Anodic trifluoromethylation of 10-undecylenic acid

The electrooxidation of a (～3: 1) mixture of trifluoroacetic and 10-undecylenic acids in MeCN with an aqueous KOH addition on different anodic catalysts was studied. The oxidation of trifluoroacetate ions that forms trifluoromethyl radicals is the key stage of the process, while 10-undecylenic acid seems to be merely an acceptor of the electrogenerated radicals, i.e., shows the chemical properties characteristic of olefins. The galvanostatic electrolysis of trifluoroacetic and 10-undecylenic acids led to a mixture of the products of trifluoromethylation of the latter and the products of coupling of the formed radical species. According to a qualitative estimation, the total yield of these products was 74%.     

Brønsted Acid‐Mediated Annulation of α‐Oxo Ketene Dithioacetals with Pyrroles: Efficient Synthesis of Structurally Diverse Cyclopenta[b]pyrroles

Brønsted acid‐mediated annulation of internal olefins α‐oxo ketene dithioacetals to pyrroles was efficiently achieved to afford cyclopenta[b]pyrroles. A pair of Brønsted acids with acid strengths, that is, trifluoroacetic acid, and para‐toluenesulfonic acid hydrate, were applied to promote the annulation reactions. The resultant products were readily oxidized to sulfones by meta‐chloroperoxybenzoic acid. Subsequent treatment with 1,8‐diazabicyclo[5.4.0]undec‐7‐ene gave desulfurized terminal olefins or [2+2] cycloaddition products from the desulfurized olefin intermediates. The present protocol provides facile access to structurally diverse cyclopenta[b]pyrrole derivatives under mild conditions.     

Formation of iron(III) meso-chloro-isoporphyrin as a reactive chlorinating agent from oxoiron(IV) porphyrin π-cation radical

Iron(III) isoporphyrin, a tautomer of porphyrin with a saturated meso carbon, is one of the isoelectronic forms of oxoiron(IV) porphyrin π-cation radical, which is known as an important reactive intermediate of various heme enzymes. The isoporphyrin has been believed to be incapable of catalyzing oxygenation and oxidation reactions. Here, we report that an oxoiron(IV) porphyrin π-cation radical can be converted to iron(III) meso-chloro-isoporphyrin in the presence of trifluoroacetic acid and chloride ion. More importantly, this study shows the first evidence that iron(III) meso-chloro-isoporphyrin is an excellent reactive agent for chlorinating aromatic compounds and olefins. The results of this study suggest that the mechanism involves electrophilic chlorination of substrate with iron(III) meso-chloro-isoporphyrin.     

A Molecularly Defined Iron‐Catalyst for the Selective Hydrogenation of α,β‐Unsaturated Aldehydes

A selective iron‐based catalyst system for the hydrogenation of α,β‐unsaturated aldehydes to allylic alcohols is presented. Applying the defined iron–tetraphos complex [FeF(L)][BF₄] (L=P(PhPPh₂)₃) in the presence of trifluoroacetic acid a broad range of aldehydes are reduced in high yields using low catalyst loadings (0.05–1 mol %). Excellent chemoselectivity for the reduction of aldehydes in the presence of other reducible moieties, for example, ketones, olefins, esters, etc. is achieved. Based on the in situ detected hydride species [FeH(H₂)(L)]⁺ a catalytic cycle is proposed that is supported by computational calculations.     

Copper-catalyzed dimerization of chromium Fischer carbene complexes: synthesis of dialkoxytrienes and their Nazarov-type cyclization to 2-alkoxy-2-cyclopentenones

Fischer carbene complexes 1 underwent a clean ligand dimerization reaction yielding functionalized olefins and trienes 4 in the presence of copper (I) catalysts. If treated with trifluoroacetic acid (TFA), trienes 4c, d, f undergo a cyclization process (Nazarov reaction) which furnishes cyclopentenone derivatives 6c, d, 7c, d and 8 in good yields. Finally, the Fischer aminocarbene 9 efficiently cyclodimerizes to the substituted arene 10 in the presence of CuBr.     

