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In this work, we show that the fungal strain Graphium sp. FIB4 was able to use phenol as the sole carbon source. Higher degradation of phenol was accomplished by alginate-immobilized mycelial mass than by mycelial suspensions of Graphium sp. FIB4. Free mycelium exhibited higher degradation rates when compared with the alginate-immobilized mycelium in the presence of 14 mM of phenol or less. Above this concentration, degradation rates by free mycelium decreased and the immobilized mycelium showed higher values. The maximum degradation rate for 8 mM phenol was found to be 20.13 mg/l × h by free mycelia and 16.24 mg/l × h by immobilized mycelial mass in the presence of 18 mM phenol. When the fungus was grown on medium without phenol, catechol 1,2-dioxygenase activity was not detected. This enzyme activity was induced at phenol concentrations as low as 0.05 mM and up to 6 mM at 24 h incubation at 30 °C, suggesting that catechol was oxidized by the ortho type of ring fission. Addition of glucose reduced phenol consumption rate, and both substrates were used simultaneously. Glucose concentrations higher than 0.075% repressed the induction of phenol oxidation by Graphium sp. FIB4 grown on glucose. But glucose did not fully repress utilization of phenol by phenol-pre-induced cells. Immobilization and addition of calcium and barium ions were detrimental to the stability of catechol 1,2-dioxygenase activity and phenol degradation by Graphium sp. FIB4.

The cell culture approach to the study of the nervous system attempts to reduce cellular complexity to various extents and to characterize the influences of extrinsic molecules on the cell population under study. To date, the main source of culture model systems to explore CNS function and dysfunction is fetal brain material from experimental animals, typically rodents. We have developed primary microglial cell cultures and focused on the concentration-dependent effects of different amino acids and growth promoting additives on microglial morphology and function. We used Basal Medium Eagle (BME) with 1g/L of glucose instead of Dulbecco's modified Eagle medium (DMEM) as serum-free condition, since BME does not contain L-Glycine (Gly) and L-Serine (Ser), and investigated the effects of these two amino acids on microglial morphology and functions by adding various concentrations of the amino acids to BME and different concentrations of ascorbic acid (10–75 μg/ml), hydrocortisone (1–7.5 nM) and DL-α-tocopherol (0.01–0.5 μg/ml) as growth promoters. Under Gly/Ser-free, serum-free condition, and growth promoters-free conditions, the majority of rat microglial cells displayed round morphology, whereas in the presence of 5 μM Gly and 25 μM Ser, which correspond to the concentrations of Gly and Ser in the cerebrospinal fluid, they extended multiple branched processes and formed clusters of rough endoplasmic reticulum. Ascorbic acid (25 μg/ml), 2.5 nM hydrocortisone and 0.05 μg/ml of DL-α-tocopherol elicited the highest level of microglial activation as measured by an increased expression of MHC class-I and MHC class-II antigens. Neuron culture experiments using the conditioned medium obtained from the different microglial culture conditions indicate neurotoxic and neurotrophic effects depending on the concentrations of amino acids as well as on the concentration of the growth promoters. These findings suggest that resting ramified microglial cells with neurotrophic activity can be induced with the combination of BME medium and small amounts of extracellular matrix growth promoters.

The reaction of 2-(2 pyridytcarbonyl)benzoic acid with thionyl chloride affords an unexpected product of the intramolecular acylation of the pyridine nitrogen atom, namely, 6,11-dioxo-6,11-dihydrobenzo[blquinotizinium chloride. At the same time, 2-(2-quinotylcarbonyl)benzoic acid forms the expected cyclic acid chloride, namely, 3-(2-gitinotyl)-3-chlorophthalide in this reaction. Both compounds acylate ammonia and primary amines, including those with bulky alkyl groups (tert-butyl, 1-adamantyl, and 1,1,3,3-tetramethylbutyl) with the formation of 2-R-3-hydroxy-3-(2pyridyl- or 2-quinolyl)isoindolines. The protonation of the pyridine nitrogen atom of N-(1,1,3,3-tetramethylbutyl)-2-(2pyridylcarbonyl)benzamide, obtained in the open amide form, is accompanied by the closing of the isoindotinone ring; the deprotonation is accompanied by ring opening.

