(CN)_6与K_2S_2O_8的固相氧化还原反应在室温下能顺利进行,但当固体KOH存在时,反应明显受到抑制.K_3Fe(CN)_6与K_2C_2O_4·H_2O室温下无反应,但与H_2C_2O_4·2H_2O在室温时即发生固相取代反应.     

胺-水二元系固液相平衡及其水合物

测定了水+三乙胺,+N,N-二甲基甲酰胺(DMF),+N,N-二甲基乙酰胺(DNA)的固液平衡相图,3个体系均有固体水合物形成,它们分别是不相合熔点水合物N(C_2H_5)_3·3H_2O、相合熔点水合物DMF·3H_2O,DMF·2H_2O,DMA·3H_2O和(DMA)_2·3H_2O.对水合物的形成进行了分析并与文献结果相比较.     

固体酸ZrO2-Ce2O3／SO4^2-催化合成丙二酸二丁酯

以含铈固体超强酸ZrO2-Ce2O3／SO4^2-为催化剂，丙二酸和正丁醇为原料合成了丙二酸二丁酯。最佳反应条件为：催化剂活化温度500℃，丙二酸100mmol，n(酸)：n(醇)=1．0：2．5，催化剂用量1g,反应时间2h，酯化率达95．8％。结果表明，加入铈有助于提高固体超强酸的使用寿命。     

草酸桥联双核Ni(Ⅱ)配合物的合成、光谱和结构

合成并表征了两个含有不同阴离子的双核镍(Ⅱ)配合物{[(tacn)Ni(H~2O)]~2(μ-C~2O~4)}I~2·2H~2O(1)和{[(tacn)Ni(H~2O)]~2(μ-C~2O~4)}(ClO~4)~2·2H~2O(2)(tacn=1,4,7-三氮杂环壬烷)。晶体结构分析表明这两个配合物中,两个Ni离子通过草酸根桥联,每个Ni离子还与一个大环配体tacn上的三个氮原子和一个水分子配位形成变形八面体结构。结晶水和配位水之间通过氢键相连。在紫外-可见区测定了配合物的固体反射谱和溶液吸收谱。     

氨基磺酸催化合成丁二酸二丁酯

研究了氨基磺酸代替硫酸作为酯催化剂,由丁二酸与正丁醇合成丁二酸二丁酯的反应,考察了反应的影响因素及氨基磺酸的重复使用性能。丁二酸3．0g(250mmol),n(丁二酸)：n(正丁醇)：n(氨基磺酸)=1．00：8．00：0．31,回流分水60min,酯收率97．4％。另外,还催化合成了癸二酸二丁酯、己二酸二丁酯和马来酸二丁酯。     

固相配位化学反应研究 52: 室温固-固相化学反应合成氨基酸铜配合物

本文报道室温固-固相化学反应一步法合成氨基酸铜配合物。trans-Cu(Gly)2.H2O、cis-Cu(GlY)2.H2O、trans-Cu(DL-Ala)2、trans-Cu(DL-Ala)2.H2O、trans-Cu(DL-Val)和trans-Cu(DL-Leu)2, 经元素分析、IR、XRD、DTA测定了配合物的组成及几何构型。并初步讨论了室温固相反应合成机理。     

XO~4^2-/ZrO~2固体超强酸催化剂上的正构烷烃反应

本文考察了SO~4^2-/ZrO~2固体超强酸催化剂上正构烷烃的反应及影响催化剂活性和选择性和各种因素。结果表明: 烷烃的骨架异构化和裂解反应在催化剂上同时进行, 烷烃的碳原子数增加, 催化剂活性提高, 裂解反应比例增加, 降低反应温度有利于骨架异构化反应; 同时催化剂的反应性能与含水量关系十分密切, 完全脱水的催化剂活性很低, 少量水的存在有利于提高催化活性, 过量的水又可使催化剂失活。根据催化剂的热重分析、红外光谱和反应数据, 提出低温时正戊烷反应主要在催化剂表面B酸位上进行, 随着反应温度升高和烷烃碳原子数增加, 催化剂表面的L酸位才显示一定的活性。     

Syntheses of copolymers containing pendant cyclic iminoethers and crosslinking reactions of these copolymers with dithiols and dicarboxylic acids

Copolymers containing pendant cyclic iminoethers were prepared by radical copolymerizations of 2-vinyl-2-oxazoline (VOZO), 5-methyl-2-vinyl-2-oxazoline (MVOZO), 4,4-dimethyl-2-vinyl-2-oxazoline (DMVOZO), 4,4-dimethyl-2-vinyl-5,6-dihydro-4H-1,3-oxazine (DMVOZI), and 4,4,6-trimethyl-2-vinyl-5,6-dihydro-4H-1,3-oxazine (TMVOZI) with styrene, methyl methacrylate (MMA), and ethyl acrylate (EA) using AIBN as an initiator. In addition, the monomer reactivity ratios of VOZO, MVOZO, DMVOZO, and DMVOZI with styrene and MMA were determined. The crosslinking reactions of these copolymers with polyfunctional thiols such as 6-(N,N-dibutyl)amino-1,3,5-triazine-2,4-dithiol (DBDT), 4,4′-oxydi(benzenedithiol) (OBDT), and pentaerythritol tetrathioglycolate (PETT), and dicarboxylic acids such as succinic acid, adipic acid, and sebacic acid were carried out at several reaction temperatures. From these results, it was found that the order of reactivity of pendant cyclic iminoethers to the thiols was VOZO > DMVOZO ≥ DMVOZI > MVOZO > TMVOZI, and that of the cyclic iminoethers to the carboxylic acids was VOZO > MVOZO ≥ DMVOZI > TMVOZI ≥ DMVOZO. Furthermore, the order of reactivity of the thiols to the cyclic iminoethers was DBDT > OBDT > PETT, and that of the dicarboxylic acids to the cyclic iminoethers was succinic acid > adipic acid > sebacic acid.     

