4-Hydroxy-2-quinolones. 112. Reaction of 2-ethoxycarbonylmethyl-4H-3,1-benzoxazin-4-one with active methylene compounds

The reaction of 2-ethoxycarbonylmethyl-4H-3,1-benzoxazin-4-one with malononitrile in dry pyridine leads to 1-hydroxy-3,6-dioxo-4,6-dihydro-3H-pyrimido[1,2-a]quinoline-5-carbonitrile. Acetoacetic and cyanoacetic esters under analogous conditions form anilides of 4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carboxylic acid while diethyl malonate gives N,N′-di-2-carboxyanilides of malonic acid. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 75–79, January, 2007.     

4-Hydroxy-2-quinolones. 90. Synthesis and antitubercular activity of 4-methyl-2-thiazolylamides of halo-substituted 4-hydroxy-2-oxo-1,2-dihydro-3-quinolinecarboxylic acids

Several variants were studied for the synthesis of esters of halogen derivatives of 4-hydroxy-2-oxo-1,2-dihydro-3-quinolinecarboxylic acids, whose reaction with 2-amino-4-methylthiazole gives the corresponding hetarylamides. Results are given for a study of the antitubercular activity of these products. Communication 89, see ref. [1]. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 71–76, January, 2006.     

4-Hydroxyquinol-2-ones. 86. Synthesis of Methyl (Ethyl) Esters of 1-Substituted 4-Amino-2-oxoquinoline-3-carboxylic Acids

Several variants of the synthesis of esters of 1-N-substituted 4-amino-2-oxoquinoline-3-carboxylic acids have been studied, one of which is recommended as preparative. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1355–1361, September, 2005.     

Lanthanide perchlorate complexes of 4-cyano pyridine-N-oxide, 4-chloro 2-picoline-N-oxide and 4-dimethyl amino-2-picoline-N-oxide

Complexes of lanthanide perchlorates with 4-cyano pyridine-1-oxide, 4-chloro 2-picoline-1-oxide and 4-dimethyl-amino 2-picoline-1-oxide have been isolated for the first time and characterized by analysis, conductance, infrared, NMR and electronic spectra. The complexes of 4-cyano pyridine-1-oxides have the composition Ln(CyPO)₆(ClO₄)₃. 2H₂O (Ln=La, Sm, Dy and Ho); Ln(CyPO)₇ (ClO₄)₃. 2H₂O (Ln=Pr, Nd, Er and Yb); and Ln(CyPO)₅ (ClO₄)₃. 2H₂O (Ln=Gd and Tb). The complexes of 4-chloro 2-picoline-1-oxide analyse for the formulae Ln(CpicO)₆ (ClO₄)₃ (Ln=La, Pr, Nd and Ho); and Ln (CpicO)₅ (ClO₄)₃ (Ln=Er and Yb), and those of 4-dimethylamino 2-picoline-1-oxide for Ln(DMPicO)₆ (ClO₄)₃ (Ln=La and Nd); Ln(DMPicO)₇ (ClO₄)₃ (Ln=Gd, Er and Yb); and Ln(DMPicO)₈ (ClO₄)₃ (Ln=Dy and Ho).     

Beiträge zum thermischen Verhalten von Sulfaten. VIII. Zum chemischen Transport von FeSO4 mit NH4Cl und von von Fe2(SO4)3 mit Cl2 oder NH4Cl. Experimente und Modellrechnungen

Contributions on the Thermal Behaviour of Sulfates. VIII. The Chemical Vapour Transport of FeSO₄ with NH₄Cl and Fe₂(SO₄)₃ with Cl₂ or NH₄Cl. Experiments and Calculations Well shaped crystals of FeSO₄ and Fe₂(SO₄)₃ can be grown by CVT (T₁? 650°C). We investigated the dependence of the transport rate on the concentration of the transport agent (Fe₂(SO₄)₃/Cl₂ and Fe₂(SO₄)₃/NH₄Cl) as well as on the temperature (FeSO₄/NH₄Cl and Fe₂(SO₄)₃/Cl₂). Using Δ_fH(FeSO₄) = ?220 kcal/ mol, C^p(T) = 30.1 + 9.9 · 10^?3 ×T and Δ_fH(Fe₂(SO₄)₃) = ?615.4 kcal/mol a satisfying agreement between thermodynamical calculations and experimental results can be reached     