When 2,5-dihydroxy-3,4,6,7-tetrachloro-2,3-dihydrobenzo[b]furan interacts in acetone with thiosemicarbazide or its 4-methyl or 4-phenyl derivative, the respective products are 5-(2,5-dihydroxy-3,4,6-trichlorophenyl)-2-(isopropylidenehydrazino)thiazole and -3-R-2-(isopropylidenazino)thiazolines, respectively. It has been shown that hydrolysis of these compounds forms 3-amino-5-(2,5-dihydroxy-3,4,6-trichlorophenyl)-2-imino(or 2-R-imino)thiazolines. These products of hydrolysis and their predecessors are oxidized to the corresponding 2-hetaryl-substituted 3,5,6-trichloro-1,4-benzoquinones.

In the reaction of 2-(2-pyridylcarbonyl)benzoyl chloride, which exists in the form of 6,11-dioxo-6,11dihydrobenzo[b]quinolizinium chloride, with p-nitroaniline, 2-(4-nitrophenylimino)-6, 11-dihydro-2H-benzo-[b]quinolizine-6, I I -dione is unexpectedly formed. When it reacts with water or methanol there is an opening of the quinolizine ring and aromatization of the quinoid fragment with the formation of 2-[4-(4nitrophenylamino)-2-pyridylcarbonyl]benzoic acid or its methyl ester. Under the action of antimony pentachloride, 2- 2-quinolylcarbonyl)benzoylchloride-3 (2-quinolyl)-3-chloro- 1, 3-dihydrobenzo[c]furan-1 -one -is converted to 3-(2-quinolyl)-1,3-dihydrobenzo[c]furan-1-on-3-ylium hexachlorantimonate, which undergoes isomerizing recyclization upon heating to 7,12-dioxo-7,12-dihydrobenzo[b/ hexachloroantimonate. The latter enters into an analogous reaction with p-nitroaniline, thereby forming 5-(4-nitrophenylimino)-7,12-dihydro-5H-dibenzo[b,f]quinolizine-7,2-dione.

4-Benzoylnicotinoyl and 3-benzoylisonicotinoyl chlorides have been found to exist in cyclic forms (3-chloro-3-phenyl-6(or 5)-azaphthalides), and their benzyl-amides also occur as the cyclic forms (azaisoindolinones). The tert-butylamides of both acids are obtained in the open amide forms. It has been shown by PMR that N-tert-butyl-4-benzoylnicotinamide displays a greater tendency to undergo closure of the isoindolinone ring (KT = 0.24 in CD3OD) than does N-tert-butyl-3-benzoylisonicotinamide (KT = 0).

The electron-impact mass spectra of various derivatives of 2-aroylbenzamides were studied. The principal pathways of fragmentation of the open and ring isomeric forms were described on the basis of an analysis of the high-resolution spectra and the DADI spectra. It is shown that peaks of ions formed in the fragmentation of the ring form, the intensities of which decrease as the volume of the substituent increases, are observed in the spectra of compounds with substituents R1 = H, CH3, and C2H5. Thermal isomerization of the ring form was proved on the basis of a study of the temperature effect on the intensities of the peaks of ions due to fragmentation of the open and ring forms when the samples are introduced through an inlet cylinder.

The structures of 1-cyanoacetyl-2-alkylhydrazines and their ring isomers, viz., 1-alkyl-5-amino-3-pyrazolones, to which they are readily cyclized, were investigated by IR, UV, and PMR spectroscopy.

The ring isomer of the corresponding acyl derivative — 5,9-dioxo-17a-hydroxy-9,10,11,16-17,17a-hexahydro-5H-dibenzo[d,e,h]phthalazino[2,3-a]cinnoline — was obtained by acylation of 1,2,3,4-tetrahydrophthalazine with anthraquinone-1-carboxylic acid chloride. Treatment of the product with thionyl chloride or hydrogen chloride gave the deeply colored 5,9-dioxo-9,10,11,16-tetrahydro-5H-dibenzo[d,e,h]phthalazino[2,3-a]cinnolinium chloride. The possibility of charge transfer between the chloride anion and the phthalazinium cation is examined as a reason for the deep coloration. This compound very readily undergoes hydrolytic oxidative cleavage at the C-N bond to give 2-(2-formylbenzyl)-3,7-dioxo-2,3-dihydro-7H-dibenzo[d,e,h]cinnoline.