Enhancements of Trifluoroacetic Acylated Five‐membered Heterocyclic Compounds Using as Additives in Dye Sensitized Solar Cells

In this study, five‐membered heterocyclic compounds are trifluoroacetic acylated for the purpose of providing more long pairs to enhance electrolyte in dye sensitized solar cells (DSSCs). Four five‐membered heterocyclic compounds will be trifluoroacetic acylated with trifluoroacetic anhydride by Friedel‐Crafts acylation: furan, thiophene, pyrrole and N‐methylpyrrole. The properties will be measured by cyclic voltage (CV), Fourier transform infrared spectroscopy (FTIR), solar simulator, and electrochemical impedance spectroscopy (EIS). We find out that furan and thiophene which we add in electrolyte as additives can increase short circuit current and photovoltaic efficiency, and furthermore, all the trifluoroacetic acylated heterocyclic compounds perform better photoelectric abilities than non‐trifluoroacetic acylated one. The photovoltaic efficiency will be increased from 4.439% to 5.197% when 1wt% trifluoroacetic acylated thiophene is added in electrolyte as additives.     

Addition of lithium aluminium hydride to olefins catalyzed by zirconium tetrachloride: A convenient route to alkanes and 1-haloalkanes from 1-alkenes

Lithium aluminium hydride adds to olefins in the presence of zirconium tetrachloride under mild conditions. This facile reaction offers a convenient laboratory method for the hydrogenation of olefins or for the preparation of 1-haloalkanes from olefins in high yield. Unstrained internal olefins appear to be unreactive.     

手性酮催化的烯烃不对称环氧化反应

手性酮是催化非官能化烯烃不对称环氧化的一类重要催化剂 ,它与过氧硫酸氢钾可原位产生对贫电子和富电子烯烃均很有效的氧化剂———手性二氧杂环丙烷 .综述了各种结构的手性酮在反式烯烃、三取代烯烃和顺式烯烃等的不对称环氧化反应中的应用研究进展 ,总结了手性酮结构及反应条件对其催化活性和不对称诱导作用的影响     

Analytical isotachophoresis utilizing computer simulation. II. Assessment of optimum separation conditions for urinary trifluoroacetic acid metabolized from anaesthetic halothane

Experimentally determined optimum separation conditions for a metabolite of anaesthetic halothane in urine, trifluoroacetic acid, were assessed by means of computer simulation of the isotachophoretic steady-state. The simulation confirmed that urinary acids and trifluoroacetic acid can be separated in the limited pH range of 3.5-3.7 buffered by beta-alanine, as far as the pH dependence of effective mobility is utilized. The separated fraction of the trifluoroacetic acid zone was identified by mass spectrometry. The simulated coefficient of the calibration curve agreed well with the observed value.     

Palladium-catalyzed highly regioselective and stereoselective decarboxylative arylation of unactivated olefins with aryl carboxylic acids

Palladium(II)-catalyzed highly regioselective and stereoselective decarboxylative arylation of unactivated olefins with aryl carboxylic acids has been developed. This method is applicable to a variety of unactivated olefins, including allylamides, long chain functionalized olefins and purely aliphatic olefins, leads to the formation of linear E-configured products in high yields. Both electron-rich and electron-deficient aryl carboxylic acids are suitable arylation reagents. It was found that the choice of solvent, catalyst precursor and oxidant had an important influence on reaction efficiency. As a co-solvent and ligand, DMSO is critical to catalysis. This chemistry expands the scope of decarboxylative arylation of olefins with aryl carboxylic acids, and provides a rapid access to useful linear arylation products of unactivated olefins.     

FCC汽油催化裂解生产低碳烯烃的研究

利用小型固定流化床实验装置研究了催化裂化（FCC）汽油在专门开发的多产低碳烯烃催化剂上的裂解性能。研究表明,反应温度对原料转化率、总低碳烯烃产率的影响最大,剂油比和水油比对低碳烯烃的产率影响较小,而随着重时空速的增大,总低碳烯烃产率略有降低;确定了FCC汽油催化裂解制低碳烯烃的实验室最优反应条件,即反应温度、剂油比、重时空速和水油比分别为660℃、12、15h^-1和0.8。根据反应条件与裂解产物的关系提出了催化裂解反应深度函数,并建立裂解产物产率与催化裂解反应深度函数之间的关联模型。随催化裂解反应深度函数的增加,乙烯产率持续增加,而丙烯和丁烯产率出现最大值,利用此模型可以对产物产率进行预测。     

High-resolution microwave studies of ring-structured complexes between trifluoroacetic acid and water

The rotational spectra of the complexes between one trifluoroacetic acid molecule and up to three water molecules have been recorded using a pulsed nozzle Fourier transform microwave spectrometer. The unambiguous assignments of them are made on the basis of the agreement between the experimentally determined rotational constants and the theoretical predictions from ab initio calculations using MP2/6-311++G(2df,2pd). All the complexes exhibit hydrogen-bonded ring structures. The fine splittings observed in some of the a-type transitions of the trifluoroacetic acid-H2O dimer were analyzed in terms of the likely tunneling motions of the hydrogens in the H2O molecule. Further calculations of the equilibrium constants for these three hydrated complexes of trifluoroacetic acid were also made to evaluate their fractions against the trifluoroacetic acid monomer in the atmosphere.     

