Theoretical Study of Rotational Isomerism in Ethyl Pseudohalides

The structure and conformational stability of ethyl pseudohalides CH₃CH₂ — XCN (X = O, S, Se) were investigated using ab initiocalculations at the MP2 level of theory with a triple- basis set augmented with polarization and diffusion functions. Full optimization was performed on the minimum energy structures as well as on the transition state forms. The relative stabilities of rotational conformers were calculated at the MP4 level using MP2 optimized reference geometries. The nature of all considered stationary points was verified by calculation of the harmonic vibrational frequencies. The calculated bond lengths, bond angles, dipole moments, and rotational constants of optimized global minima structures agree very well with the corresponding experimental data obtained from microwave spectroscopic studies. Also, available experimental frequencies are in good accord with the theoretical values. For ethyl cyanate CH₃CH₂ — OCN, the antiperiplanar (trans) form is predicted to be more stable than the synclinal (gauche) form, and the synperiplanar (cis) form corresponds to the transition state. For both ethyl thiocyanate CH₃CH₂ — SCN and ethyl selenocyanate CH₃CH₂ — SeCN, the gaucheform is the global minimum while the trans-conformer is a local minimum and the cis-form is a transition state.     

Practical and Scalable Synthesis of Ethyl (R)-Piperidine-3-acetate

A practical and scalable synthesis of ethyl (R)-piperidine-3-acetate was achieved from commercially available 3-pyridylacetic acid in 76% overall yield. The practical synthesis was demonstrated on 100-g scale. One-pot reductive N-ethylation of the pyridinium salt with acetonitrile gave an N-ethyl piperidine derivative.     

Facile preparation and properties of superhydrophobic nanocellulose membrane

Superhydrophobic nanocellulose membrane was prepared by synergistically modifying biodegradable nanocellulose with low-carbon perfluoroorganosiloxane and ethyl orthosilicate. The effects of four kinds of low-carbon perfluoroorganosiloxanes with different structures and their ratio to ethyl orthosilicate on the hydrophobic properties of nanocellulose membrane were investigated, and then FT-IR, XPS, XRD, SEM, TEM, AFM, TG and contact angle goniometer were used to characterize the structure and hydrophobic properties of nanocellulose membrane before and after modification. It is found that when the molar ratio of 1H,1H,2H,2H-perfluorooctyltrimethoxysilane (PFOTMS) to ethyl orthosilicate (TEOS) is 1, the modified nanocellulose membrane PFOTMS-TEOS-CNF is loaded with silica nanoparticles both inside and on its surface, and a micro-nano hierarchical rough morphology with low surface energy is constructed. At this point, the root-mean-square roughness (Rq) of nanocellulose membrane is 112 nm, and the static contact angle of water droplet is 153.5°, successfully realizing superhydrophobicity. In addition, compared to unmodified nanocellulose membrane, PFOTMS-TEOS-CNF with better thermal stability includes an additional maximum weight loss rate temperature (491.2 °C). The above advantages markedly improve the shortcomings of pristine nanocellulose, such as superhydrophilicity and insufficient thermal stability, and also broadens its high-value application in many fields.     

Pinacol Coupling of Aromatic Aldehydes and Ketones in Ethyl Acetate Mediated by TiCl4‐Mg

Titanium tetrachloride in ethyl acetate can be reduced by Mg powder to the corresponding low‐valent titanium complexes, which can reduce some aromatic aldehydes and ketones to the corresponding pinacols in 38–85% yields within 15–60 min at rt with stirring.     

A new multicomponent approach to highly functionalized 2,3-dihydroisoxazoles

The synthesis of highly functionalized 2,3-dihydroisoxazoles by a one-pot multicomponent reaction of an aldehyde, hydroxamic acid, and malononitrile or methyl cyanoacetate is described.     

Microwave Assisted Synthesis of Some Novel Thiopyrano[2,3-b]quinolines as a New Class of Antimicrobial Agent

A series of novel substituted thiopyrano[2,3-b]quinolines 4a–e , 5a–e , and 6a–e were prepared from substituted 3-formyl-2-mercapto quinolines 2a–e , on reaction with ethyl acetoacetate, diethyl malonate, and ethyl cyanoacetate 3a–c by microwave irradiation in the presence of piperidine. Synthesized compounds were evaluated for antimicrobial activities. Among the compounds tested, 7-chloro-2-oxo-2H-thiopyrano[2,3-b]quinoline-3-carbonitrile 6d and 7-nitro-2-oxo-2H-thiopyrano[2,3-b]quinoline-3-carbonitrile 6e were highly active against S. aureus and M. roseus.     

Thermal-Induced Dimerization Cyclization of Ethyl N-(Styrylcarbamoyl)acetates: Formation of 4-Hydroxy-2(1H)-pyridone-3- carboxamide Derivatives

Thermal-induced dimerization cyclization of ethyl N-(styrylcarbamoyl)acetate derivatives has been investigated, leading to 4-hydroxy-2(1H)-pyridone-3-carboxamide derivatives with good yields in diphenyl ether on 200–210 °C. Ethyl N-(styrylcarbamoyl)acetate derivatives readily provided the intermolecular cyclization products 4-hydroxy-2(1H)-pyridone-3-carboxylates on reflux in xylene. In addition, several related 3-acetyl-4-hydroxy-5-phenylpyridin-2(1H)-ones have been prepared. It provided an efficient preparation of 4-hydroxy-2(1H)-pyridone-3-carboxamide derivatives.     

2,4-二甲基吡咯-3,5-二羧酸二乙酯的合成——推荐一个大学有机化学实验

采用Knorr吡咯合成法,以乙酰乙酸乙酯和亚硝酸钠为原料,在醋酸和锌粉作用下采用“一锅法”得到2,4-二甲基吡咯-3,5-二羧酸二乙酯。本实验涉及到控温、回流、重结晶、熔点测定、红外光谱及核磁共振等实验操作和分析检测方法。该实验原料简单易得、产物收率高,结合波谱解析方法,可以培养和提高学生合成实验的能力,加强学生对杂环合成和波谱解析的理解与分析。     

微波协同阳离子交换树脂催化合成阿魏酸乙酯

以732型强酸性阳离子交换树脂为催化剂,在微波辐射下用阿魏酸与乙醇酯化合成了阿魏酸乙酯.通过单因素实验,考察了催化剂活化方法对催化剂活性的影响,结果表明,微波法活化阳离子交换树脂的催化性能好.通过单因素实验和正交实验,考察了催化剂用量、醇酸摩尔比、微波辐射时间、微波辐射功率等因素对反应的影响.确定了最佳反应工艺条件:阿魏酸0.1mol,酸醇摩尔比5:1,催化剂用量为反应物质量的35%,微波功率300w,反应时间30min,产率达84.2%.732型树脂催化剂可再生循环使用,重复使用4次,产率不低于80%.