N-Unsubstituted and N-monosubstituted amides of 2-(4-dimethylaminobenzoyl)benzole acid exist in the chain form of 3-hydroxyisoindolinones in the crystalline state and in solutions in dioxane, whereas the tautomeric amide ? hydroxyisoindolinone equilibrium occurs (except for the methyl derivative) in more polar solvents. The analogous N-(1-adamantanyl)amide exists in the open form and does not undergo cyclization under alkaline catalysis conditions; protonation of the dimethylamino group is accompanied in all cases by splitting out of water to give compounds with a quinoid structure; an equilibrium between the protonated and quinoid forms, which is shifted markedly to favor the latter, is observed for some compounds.

By the interaction of 2, 5-dihydroxy-3, 4, 6, 7-tetrachloro-2, 3-dihydrobenzo(bjfuran with salts of N-monosubstituted dithiocarbamic acids, followed by oxidation of the resulting products by benzoquinone, 3-substituted S-(3,5,6-trichloro-1,4-benzoquinon-2-yl)thiazoline-2-thiones have been obtained. An alternative method of synthesis is also proposed, including reaction of the original benzofuran with N-substituted N',N'-dimethylthioureas, cyclization of the resulting thiouronium salt to form 3-substituted 5-(2, S-dihydroxy-3, 4, 6-trichlorophenyl)-2-dimethylattiinothiazolium cations, treatment of these cations with hydrogen sulfide, and subsequent oxidation of the hydroquinone fragment to quinone.

The reaction of thiourea of N-substituted thioureas with 2-(2-N,N-diethylaminoethenyl)-3,5,6-trichloro-1,4-benzoquinone leads, through the formation of 2,5-dihydroxy-3,4,6,7-tetrachlorocoumaran, to 2-amino-5-(2,5-dihydroxy-3,4,6-trichlorophenyl)thiazoles (which exist in the form of betaines), the oxidation of which leads to 2-amino-5-(3,5,6-trichloro-1,4-benzoquinon-2-yl)thiazoles.

An original method has been developed for the synthesis of a number of pyridyl- and quinolylcarbonylarenecarboxylic acids by condensing anhydrides of aromatic dicarboxylic acids with picolinic and quinaldic acids. The characteristics of the IR spectra of the compounds synthesized are given, and their ring-chain equilibrium transformations are discussed. It has been shown that the protonation of the nitrogen atom of the heterocycle stabilizes the cyclic form.

The electron impact mass spectra and DADI spectra of anils of N-alkyl-2-benzoylbenzamides and 2-alkyl-3-arylamino-3-phenylisoindolinones isomeric to them, as well as certain 2-substituted 3-alkyl(aryl)amino-3-phenylisoindolinones, were studied. The main direction of the decomposition were described. It was established that transition from 2-aroylbenzamides to their imines leads to a substantial stabilization of the cyclic isomeric form. A stabilization of the cyclic form with increasing steric volume of the alkyl substituent at the azomethine nitrogen atom was noted. The presence of a phenyl substituent at the nitrogen atom of the amide group destabilizes the cyclic form. A mechanism of isomerization explaining these phenomena is proposed.

2-(2-Aminophenyl)-4-hydroxy-3-phenyl-1-isoquinolone was unexpectedly obtained in the reaction of 3-(α-bromobenzyl)-3-bromophthalide with o-phenylenediamine. The isoquinolone in chloroform undergoes autooxidation by air oxygen to give 2-(2-aminophenyl)-3-hydroperoxy-3-phenyl-1,4-dioxo-1,2,3,4-tetrahydroisoquinoline, which is subsequently converted to N-(2-benzamidophenyl)phthalimide. A mechanism is proposed for the rearrangement of the hydroperoxide.

Imines of N-monosubstituted 2-benzoylbenzenesulfonamides or their ring isomers, viz., 3-amino-3-phenylbenzoisothiazoline 1,1-dioxides, were synthesized by condensation of the dilithium derivatives of N-monosubstituted benzenesulfonamides with benzonitrile. Interconversions of the isomers were realized for the N-phenyl derivative. The introduction of bulky isopropyl or tert-butyl substituents at the sulfonamide nitrogen atoms stabilizes the open structure. The ring isomers of the N-acylimines, viz., 3-acylamino-3-phenylbenzoisothiazoline 1,1-dioxides, are formed exclusively in the acylation of both the open and ring isomers.

