Ionic liquids as efficient phase-transfer catalysts for the solid base-promoted monoalkylation of diethyl malonate

Ionic liquids （ILs） based on 1,3-dialkylimidazolium and tetraalkylammonium cations were employed as a series of efficient, environmentally benign phase-transfer catalysts （PTCs） for the base-promoted monoalkylation of diethyl malonate. The influence of various heterogeneous bases on yields was studied. Good yields and high selectivity were obtained. Solvent-free, mild reaction condition, short reaction time, and easy purification were the merits of this method. The catalytic system （IL-hase） could also be recycled after the extraction of products with ether.

A Novel Synthesis of Dimethyl Malonate by Carbonylation of Methyl Chloroacetate Catalyzed by Cobalt Complex

A novel method of preparing dimethyl malonate by carbonylation of methyl chloroacetate catalyzed by Na[Co(CO)(4)] was proposed. Na[Co(CO)(4)] was synthesized in situ in the presence of Na2S2O3 and iron powder. The effects of some reaction parameters such as temperature. CO pressure and the concentrations of catalyst on the yields of dimethyl malonate were discussed. The kinetic data were studied and a possible reaction mechanism was proposed.

A Facile Synthesis of 5-Monosubstituted Isopropylidene Malonates

Introduction 5-Monosubstituted isopropylidene malonates arc important synthetic organic intermediates. Since isopropylidene malonate has a stronger acidity （pK;=4.57）, its direct alkylation with alkyl halides usually gives 5,5-disubstitutcd isopropylidene malonates.

Condensation of Aromatic Aldehydes with Isopropylidene Malonate or 5,5-Dimethyl-1,3-cyclohexanedione without Catalyst

The condensation of aromatic aldehydes with isopropylidene malonate or 5,5-dimethyl-1,3-cyclohexanedione is carried out by DMF as solvent without catalyst.

Syntheses and Characterization of Two Novel Copper(II) Malonate Complexes Functionalized with 3,3’-Bis(pyrazolyl)pentane and 4,4’-Trimethylenedipyridine

Two novel copper complexes (1,2) with N,O-donor ligands were synthesized by reaction of copper(II) malonates with 3,3’-bis(pyrazolyl)pentane and 4,4’-trimethylenedipyridine in methanol at moderate temperature. These compounds were characterized by elemental analysis, UV-VIS, IR spectroscopies and powder X-ray diffraction analyses. Compound (1) melts at higher temperature (202°C) than compound (2) (100°C). The IR spectra showed typical vibrations related to C=N and C=C, characteristic of pyrazolyl and pyridine ligands.

Synthesis,Characterization and Thermal Decomposition Behaviour of Tri-aquo Lanthanum(Ⅲ)Malonate Bimalonate

A new complex of malonic acid with lanthanum,La(Hmal)·(mal)·3H_2O,was synthesized and characterized by elemental analysis and IR spectra.The thermal decomposition process and their kinetic parameters n and E_a were studied by means of TG and DTG.All of the intermediate and end products were determined and characterized by the mass loss in TG curve,elemental analysis and IR spectra.

Catalytic[2+2+2]Tandem Cyclization with Alkyl Substituted Methylene Malonate Enabling Concise Total Synthesis of Four Malagasy Alkaloids

Myrtoidine and malagashanine,highly complex indole alkaloids,are effective adjuvants in developing cures for plasmodium malaria and potent multi-drug resistant agents.Despite nearly 30 years of progress,myrtoidine and the related family of Malagasy alkaloids still present formidable challenges for synthetic chemists.Here,we developed a diastereoselective[2+2+2]tandem cyclization reaction with alkyl-substituted methylene malonate,enabling highly efficient collective total synthesis of four Malagasy alkaloids from commercially available tryptamines within 10-13 steps.The synthetic strategy included rapid and highly stereoselective assembly of the tetracyclic indoline core containing 5-7 contiguous stereogenic carbon centers,rarely seen in indole alkaloids.Among the four natural products,(±)-myrtoidine,(±)-11-demethoxymyrtoidine,and(±)-12-hydroxymalagashanine were synthesized for the first time,and the work on(±)-malagashanine represented the shortest synthetic route so far.Our current study should enable further explorations of chemical and biological spaces based on myrtoidine,malagashanine,and related natural products.

