Reaction of cis- and trans-4-alkoxycarbonylamino-3-hydroxythiophans with thionyl chloride

The reaction of cis- and trans-4-alkoxycarbonylamino-3-hydroxythiophans with thionyl chloride gives chlorosulfites. trans-4-Alkoxycarbonylamino-3-chlorosulfito-thiophans are converted to cis-3a,4,6,6a-tetrahydrothieno[3,4-d]oxazolidone by heating or by treatment with pyridine. cis-4-Carboalkoxyamino-3-hydroxythiophans form 3-carboalkoxy-3a,4,6,6a-tetrahydrothieno[3,4-d]oxathiazolidones.     

Study of the reaction of cis- and trans-4-acylamino-3-hydroxythiophans with thionyl chloride

The reaction of cis- and trans-4-acylamino-3-hydroxythiophans with thionyl chloride was studied. It was found that chlorosulfites are initially formed with retention of the configuration of the starting compound. 2-Substituted 3a,4,6,6a-tetrahydrothieno[3,4-d]oxazoline is formed from trans-4-acylamino-3-chlorosulfitothiophans by thermal reaction or in the presence of pyridine, whereas trans-4-acylamino-3-chlorothiophans are obtained from cis-4-acylamino-3-chlorosulfitothiophans; both reactions proceed with inversion of configuration.     

Stereospecific substitution of a hydroxy group by a chlorine atom in isomeric 2,3-disubstituted 3-hydroxytetrahydrothiophenes

The stereospecific synthesis of the three possible isomers of 4-amino-3-chloro-2-(4-methoxycarbonylbutyl)tetrahydrothiophene hydrohalides from the corresponding isomers of 4-amino-3-hydroxytetrahydrothiophene by the action of thionyl chloride was realized. Three isomers of 4-ureido-3-chloro-2-(4-methoxycarbonylbutyl)tetrahydrothiophene were obtained from the 3-chlorotetrahydrothiophene derivatives. The configurations of the isomeric compounds obtained were proved by ¹H and ¹³C NMR spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 327–333, March, 1991.     

Naphth[1,2-d]oxazole intermediates in the preparation of 3-hydroxy-4-(1-alkyl-3-methyl-5-hydroxy-4-pyrazolyl)-azo-1-naphthalenesulfonamide dyes

Acylation of 4-amino-3-hydroxy-1-naphthalenesulfonic acid ( 3 ) with benzoyl chloride in pyridine gave pyridinium 3-hydroxy-4-(N-benzoylamino)-1-naphthalenesulfonate ( 12 ) which was converted by thionyl chloride followed by diethylamine into N,N-diethyl-2-phenylnaphth[1,2-d]oxazole-5-sulfonamide ( 14 ). The naphthoxazole moiety was hydrolyzed with potassium hydroxide and the resulting N,N-diethyl-4-amino-3-hydroxy-1-naphthalenesulfonamide ( 11 ) coupled with 1-alkyl-3-methyl-5-pyrazolones. The 2-phenylnaphth[1,2-d]oxazole intermediates and various by-products were investigated.     

Polyfunctional imidazoles: VI. Synthesis of 2-amino-1-aryl-4-chloro-1H-imidazole-5-carboxylic acids derivatives

Aryl-2,4-dichloro-5-formylimidazoles by a successive treatment with hydroxylamine and thionyl chloride were converted into 1-aryl-2,4-dichloroimidazole-5-carbonitriles which by the action of sodium azide and tin(II) chloride were transformed into 2-amino-1-aryl-4-chloroimidazole-5-carbonitriles. The consecutive reactions of 2-azido-1-aryl-4-chloro-5-formylimidazoles with N-bromosuccinimide, methanol, or amides led to the formation of methyl esters and amides of 2-azido-1-aryl-4-chloroimidazole-5-carboxylic acids. The reduction of the latter with tin(II) chloride resulted in the corresponding derivatives of 2-amino-1-aryl-4-chloroimidazole-5-carboxylic acids, and the reduction of 2-azido-1-aryl-4-chloroimidazole-5-carboxylic acids was accompanied with decarboxylation and yielded 2-amino-1-aryl-4-chloroimidazoles.     

