Anil-Synthese. 21. Mitteilung. Über die Herstellung von stilbenyl-derivaten des pyrazols

Preparation of Stilbenyl Derivatives of Pyrazoles Schiffs bases derived from 1-, 3- and 5-(p-formylphenyl)phenylpyrazoles and p-chloroaniline are reacted with various p-tolyl substituted aromatic heterocycles in the presence of dimethylformamide and potassium hydroxide or potassium t-butoxide to yield the corresponding heterocyclic substituted stilbenes (anil synthesis). Introduction of a chloro substituent in the 4- and 4,5-positions of the pyrazole system causes a decrease in yield and a hypsochromic shift in the absorption and fluorescence maxima of the title compounds.     

Anil-Synthese. 20. Mitteilung. Über die Herstellung von Stilbenyl-Derivaten des 1,2,4,-Oxadiazols

Preparation of Stilbenyl Derivatives of 1,2,4-Oxadiazoles Schiffs bases derived from 3- and 5-(p-formylphenyl)-phenyl-1,2,4-oxadiazoles and chloroanilines are reacted with various p-tolyl substituted aromatic heterocycles in the presence of dimethylformamide and potassium hydroxide to yield the corresponding heterocyclic substituted stilbenes (‘Anil synthesis’). The reactivity of 5-[4-(chlorophenylimino-methyl)phenyl]-3-phenyl-1,2,4-oxadiazoles is very low and side reactions will predominate.     

Anil-Synthese 18. Mitteilung. Über die Herstellung von Styryl-Derivaten des 3-Phenyl-benzisoxazols

Preparation of styryl derivatives of 3-phenyl-benzisoxazole 3-(p-Tolyl)-1,2-or 2, 1-benzisoxazoles and 6-methyl-3-phenyl-1,2-benzisoxazoles react with anils of aromatic aldehydes in the presence of dimethylformamide and potassium hydroxide or potassium t-butoxide to yield the corresponding 3-(stilben-4-yl)-1,2- or 2,1-benzisoxazoles and the 3-phenyl-6-styryl-1,2-benzisoxazoles respectively (‘Anil Synthesis’). Further, the Schiff's bases derived form chloroanilines and 3-(p-formylphenyl)-1,2-benzisoxazoles yield, with methyl-and p-tolyl substituted heterocyles the corresponding heterocyclic substitued styryl and stilbenyl derivatives.     

Anil-Synthese. 23. Mitteilung. Über die Herstellung von Styryl- und Stilbenyl-Derivaten des Pyrimidins

Preparation of Styryl and Stilbenyl Derivatives of Pyrimidines 2- and 4-(p-Tolyl)-substituted pyrimidines react with anils of hetero-aromatic aldehydes in the presence of dimethylformamide and potassium hydroxide or potassium t-butoxide to yield the corresponding 2- and 4-[4″-(heteroaryl)stilben-4′-yl]pyrimidines or the 2- and 4-[a-(heteroaryl)-4′-styryl]pyrimidines respectively (‘Anil synthesis’). Furthermore, the Schiff′s bases derived from p-chloroaniline and 4-(pyrimidine-2-yl and 4-yl)benzaldehydes give, with methyl- and with p-tolyl-substituted heterocycles, the corresponding heterocyclic substituted styryl and stilbenyl derivatives. Alkyl-, alkoxy- or phenyl-substituted pyrimidines undergo also the ‘Anil synthesis’.     

Anil-Synthese. 15. Mitteilung. Über die Herstellung von heterocyclisch substituierten Stilbenyl-Derivaten des 2H-1,2,3-Triazols

Preparation of heterocyclic substituted stilbenyl derivatives of 2H-1,2,3-triazole Schiff's bases derived from 2- and 4-(p-formylphenyl)-2H-1,2,3-triazoles and o- or p-chloroaniline are reacted with various p-tolyl substitued aromatic heterocycles in the presence of dimethylformamide and potassium hydroxide or potassium t-butoxide to yield the corresponding heterocyclic substituted stilbenes (“Anilsynthesis”). In order to avoid opening of the 2H-1,2,3-triazole ring, the reaction is carried out without external heating. In many cases an improvement in yield is obtained by irradiation with UV. light at the beginning of the reaction.     

