Synthesis and Properties of 1,3-Diaryl-5,6-dihydro-8H-imidazo[2,1-c]-1,4-oxazinium Bromides

It has been established that the condensation of 3-(4-methoxyphenylamino)-5,6-dihydro-2H-1,4-oxazine with substituted phenacyl bromides occurs at the exocyclic nitrogen atom with formation of 3-aryl-3-hydroxy-1-(4-methoxyphenyl)-2,5,6,8-tetrahydro-3H-imidazo[2,1-c]-1,4-oxazinium bromides. By treatment of the latter with acetic anhydride 3-aryl-1-(4-methoxyphenyl)-5,6-dihydro-8H-imidazo[2,1-c]-1,4-oxazinium bromides are formed. The structures of the compounds synthesized were determined via ¹H NMR spectroscopy and X-ray diffraction.     

Synthesis and study of some properties of 1-aryl-2-oxo-1,2,3,6-tetrahydro[1,4]diazepino[6,5-b]indole 4-oxides

A number of 1-aryl-2-oxo-1,2,3,6-tetrahydro[1,4]diazepino[6,5-b]indole 4-oxides were synthesized based on 3-[N-aryl-N-(chloroacetyl)amino]-2-formylindoles. The nature of the substituent in the 1-aryl fragment has a pronounced influence on the course of reactions throughout the whole sequence of transformations during the synthesis of diazepinoindoles. The reduction of 4-oxides by formamidinosulfinic acid, hydrogen in the presence of Pd/C, and sodium bisulfite was studied. The structures of the reaction products were confirmed using IR and ¹H NMR spectroscopy and mass spectrometry.     

Synthesis and characterization of cerium,thorium, and uranyl complexes with ( E )-4-(4-methoxyphenoxy)-4- oxobut-2-enoic acid

(E)-4-(4-Methoxyphenoxy)-4-oxobut-2-enoic acid and its Ce(IV), Th(IV), and UO₂(II) complexes were synthesized and characterized by MS, elemental analysis, IR, UV, TG-DTA, and NMR. The complexes have composition [CeL₂(OH)₂ · 2H₂O] · H₂O, [ThL₂(OH)₂ · 2H₂O] · H₂O, and [UO₂L₂ · 2H₂O] · H₂O. Molar conductance data confirm that the three complexes are nonelectrolytes. The IR and NMR results show that the carboxylates coordinate to the metal ions bidentate, and the ester carboxylic groups do not take part in coordination. Luminescence spectra of the ligand and complexes in DMSO at room temperature were also studied showing strong luminescence of the metal ions.     

Synthesis of aromatic polyethers by Scholl reaction. V. Synthesis and polymerization of 1,3-bis[4-(1-naphthoxy) benzoyl]benzene, 1,4-bis[4-(1-naphthoxy)benzoyl]benzene,bis[4-(1-naphthoxy)phenyl]methane, 1,3-bis[4-(1-naphthoxy) phenylmethyl]benzene,and 1,4-bis-[4-(1-naphthoxy)phenylmethyl]benzene

This article describes the synthesis and the cation-radical polymerization (Scholl reaction) of 1,3-bis[4-(1-naphthoxy) benzoyl] benzene ( 6 ) and 1,4-bis[4-(1-naphthoxy) benzoyl]- benzene ( 7 ) initiated by FeCI₃. This polymerization produced poly(ether ether ketone ketone)s (PEEKK) of number average molecular weight (M?_n) up to 5400 g/mol. The synthesis of bis[4-(1-naphthoxy) phenyl] methane ( 8 ), 1,3-bis[4-(1-napthoxy) phenylmethyl] benzene ( 9 ), and 1,4-bis[4-(1-naphthoxy) phenylmethyl] benzene ( 10 ) are also described. Polyethers of M?_n up to 15400 g/mol at a FeCl₃/monomer molar ratio of 2/1 were obtained. An increased polymerizability of the monomers 9 and 10 containing two CH₂ groups versus that of the corresponding monomers containing two carbonyl groups ( 6 and 7 ) was observed. This enhanced polymerizability was explained based on the increased nucleophilicity of monomers 9 and 10 .     

