Synthesis of Heterocyclic Compounds Containing Perfluoroalkyl Groups. Reactions of Perfluoro(2-methyl-2-pentene) and Perfluoro(5-aza-4-nonene) with N,S-Dinucleophiles

Perfluoro(2-methyl-2-pentene) and perfluoro(5-aza-4-nonene) react with 1,4,5,6-tetrahydropyrimi-dine-2-thiol, pyridine-2-thiol, and 1,2,4-triazole-3-thiol to afford fused heterocyclic systems, while their reactions with tetrahydrothiazole-2-thione and pyrimidine-2-thiol result in replacement of the fluorine atom at the double bond. Treatment of 3,3,3-trifluoro-1-pentafluoroethyl-2-trifluoromethyl-1-pentenyl isothiocyanate with ammonia gives N-(3,3,3-trifluoro-1-pentafluoroethyl-2-trifluoromethyl-1-propenyl)thiourea which undergoes ring closure to 4-tetrafluoroethylidene-5,5-bis(trifluoromethyl)-4,5-dihydrothiazol-2-amine. Possible cyclization paths and the effect of the 1,3(N,S)-dinucleophile nature on the direction of nucleophilic addition at the double bond are discussed.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 3, 2005, pp. 441–446.Original Russian Text Copyright © 2005 by Furin, Zhuzhgov.     

Derivatives of 4-aza-9-fluorenone

Derivatives of 1,3-indandione containing in position 2 a carbon chain with a δ-carbonyl group cyclize on heating with ammonium acetate in glacial acetic acid to form derivatives of 1,4-dihydro-4-aza-9-fluorenone. The latter are readily oxidized to the corresponding 4-aza-9-fluorenones. The IR and UV spectra of the compounds obtained are discussed.     

Colorimetric Determination of Some Important Hydrazine Derivatives

ABSTRACT

A simple and rapid colorimetric method for the determination of isoniazid, iproniazid phosphate, phenylhydrazine hydrochloride and hydrazine hydrate is described. The method is based on the formation of a Schiff base when these compounds react with 4-dimethylaminocinnamaldehyde and measurement of the condensed products at 370–555nm. The procedure has been successfully applied to the assay of the pharmaceutical preparations containing the studied drugs and hydrazine, and phenylhydrazine mixture, and the results are compared to the official methods. All the different experimental conditions are studied and incorporated into the procedure.     

Reactions of 1,5-Diketones with Ammonia and Its Derivatives. (Review)

Published data and the authors' own experimental results on the reaction of aliphatic, semicyclic, and oxosemicyclic 1,5-diketones and alkylidene- and arylidene-2,2-dicyclanones with ammonia, ammonium acetate, and XNH₂ derivatives, where X = Alk, Ar, OH, NH₂, PhNH, ArCONH, and CHO, are reviewed. The characteristics and the relationships governing the transformations into azaheterocycles in relation to the nature of the reagents and the reaction conditions are discussed.     

Synthesis and Reactions of Some 1-Thiapyran-4-One Derivatives

The preparation of some 3,5-diarylidene-1-thipyran-4-one derivatives (Ia-e) was described. Oxidation of Ia, b and Ie with hydrogen peroxide gave the corresponding dioxides (IIa-c). Reaction of the 1-thiapyran-4-one derivatives with bromine, Grignard reagents, and amines were studied. Structural assignments are supported by spectral (UV, IR, and ¹HNMR) data.     

Some Reactions with 3-(2-Chloro-7-Methylquinolinyl) Chalcone Derivatives

The preparation of some new 3-quinolinylchalcone derivatives was described. Their reaction with hydrazines, hydroxylamine hydrochloride, malononitrile and ethyl cyanoacetate gave the corresponding pyrazoline, isoxazoline, cyanopyridine and cyanopyridone derivatives, respectively. The biological activity of some of the products was evaluated.     

On the Reaction of Some Saccharin Derivatives with Hydrazine and Other Nucleophils

Summary.  The reaction of methyl saccharin-2-acetate with hydrazine gave no 3-hydrazino derivative of saccharin as reported in literature, but yielded with ring opening the benzohydrazide derivative. The analogue reaction was observed when saccharin-2-(2-propionate) was reacted with hydrazine. Furthermore, using an excess of hydrazine, the ester group was transformed into the carbohydrazide too. All hydrazides were fully characterized as hydrazones by reactions with different ketones. The 3-thioxo compounds were prepared by reactions with P₂s₅, but the yield was improved by using Lawesson’s reagent. No attack at the ester group was observed. Finally, reactions of the saccharin-2-carboxylate with some amino acids gave substituted benzamides by attack at position 3 and ring opening. In none of the reactions of the saccharin derivatives with nitrogen nucleophiles a formal substitution of the 3-oxo group was observed. Corresponding author. E-mail: ottohh@pharmazie.uni-greifswald.de Received July 4, 2002; accepted August 1, 2002 Published online February 20, 2003     

Pseudoesters and Derivatives XXXV. Reactions of 4-Substituted-5-(Ethylthio)Furan-2(5H)-Ones Anions with Alkylating Agents

Alkylation of anions derived from 5-ethylthio-4-substituted furanones (1–3) is described. The regioselectivity depends on the alkylating agent but mainly on the nature of the substituent. The alkylation of 4-methoxyfuranone 3 proceeds regioselectively to afford the 5-alkylated derivative as sole product.     