625 nm低能量光子作用下WO3-x光催化烯烃异构化

烯烃异构化广泛用于合成药物、高强度材料和精细化学品.近年来,光催化烯烃异构化的发展解决了传统烯烃异构化的设备腐蚀、活性和选择性较差等问题.如Pd@TiO2和Pd配合物均可用于烯烃的光催化异构化,但仅对烯丙基苄基衍生物有效.K(o)nig等利用可见光、Co(acac)2和合适的配体实现了烯烃位置可控的异构化,但该反应仅限于末端烯烃.因此,需要开发一种简单高效的光催化烯烃异构化方法,一方面可以通过光催化烯烃异构化将末端烯烃或内烯烃转化为一个或多个位置异构化产物,将石油衍生物中存在的烯烃混合物转化为有价值的单一烯烃产品,另一方面能够大幅提高光催化烯烃异构化的效率.本文研究发现,在625 nm光照射下,氧缺陷WO3-x表现出较好的催化1-癸烯异构化活性.该催化剂不仅可以将各种链状和环状末端烯烃转化为相应的内烯烃异构体,而且能够将内烯烃混合物转化为单一末端烯烃产品.通过控制烯烃碳链的长度可以得到热力学和动力学异构化产物,当烯烃的碳数小于13时,主要得到动力学产物.在无光照时没有检测到产物,说明只有在光照下反应才能进行.WO3-x的氧缺陷使WO3-x的漫反射紫外可见(DR UV-vis)光谱在大于450 nm时出现了局域表面等离子体共振(LSPR)强吸收.不同波长光照下1-癸烯异构化反应转化率的变化趋势与WO3-x的DR UV-vis光谱一致,而且在625 nm红光照射下,1-癸烯的转化率最高达到99.4％,进一步说明反应是由光驱动的.625nm的光可以将WO3-x价带上的电子激发到缺陷能级,且该电子可以进一步被转移到WO3-x吸附的烯烃上(激发电子转移路径).为进一步研究氧缺陷对光催化烯烃异构化活性的影响,在300℃焙烧不同时间得到氧缺陷含量不等的WO3-x样品.X射线衍射谱、DR UV-vis光谱、X射线光电子能谱和电子顺磁共振光谱结果表明,随着焙烧时间的增加,催化剂中氧缺陷含量逐渐减少,其光催化1-癸烯异构化活性逐渐降低,证明催化剂中氧缺陷的存在可以提高其光催化性能.利用原位漫反射傅里叶变换红外光谱研究了氧缺陷对烯烃表面吸附和中间体形成的影响.结果 表明,WO3-x表面氧缺陷产生的不饱和W5+位点会与烯烃配位从而原位形成表面π配合物和π-烯丙基钨中间体.通过在反应体系中添加4-叔丁基邻苯二酚证明了反应是通过自由基机理进行的.综上所述,WO3-x与625 nm红光结合,实现了烯烃的光催化异构化.通过调节烯烃的碳链长度,可得到热力学和动力学产物,且该催化体系可以将石油衍生物中的内烯烃混合物转化为单一末端烯烃产品.WO3-x的氧缺陷既可以提高其光捕获能力,又可以用作光催化烯烃异构化的吸附和活化位点.本文提供了一种利用低能量光子进行烯烃高效选择性异构化的简便方法,该方法是传统烯烃异构化方法的补充.     

Cu-Fe基催化剂上合成气直接制取低碳烯烃的研究

我们采用浸渍法制备了γ-Al2O3负载的Cu-Fe基催化剂,并结合其反应性能和XRD、H2-TPR和XPS等表征结果研究了其催化合成气直接制低碳烯烃的反应行为.结果表明,合成气直接制低碳烯烃Cu-Fe基催化剂的活性组分Cu和Fe之间存在明显的协同效应,Cu-Fe基催化剂表现出优异的合成气直接制低碳烯烃反应性能;Cu基催化剂中引入少量Fe组分明显提高了活性组分Cu的分散度,促进了Cu活性组分的还原,进而有利于催化剂反应性能的改进.初步推断Cu-Fe基催化剂上合成气转化生成低碳烯烃的主要反应历程为CO加氢生成含氧化合物(醇醚等)后再脱水生成低碳烯烃.     