The base-promoted dehydration of rac.-trans-tetrahydro-6-hydroxy-4-[(2-(dimethylamino)ethyl]-7-(4-methoxyphenyl)-1,4-thiazepin-5(2H)-one

The base-catalyzed alkylation of rac.-trans-tetrahydro-6-hydroxy-7-(4-methoxyphenyl)-1,4-thiazepin-5(2H)-one ( 1 ) with dimethylaminoethyl chloride in dimethyl sulfoxide provided predominantly rac.-trans-tetrahydro-6-hydroxy-4-[(2-dimethylamino)ethyl]-7-(4-methoxyphenyl)-1,4-thiazepin-5(2H)-one ( 2 ) and in addition, 2,3-dihydro-4-[2-(dimethylamino)-ethyl]-7-(4-methoxyphenyl)-1,4-thiazepin-5(4H)-one ( 3 ). A plausible mechanism is postulated for the dehydration of the rac.-trans-amide 2 .     

Photocrosslinkable polymers based on 4-[5-(4-hydroxyphenyl)-3-oxopenta-1,4-dienyl]phenyl-2-methacrylate: photocrosslinking studies and reactivity ratios with vinylcyclohexane

1,5-Bis(4-hydroxyphenyl)penta-1,4,dien-3-one (HPD) was synthesized using p-hydroxybenzaldehyde and acetone in the presence of hydrogen chloride gas. Acrylated derivative of HPD 4-[5-(4-hydroxyphenyl)-3-oxopenta-1,4-dienyl]phenyl-2-methacrylate (HPPMA) was synthesized by reacting HPD and methacryloyl chloride in the presence of triethylamine at 0-5 °C. Homo- and co-polymer (with vinylcyclohexane (VC)) of HPPMA was carried out in methyl ethyl ketone using benzoyl peroxide (BPO) under nitrogen atmosphere at 70 ± 1 °C. All the monomer and polymers were characterized by IR and NMR techniques. Monomer reactivity ratios were calculated using Fineman-Ross (FR), Kelen-Tudos (KT) and extended Kelen-Tudos (ex-KT) methods. Photocrosslinking nature of the polymer samples were carried out in solution phase using tetrahydrofuran (THF) solvent under high frequency UV light. Rate of photocrosslinking of the polymer samples were measured for poly(HPPMA) and for poly(VC-co-HPPMA). Thermal stability of the polymer samples was recorded using thermogravimetric analysis (TGA) method. Molecular weights (M_w and M_n) of the polymer samples were determined using gel permeation chromatographic (GPC) technique.     

A novel synthesis of 14-(hydroxymethylalkyl) derivatives of dibenzoxanthenes and 3,3-dimethyl-4-(2-hydroxy-1-naphthyl)benzo[f]chroman

Several reactions of 2-naphthol with 2-alkyl-2-hydroxymethylaldehydes have been investigated. Novel synthesis of 14-(hydroxymethyl)alkyldibenzo[a,j]xanthenes and 3,3-dimethyl-4-(2-hydroxy-1-naphthyl)benzo[f]chroman has been realized.     

Hydrolysis of Bis[5,5-dimethyl-3-(4-oxa-1-azoniacyclohexylidene)-1-cyclohexenyl] Sulfide Diperchlorate

Hydrolysis of bis[5,5-dimethyl-3-(4-oxa-1-azoniacyclohexylidene)-1-cyclohexenyl] sulfide diperchlorate, as well as of bis(5,5-dimethyl-3-thioxo-1-cyclohexenyl) sulfide, in the system MeCN-Et₃N yields a mixture of bis(5,5-dimethyl-3-oxo-1-cyclohexenyl) sulfide and isomeric 5,5-dimethyl-3-oxo-1-cyclohexenyl 3,3-dimethyl-5-oxo-1-cyclohexenyl sulfide. The structure of the products and their ratio were established by ¹H and ¹³C NMR and IR spectroscopy.     