On the Reaction of Some Saccharin Derivatives with Hydrazine and Other Nucleophils

 The reaction of methyl saccharin-2-acetate with hydrazine gave no 3-hydrazino derivative of saccharin as reported in literature, but yielded with ring opening the benzohydrazide derivative. The analogue reaction was observed when saccharin-2-(2-propionate) was reacted with hydrazine. Furthermore, using an excess of hydrazine, the ester group was transformed into the carbohydrazide too. All hydrazides were fully characterized as hydrazones by reactions with different ketones. The 3-thioxo compounds were prepared by reactions with P₂s₅, but the yield was improved by using Lawesson’s reagent. No attack at the ester group was observed. Finally, reactions of the saccharin-2-carboxylate with some amino acids gave substituted benzamides by attack at position 3 and ring opening. In none of the reactions of the saccharin derivatives with nitrogen nucleophiles a formal substitution of the 3-oxo group was observed.     

Reactions of [Fluoro(methylsulfonyloxy)iodo]benzene: III. Reactions of [Fluoro(methylsulfonyloxy)iodo]benzene with Norbornene and Some Its Derivatives

Reactions of [fluoro(methylsulfonyloxy)iodo]benzene with norbornene, cis-5-norbornene-endo-2,3-dicarboxylic acid, and cis-5-norbornene-endo-2,3-dicarboxylic anhydride were studied. A new mild procedure was developed for introduction of fluoro and sulfonyloxy or two sulfonyloxy groups into molecules of norbornene and its derivatives.     

Some Reactions of 5-(3 or 4-Pyridyl)-1,3,4-Oxadiazoles with Amines and Hydrazines

2-Amino-and 2-hydrazino-5-(3 or 4-pyridyl)-1, 3, 4-oxadiazoles [II_i-k] have been prepared by racting 2-chloro derivatives with the corresponding amines or hydrazines, the 2-hydrazino (II_i-k) compounds that obtained were heated with carbon disulphide and alcoholic potassium hydroxide where 5-(3 or 4-pyridyl)-1,3,4-oxadiazolo (2,3-C)-1,2,4-triazole 5-thione (III_a-c) were obtained, the given structures were biologically screened.     

Synthesis of 2-(3,3-Dicyano-2-propenylidene)-4,4,5,5-tetramethyldioxolane and Its Reactions with Hydrazine and Primary Amines

Reactions of 2-(-ethoxyvinyl)-4,4,5,5-tetramethyl-4,5-dihydro-1,3-dioxol-1-ium salts with cyanomethylene compounds gave the corresponding 2-(2-propenylidene)-1,3-dioxolane derivatives which reacted with hydrazine and primary amines to afford, respectively, 3-(2-hydroxy-1,1,2-trimethylpropoxy)pyrazole and 1-substituted 6-amino-5-cyanopyridin-2(1H)-ones.     

Convenient Methodology for Some Heterocyclization Reactions with Thioxopyrimidine Derivatives

Russian Journal of Organic Chemistry - A simple and efficient method for derivatization of the pyrimidine nucleus is developed. The readily available 6-amino-2-thioxo-2,3-dihydropyrimidin-4(1H)-one...     

4-Phosphoranylidene-5(4H)-oxazolones II. Reactions with alkylating agents

Summary When treated with alkyl halides at 20–90°C without solvent or in acetonitrile, 4-phosphoranylidene-5(4H)-oxazolones (1) give 4-C-alkylation products4 in good yields. Alkylation of1 with alkyl triflates in CH₂Cl₂ at room temperature results in O-alkylation products5. No O-to 4-C-alkylation rearrangement can be observed. The spectroscopic properties of the alkylation products are reported and discussed.

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4-Phosphoranyliden-5(4H)-oxazolone, 2. Mitt. Reaktionen mit Alkylierungsreagentien

Zusammenfassung Behandlung von 4-Phosphoranyliden-5(4H)-oxazolonen (1) mit Alkylhalogeniden bei 20–90°C ohne Lösungsmittel oder in Acetonitril liefert in guten Ausbeuten die 4-C-alkylierten Produkte4. Alkylierung von1 mit Alkyltriflaten in CH₂Cl₂ bei Raumtemperatur ergibt O-alkylierte Produkte (5). E6 wurde keine Umlagerung von O-alkylierten zu C-alkylierten Verbindungen beobachtet. Die spektroskopischen Eigenschaften der Alkylierungsprodukte werden berichtet und diskutiert.

     

Derivatives of 5-(Dimethylamino)-4-tosyl-1,3-oxazole-2-carbaldehyde and Its Analogs

Treatment of N-(2,2,2-trichloro-1-tosylethyl)dichloroacetamide with excess dimethylamine, piperidine, or morpholine gave substituted aminals of the oxazole series, whose facile acid hydrolysis provided 5-(dimethylamino)-4-tosyl-1,3-oxazol-2-carbaldehyde and its analogs having the piperidino and morpholino group in the 5 position of the oxazole ring. The resulting aldehydes and their aminals were condensed with phenylhydrazine, thiosemicarbazide, N-alkylrhodanines, and 1,3-dimethylbarbituric acid to obtain 2,5-disubstituted derivatives of 4-tosyl-1,3-oxazole.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 1002–1006.Original Russian Text Copyright © 2005 by Vyzhdak, Danielova, Kiselev, Drach.