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The oxidation of naphthylcycloalkenes with hydrogen peroxide or MCPBA followed by acid catalyzed rearrangement of diol (epoxide), afforded a series of naphthylcycloalkanones in a very simple manner. The conditions allow preparation of naphthylcycloalkanones on a multigram scale.

Twenty-four 3- and/or 4-alkyl-substituted 1-aminonaphthalene-2-carbonitriles and their analogues were prepared and evaluated for growth-inhibiting activity against four phytopathogenic fungi: Fusarium culmorum, Alternaria brassicicola, Botrytis cinerea and Penicillium expansum. The results obtained were compared with the activity of a commercial fungicide. The highest fungistatic activity was revealed by amino nitriles having hydrogen atoms or only one short alkyl group (CH3, C2H5) at the 3- or 4-position of the naphthalene system. The minimum values of calculated EC50 and EC95 indexes were 1.1 and 5.1 mg litre-1, respectively. These values were considerably lower than those for the reference fungicide.

Cyclization of ethyl (E)/(Z)-[2-(1-cyclohexen-1-yl)cyclohexylidene]cyanoacetate (2) in cold concentrated sulfuric acid affords 10-amino-1,2,3,4,5,6,7,8-octahydrophenanthrene-9-carboxylic acid (4) and 3,5,6,7,8,8a-hexahydro-3-oxospiro-[1H-2-benzopyran-1,1′-cyclohexane]-4-carbonitrile (5). The o-amino acid 4 is employed in the synthesis of several 1,2,3,4,5,6,7,8-octahydrophenanthrene derivatives: the carboxylic acid 6, o-hydroxy carboxylic acid 7, and the amine 8. The lactone 5 undergoes decarboxylation on heating yielding a mixture of unsaturated nitriles 9 and 10 which are cyclized to the amine 8.

Cyclization and a rearrangement in concentrated sulfuric acid of 2-(4-substituted-phenyl)propylidenemalonodinitriles ( 1 ) into 1-amino-4-methyl-6-substituted-naphthalene-2-carbonitriles ( 5 ) appears to involve a series of steps such as ipso electrophilic attack of the protonated nitrile function on the para position of the phenyl group, opening of a spirobenzenium cation or its transformation, and ring reclosure to the naphthalene framework with participation of the secondary alkyl carbocation as an active electrophile.

Cyclization of ethyl (E)/(Z)-[2-(1-cyclohexen-1-yl)cyclohexylidene]cyanoacetate (2) in cold concentrated sulfuric acid affords 10-amino-1,2,3,4,5,6,7,8-octahydrophenanthrene-9-carboxylic acid (4) and 3,5,6,7,8,8a-hexahydro-3-oxospiro-[1H-2-benzopyran-1,1′-cyclohexane]-4-carbonitrile (5). The o-amino acid 4 is employed in the synthesis of several 1,2,3,4,5,6,7,8-octahydrophenanthrene derivatives: the carboxylic acid 6, o-hydroxy carboxylic acid 7, and the amine 8. The lactone 5 undergoes decarboxylation on heating yielding a mixture of unsaturated nitriles 9 and 10 which are cyclized to the amine 8.

Cyclization and a rearrangement in concentrated sulfuric acid of 2-(4-substituted-phenyl)propylidenemalonodinitriles ( 1 ) into 1-amino-4-methyl-6-substituted-naphthalene-2-carbonitriles ( 5 ) appears to involve a series of steps such as ipso electrophilic attack of the protonated nitrile function on the para position of the phenyl group, opening of a spirobenzenium cation or its transformation, and ring reclosure to the naphthalene framework with participation of the secondary alkyl carbocation as an active electrophile.

The reaction of arylidenemalonodinitriles with ethyl pyruvate and malonodinitrile affords in one step ethyl 3-amino-2, 4-dicyano-5-arylbenzoates (2) which are then used in synthesis of 3-amino-5-arylbenzoic acids (4).

Condensation of diphenylacetaldehydes and 1,1-diphenylacetones with malonodinitrile and cyclization of obtained aryl-ylidenemalonodinitriles in concentrated sulfuric acid leads to 1-amino-4-arylnaphthalene-2-carbonitriles. The benzannulation reaction is accompanied by a quasi-aromatic rearrangement. Preliminary tests of some synthesized aminonitriles have revealed their considerable biological activity against phytopathogenic fungi.

Ylidenemalonodinitrile (3,3-bis(4-chlorophenyl)-1-propene-1,1-dicarbonitrile), precursor of fungicidal compounds, synthesized in Knoevenagel reaction appears in solution in two forms, not separable by TLC chromatography. The ratio of both forms: that predicted from the Knoevenagel condensation scheme, and the second one, was preserved in the recrystallization cycle, as estimated from NMR spectra. It was assumed that forms corresponding to two tautomers originated by shifting a carbon–carbon double bond CAryl 2 HC–CHC(CN) 2 vs. Aryl 2 CCH–CH(CN) 2 ). Crystal structure analysis identified in the solid state only one tautomer corresponding to the first form dominating in solution. In the refined model of the crystal structure both CC bond and relevant hydrogen atoms were located univocally. Energy calculations carried out in vacuum and in solution confirmed energetic preference for tautomer present in the solid state.