Preparation and Structure of (E)-1-(3′-Hydroxy-2-Furanyl)-3-(3″-Hydroxy-4″-Methoxyphenyl)-2-Propen-1-One

Abstract

A facile procedure is presented for the synthesis of (E)-1-(3′-hydroxy-2′-furanyl)-3-(3″-hydroxy-4″-methoxyphenyl)-2- propen-1-one (6). Galactosylisomaltol (1) was condensed with isovanillin (2) under strong alkaline conditions at 25 [ddot]C to form (E)-1-(3′-O-β-D-galactopyranosyloxy-2′-furanyl)-3-(3″- hydroxy-4″-methoxyphenyl)-2-propen-1-one (4). (E)-1-(3′-hydroxy-2′-furanyl)-3-(3″-hydroxy-4″-methoxyphenyl)-2-propen-1-one (6) was obtained by acid hydrolysis of 4 in a 53.9% yield. This hetero-cyclic 2-propen-1-one was characterized on the basis of spectral data (IR and ¹H NMR), physicochemical properties, and conversion to a mono-O-acetyl derivative.     

Extraction of hydrochloric and nitric acid with 1-{[2-(2,4-Dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]-methyl)-1H-1,2,4-triazole and (RS)-1-(4-Chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-yl-methyl)-pentan-3-ol

Extraction of hydrochloric and nitric acid with 1-{[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]-methyl}-1H-1,2,4-triazole (propiconazole) and hydrochloric acid with (RS)-1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-yl-methyl)-pentan-3-ol (tebuconazole) was studied. It is established that extraction of acids proceeds with the formation of monosolvates as an exothermic process. Effective extraction constants of acids are evaluated. By means of the IR and ¹H NMR spectroscopy it was shown that the protonaccepting center of tebuconazole is N⁴ atom of the triazole ring.     

Synthesis of some cyclopentenones and crystal structure of 4-hydroxy-3,4-bis(4-methoxyphenyl)-5,5-dimethyl-2-cyclopenten-1-one

Abstract  

Sodium-hydroxide-catalyzed condensation of di-p-methyl- and di-p-methoxybenzil with acetone derivatives was investigated in methanol. Di- and trisubstituted products were obtained as cyclopentenones, while tetraaryl-substituted systems were isolated as cyclopentadienones. The structures of the products were identified by elemental analysis, infrared (IR), nuclear magnetic resonance (¹H NMR), and mass spectroscopy. The solid-state structure of 4-hydroxy-3,4-bis(4-methoxyphenyl)-5,5-dimethyl-2-cyclopenten-1-one was further studied by single-crystal X-ray diffraction analysis. The title compound crystallizes in an orthorhombic space group and intermolecular O–H···O and C–H···O hydrogen bonds stabilize the crystal lattice.     

POLY [N-(4-PYRIDINIUM DICHROMATE)-P-STYRENE SULPHONAMIDE] AS AN EFFICIENT REAGENT FOR OXIDATION OF ALCOHOLS

POLY [N-(4-PYRIDINIUM DICHROMATE)-P-STYRENE SULPHONAMIDE] is readily prepared. It is a stable, mild, and efficient oxidizing reagent that can be used for oxidation of different alcohols to their corresponding carbonyl compounds in approtic solvents. This polymer can be synthesized from the reaction between poly [N-(4-pyridyl)-p-styrene sulphonamide] and CrO ₃ in a minimum amount of water. The latter polymer was prepared by free radical polymerization of [N-(4-pyridyl)-p-styrene sulphonamide] by using azobis(isobutyronitrile) (AIBN) as an initiator. N-(4-pyridyl)-p-styrene sulphonamide was synthesized from commercial 4-vinyl benzene sulphonic acid sodium salt and 4-amino pyridine. POLY [N-(4-PYRIDINIUM DICHROMATE)-P-STYRENE SULPHONAMIDE] can oxidize both aliphatic and aromatic alcohols in good yields at a temperature of 38°C and in CH ₂ Cl ₂ as solvent. One advantage in using this reagent is the mild condition of the reaction system. The synthesized compounds including polymeric reagent and carbonyl compounds were identified by HNMR and IR spectroscopy.     