Approaches to novel AB heteroaromatic polyamides based on cyanoimidazoles

We report the synthesis of several AB monomers based on 2-amino-4,5-dicyanoimidazole. Polymerization of the monomers to poly(imidazoleamide)s, by several methods is described. Amino acids 2-amino-4-cyano-1-methyl-5-imidazolecarboxylic acid and 2-amino-5-cyano-1-methyl-4-imidazolecarboxylic acid were prepared by mono-ethanolysis of 2-amino-4,5-dicyanoimidazole followed by methylation of the 1-nitrogen. The resulting regioisomeric mixture of ethyl esters was separated by fractional crystallization and hydrolyzed to the desired amino acids. The regioisomeric structure was determined by NOE studies of the decarboxylated amino acids. The corresponding acid chlorides were prepared with thionyl chloride and isolated as the HCl salts. Activated esters were prepared by reacting the acid chlorides with alcohols such as 1,1,1-trifluoroethanol and 2-chlorophenol. Model compounds were prepared by the acylation of aminocyanoimidazoles but yields were low. The low nucleophilicity of the aminocyanoimidazolecarboxylic acids was partially overcome by the use of the acylation catalyst 4-dimethylaminopyridine (DMAP) and the activating agent silicon tetrachloride. The acid chlorides were polymerized in amide solvents such as hexamethyl phosphoramide with pyridine and DMAP. A copolyamide consisting of both regioisomers was prepared from a regioisomeric mixture of the acid chlorides. In addition, aminolysis of 2-chlorophenyl 2-amino-4-cyano-1-methyl-5-imidazolecarboxylate resulted in a low yield of poly(imidazoleamide). Poly(imidazoleamide)s were red to tan which suggest conjugation along the polymer backbone. The solubility of the polyamides varied from amide solvents to sulfuric acid depending on the regioisomeric structure and molecular weight. The molecular weight of the heteroaramids was in the range from 1500 to 4000 based on viscosity measurements in sulfuric acid. The poly(imidazoleamide)s were thermally stable in excess of 300°C under air and nitrogen atmosphere. © 1993 John Wiley & Sons, Inc.     

Study of the structure and inversion of 4-benzamido-trans-3-hydroxy-trans-2-carbomethoxythiophan

The structure of stereoisomeric 4-benzamido-3-hydroxy-2-carbomethoxythiophans was established by means of PMR and IR spectroscopy. The inversion of the trans,trans-isomer to the cis,trans-isomer was detected and studied. The inversion during the action of thionyl chloride in pyridine proceeds through the intermediate formation of tetrahydrothieno[3,4-d]oxazoline. The substituent in the 2 position does not undergo inversion. Tetrahydrothienooxazoline is not formed from 4-benzamido-2-carbomethoxy-4,5-dihydrothiophene.     

Conversions of polyfunctional 3-amino-1(2H)iso quinolines

The acylation of 3-amino-4-cyano-1(2H)isoquinolines with benzoyl chloride leading to the formation of 1,3 oxazino[4,5-clisoquinoline-6-ones has been studied. Previously undescribed 1-aminopyrimido[4,5-cJisoquinolirt 6-ones have been obtained by the reaction of the appopriate 3-amino-](2H)isoginolones with formamide. Nucleophilic replacement has been carried out with 3-amino-1-chloroisoquinoline by the action of sodium hydroxide, primary alcohols, hydrazine hydrate, and various amines. 1,2,4-Triazino[2,3-b]isoginolone has been synthesized by condensing 2,3-diamino-1 (2H)isoquinolone with mesoxalic acid ethyl ester.     

4-Hydroxy-2-quinolones 140. Synthesis and diuretic activity of arylalkylamides of 4-methyl-2-oxo-1,2-dihydro-quinoline-3-carboxylic acid

The interaction of 4-methyl-2-oxo-1,2-dihydroquinoline-3-carboxylic acid with thionyl chloride in oxygen-containing solvents leads to the formation of a significant amount of colored side products, consequently it was proposed the reaction be carried out in carbon tetrachloride. The synthesis of a series of amides was effected by the amidation of the obtained acid chloride with appropriate primary arylalkylamines. Results are presented of a study of the effect of the synthesized compounds on the urine-excreting function of the kidney. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 78–87, January, 2008.     

Reactions of Furoxandicarbaldehyde Dioxime with Dehydrating Agents

Dehydration of furoxan-3,4-dicarbaldehyde dioxime by the action of thionyl chloride or trifluoroacetic anhydride in the presence of a base under certain conditions can be stopped at the stage of formation of 4(3)-hydroxyiminomethylfuroxan-3(4)-carbonitrile.     

