Synthesis of New Estrone Derivatives Using Excess Oxalyl Chloride

The synthesis and structure elucidation of three new estrone derivatives chloro-oxo-acetic acid (estra-1,3,5(10)-trien-17-on-3-yl methyl) ester (2), oxalic acid mono (estra-1,3,5(10)-trien-17-on-3-yl methyl) ester (3), and ethyl (3-methoxyestra-1,3,5(10)-trien)-17-yl oxalate (5) have been described.     

Polysulfonylamines. CXXXII.

The crystal structure of the title compound, C₅H₇N₂⁺·C₁₂H₁₀NO₄S₂⁻, consists of two independent cation–anion pairs, A and B. Within each pair, the H—N—C—N*—H grouping (N*—H is the pyridinium function) and one N—S—O moiety of the anion are linked by N*—H⃛N and N—H⃛O hydrogen bonds to form an antidromic ring motif of type R²₂(8). The remaining amino donors give rise to N—H⃛O hydrogen bonds, connecting the ion pairs into A–B–A–B– chains. The structure testifies to the persistence of the R²₂(8) motif in question, which was previously detected as a highly robust supramolecular synthon in a series of onium di(methane­sulfonyl)­amidates. The structure is pseudosymmetric; the anion positions correspond to space group P2₁/n, but those of the cations do not.     

草酰氯和2,3-丁二酮的紫外光解

羰基化合物的光解一直是分子反应动力学研究感兴趣的课题之一,近年来许多研究小组用不同的实验方法对气相羰基化合物特别是丙酮分子的紫外光解进行了广泛的研究[14],然而对一个分子中含有两个羰基的二酮类分子却很少研究.早期对(ＣｌＣＯ)2和(ＣＨ3ＣＯ)2的光解反应研究主要集中在液相宏观动力学方面[5-7],这些研究都没有在分子的层次上进行考察,因此对它们的紫外光解机理并不清楚,例如两者光解首先发生的是Ｃｌ或ＣＨ3基的脱落,还是分子中央的Ｃ-Ｃ键断裂?光解后剩余的自由基第二步解离是光解还是热解?光解后碎片的能量分布如何?等等.为此…     

Direct Synthesis of Aromatic Nitriles from Aldehydes Using Hydroxylamine and Oxalyl Chloride

Various aromatic and heterocyclic nitriles were prepared in good to high yields in a direct one‐pot process by heating the corresponding aldehydes with hydroxylamine and oxalyl chloride as reagents.     

Molecular Spectra and Dissociation Dynamics of Oxalyl Chloride: Effect of External Electrical Fields

Oxalyl chloride is a highly toxic and caustic substance, which widely exists in human production and life as a kind of volatile organic compound. Based on the density functional theory B3 LYP at 6-311++G(d, p) level, the influences of external electric field on the bond length, bond energy, dipole moment and dissociation mechanism are optimized. The results indicate that the C_1–Cl_3 bond length increases while the C_4–Cl_6 bond decreases. At the same time, the carbon-carbon bond length gradually increases with the increase of electric field. The total energy decreases while the dipole moment gradually increases with the increase of electric field. In the infrared spectra, the vibration frequency of the carbon-chlorine(C_4–Cl_6) bond decreases while the vibration frequency of the carbon-oxygen bond increases. In the ultraviolet-visible spectra, the wavelength of the strongest absorption peak increases as the external electric field increases and shows an observable red shift phenomenon. Additionally, single point energies of oxalyl chloride along the carbon-carbon bond are scanned with the equation-of-motion coupled cluster method restricted to single and double excitations(EOM-CCSD) method and the potential energy curves under different external electric fields are obtained. The dissociation barrier in potential energy curve decreases because of the breakage of carbon-carbon bond with the increase of external electric field. These results provide reference for further researches on the properties of oxalyl chloride and offer a theoretical basis for the study of oxalyl chloride degradation.     

草酰氯一价正离子构象及其碳—碳键反应活性的理论研究

用密度泛函方法BHandHLYP在6-311+G（d）和6-311+G（2df）水平上对草酰氯 的一价正离子［（ClCo）_2~+］作了构象分析，结果表明，（ClCo）_2~+具有平面 反式和交叉式两种稳定构象，交叉构象存在超共轭现象，此外，对草酰氯离子、中 性分子各解离通道初级反应的Gibbs自由能的计算，发现草酰氯离子C—C键解离通 道的反应活性大于中性分子，对该通道进一步做了反应机理研究，证实了热力学结 论，并且与实验相一致，对草酰氯离子的振动频率和键耦合常数的研究表明其碳— 碳键解离具有选键性。     

Heterocycles. LXXXII. Some investigations on 1,2,3-benzotriazines

Various 4-substituted 1,2,3-benzotriazines ( 2, 6, 7 ) have been prepared and of particular interest was the 4-azido derivative ( 11 ) as a potential azidotetrazolo tautomerism exhibiting compound. However, no such interconversion could be established and this compound exists exclusively in the azido form. 2,5-bis-(Arylamino)-1,3,4-thiadiazoles (9) have been found to result from the reaction between 4-hydrazino-1,2,3-benzotriazine and aryl isothiocyanates. In addition, a ring opening reaction between 4-hydrazino-1,2,3-benzotriazine gave 2-(tetrazol-5″-yl)-2′,4′-dihy-droxyazobenzene ( 10 ) and photochemical conversion of the 4-azido derivative gave s-tetrazino-[2,3-b:5,6-b′]diindazole(12).     