Kinetic Study of the Degradation of PAC-1 and Identification of a Degradation Product in Alkaline Condition

A selective and validated stability-indicating LC method was developed for the kinetic study of the degradation of PAC-1, which was carried out in aqueous solutions at 37, 60, 80 and 100 °C with pH 1.5–9.0. Separation was performed on a Kromasil C₁₈ column with acetonitrile–water–fomic acid (30:70:0.1, v/v/v) as mobile phase with a flow rate of 1.0 mL min⁻¹ at 281 nm. The degradation rate obtained indicated a first-order reaction law and the activation energy (E _a) was calculated. The results showed that temperature and pH values were significant factors affecting the degradation of PAC-1. An unknown degradation product in alkaline condition was isolated using a reverse-phase semi-preparative LC system. The structure of the degradation product is identified as 2-hydroxy-3-(2-propenyl)-[[2-hydroxy-3-(2-propenyl)phenyl]methylene]hydrazone utilizing the ¹H NMR, ¹³C NMR, IR and Q-TOF-MS techniques.

     

Synthesis and spectral analysis of (±)-cis-N-[1-(2-hydroxy-2-phenyl-ethyl)-3-methyl-4-piperidyl]-N-phenylpropanamide and (±)-cis-N-[1-(2-hydroxy-1-phenylethyl)-3-methyl-4-piperidyl]-N-phenylpropanamide

Treatment of (±)-cis-N-(3-methyl-4-piperidyl)-N-phenylpropanamide (2) with styrene oxide (1) yielded a mixture of (±)-cis-N-[1-(2-hydroxy-2-phenylethyl)-3-methyl-4-piperidyl]-N-phenylpropanamide (3) and (±)-cis-N-[1-(2-hydroxy-1-phenylethyl)-3-methyl-4-piperidyl]-N-phenylpropanamide (4) . The structure of compound 3 was confirmed by an unambiguous synthesis via (±)-cis-N-[1-(2-oxo-2-phenylethyl)-3-methyl-4-piperidyl]-N-phenylpropanamide (6) . The proton and carbon-13 resonances of compounds 3 and 4 were assigned with the aid of two-dimensional heteronuclear correlation experiments.     

Synthesis and properties of <Emphasis Type="Italic">O,O</Emphasis>-dialkyl [1-hydroxy-3-(dialkylamino)-2,2-dimethylpropyl]phosphonates

O,O-Dialkyl [1-hydroxy-3-(dialkylamino)-2,2-dimethylpropyl]phosphonates were prepared for the first time. By means of NMR ¹H, IR spectroscopy and quantum-chemical calculations the presence in them of various H-bonds was established. In the crystalline state P=O…HO intermolecular hydrogen bonds favor the formation of cyclic dimer associates D _P=O. In the liquid state and concentrated solutions P=O…HO and N…HO intermolecular hydrogen bonds cause the formation of cyclic dimer associates D _P=O and D_N, and intramolecular hydrogen bonds provide the existence of different conformations of the monomer form MN, the most stable among them with the non-strained six-membered …NCCCOH… ring.     

Synthesis, Structure, and Growth-Regulating Activity of 1-(6,9-Dimethyl-1,4-dioxa-8-azaspiro[4,5]dec-8-ylmethyl)-1H-pyridin-2-one

1-(6,9-Dimethyl-1,4-dioxa-8-azaspiro[4,5]dec-8-ylmethyl)-1H-pyridin-2-one was prepared by the Mannich reaction from 6,9-dimethyl-1,4-dioxa-8-azaspiro[4,5]decane, formaldehyde, and pyridin-2-one in alcohol. Its structure was proved by NMR spectroscopy. This compound exhibits a growth-regulating activity.     