Producing malonate in Saccharomyces cerevisiae via theβ‑alanine pathway

Malonate is a high-value chemical that can be used to produce value-added compounds.Due to the toxic by-products and low product yield for malonate production through hydrolysis of cyanoacetic acid,microbial production methods have attracted significant attention.Previously,theβ-alanine pathway has been engineered in Escherichia coli for malonate production.In this study,theβ-alanine pathway was constructed in Saccharomyces cerevisiae by introducing the heterologous genes of BcBAPAT and TcPAND to convert l-aspartate to malonic semialdehyde,combining with co-expression genes of AAT2 and UGA2 to improve precursor supply and malonate producing.Through delta sequence-based integration of the two heterologous genes,the engineered strain produced with 7.21 mg/L malonate was screened.Further,replaced the succinic semialdehyde dehydrogenase gene UGA2 with yneI from E.coli which was utilized to produce malonate in previous study,increased the malonate titer to 7.96 mg/L in flask culture.Following optimization,fermentation of the final engineered strain in shake flasks yielded a maximum malonate titer of 12.83 mg/L,and this was increased to 91.53 mg/L during fed-batch fermentation in a 5 L bioreactor which increased by two-fold compared with that of the engineered strain overexpressing UGA2.

Research of Technique for Synthesizing Carbonyl Diethyl Malonate

Diethyl malonate being an initial raw material, processed with chlorination-replacement-desalination-vacuum rectification, is used to produce carbonyl diethyl malonate. An experiment for optimization determines that the best reaction condition was： （1 reaction for 7 h at 10 ℃ with mole-ratio being 2.4 ＂ 1 between chloride and raw material （diethyl malonate）; （2 reaction for 4.5 h at 118 ℃ with mole-ratio being 1.2 ： 1 between the anhydrous sodium acetate and intermediate I. The final product carbonyl diethyl rnalonate recovery ratio reaches up to as high as 79.12% with a purity of 96.4%, which meets the market requirement. This synthesis technique has the advantages of simple process, moderate reaction conditions, high yield and low cost, being suitable for industrial scale production.

CuCl2/8-Hydroxyquinoline-catalyzed α-Arylation of Diethyl Malonate with Aryl Bromides

A general and efficient coupling of aryl bromides with diethyl malonate is presented. The reaction provided the α-arylated diethyl malonates in moderate to good yields with a low loading of CUC12（5%, molar fraction） and 8-hydroxyquinoline（5% , molar fraction）. This method has good compatibility for a wide range of aryl bromides.

Synthesis and structures of malonate derivative-calix [4] arene conjugates

A series of malonate derivatives-calix[4]arene conjugates were synthesized through Knoevenagel condensation reaction between formyl-tetrapropoxycalix[4]arene and malonate derivatives. The structures of the resulting malonate derivative functionalized calix[4]arenes were characterized by NMR spectroscopy, mass spectrometry and even single crystal X-ray diffraction analysis.

Spectroscopic studies of gel-grown lanthanum malonate crystals

Lanthanum malonate crystals were grown by single tube ionic diffusion through silica gel. The crystallinity of the grown crystals was analyzed by powder X-ray diffraction studies. Fourier transform infrared spectroscopy （FTIR） and fourier transform （FT） Raman studies confirmed the presence of functional groups in the title compound. The optical band gap energy of the material was extracted from diffuse reflectance spectrum.

Malone顺性灌肠治疗神经性大便失禁

目的:评价Malone顺性灌肠治疗神经性大便失禁的临床疗效。方法:1998年10月～1999年12月间对14例伴有大便失禁的脊髓拴系综合征患者(4～13岁)施行Malone手术,术后间断经阑尾造瘘口插管灌肠。对手术效果及肛门功能分别进行量化评分。结果:14例随访时间6个月～1年,2例造瘘口闭塞。余12例手术效果评分为21.4±1.3;肛门功能临床主观评分5郾05±0郾76,较术前(1郾23±0.64)明显增加(P<0郾01),其中优9例,良3例,差2例。结论:Malone顺性灌肠是治疗神经性大便失禁的有效方法,可明显提高患儿的生活质量。

一种新的血吸虫传播指数的构建及其应用

血吸虫传播指数可以通过数学模型直接对血吸虫的流行概况进行总体评估和预报。因此基于血吸虫流行传播机理,提出用极端气温对以往"改良Malone血吸虫传播指数"模型进行改进,参照前人洪青标等的研究成果,构建了"再改良Malone血吸虫传播指数"模型;然后引用世界粮农组织(FAO)与中国科学院地理科学与资源研究所的气象资料,用新模型对中国血吸虫病疫区内血吸虫传播指数的空间差异进行了定量计算和分等划区;用流行区与非流行区传播指数界线900为准,新模型将旧模型的河南省南部、安徽省北部、江苏省北部由原来的传播等级"中"转变成了"低"与"很低";还意外地发现了中国东部血吸虫病流行与并非流行区的界线与中国东部1月份-2℃等温线吻合得非常好。最后讨论了本研究作为一个"气象模型"的计算结果与现实血吸虫病疫情之间还有一些因子需要考虑,并提出了模型本身在计算过程中存在的一些问题和今后改进的方向。

Nuclear TAR DNA-binding protein 43 A new target for amyotrophic lateral sclerosis treatment