Anil-Synthese. 24. Mitteilung. über die Herstellung von Styryl- und Stilbenyl-Derivaten des 1H-Benzotriazols

Preparation of Styryl and Stilbenyl Derivatives of 1H-Benzotriazoles 1-(p-Tolyl)-substituted 1H-benzotriazoles react with anils of aromatic aldehydes in the presence of dimethylformamide and potassium hydroxide to yield the corresponding 1-(styr-4′-yl)-1H-benzotriazoles and 1-(stilben-4′-yl)-1H-benzotriazoles, respectively (‘anil synthesis’). Further, under the same reaction conditions, the Schiff's bases derived from p-chloroaniline and 4-(1′H-benzotriazol-1′-yl)benzaldehydes give, with p-tolyl-substituted heterocycles, the corresponding heterocyclic substituted stilbenyl derivatives.     

12. Anil-Synthese. 17. Mitteilung. Über die Herstellung von styryl-derivaten des 2-phenyl-4H-1,2,4-triazolo [1,5-a]pyridins

Preparation of styryl derivatives of 2-phenyl-4H-1,2,4-triazolo [1,5-a]pyridine 7-Methyl-2-phenyl- and 2-(3-chloro-4-methylphenyl)-4H-1,2,4-triazolo[1,5-a]-pyridines react with anils of aromatic aldehydes in the presence of dimethyl-formamide and potassium hydroxide at 20–45° to yield the 2-phenyl-7-styryl- and 2-(2-chloro-stilben-4-yl)-4H-1,2,4-triazolo [1,5-a]pyridines respectively (‘Anil Synthesis’). Further, the Schiff's bases derived from o-chloroaniline and 2-(p-formyl-phenyl)- and 7-formyl-2-phenyl-4H-1,2,4-triazolo [1,5-a]pyridine yield, with methyl- and with p-tolyl-substituted heterocycles, the corresponding heterocyclic substituted styryl and stilbenyl derivatives.     

Synthesis of ribonucleosides of 4(5)-cyano-5(4)-methylimidazole and related 4-substituted-5-methylimidazole ribosides

4-Cyano-1-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)-5-methylimidazole ( 4 ) and its corresponding 5-cyano-4-methyl substituted isomer ( 5 ) have been obtained by ribosylation of 4(5)-cyano-5(4)-methylimidazole ( 3 ) via the mercuric cyanide method or by ribosylation of the trimethylsilyl derivative of 3 . Treatment of 4 with methanolic ammonia, ammonium chloride in liquid ammonia and potassium hydrosulfide provided 4-cyano-1-β-D-ribofuranosyl-5-methylimidazole ( 6 ), 1-β-D-ribofuranosyl-5-methylimidazole-4-carboxamide ( 2 ) and 1-β-D-ribofuranosyl-5-methylimidazole-4-thiocarboxamide ( 11 ) respectively. Reaction of 6 with hydroxylamine afforded the corresponding 4-carboxamidoxime substituted nucleoside ( 13 ) which on catalytic reduction in the presence of ammonium chloride, was transformed into 1-β-D-ribofuranosyl-5-methylimidazole-4-carboxamidine ( 14 ) as hydrochloride salt.     

The Synthesis,Spectral, and Electrochemical Characterization of Novel Alkoxybenzoquinone Derivatives

The novel monosubstituted benzoquinone compounds 3e , 3g , 3h ; 2,5‐O‐ substituted benzoquinone compounds 4a , 4b , 4c , 4d , 4e 4g and known compound 4h and 2,6‐O‐ substituted benzoquinone compounds 5e , 5f , 5g , 5h were obtained by the reaction of p‐chloranil ( 1 ) and related alcohol compounds in potassium carbonate (K₂CO₃) solution of acetonitrile or chloroform with Et₃N. The novel cyclic compounds 7 , 8 and 10 , 11 were obtained from the reaction of p‐chloranil ( 1 ) and diols in potassium carbonate (K₂CO₃) solution of acetonitrile at room temperature. The structures of novel compounds were characterized by using micro analysis, FT‐IR, ¹H‐NMR, ¹³C‐NMR, MS and cyclic voltammetry.     

Tetrazole compounds. 10. Novel tetrazolylindoles by fischer indolization of substituted tetrazolylacetaldehyde phenylhydrazones

The acid-catalyzed reaction of substituted phenylhydrazines 1 with 1-aryl-5-(2-dimethylaminovinyl)-1H-tetrazoles 2 afforded (1-aryl-1H-tetrazol-5-yl)acetaldehyde phenylhydrazones 3 which on heating in acetic acid/perchloric acid underwent a Fischer indolization to give substituted 3-(1-aryl-1H-tetrazol-5-yl)-indoles 4a-k. Indoles of this type are also formed on subjecting 1 and 2 directly to indolization conditions; thus, starting from phenylhydrazine the tetrazolylindoles 41-s were obtained by a one-pot procedure. Indolization of corresponding N_α-methylphenylhydrazones 5 resulted in 1-methyl-3-(1-aryl-1H-tetrazol-5-yl)indoles 6 .     