A study of the products of the reaction of epichlorohydrin with aromatic amines

The halogenation of 1,2,3,4-tetrahydrobenzo[h]quinoline and of 3-hydroxy-1,2,3,4-tetrahydrobenzo[h]quinoline and its O-benzoyl and N,O-dibenzoyl derivatives has been studied. The action of thionyl chloride or bromide on 1,2,3,4-tetrahydrobenzo[h]quinoline at room temperature gives 6-chloro-1,2,3,4-tetrahydrobenzo[h]quinoline and 6-bromo-1,2,3,4-tetrahydrobenzo[h]quinoline. When 6-chloro-3-hydroxy-1,2,3,4-tetrahydrobenzo[h]quinoline is heated with thionyl chloride, aromatization of the tetrahydropyridine ring takes place, and when 6-bromo-3-hydroxy-1,2,3,4-tetrahydrobenzo[h]quinoline is heated with thionyl chloride, in addition to the aromatization of the tetrahydropyridine ring the bromine atom is replaced by a chlorine atom with the formation of 6-chlorobenzo[h]quinoline. 6-Bromobenzo[h]quinolme has been obtained by heating 3-hydroxy-1,2,3,4-tetrahydrobenzo[h]quinoline with thionyl bromide.For Communication IV, see [6].Translated from Khimiya Geterotsiklicheskikh Soedinenii.Vol. 6,No.7, pp. 969–973, July, 1970.     

Synthesis and Oxidation of 1,3-Diamino- and 1-Amino-3-azidoindazoles

The amination of 3-amino- and 3-azidoindazoles by hydroxylamine-O-sulfonic acid in an alkaline medium yields previously unreported 1,3-diamino- and 1-amino-3-azidoindazoles. These products undergo slow autoxidation in chloroform solution to give 4-aminobenzo-1,2,3-triazine. The action of formic or acetic acid on 3-amino-1-benzylideneaminoindazole leads to recyclization and formation of 3-amino-2-benzylindazole, which is also formed in the catalytic hydrogenation of 1-benzylamino-3-nitro- and 1-benzylideneamino-3-nitroindazoles.     

Synthesis of Heterocycles from the Products of Anionic Arylation of Unsaturated Compounds. 7. Products of Haloarylation of Acrylic Acid and Its Esters in the Synthesis of Benzo[b]thiophene Derivatives

3-Chloro-2-chlorocarbonylbenzo[b]thiophenes were obtained on oxidation of Meerwein reaction products, viz. 3-aryl-2-halopropionic acids and their esters, with thionyl chloride in the presence of N-benzyl-N-methylmorpholinium chloride. Disubstituted thioureas were synthesized by the reaction of these compounds with ammonium thiocyanate and aromatic amines, and were cyclized by interaction with iodoacetic acid with the formation of 4-thiazolidinone derivatives. The same cyclization in the presence of aromatic aldehydes leads to the formation of the corresponding 5-arylidene-substituted 4-thiazolidinones.     

Synthetic and structural studies of some chloro-substituted methyl 2,1-benzisoxazole-3-carboxylates and related compounds

Methyl 5-chloro- and 5,7-dichloro-2,1-benzisoxazole-3-carboxylates have been synthesized by treatment of o-nitromandelic and 5-chloro-2-nitroamandelic methyl esters, respectively, with thionyl chloride under appropriate reaction conditions. The structural assignments of both heterocyclic products were based on elemental and spectral analyses, and their conversion to the corresponding 5-chloro- and 5,7-dichloro substituted 2,1-benzisoxazole-3-carboxylic acids and isatins. Methyl α-chloro-o-nitrophenylacetate and o-nitrophenylcarbomethoxymethinyl sulfite were also obtained from reactions of methyl o-nitromandelate and thionyl chloride. A possible reaction mechanism involving two consecutive nucleophilic substitutions of methyl o-nitromandelate with thionyl chloride was proposed to account for the formation of methyl 5-chloro-2,1-benzisoxazole-3-carboxylate.     

Research on imidazo[1,2-a]benzimidazole derivatives. 22. Synthesis of 2,3-dihydroimidazo[1,2-a]benzimidazoles starting from 2-imino-3-(2-hydroxyethyl)benzimidazolines

A -elimination reaction with the formation of 2-imino-3-vinylbenzimidazolines occurs simultaneously with intramolecular alkylation and the formation of an imidazoline ring in the action of alcoholic alkali on 2-imino-3-(2-chloroethyl) benzimidazolines. The thermolysis of 3-chlorethyl-substituted imines without a solvent or in an inert solvent leads exclusively to 2,3-dihydroimidazo[1,2-a] benzimidazoles. An attempt to obtain the latter directly from 2-imino-3-(2-hydroxyethyl) benzimidazolines by the action of a mixture of thionyl chloride and acetic anhydride on them also leads to ambiguous results.See [1] for communication 21.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 918–925, July, 1986.     