Synthese des 4-Hydroxy-6,6-dimethyl-5,6-dihydro-2H-thiopyran-2-thions bzw. -ons und der entsprechenden Tautomeren

The tautomers 4-hydroxy-6,6-dimethyl-5,6-dihydro-2H-thiopyran-2-thione (4 a) and 2-mercapto-6,6-dimethyl-5,6-dihydro-4H-thiopyran-4-one (4 b) resp. were synthesized by hydrolysis of 4-amino-5,6-dihydro-2H-thiopyranthiones6,8. On methylation of4 a,b only the S-methyl product7 is formed. Hydrolysis of 4-amino-2-methylthiothiopyranyliden iodides11 leads—depending on the amino group of11—either to the thiopyranone7 or to the 4-imino-thiopyranes12 and to -amino-,,,-unsaturated-methyldithio carboxylates13. On reaction of4 a,b with hydrogenperoxyd the tautomers 4-hydroxy-5,6-dihydro-2H-thiopyran-2-one5 a and 5,6-dihydro-2H-thiopyran-2,4(3H)diones5 b resp. are formed.4 a,b and5 a,b undergo an aminolysis with prim. and sec. amines to the corresponding 4-amino-2H-thiopyran-2-thiones6,8 and -ones10 resp. On heating in alcohols the 4-alkoxy-thiopyrane-2-thiones and -ones9,14 are formed from4 a,b and5 a,b resp.

     

Reactions of aminoquinolines with unsaturated carboxylic acids. 4. Synthesis of 4-carboxy-1-quinolyl-2-pyrrolidinones

1-Quinolyl-4-carboxy-2-pyrrolidinones have been synthesized by the reaction of aminoquinolines with itaconic acid. Decyclization of the products gave 2-(quinolylaminomethyl)succinic acids.For Communication 3, see [1].Kaunus Technological University, Kaunas 3028, Lithuania Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 932–935, July, 2000.     

4-hydroxy-2-quinolones. 42. Synthesis and biological activity of 1-R-2-oxo-3-(2H-1,2,4-benzothiadiazine-1,1-dioxid-3-yl)-4-hydroxyquinolines

A preparative method for the synthesis of 1-R-2-oxo-3-(2H-1,2,4-benzothiadiazine-1,1-dioxid-3-yl)-4-hydroxyquinolines has been developed. The diuretic and antitubercular activity of the obtained compounds have been studied.For Communication 41 see [1].National Pharmaceutical Academy of Ukraine, Khar'kov 310002; e-mail: igor@uiv.kharkov.ua. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 409–414, March, 2000.     

2-Polyfluoroalkylchromones. 6. Synthesis of substituted 2-morpholino-2-trifluoromethylchroman-4-ones

Morpholine adds smoothly at the double bond of substituted 5- and 8-nitro-2-trifluoromethylchromones to form the corresponding 2-morpholino-2-trifluoromethylchroman-4-ones. 6-Methoxy-5-nitro-2-trifluoromethylchromone adds also benzylamine, whereas 7-methoxy-8-nitro-2-trifluoromethylchromone undergoes ring opening under the action of benzylamine to give 3-benzylamino-4,4,4-trifluoro-1-(2-hydroxy-4-methoxy-3-nitrophenyl)but-2-en-1-one.     

4-Hydroxy-2-quinolones. 39. Structure of 6-bromo-4-hydroxy-1-isoamyl-2-oxo-3-quinolinecarboxylic acid

S-(–)-1-phenylethylamide of 6-bromo-4-hydroxy-1-isoamyl-2-oxo-3-quinolinecarboxylic acid was synthesized. X-ray diffraction investigation of this product was carried out to determine its absolute configuration.For communication 38, see ref. [1].National Pharmaceutical Academy of Ukraine, 310002 Kharkov, Ukraine Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 64–69, January, 2000.     