Heteropolycyclic molecules. Part IX. Synthesis of some new benzo[b]thiophene,oxofluoreno[4,3-b]thiophene,cyclic hydrazides and acridine compounds

p-Tolyl 2-thienyl ketone (I) condensed with dimethyl succinate in the presence of potassium t-butoxide to give the trans (SC₄H₃/CO₂Me) half-ester (IIIa) whose configuration was deduced by cyclization to the corresponding benzo[b]thiophene derivatives. Carbamates, esters, cyclic hydrazides and substituted phenolic and acetic acids useful as antibacterial and antiinflamatory agents were obtained. The reaction of ketone I with malononitrile to give ylidenemalononitrile II was also considered.     

Synthesis of substituted pyrido[3´,2´:4,5]thieno[3,2-c]isoquinolin-5(6H)-ones and their sulfinyl and sulfonyl derivatives

A method for the synthesis of previously unknown pyrido[3´,2´:4,5]thieno[3,2-c]isoquinolin-5(6H)-ones was suggested, which includes a condensation reaction of substituted 3-cyanopyridine-2(1H)-thiones with methyl 2-(chloromethyl)benzoate and subsequent treatment of the condensation products with potassium tert-butoxide. The oxidation of the condensation products to sulfoxides or sulfones and subsequent treatment of these compounds with potassium tert-butoxide led to substituted pyrido[3´,2´:4,5]thieno[3,2-c]isoquinolin-5(6H)-one 11-oxides or substituted pyrido[3´,2´:4,5]thieno[3,2-c]isoquinolin-5(6H)-one 11,11-dioxides.

     

11. Anil-Synthese. 16. Mitteilung. Über die Herstellung von styryl-derivaten des 2-phenyl-imidazo [1,2-a]pyridins

Preparation of styryl derivatives of 2-phenyl-imidazo [1, 2-a]pyridine 2-(p-Tolyl)-imidazo [1, 2-a]pyridines and 7-methyl-2-phenyl-imidazo [1,2-a]-pyridines can be converted, in dimethylformamide, on reaction with anils of aromatic aldehydes in the presence of potassium hydroxide or potassium t-butoxide, into the corresponding 2-(stilben-4-yl)- and 2-phenyl-7-styry1-imidazo [1, 2-a]-pyridines (‘Anil-Synthesis’). The 2-(p-tolyl)-imidazo [1,2-a]pyridines react far less readily than the 7-methyl-2-phenyl-imidazo[1,2-a]pyridines.     

Syntheses of polymerizable hydroquinone derivatives

Several polymerizable hydroquinone derivatives were prepared by the Williamson synthesis. Thus, hydroquinone mono(p-vinylbenzyl) ether (III-1), hydroquinone methyl p-vinylbenzyl ether (III-4), and hydroquinone benzyl p-vinylbenzyl ether (III-5), tert-butylhydroquinone mono(p-vinylbenzyl) ether (III-2), and 2,5-di-tert-butylhydroquinone mono(p-vinylbenzyl) ether (III-3) were synthesized by the reactions of p-chloromethylstyrene with the corresponding hydroquinone derivatives in alcoholic potassium hydroxide or with their potassium salts in dipolar aprotic solvents. All monomers were found to polymerize by free-radical initiation except III-3, which required a cationic initiator.     

A carbon-13 Nmr assignment study of 3,5-diarylisoxazoles

The assignment of the carbon-13 nmr resonances of 3-(aryl)-5-phenylisoxazoles (I) and 3-phenyl-5-(aryl)-isoxazoles (II) in dimethylsulfoxide-d₆ has been made. The assignments were made by using model compounds, chemical shift arguments, coupling with fluorine substituents, and shifts resulting from quaternization of the isoxazole ring. A carbon-13 nmr method for distinguishing between I and II which can be produced simultaneously by certain synthetic methods is presented.     

4-(对取代苯基)-2-[2-(取代苯基)呋喃-4-甲酰胺]-1',3',4'-均三唑[1,2-d]-1,3,4-噻二唑类衍生物的合成和生物活性

以1-氨基-5-巯基-2-(对取代苯基)-1,3,4-均三唑和5-取代苯基-2-呋喃甲酰异硫氰酸酯为原料, 合成了10个未见文献报道的含苯环连呋喃的均三唑并噻二唑类衍生物, 通过元素分析, ¹H NMR, IR和MS确定化合物的结构, 初步生物活性测试表明标题化合物具有一定的除草活性.     