Establishment of the configuations of hexahydro-4-(4-ethoxycarbonyl-butyl)-3a-hydroxy-2-oxo-1H-thieno[3,4-d]imidazoles from PMR spectral data

The configurations of isomeric hexahydro-4-(4-ethoxy-carbonylbutyl)-3a-hydroxy-2-oxo-1H-thieno[3,4-d]imidazoles were determined by PMR spectroscopy by means of angular and temperature dependences of the vicinal spin-spin coupling constants (SSCC).Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 540–543, April, 1987.     

Synthesis, characterization, and biological activities of some transition metal(II) complexes with the thiosemicarbazone derived from 4-[1-(4-methylphenylsulfonyl)-1H-indol-3-yl]but-3-en-2-one

A new 4-[1-(4-methylphenylsulfonyl)-1H-indol-3-yl]but-3-en-2-one thiosemicarbazone (HL) was synthesized derived from 4-[1-(4-methylphenylsulfonyl)-1H-indol-3-yl]but-3-en-2-one. Four transition metal(II) complexes of HL have been prepared. Elemental analysis, molar conductivity, IR, UV, ¹H NMR spectra, and TG-DTA have been used to characterize these complexes. The complexes have the general formula ML₂, where M = Zn, Cu, Co, and Ni. The ligand and its complexes have been studied for their possible biological activity including anti-inflammatory, antibacterial, and antitumour activity in vitro.     

Synthesis and Characterization of Archetypal Ladder-Like Dibutyloxotin Cluster Derived from Sterically Encumbered 4-[(<Emphasis Type="Italic">E</Emphasis>)-2-(4-hydroxy-5-methylphenyl)-1-diazenyl]benzoate

Reaction of Bu₂SnO with 4-[(E)-2-(4-hydroxy-5-methylphenyl)-1-diazenyl]benzoic acid in toluene yielded a tetranuclear tin cluster {[Bu₂Sn(O₂CC₆H₄(N=N(C₆H₃-4-OH-5-CH₃))-p)]₂O}₂·2EtOH (1). The complex 1 was characterized using IR spectroscopy, NMR, elemental analysis and single-crystal X-ray diffraction. The compound is a centrosymmetric tetranuclear bis(dicarboxylatotetrabutyldistannoxane) complex containing a planar Sn₄O₂ core in which two μ ₃-oxo O-atoms connect an Sn₂O₂ ring to two exocyclic Sn-atoms. The four carboxylate ligands display two different modes of coordination: syn–syn O, O′-bridging and mono atomic bridge. In the complex, the geometry around the tin atoms is distorted trigonal bipyramidal with an additional longer Sn···O contact.     

Etude de composés d'addition d'acides de Lewis,XXXIV [1] Composés d'addition de benzoquinone-1, 4 avec TiCl4

The adduct 1,4-benzoquine · TiCl₄ has been prepared in CH₂Cl₂ solution at about ?60°. Its IR. spectrum has been recorded at the same temperature. The experimental study of the vibrational frequencies has been completed by the calculation of the fundamental vibrations in the molecular plane, using Wilson's FG method, with slightly simplified models of 1,4-benzoquinone · TiCl₄ (13 masses) and 1,4-benzoquinone · 2 TiCl₄ (14 masses); analysis by use of internal and symmetry coordinates. An assignment of most of the observed bands is proposed and the conclusion is reached that the complex, when solid, is (1,4-benzoquinone · TiCl₄)_n. The force constants F(C? O) are 9,85 · 10⁵ dyne/cm for the quinone and 8,8 · 10⁵ dyne/cm for the disturbed carbonyl bond of the polymerized complex in the model proposed. At ordinary temperature in benzene solution of the components the adduct 1,4-benzoquinone. TiCl₄ · benzene precipitated; with the help of the models, the fundamental vibrations of its IR. spectrum have been assigned.