Abnormal TAR DNA-binding protein 43 （TDP-43） inclusion bodies can be detected in the degen- erative neurons of amyotrophic lateral sclerosis. In this study, we induced chronic oxidative stress injury by applying malonate to cultured mouse cortical motor neurons. In the later stages of the malonate insult, TDP-43 expression reduced in the nuclei and transferred to the cytoplasm. This was accompanied by neuronal death, mimicking the pathological changes in TDP-43 that are seen in patients with amyotrophic lateral sclerosis. Interestingly, in the early stages of the response to malonate treatment, nuclear TDP-43 expression increased, and neurons remained relatively intact, without inclusion bodies or fragmentation. Therefore, we hypothesized that the increase of nuclear TDP-43 expression might be a pro-survival factor against oxidative stress injury. This hypothesis was confirmed by an in vitro transgenic experiment, in which overexpression of wild type mouse TDP-43 in cultured cortical motor neurons significantly reduced malonate-induced neuronal death. Our findings suggest that the loss of function of TDP-43 is an important cause of neuronal degen- eration, and upregulation of nuclear TDP-43 expression might be neuroprotective in amyotrophic lateral sclerosis.

Synthesis and Crystal Structure of a Novel Hetero-bimetallic Complex with a Three-dimensional Network Structure: Bis(malonato)tetra(aqua)calcum(II)cobalt(II)

The title complex [CaCo（C3H2O4）2（H2O）4]n with a formula of C6HI2CaCoO12 and Mr=375.17 has been synthesized and structurally characterized by X-ray diffraction. The crystal is of monoclinic, space group C2/c with a = 14,195（9）, b = 7.708（5）, c = 13.441（8） A, β =119.575（9）°, V = 1279.0（14） A3, Dc= 1.948 g/cm^3,μ=1.803 mm^-1, F（000） = 764 and Z = 4. The final R = 0.0245 and wR = 0.0652 for 1344 observed reflections with I 〉 2σ（I）. The structure of the title complex consists of CaO8 polyhedra and CoO6 octahedra linked together by malonate ligands. The Ca（Ⅱ） cation on a twofold axis is coordinated by two water molecules and six malonate O atoms. The Co（Ⅱ） cation which lies in a centre of symmetry in an octahedral arrangement is coordinated by four malonate O atoms and two water molecules, The structure comprises alternating layers along the [101] plane, with the shortest Co-Co distance of 6.961（5）A. The whole 3D structure is maintained and stabilized by the presence of hydrogen bonds.

Synthesis and Structural Investigation of ｛CpEu〔CH（COOC2H5）2〕〔μ-CH（COOC2H5）2〕｝2

The title complex {CpEu CH(COOC 2H 5) 2 μ CH(COOC 2H 5) 2 } 2 crystallizes in the triclinic system, space group P1 with unit cell constants a=9.108(1), b=11.580(2), c=11.705(2) , α=70.42(1)°, β=73.83(1)°, γ=78.60(1)°, D c =1.602 g/cm 3 , M r=1070.76, V=1109.7(3) 3, Z=1, μ (Mo Kα )=28 66 cm 1 and F(000)=536, T=296K, R=0.028, R w =0.037. The geometry around the Eu ion can be described as a pentagonal bipyramid.

可控性Malone顺行灌肠的护理体会

大便失禁和顽固性便秘是小儿肛门直肠畸形术后常见的问题,至今仍是一个难以解决的课题。1990年Malone等[1]提出应用顺行灌肠的方法进行肠道管理,可有效解决失禁及便秘的问题。我们根据2013年8月至2016年8月15例行Malone顺行灌肠（malone antegrade continence enema,MACE）患儿的护理经验,讨论护理对于Malone顺行灌肠的重要性。

Synthesis and Crystal Structure of a Ternary Complex:[Ni(phen)_2(pmal)]·8H_2O

A new ternary complex [Ni（phen）（pmal）]·8H2O （phen = 1,10-phenanthroline, pmal^2- = phenethyl malonic acid） has been synthesized by the reaction of nickel acetate, phen and phenethyl malonic acid. Elemental analysis, IR spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure. Crystal data for this complex： triclinic system, space group PI^-, a = 10.387（5）, b = 13.112（6）, c = 14.229（6） °A, α= 76.176（7）, β = 83.778（8）, γ = 71.770（6）°, C35H42N4O12Ni, Mr= 769.44, Z = 2, F（000） = 808, V = 1786.1°A^3, Dc = 1.431 g/cm^3,μ= 0.612 mm^-1, the final R = 0.0653 and wR = 0.1033 for 9379 （Rint = 0.0244） independent reflections and 4730 observed reflections （I〉 2σ（I））. Structural analysis shows that the coordination geometry of Ni（Ⅱ） is a distorted octahedron. A novel two-dimensional structure is constructed from （H2O）4 and （H2O）12 water clusters, and the complex forms a 3-D network supramolecular structure by hydrogen bonds and π-π stacking of neighboring phens.