Samarium diiodide promoted formation of 1,2-diketones and 1-acylamido-2-substituted benzimidazoles from N-acylbenzotriazoles

N-Acylbenzotriazoles, when treated with samarium diiodide in THF, undergo self-coupling reaction to afford 1,2-diketones in good to excellent yields; while when treated with samarium diiodide in CH₃CN, they undergo ring-opening reaction to afford 1-acylamido-2-alkyl (or aryl) benzimidazoles in reasonable to good yields. A plausible mechanism was suggested.     

无溶剂微波照射下2－取代苯并咪唑的合成

用PPA作催化剂，在无溶剂微波照射下合成了10种2－取代苯并咪唑，为该类化 合物的合成提供了一种新方法。与常规方法相比，反应时间大大缩短，产率与传统 合成方法相当。     

13C-NMR Chemical Shifts in 1,3-Benzazoles as a Tautomeric Ratio Criterion

Benzimidazole is an important heterocyclic fragment, present in many biologically active compounds with a great variety of therapeutic purposes. Most of the benzimidazole activities are explained through the existence of 1,3-tautomeric equilibrium. As the binding affinity of each tautomer to a protein target depends on an established bioactive conformation, the effect of tautomers on the ligand protein binding mechanism is determinant. In this work, we searched and analyzed a series of reported ¹³C-NMR spectra of benzazoles and benzazolidine-2-thiones with the purpose of estimating their tautomeric equilibrium. Herein, several approaches to determine this problem are presented, which makes it a good initial introduction to the non-expert reader. This chemical shift difference and C4/C7 signals of benzimidazolidine-2-thione and 1-methyl-2-thiomethylbenzimidazole as references were used in this work to quantitatively calculate, in solution, the pyrrole–pyridine tautomeric ratio in equilibrium. The analysis will help researchers to correctly assign the chemical shifts of benzimidazoles and to calculate their intracyclic or exocyclic tautomeric ratio as well as mesomeric proportion in benzimidazoles.     

Isomerization in the Oxidative Cyclocondensation of 2-Aroylmethyl-1H-benzimidazoles with o-Aminothiophenol

Oxidative cyclocondensation of 2-aroylmethyl-1H-benzimidazoles with o-aminothiophenol gave the previously unknown 3-aryl-2-(2-benzimidazolyl)-4H-1,4-benzothiazines and (or) the isomeric 2H-1,4-benzothiazines. 2-(4-Nitrophenacyl)-1H-benzimidazole and 2-phenacylbenzothiazole gave 4H-1,4-benzothiazines which are not liable to isomerize but the reaction of the first compound is complicated by a hydrolytic fission which yields 2-[2-(4-nitrobenzoylamino)phenylthiomethyl]benzimidazole. A mixture of dimethylsulfoxide, acetic acid, and water was used as oxidant and solvent. The effect of the substituent and of the solvent on the tendency of the products to undergo prototropic isomerization in the benzothiazine ring have been studied.     

Xanthan Sulfuric Acid: An Efficient Bio‐supported and Recyclable Solid Acid Catalyst for the Synthesis of 2‐Aryl Thiadiazolo Benzimidazoles

Xanthan sulfuric acid is an efficient solid acid catalyst for the preparation of 2‐aryl benzimidazoles in excellent yields. This method is applicable for the reaction of benzo[c][1,2,5]thiadiazole‐4,5‐diamine with aldehydes by simple physical grinding at room temperature. The salient features of the present methodology is cheaper process, easy synthesis of stable catalyst and the catalyst can be easily recycled without significant loss of activity.     

Formation of Unsymmetrical 2-(Diacylmethylene)-2,3-dihydro-1H-benzimidazoles During Acidolysis of 1-Benzoyl-2-(β-benzoyloxy-β-phenylvinyl)-1H-benzimidazole

The reaction of 1-benzoyl-2-(-benzoyloxy--phenylvinyl)-1H-benzimidazole with carboxylic acids was investigated. A convenient method was developed for the synthesis of unsymmetrical 2-(diacylmethylene)-2,3-dihydro-1H-benzimidazoles. 2-(4-Pyrazolyl)-1H-benzimidazoles were obtained by the reaction of 2-(benzoylformylmethylene)-2,3-dihydro-1H-benzimidazole with hydrazine.     

Synthesis of 5-(1H-benzimidazol-2-yl)-1H-pyrazolo-[3,4-<Emphasis Type="Italic">b</Emphasis>]pyridines by the <Emphasis Type="Italic">p</Emphasis>-(dimethylamino)benzaldehyde modification of Hantzsch reaction

The reactions of p-(dimethylamino)benzaldehyde with 5-amino-3-methyl-1-phenylpyrazole and 2-RCOCH₂-1H-benzimidazoles have produced 5-(1H-benzimidazol-2-yl)-1H-pyrazolo[3,4-b]pyridines. The transformation includes the formation of compounds in accordance with a Hantzsch reaction containing a 1,4-dihydropyridine ring, and is completed by the aromatization either by the splitting off of N,N-dimethylanyline or oxidation. The splitting is produced by acetic acid and the oxidation by a nitrocompound. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 578–584, April 2007.     

新型单组分磷氮膨胀阻燃剂的合成

以新戊二醇与三氯氧磷为原料,合成了5,5-二甲基-1,3-二氧杂己内磷酰氯;进而将5,5-二甲基-1,3-二氧杂己内磷酰氯分别与苯并咪唑类衍生物反应,得到三种新型单组分磷氮膨胀阻燃剂(Ⅲa-c).利用IR1、HNMR、质谱及元素分析等表征了Ⅲa-c三种化合物的结构;并利用热重分析考察了三种化合物的热稳定性能.结果表明,目标产物Ⅲa-c均有较好的成炭性和热稳定性,600℃时残炭质量分数分别达26.93%、23.62%及18.75%.     

A theoretical and experimental study of the NMR spectra of 4,5,6,7‐tetrafluorobenzazoles with special stress on PCM calculations of chemical shifts

The chemical shifts and several ¹⁹F–¹⁹F, ¹³C–¹⁹F and ¹H–¹⁹F spin‐spin coupling constants (SSCSs) of eight 4,5,6,7‐tetraflurobenzazoles (three benzimidazoles, three benzimidazolinones and two indazoles) have been determined. The chemical shifts were discussed using gauge including atomic orbital‐density functional theory calculations taking into account solvent effects (polarizable continuum model) and, for the solid state, hydrogen bonds (clusters up to three molecules). Copyright © 2015 John Wiley & Sons, Ltd.