Allicin--diallyl thiosulfinate--is the main biologically active component of freshly crushed garlic. Allicin was synthesized as described elsewhere and was tested for its inhibitory ability against jack bean urease in 20 mM phosphate buffer, pH 7.0 at 22 degrees C. The results indicate that allicin is an enzymatic inactivator. The loss of urease activity was irreversible, time- and concentration dependent and the kinetics of the inactivation was biphasic; each phase, obeyed pseudo-first-order kinetics. The rate constants for inactivation were measured for the fast and slow phases and for several concentrations of allicin. Thiol reagents, and competitive inhibitor (boric acid) protected the enzyme from loss of enzymatic activity. The studies demonstrate that urease inactivation results from the reaction between allicin and the SH-group, situated in the urease active site (Cys592).

The study has been carried out to evaluate the feasibility of synthesis of 1-methyl-, 2-methyl-, 1,2-dimethyl-, and 1-ethyl-2-methylphenanthrene through the annulation of the naphthalene system with the exploitation of the dicyanovinyl moiety of 2-naphthylalkylidenemalonodinitriles as an active electrophile in cold solutions of concentrated sulfuric acid. 2-(2-Naphthyl)propanal ( 3 ), 1-(2-naphthyl)propan-2-one ( 9 ), 3-(2-naphthyl)butan-2-one ( 14 ), and 3-(2-naphthyl)pentan-2-one ( 19 ) had been condensed with malonodinitrile to afford 2-naphthylalkylidenemalonodinitriles which were then cyclised to give 4-amino-1-methylphenanthrene-3-carbonitrile ( 5 ), 4-amino-2-methylphenanthrene-3-carbonitrile ( 11 ), 4-amino-1,2-dimethylphenanthrene-3-carbonitrile ( 16 ), and 4-amino-1-ethyl-2-metylphenanthrene-3-carbonitrile ( 21 ). The nitrile function has been removed from the aminonitriles, with the exception of 21 , through hydrolysis and decarboxylation in alkaline ethanolic solutions under elevated pressure (∼3 MPa) and temperature 220–230°C to give the respective 4-amino-methylphenanthrenes. Diazotisation of the phenanthreneamines and the reaction with hypophosphorus acid has lead to the methylphenanthrenes in moderate yields (50–52%).

The relative mutagenic potentials of 11-amino-16,17-dihydro-15 H -cyclopenta[a]phenanthrene, its 17-keto derivative, and 2- and 5-aminochrysene have been compared in Salmonella typhimurium TA98 and TA100 in the presence of a postmitochondrial liver preparation from Aroclor 1254 induced rats. The 11-amino hydrocarbon is a very weak mutagen (0.27 revertants/nmol), whereas the 11-amino-17-ketone is much more active (129 revertants/nmol). 2-Aminochrysene is the most mutagenic arylamine (∼500 revertants/nmol) among these compounds, but its 5-amino isomer is much less active (0.9 revertants/nmol). Possible reasons for these marked differences are suggested. Use of TA98 with over-expressing O -acetyltransferase (YG 1024) and deficient in this enzyme (TA98/l,8-DNP 6 ) with the 11-amino-17-ketone and with 5-aminochrysene clearly indicates the importance of this enzyme in their bioactivation, implying oxidation of the amino group to the hydroxylamine in both these compounds.

A synthesis of a variety of 5'-amino- m -terphenyls ( 6 ) and 3,5-diarylaminobenzenes through an efficient elimination of cyano groups from 5'-amino-4',6'-dicyano- m -terphenyls ( 4 ) using sodium hydroxide in ethanol at 220°, is described, The starting o-aminonitriles ( 4 ) are conveniently prepared from arylidenemalonodinitriles ( 1 ) and 1-arylethylidenemalonodinitriles ( 2 ). This strategy is applied for the synthesis of an aminoquaterphenyl ( 13 ) and a diaminoquinquephenyl ( 16 ).

The reaction of arylidenemalonodinitrilcs with a variety of acetophenone anils leading to 5′-amino-1,1′:3′,1″-terphenyl-2′,6′-dicarbonitriles has been investigated. The mechanism of the exchange reaction between arylidenemalonodinitrilcs and 1-arylethylideneaminobenzenes is proposed.

Substitution d'un chlore par un groupe tosyl par reaction de methyl-2(phenyl-2-, t-butyl-2-) dichloro-3,3 acrylonitriles avec le p-toluenesulfinate de sodium

Chelating properties of 1,3-bis(2-hydroxyhexafluoro-2-propyl)benzene (1,3-BHPB) and 1,4-bis(2-hydroxyhexafluoro-2-propyl)benzene (1,4-BHPB) have been investigated. We reported previously on the synthesis of dimethyl sulfoxide complexes with 1,3-BHPB and 5-perfluoroalkyl-substituted-1,3-BHPB [1]. Their structure was presented as 1:1 complexes involving chelation of one molecule of Me 2 SO by two hydroxy groups of a molecule of 1,3-BHPB. On the basis of X-ray investigation of 1,3-BHPB-Me 2 SO complex a revised linear structure is assigned to this compound. Both oxygen atoms of 1,4-dioxane and 1,4-benzodioxane are chelated in similar manner by 1,3-BHPB to afford stable complexes with m.p. 65–66° and 44–46°, respectively. The ratio of 1,3-BHPB and dioxanes in these compounds (2:1) is estimated from 1 H-NMR spectra. In contrast with these complexes, 1,4- BHPB and 1,4-dioxane form a compound in 1:1 ratio (m.p. 98–99°). Pyridine and 1,3- or 1,4-BHPB furnishes 1:1 complexes with m.p. 60° and 65–66°, respectively. The BHPB-pyridine complexes are recrystallized from petroleum ether and afford well formed colorless crystals which sublime in vacuo. 1,4-BHPB and Me 2 SO afford a 1:1 complex with m.p. 104°.