Chemistry of 2-Methylene-2,3-dihydrofuran-3-ones: XVIII. Reaction of Oxalyl Chloride with Acetophenone and Dibenzoylmethane

Treatment of acetophenone and dibenzoylmethane with excess oxalyl chloride gave heterocyclization products, 2-(3-oxo-5-phenyl-2,3-dihydrofuran-2-ylidene)-5-phenyl-2,3-dihydrofuran-3-one and a mixture of 4-benzoyl-5-phenyl-2,3-dihydrofuran-2,3-dione with 4-benzoyl-2-dibenzoylmethylene-5-phenyl-2,3-dihydrofuran-3-one.     

Examining Trichloroisocyanuric Acid and Oxalyl Chloride in Complementary Approaches to Fluorination of Group 15 Heteroatoms

A mild, oxidative fluorination approach to a variety of fluorinated phosphorus compounds using trichloroisocyanuric acid (TCICA) and KF was developed as a complement to a recent study on deoxygenative fluorination using oxalyl chloride. Herein, the syntheses of several fluorinated organophosphorus compounds are reported, and both TCICA/KF and oxalyl chloride/KF conditions are compared and contrasted throughout. Initial investigations of the method on other group 15 heteroatoms (i. e., As, Sb, and Bi) are also reported, with varied success. This work notably extends the known TCICA/KF reactivity series to another group of elements beyond previously studied chalcogens (S, Se, and Te) and halogens (iodine) and expands the utility of the previously reported oxalyl chloride/KF method.     

The Annelation for Enaminoureides of 3,3-Dimethyl-1,2,3,4-tetrahydroisoquinoline Series by Action of Oxalyl Chloride and Ninhydrin

By reaction of Ritter cyclization of cyanoacetylureas with dimethylbenzylcarbinoles the corresponding enaminoureides were obtained, derivatives of 3,3-dimethyl-1,2,3,4-tetrahydroisoquinoline. The polyfunctional character of obtained compounds is confirmed by the structure of products of reaction with some electrophiles: phenyl isocyanate reacts at the γ-C atom of enamine and CONH₂ group of urea, under the action of oxalyl chloride annelation of a pyrrole cycle occurs with the formation of a derivative of 2,3-dioxopyrrolo[2,1-a]isoquinoline. Reaction with ninhydrin occurs similary with enaminoamides having hydrogen atoms at the amide nitrogen: a pyrrole ring is fused with the formation of a system of indeno[1,2-b]pyrrole.     

基于3种荧光化合物检测草酰氯气体的化学发光试纸法

研究了3种发光材料聚芴(PF)、5,5'-双(9,9-二辛基芴)-2,2'-联噻吩(F-T-T-F) 和4,7-双(5-(9,9-二丙基芴)噻吩)苯并噻二唑(3FT-BTD) 的固态化学发光。 将这3种材料吸附于滤纸上得到了相应的检测试纸,研究了其与草酰氯蒸气的相互作用。 与溶液体系相比,基于试纸的固态化学发光时间可以延长至8~10 min。 该方法对草酰氯蒸气的检测限较低,分别为0.013 mg/m³(PF)、0.27 mg/m³(F-T-T-F)和1.8 mg/m³(3FT-BTD)。 制备的检测试纸可以反复暴露于草酰氯蒸气中引发化学发光,发光强度没有明显的降低,说明试纸有很好的重复使用性。 由于该试纸对草酰氯有选择性的作用,因此可以对毒性草酰氯气体进行简便的可视化检测。     

Synthesis of Anti-Inflammatory Spirostene-Pyrazole Conjugates by a Consecutive Multicomponent Reaction of Diosgenin with Oxalyl Chloride,Arylalkynes and Hydrazines or Hydrazones

Steroid sapogenin diosgenin is of significant interest due to its biological activity and synthetic application. A consecutive one-pot reaction of diosgenin, oxalyl chloride, arylacetylenes, and phenylhydrazine give rise to steroidal 1,3,5-trisubstituted pyrazoles (isolated yield 46–60%) when the Stephens–Castro reaction and heterocyclization steps were carried out by heating in benzene. When the cyclization step of alkyndione with phenylhydrazine was performed in 2-methoxyethanol at room temperature, steroidal α,β-alkynyl (E)- and (Z)-hydrazones were isolated along with 1,3,5-trisubstituted pyrazole and the isomeric 2,3,5-trisubstituted pyrazole. The consecutive reaction of diosgenin, oxalyl chloride, phenylacetylene and benzoic acid hydrazides efficiently forms steroidal 1-benzoyl-5-hydroxy-3-phenylpyrazolines. The structure of new compounds was unambiguously corroborated by comprehensive NMR spectroscopy, mass-spectrometry, and X-ray structure analyses. Performing the heterocyclization step of ynedione with hydrazine monohydrate in 2-methoxyethanol allowed the synthesis of 5-phenyl substituted steroidal pyrazole, which was found to exhibit high anti-inflammatory activity, comparable to that of diclofenac sodium, a commercial pain reliever. It was shown by molecular docking that the new derivatives are incorporated into the binding site of the protein Keap1 Kelch-domain by their alkynylhydrazone or pyrazole substituent with the formation of more non-covalent bonds and have higher affinity than the initial spirostene core.