Reactions of N-thiobenzoyl-α-amino-acids and related N-substituted thiobenzamides with trifluoroacetic anhydride

5-(2'-Benzamidoacyloxy)thiazoles are formed by the reaction of N-thiobenzoyl-α-amino-acids with trifluoroacetic anhydride. Corresponding esters on similar treatment undergo isosteric S-O exchange, giving N-benzoyl-α-amino-acid esters. While these are further examples of the differences shown in the reactions of N-(2-carboxyalkyl)thiobenzamides compared with their benzamide analogues, N^α-thiobenzoyl-α-amino-acid amides are found to undergo cyclisation in trifluoroacetic anhydride to give 5-trifluoroacetamido-thiazoles, following the same reaction path as their N-benzoyl analogues. Terminal N-thiobenzoyl dipeptides give 5-(N-2-carboxyalkyl) trifluoroacetamido-thiazoles on treatment with trifluoroacetic anhydride, and it is established that trifluoroacetic anhydride fails to cleave the amide group of terminal N-thioacyl dipeptides, and is therefore not a suitable reagent for Edman-type sequence analysis of polypeptides.The present work completes a project establishing routes from α-amino-acids to thiazoles carrying a heteroatom (O, N or S) at the 5-position.     

Adamantylation of N-aryl and N-arylalkyl acetamides in trifluoroacetic acid

Russian Chemical Bulletin - Alkylation of N-aryl and N-arylalkyl acetamides with hydroxy adamantane derivatives in trifluoroacetic acid was studied. The differentiating effect of trifluoroacetic...     

Iodoamidation of olefins with chloramine salts and iodine in aqueous media

An efficient, unique, and convenient method for the iodoamidation of olefins with chloramine salts and I(2) in aqueous media is described. This method was applicable to a wide range of olefins, including aromatic, aliphatic, and electron-deficient olefins.     

Sulfonation chemistry of some small molecule models of EPDM rubbers. II. The structure of intermediate adducts

As previously reported, our initial investigation was concerned with the bicyclic olefins, ethylidene norbornane, and dihydrodicyclopentadiene. The former produced a skeletally rearranged γ-sultone and the latter an allylic sulfonic acid. In an attempt to further clarify the mechanisms of the sulfonation of these two models and to extend the study to models of other types of EPDM, we have now examined the sulfonation of several other model olefins. In addition to the bicyclic olefins reported previously, we have studied the sulfonation of monocyclic type II and III olefins and cyclic type I and type II olefins. The results showed that the bicyclic olefins behaved differently from their monocyclic analogs reinforcing earlier speculation as to a synchronous reaction mechanism. Exocyclics gave allylic sulfonic acids while endocyclics produced β-sultones, which is the exact reverse of what was observed for the bicyclic counterparts. Acyclic type II olefins produced “stable” β-sultones, and the influence of the sulfonating reagent on the subsequent chemistry is discussed. Type I olefins, curiously, gave a complex mixture of initial products which tended to rearrange to essentially a single thermodynamic product. The results of the investigation suggest that based on these models, each of the three major types of EPDM should have a different sulfonation mechanism.     

Convenient synthesis of 4-triflouromethylpyrazoles by cyclization of triflouroacetylated hydrazones

Several 4-trifluoromethyl-1-alkylpyrazoles were synthesized in good yields by trifluoroacetic anhydride-pyridine induced cyclization reaction of acylhydrazones prepared from aldehyde dialkylhydrazones and trifluoroacetic anhydride.     

烯烃在催化裂化催化剂上反应机理的初步研究

在自制的微反-色谱装置上,进行了单体烯烃和催化裂化汽油在不同条件下的催化裂化反应实验。对单体烯烃的裂化反应规律和汽油中的烯烃在半再生催化剂和待生催化剂上的催化裂化反应规律进行对比分析。结果表明,单体烯烃反应中,C6及C6以下的烯烃主要发生骨架异构和双键异构反应,氢转移和直接裂化反应发生的较少。C7以上的烯烃95%以上发生转化,高温下直接裂化生成C3、C4,氢转移和异构化比率较大。汽油中的烯烃转化主要集中在C7以上,烯烃之间存在一定的交互作用,单体烯烃的催化裂化反应规律可以初步预测汽油中烯烃的转化。催化剂上的结焦类型对汽油中的烯烃的转化方式没有影响。