Abstract: It was established by IR, UV, and PMR spectroscopy that N-unsubstituted and N-(n-alkyl, sec-alkyl, or aryl)-2-(2-imidazolylcarbonyl)benzamides obtained from imidazo[1,2-b]isoquinoline-5,10-dione and ammonia or amines have the 3-hydroxy-3-(2-imidazolyl)isoindolinone chain structure in the crystalline state and in solutions in dimethyl sulfoxide. The N-(tert-alkyl)amides exist in the open form under these conditions. Protonation of the imidazole nitrogen atom in the N-(tert-butyl)amide molecule leads to its cyclization to 3-hydroxyisoindolinone.

Reaction of chloranil with excess pyridine gives the poorly stable 2,5-di(N-pyridinium)-3,6-dichloro-1,4-benzoquinone dichloride which is readily hydrolyzed to give the bisbetaine of 2,5-di(N-pyridinium)-1,4-benzoquinone-3,6-dioxide. Treatment with acid gives its mono- and bisprotonated derivatives as the perchlorate and dibromide and bromination gives the betaine 2-bromo-2,5-di(N-pyridinium)-5-cyclohexene-1,3,4-trione-6-oxide perbromide. The reaction of malonodinitrile with 2,5-di(N-pyridinium)-3,6-dichloro-1,4-benzoquinone dichloride in situ gives the poorly stable bisbetaine of 2,5-di(N-pyridinium)-7,7,8,8-tetracyanoquinodimethane-3,6-dioxide.

In the reaction of 2-dimethylamino-5-(3,5,6-trichloro-1,4-benzoquinon-2-yl)thiazole with primary and secondary amines, the chlorine atom at the 5-position of the benzoquinone ring is substituted, according to the 13C NMR spectroscopy data, by an amino group. The chemical, spectroscopic, and electrochemical properties of 5-(5-amino-3,6-dichloro-1,4-benzoquinon-2-yl)-2-dimethylaminothiazoles were revealed.

In reaction with potassium butylxanthate and sodium tert-butyltrithionate, 2,5-dihydroxy-3,4,6,7-tetrachloro-2,3-dihydrobenzo[b]furan forms the products from nucleophilic substitution of a chlorine atom, i.e., O-butyl S-(2,5-dihydroxy-4,6,7-trichloro-2,3-dihydrobenzo[b]furan-3-yl) xanthate and S-tert-butyl S′-(2,5-dihydroxy-4,6,7-trichloro-2,3-dihydrobenzo[b]furan-3-yl) trithiocarbonate respectively. Recyclization of the xanthate in concentrated sulfuric acid gave 4-(2,5-dihydroxy-3,4,6-trichlorophenyl)-1,3-dithiol-2-one, which was oxidized by iron trichloride to the corresponding benzoquinone. Cyclization of the trithiocarbonate in the presence of trifluoroacetic and p-toluenesulfonic acid led to 7-hydroxy-5,6,8-trichloro-3a,8b-dithiolo[4,5-b]benzo[d]furan-2-thione.

In reaction with primary aromatic amines, 3-aryl-3-chloroperinaphthalides form 3-aryl-3-arylaminoperinaphthalides. The ring—chain tautomerism of these compounds has been studied and isomerization has been realized in the 2,3-diaryl-3-hydroxy-2,3-dihydro-1H-benz[d,e]isoquinolin-1-ones.

In reactions with 3-chloro-3-phenylphthalides, aromatic amines attack the primary and tertiary carbon atoms to give a mixture of 2-aryl-3-hydroxy-3-phenylisoindolinones and 3-arylamino-3-phenylphthalides. The effect of the nucleophilicity of the amine on the primary direction of attack was studied. The ring-chain tautomerism of 3-arylamino-3-phenylphthalides and 2-benzoylbenzoic acid arylimines was studied by IR and UV spectroscopy.