UNPRECEDENTED OUTCOME OF BASE-PROMOTED NEBER REARRANGEMENT OF O-MESYLOXIME OF 2-ARYL-1,2,3,4-TETRAHYDRO-1-METHYLSUL FONYL-4-QUINOLONE- SYNTHESIS OF 4-AMINO-2-ARYLQUINOLINES

Abstract

O-Mesyloximes derived from 2-aryl-1,2,3,4-tetrahydro-1-methylsulfonyl-4-quinolones react with sodium ethoxide in ethanol to afford the 4-amino-2-arylquinolines in high yield. No traces of the 3-amino-2-aryl-4-quinolones expected from the Neber rearrangement of the substrates were detected or isolated from the reaction mixture. The structures of the products were determined using a combination of ¹H NMR, ¹³C NMR, IR and mass spectroscopic techniques.     

Facile Synthesis of Some New Pyrazole-Based 2-Thioxo-4-thiazolidinone

5-Ethoxymethylene-2-thioxo-4-thiazolidinone (1) reacts with hydrazine hydrate at room temperature to afford 5-(hydrazinylmethylene)-2-thioxo-4-thiazolidinone (3). Compound 3 condensed with different aromatic aldehydes 6a–d in ethanol in the presence of a few drops of piperidine to give the corresponding Schiff’s bases 7a–d. On the other hand, compound 3 reacts with o-hydroxybenzaldehyde derivatives 8a and 8b in refluxing ethanol catalyzed by a few drops of piperidine to yield 1H-inadzolyl-2-thioxo-4-thiazolidinones 9a and 9b. Reaction of compound 3 with α-ketoesters 10a and 10b or α-diketones 10c–e in refluxing glacial acetic acid furnished the pyrazolyl-2-thioxo-4-thiazolidinone derivatives 11a–e. Also, compound 3 reacts with some different enaminones 12a–f in refluxing glacial acetic acid to afford the new pyrazolyl-2-thioxo-4-thiazolidinone derivatives 13a–f. Pyrazoles 15a–d was obtained via reaction of compound 3 with chalcones 14a–d in dimethylformamide (DMF). The structures of all the newly synthesized products were confirmed on the basis of their elemental and spectral data, and a plausible mechanism has been postulated to account for their formation.     

4-hydroxy-2-quinolones. 40. Synthesis and biological properties of anilides of 1H-2-oxo-4-hydroxyquinoline-3-carboxylic acid

An improved method for the synthesis of anilides of 1H-2-oxo-4-hydroxyquinoline-3-carboxylic acid was proposed. Results of the study of antithyroid and anti-tuberculosis activity of the compounds synthesized are presented.For the Communication 39, see [1].National Pharmaceutical Academy of Ukraine, Kharkov 31002. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 203–206, February, 2000.     

4-hydroxy-2-quinolones. 43. Thermolysis of ethyl esters of 1-R-2-oxo-4-hydroxy-quinoline-3-carboxylic acids

Ethyl esters of 1-R-2-oxo-4-hydroxyquinoline-3-carboxylic acids under thermolysis conditions are converted to 5,9-di-R-6,7,8-trioxodiquinolino[3,4-b;3,4-e]-4H-pyrans. One of the synthesized compounds was studied by X-ray diffraction.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 516–522, April, 2000.     

4-Hydroxy-2-quinolones. 152*. 3-acetyl-4-hydroxy-2-oxo-1,2-dihydroquinoline and its biologically active derivatives

A synthesis and study of the spatial structure of 3-acetyl-4-hydroxy-2-oxo-1,2-dihydroquinoline have been carried. 1-R-4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carboxylic acids [1-(4-hydroxy-2-oxo-1,2-dihydroquinolin-3-yl)ethylidene]hydrazides were prepared from this compound by two routes. A comparative analysis of the antitubercular properties of the synthesized compounds and of the closely structurally related N,N′-di(1-R-4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carbonyl)hydrazines has been performed. *For Communication 151 see [1]. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 214–222, February, 2009.     