Synthesis of some thiazolyl and thiadiazolyl derivatives of substituted furan and pyrrole

Four series of substituted furan and pyrrole have been synthesized. The first series was prepared by cyclization of the key intermediates ethyl 5‐[(4‐substituted thiosemicarbazido)methyl]‐2‐methylfuran‐3‐carboxylates 2a‐2d and 1‐[(4‐acetyl‐5‐methyl‐1H‐pyrrol‐2‐yl)methylene]‐4‐substituted thiosemicarbazides 8a‐8d with chloroacetic acid or (ethyl bromoacetate) to afford the corresponding 4‐oxo‐3‐substituted thiazolidin‐2‐ylidene 3a‐3d or 3‐substituted thiazolidin‐4‐one 9a‐9d . On the other hand, heating of the intermediates 2a‐2d or 8a‐8d with acetic anhydride afforded the corresponding (N‐substituted acetylamino)‐2,3‐dihydro‐[1,3,4]thiadiazol‐2‐yl derivatives 4a‐4d and [1,3,4]thiadiazol‐2‐yl‐N‐substituted acetamide 10a‐10d respectively, while cyclization with p‐bromophenacyl bromide gave rise to the corresponding 3‐substituted thiazol‐2‐yl‐ylidene 5a‐5d and 11a‐11d respectively. Furthermore, 4‐oxo‐3‐substituted thioureido‐thiazolidin‐2‐yl 6a‐6d or 4‐oxo‐thiazolidin‐3‐yl‐3‐substituted thiourea 12a‐12d were obtained by reaction of the intermediates 2a‐2d or 8a‐8d with thioglycolic acid. Some of the synthesized compounds showed promising antimicrobial activities.     

Reaction of aryl-β-nitrovinyl ketones with hydrogen halides. Preparation of isoxazoles

A study is made of the reactions of aryl--nitrovinyl ketones with hydrogen chloride, hydrogen bromide, and hydriodic acid. It is shown that reaction leads to cyclization forming substituted isoxazoles, and that with hydrogen bromide and hydriodic acid, cyclization is accompanied by reduction. The action of hydrogen chloride on phenyl--nitrovinyl ketone gives 3, 4-dichloro-5-phenylisoxazole, while hydrogen bromide gives 5-phenyl- and 3-bromo-5-phenylisoxazoles, and hydriodic acid 5-phenylisoxazole. Chlorination of 3-chioro-5-phenylisoxazole and bromination of 3-bromo-5-phenyl-isoxazole are methods of synthesizing 3, 4-dichloro- and 3, 4-dibromo-5-phenylisoxazole, respectively. The general equations for the reactions are given.     

Kinetics of the Reactions of 4-Nitrochlorobenzene with Substituted Phenols in the Presence of Potassium Carbonate

The kinetics of 4-nitrochlorobenzene (4-NCB) reactions with substituted phenols in the presence of potassium carbonate in N,N-dimethylacetamide was studied. Depending substituents, the reactivity of the phenols is changed in the series 3-NO₂> 4-Cl > H > 4-Br > 3-CH₃> 3-NH₂, which is consistent with the series of their acidity. The reaction rates satisfactorily correlate with the pK _avalues of the corresponding substituted phenols. Based on kinetic data (first-order and zero-order reactions with respect to phenol and 4-NCB, respectively, and the consistency of the reactivity and acidity of substituted phenols), the deprotonation of phenols is considered as the rate-determining step of the overall reaction under the test conditions. A reaction scheme was proposed for the synthesis of diaryl ethers in the presence of potassium carbonate. It involves a heterogeneous step of phenol deprotonation, which takes place on the surface of potassium carbonate, and a homogeneous step of the interaction of potassium phenolates with 4-NCB. Under the reaction conditions, the resulting bicarbonate decomposes with the formation of potassium carbonate and with the release of carbon dioxide and water.     

Anil-Synthese 22. Mitteilung über die Herstellung von Styryl-und Distyryl-Derivaten des Pyridins

Preparation of Styryl and Distyryl Derivatives of Pyridine 2,4-, 2,5- and 2,6-Dimethylpyridines react with anils of aromatic aldehydes in the presence of dimethylformamide and potassium hydroxide to yield the corresponding distyrylpyridines (‘anil synthesis’). Under the same reaction conditions (4-methylstyryl)pyridines are converted to (stilbenylvinyl)pyridines. Similarly, the Schiff's base derived from pyridine-3-carbaldehyde and p-chloroaniline on treatment with methyl- and p-tolyl-substituted aromatic heterocycles gives the corresponding (heteroaryl-styryl)pyridines, whereas with the Schiff's bases derived from pyridine-2- and -4-carbaldehyde side reactions, such as dimerization followed by disproportionation predominate.