1-酰基苯并咪唑及3-酰基-2-硫代噻唑烷酮衍生物的合成

苯并咪唑类化合物在杀菌剂研究中已取得可喜的结果,如苯菌灵、多菌灵,具有生物活性的酰基苯并咪唑类化合物已见报道,Richmond等研究发现保护性杀菌剂克菌丹在植物体内被代谢成具有内吸活性的含酰基硫代噻唑烷酮的氨基酸,杀菌和杀线虫剂N-244的结     

Synthesis and selected reactions of 4-(diethoxyphosphorylmethyl)-3-furoic acid

Reduction of 4-(ethoxycarbonyl)-3-furoyl chloride with sodium borohydride in dioxane-DMF mixture leads to an ethyl 4-hydroxymethylfuran-3-carboxylate. The treatment of the latter with thionyl chloride at boiling yields the corresponding chloromethyl derivative. The obtained chloride reacts with one equivalent of sodium iodide in acetone at room temperature to form iodomethylfuran. Halomethylfurans synthesized are phosphorylated with sodium diethyl phosphite and triethyl phosphite to give ethyl 4-(diethoxyphosphorylmethyl)-3-carboxylate. The hydrolysis of this substance with one equivalent of potassium hydroxide in ethanol gives the corresponding furoic acid. Treating this substance in succession with ethyl chloroformate and sodium azide yields furoyl azide which while heating in toluene undergoes rearrangement to phosphorus-containing 3-furylisocyanate. Heating the latter with a mixture of acetic acid and acetic anhydride gives N-[4-(diethoxyphosphorylmethyl) furyl-3]acetamide. 4-(Diethoxyphosphorylmethyl)-3-furoic acid reacts with thionyl chloride to form the corresponding furoyl chloride. Its reduction with sodium borohydride in dioxane-DMF mixture leads to the phosphorylated 3-furylmethanol. Aminomethylation of its acetate with dimethylmethyleneiminium chloride in acetonitrile does not proceed at the ring. Instead of that the unstable ester of 3-(dimethylamino) propionic acid and the phosphorylated 3-furylmethanol are formed. In slightly basic medium free Mannich base decomposed to give the starting acetate.     

Direct Transformation of Anthrone and Its Derivatives into Monothioanthraquinone S-Oxides

The reaction of anthrone with thionyl chloride in benzene yields 10-(chlorosulfinyl)anthrone, whilein DMF monothioanthraquinone S-oxide is formed; 4-substituted anthrones react with thionyl chloride in DMFin a similar way. The reaction of 4'5-dichloroanthrone with thionyl chloride results in dimerization of thesubstrate, formation of the corresponding bianthracenedione.     

Synthesis of derivatives of <Emphasis Type="Italic">o</Emphasis>-aminoacetophenone and <Emphasis Type="Italic">o</Emphasis>-aminobenzyl alcohol

Oxidation of 2′-hydroxy-8-methylspiro[4H-benz-1,3-oxazin-2-one-6,1′-cyclopentane] or N-mesyl-2-(cyclopent-1-en-1-yl)-6-methylaniline provided the corresponding ketones. The rearrangement of these ketones oximes under treatment with thionyl chloride gave rise to nitriles of 5-(2-amino-3-methylphenyl)-5-oxopentanoic or 5-(2-methanesulfamido-3-methylphenyl)-5-hydroxypentanoic acids. By heating 5-(2-acetylamido-3-methylphenyl)-5-oxopentanoic acid with LiH in THF3-(2,8-dimethylquinol-4-on-3-yl)propanoic acid was obtained.     

Synthesis of 4H-[1]benzopyrano[3,4-c][1,2,5]thyadiazol-4-one and its reactions with some nucleophilic and electrophilic agents

The reaction of 3,4-diaminocoumarin with thionyl chloride gave 4H-[1]benzopyrano[3,4-c][1,2,5]thiadiazol-4-one (II), which was cleaved by the action of nucleophilic agents to the corresponding 4-(2-hydroxyphenyl)-1,2,5-thiadiazole-3-carboxylic acid derivatives. The nitration of II leads to the 8-nitro or 6,8-dinitro derivative; the latter was isolated in the form of 4-(2-hydroxy-3,5-dinitrophenyl)-1,2,5-thiadiazole-3-carboxylic acid.See [3] for our preliminary communication.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 977–981, July, 1988.