Synthesis of 4-azacyclopent-2-enones and 5,5-dialkyl-4-azacyclopent-2-enones

Three different methods are reported for the preparation of 4-azacyclo-2-enones 1, two of which allow the preparation of the compounds in optically active form. In addition, a facile route to 4-aza-5,5-dimethylcyclopent-2-enones 2 is disclosed.     

4-Hydroxyquinol-2-ones. 87. Unusual Synthesis of 1-R-4-Hydroxy-2-oxo-1,2-dihydroquinoline-3-carboxylic Acid Pyridylamides

4-Chloro-2-oxo-1,2-dihydroquinoline-3-carboxylic acids and their esters react with aminopyridines in refluxing DMF to give the corresponding 4-hydroxy-2-oxo-1,2-dihydroquinoline-3-carboxylic acid pyridylamides. Their structures were proved by ¹H NMR and mass spectroscopy, counter synthesis, and by X-ray analysis. A possible mechanism is proposed for the indicated chemical reaction. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1362–1371, September, 2005.     

Cyanoacetylene and Its Derivatives. 30. Reactions of 2,3-Dimercaptoquinoxaline with 3-Phenyl-2-propynonitrile and 4-Alkyl-4-hydroxy-2-alkynonitriles

The reaction of 2,3-dimercaptoquinoxaline with 3-phenyl-2-propynonitrile (~10 mass % KOH, 20-25°C, 5 h, dioxane) gave the S,S-diadduct (as with unsubstituted acetylene). 2,3-Dimercaptoquinoxaline reacted with 4-alkyl-4-hydroxy-2-alkynonitriles to give 2-cyanomethyl-2-(1-hydroxy-1-alkyl)-1,3-dioxolano[4,5-b]quinoxalines or 3-cyanomethylene-8-imino-2,2,6,6-tetramethyl-1,7-dioxa-4-thiaspiro[4.4]nonane.     

Dehydration of 4-hydroxy-4-methyl-3-phenylamino-oxazolidin-2-ones

The dehydration of two 5,5-disubstituted 4-hydroxy-4-methyl-3-phenylaminooxazolidin-2-ones into the corresponding 4-methylene-3-phenylaminooxazolidin-2-ones has been carried out. The structure of the products was confirmed by X-ray diffraction analysis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1512–1517, October, 2004.     

Synthesis and structural characterization of [PhE(BNMe2)2]2 (E = P or As): Six-Membered P2B4 and As2B4 Rings with Unusual Structures

The reaction of either Li₂PPh or Li₂AsPh with the diborane(4) derivative B₂(NMe₂)₂Br₂ affords the compounds [PhP(BNMe₂)₂]₂ ( 1 ) or [PhAs(BNMe₂)₂]₂ ( 2 ) in good yield. Both 1 and 2 have cyclic structures featuring non-planar P₂B₄ or As₂B₄ six-membered rings which have chair configurations. Although all four borons in each ring have planar coordination, the two phosphorus or arsenic centers have different degrees of pyramidalization. Bond distances within the rings indicate that the B? B, B? P or B? As bonds are single, whereas the exo-B? N bond lengths are consistent with significant π-bonding. The ring structures of 1 and 2 are in sharp contrast to the related boron-nitrogen species (t-BuN)₂N₄Me₄ which has a nido-N₂B₄ framework. The attempted synthesis of the nitrogen analogue of 1 or 2 by using a similar approach did not result in the isolation of [PhN(BNMe₂)₂]₂, instead the tetramino diborane(4) species [B(NMe₂)NHPh]₂ ( 3 ), which has a structure similar to other tetramine diborane(4) compounds, was isolated.