Cu(OAc)2.H2O与1-苯基-3-甲基-4-苯甲酰基吡唑啉酮-5(HPMBP)的固相配位化学反应

在低加热条件下(<100℃), 研究了Cu(OAc)2.H2O与1-苯基-3-甲基-4-苯甲酰基吡唑啉酮-5-(HPMBP)两种异构体(烯醇式与酮式)的固相配位化学反应, 结果表明两种异构体与Cu(OAc)2.H2O固相化学反应活性并不相同。通过IR, UV测定, 发现酮式异构体在与Cu(OAc)2.H2O的固相反应过程中, 其自身经过了一个由酮式到烯醇式的固相异构化。     

Characterization of nitrogen-blanketed wave soldering reactions using thermal analysis

Thermal analysis techniques have been employed to elucidate the mechanism of low solids soldering flux activation. Metal oxides (SnO, PbO and PbO₂) are converted to carboxylate salts, which are displaced in the solder wave, rendering a solderable metal surface. Neither of the activators tested, namely succinic acid and adipic acid, react with SnO₂ at soldering wave temperatures and therefore cannot yield a solderable surface when SnO₂ is present. Further, adipic acid reacts with SnO to form a salt that can decompose to cyclopentanone, so the preheating of the printed circuit board must be carefully controlled to yield a solderable surface.     

Decomposition in Prolonged Storage of KF · H<Subscript>2</Subscript>O<Subscript>2</Subscript> Stabilized with Carboxylic Acids

Decomposition of KF · H₂O₂ stabilized with carboxylic acids (maleic, fumaric, succinic, adipic) in storage for more than three years at 20°C was studied. Rate constants of decomposition of stabilized KF · H₂O₂ were determined in different time intervals. The chemical reactions in the system KF-H₂O₂-carboxylic acid in the stage of preparation of solid KF · H₂O₂ stabilized with carboxylic acid and those during prolonged storage of the final product are discussed.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 2, 2005, pp. 287–291.Original Russian Text Copyright © 2005 by Titova, Nikol’skaya, Buyanov, Pudova, Karzhavina.     

Investigating isomerization reactions in solid state by using simultaneous high overtone pumping and Raman detection

Formation of the unstable cis-formic acid in solid argon matrix is induced by direct excitation of the 6<--0 transition of the nu(OH) vibration of the trans-formic acid. The experiment utilizes strongly focused laser beam that produces relatively high isomerization rate despite the low cross section of the absorption. Raman spectroscopy in a backscattering geometry is used for detection of the reactants and the products. This experimental arrangement allow us to use the same laser source for simultaneous pumping and Raman excitation, and it also guarantees that the excited and probed volumes overlap. The presented method has a high potential for solid state investigations of chemical reactions on the ground electronic state.     

固态有机反应新进展

总结了一些典型的固态有机反应。由于固态反应的特性，多数固态有机反应表现出较溶液中更高的反应效率和更好的选择性，在某些情况下，利用光活性主体与反应物形成包结物，可实现对映选择性的不对称固态合成。     

稀土固体超强酸SO~4^2^-/TiO~2/La^3^+催化合成水杨酸 异丁酯

研究了以稀土固体超强酸SO~4^2^-/TiO~2/La^3^+为催化剂,水杨酸和异丁醇为原料合成水杨酸异丁酯,并考察了影响反应的因素。结果表明,醇酸比为3:1,催化剂用量为1.0g(水杨酸为0.1mol的情况下),带水剂苯为15mL,反应时间为3.0h是最适宜的反应条件,酯化率达96.2%。     

Cluster phase chemistry: gas-phase reactions of anionic sodium salts of dicarboxylic acid clusters with water molecules

A homologous series of anionic gas-phase clusters of dicarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid) generated via electrospray ionization (ESI) are investigated using collision-induced dissociation (CID). Sodiated clusters with the composition (Na(+))(2)(n+1)(dicarboxylate(2-)(n+1) for singly charged anionic clusters, where n = 1-4, are observed as major gas-phase species. Isolation of the clusters followed by CID results mainly in sequential loss of disodium dicarboxylate moieties for the clusters of succinic acid, glutaric acid, and adipic acid (C4-C6). However, all oxalate (C2) and malonate (C3) clusters and dimers (n = 1) of succinate (C4) and glutarate (C5) exhibit more complex chemistry initiated by collision of the activated cluster with water molecules. For example, with water addition, malonate clusters dissociate to yield sodium acetate, carbon dioxide, and sodium hydroxide. More generally, water molecules serve as proton donors for reacting dicarboxylate anions in the cluster and introduce energetically favorable dissociation pathways not otherwise available. Density functional theory (DFT) calculations of the binding energy of the cluster correlate well with the cluster phase reactions of oxalate and malonate clusters. Clusters of larger dicarboxylate ions (C4-C6) are more weakly bound, facilitating the sequential loss of disodium dicarboxylate moieties. The more strongly bound small dicarboxylate anions (oxalate and malonate) preferentially react with water molecules rather than dissociate to lose disodium dicarboxylate monomers when collisionally activated. Implications of these results for the atmospheric aerosol chemistry of dicarboxylic acids are discussed.