It was found that, depending on the structure of substituents R1 and R2, the nucleophilic agent in the reaction of 2-R1-3-chloro-3-phenylisoindolinones II with primary amines (R2NH2) and diethylamine primarily attacks the primary or tertiary carbon atom of the isoindolinone (II) molecule to give 2-R1-3-amino-3-phenylisoindolinones (III), substituted imines of 2-benzoyl-benzamides (IV), and their cyclization products — 2-R2-3-amino-3-phenylisoindolinones (V). The structures of the synthesized 2-substituted 3-alkylamino- and 3-arylamino-3-phenyliso-indolinones were established by IR spectroscopy and acid hydrolysis to 2-substituted 3-hydroxy-3-phenylisoindolinones.

The rate constants of cyclization and the constant of ring-chain equilibrium of N-isopropyl-2-cyano-substituted benzamide and benzamide and benzenesulfamide by the methods of PMR and IR spectroscopy, and it was shown that in the transition from 2-cyanobenzamides to 2-cyanobenzenesulfamides a sharp destabilization of the cyclic isomeric form is observed; however, the cyclization of 2-cyanobenzenesulfamides proceeds at a higher rate than the cyclization of 2-cyanobenzamides.

A number of N-monosubstituted 2-cyanobenzenesulfonamides (A) and their chain isomers — 2-substituted 3-iminobenzothiazoline 1,1-dioxides (B), which are formed as a result of intramolecular nucleophilic addition of the sulfonamido group to the C=N bond - were synthesized by acylation of primary amines with 2-cyanobenzenesulfonyl chloride. The inter conversions of the isomers -A ? B under alkaline-catalysis conditions and B?A under thermal conditions — were accomplished for the first time. The influence of the electronic and steric effects of the substituent attached to the nitrogen atom on the relative stabilities of the open and chain isomers was ascertained. The A?B equilibrium constants in solutions in a mixture of dioxane and triethylamine were determined by IR spectroscopy.

It has been established that 2-(tert-butyl)-3-hydroxy-3-(4-chlorophenyl)isoindolinone and N-(tert-Alkyl)-2-aroylbenzamides are dealkylated in concentrated sulfuric acid to give 3-hydroxy-3-arylisoindolinones. The reaction is realizable. only when there is a tert-alkyl group attached to the nitrogen atom. The reaction mechanism is discussed on the basis of data on the change with time in the electronic spectra of the investigated compounds in concentrated sulfuric acid and a comparison with the spectra of model structures.

The ring-chain tautomeric equilibrium constants (K) of aryl-ring-substituted 3-arylamino-3-phenylphthalides in dioxane were measured by UV spectroscopy. A satisfactory linear correlation between log K/K0 and the s+ constants of the substituents in the aryl ring was found.

A method has been developed for the synthesis of (3,5,6-trichloro-1,4-benzoquinone-2-yl)chloroacetaldehyde by the oxidative ring opening of 2,5-dihydroxy-3,4,6,7-tetrachlorocoumaran with nitrogen oxides. The ion-radical salt of (3,5,6-trichloro-1,4-benzoquinone-2-yl)chloroacetaldehyde with N,N,N',N'-tetramethyl-p-phenylenediamine (1:1) has been synthesized. The reaction of 2,5-dihydroxy-3,4,6,7-tetrachlorocoumaran-3-yl) with pyridine gave N-(2,5-dihydroxy-4,6,7-trichlorocoumaran-3-yl)pyridine chloride, which is also formed from the opening of the coumaran ring.

It has been established by IR spectroscopy that the N,N'-dimethylhydrazides of 2-aroylbenzoic and benzil-o-carboxylic acids, with the exception of 2-mesitoylbenzoic acid, have the ring structure of 4-aryl- or 4-benzoyl-4-hydroxy-2,3-dimethyl-3,4-dihydrophthalazinones. The action of electrophilic agents on 4-hydroxy-2,3-dimethyl-4-phenyl-3,4-dihydrophthal-azinone under mild conditions leads to N(3)-demethylation with the formation of 2-methyl-4-phenylphthalazinone.

Three crystalline modifications of the N-chloroacetyl derivative were obtained in the chloroacetylation of 2-(2-aminophenyl)-4-hydroxy-3-phenyl-1-isoquinolone. It was established by IR spectroscopy that they differ with respect to isomeric composition and the character of the intermolecular hydrogen bonds. For the first time, both keto-enol tautomeric forms were isolated in individual form in the 4-hydroxy-1-isoquinolone series.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.