Synthesis of new polydentate tweezers ligands of amido-amine type

A series of new tweezers amido-amine ligands containing pyrrole, bipyrrole, and dipyrrolylmethane fragments were synthesized by reaction of 2-thioxothiazolidin-3-yl derivatives of α-pyrrolecarboxylic acids {5-[1-(5-carboxy-3-methyl-4-phenyl-1H-pyrrol-2-yl)-1-methylethyl]-4-methyl-3-phenyl-1H-pyrrole-2-carboxylic acid, 5-[(5-carboxy-3-methyl-4-phenyl-1H-pyrrol-2-yl)phenylmethyl]-4-methyl-3-phenyl-1H-pyrrole-2-carboxylic acid, 5-(5-carboxy-3-methyl-4-phenyl-1H-pyrrol-2-yl)-4-methyl-3-phenyl-1H-pyrrole-2-carboxylic acid, and 3,4-dimethyl-pyrrole-2,5-dicarboxylic acid} with o-phenylenediamine. All compounds obtained were characterized by elemental analysis, NMR and mass spectra.     

Hydrogenolysis of 7-phenyltricyclo[4.1.0.0<Superscript>2,7</Superscript>]heptan-1-carboxylic acid. Synthesis of ketones with tricyclo[4.4.0.0<Superscript>2,7</Superscript>]decane and tricyclo[5.4.0.0<Superscript>2,8</Superscript>]undecane skeletons

Hydrogenation of 7-phenyltricyclo[4.1.0.0^2,7]heptane-1-carboxylic acid over Raney nickel occurred in the syn-stereoselective fashion to give anti-7-phenylbicyclo[3.1.1]heptane-exo-6-carboxylic acid. The latter was used to synthesize 4,5-benzotricyclo[4.4.0.0^2,7]dec-4-en-3-one and two isomeric higher homologs, 5,6-benzotricyclo[5.4.0.0^2,8]undec-5-en-3-and-4-ones.     

Synthesis of 1-(1,3-dialkyl-2-oxo-2,3-dihydro-1<Emphasis Type="Italic">H</Emphasis>-imidazo-[4,5-<Emphasis Type="Italic">b</Emphasis>]pyridin-5-yl)-5-oxopyrrolidine-3-carboxylic acids

Nitration of 2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-one gave its 5-nitro derivative which was subjected to alkylation with dimethyl sulfate, diethyl sulfate, and benzyl(dimethyl)phenylammonium chloride. The resulting 1,3-dimethyl-, 1,3-diethyl-, and 1,3-dibenzyl-5-nitro-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-ones were reduced to the corresponding 1,3-dialkyl-5-amino-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-ones, and the latter reacted with itaconic acid to produce 1-(1,3-dialkyl-2-oxo-2,3-dihydro-1H-imidazo[4,5-b]pyridin-5-yl)-5-oxopyrrolidine-3-carboxylic acids. 1-(2-Oxo-2,3-dihydro-1H-imidazo[4,5-b]pyridin-5-yl)-5-oxopyrrolidine-3-carboxylic acid was obtained by analogous reaction with 5-amino-2,3-dihydro-1H-imidazo[4,5-b]-pyridin-2-one.     

Synthesis of new 1-(3,4-dimethylphenyl)-1,5-dihydropyrazolo[3,4-<Emphasis Type="Italic">d</Emphasis>]pyrimidin-4-one derivatives

New substituted pyrazolo[3,4-d]pyrimidin-4-ones have been synthesized as a result of a series of transformations including hydrolysis of ethyl 5-amino-1H-pyrazole-4-carboxylates, cyclization of the carboxylic acids thus obtained to pyrazolo[3,4-d][1,3]oxazin-4(1H)-ones, and treatment of the latter with substituted anilines. The final pyrazolo[3,4-d]pyrimidin-4-one derivatives can also be synthesized from 5-(arylamido)-1H-pyrazole-4-carboxylic acids in the presence of a catalytic amount of anhydrous zinc(II) chloride.     

Synthesis of benzo[<Emphasis Type="Italic">f</Emphasis>]quinoline derivatives by three-component condensation of tetronic acid with naphthalen-2-amine and formaldehyde

New derivatives of benzo[f]furo[3,4-b]quinoline, spiro[benzo[f]quinoline-2,3′-furan], and benzo[f]-quinoline-2-carboxylic acid were synthesized with high selectivity by three-component condensation of tetronic acid with naphthalen-2-amine and formaldehyde.     

Synthetic approaches to physiologically active polycyclic compounds: VII. Synthesis of 2-(7-Hydroxybicyclo-[3.3.1]non-3-ylmethyl)propane-1,3-diol

2-(endo-7-Hydroxybicyclo[3.3.1]non-exo-3-ylmethyl)propane-1,3-diol was synthesized in seven steps starting from endo-7-hydroxybicyclo[3.3.1]nonane-exo-3-carboxylic acid. The title compound attracts interest as intermediate product for the synthesis of potential tubulin ligands.     

Synthesis of heterocycles from arylation products of unsaturated compounds: XVIII. 5-Arylfuran-2-carboxylic acids and their application in the synthesis of 1,2,4-thiadiazole, 1,3,4-oxadiazole,and [1,2,4]triazolo[3,4-<Emphasis Type="Italic">b</Emphasis>][1,3,4]thiadiazole derivatives

Arylation of furan-2-carboxylic acid or its methyl ester with arenediazonium chlorides in the presence of copper(II) chloride gave the corresponding 5-arylfuran-2-carboxylic acids or methyl 5-arylfuran-2-carboxylates. 5-Arylfuran-2-carbonyl chlorides reacted with potassium thiocyanate and then with 5-methyl-1,2-oxazol-3-amine to give 5-aryl-N-[3-(2-oxopropyl)-1,2,4-thiadiazol-5-yl]furan-2-carboxamides as a result of recyclization of intermediate isoxazolylthiourea derivatives. The reactions of 5-arylfuran-2-carbonyl chlorides with 5-(2-furyl)-1H-tetrazole involved opening of the tetrazole ring with elimination of nitrogen molecule and led to the formation of 2-(5-arylfuran-2-yl)-5-(2-furyl)-1,3,4-oxadiazoles. 3-Substituted 6-(5-arylfuran-2-yl)-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazoles were obtained by condensation of 5-arylfuran-2-carboxylic acids with 5-substituted 4-amino-4H-1,2,4-triazole-3-thiols in phosphoryl chloride.     

Reaction of Zinc Enolates Formed from 1-Aryl-2,2-dibromoalkanones and Zinc,with Substituted 2-Oxochromene-3-carbohydrazides

Zinc enolates formed from 1-aryl-2,2-dibromoalkanones and zinc react with N′-methyl-N′-phenyl- and N′-benzylidene-N-phenylhydrazides of 2-oxochromene-3-carboxylic acid to form the corresponding hydrazides of 1-alkyl-1-aroyl-2-oxo-1a,7b-dihydrocyclopropa[c]chromene-1a-carboxylic acid as a single geometric isomer.     

Synthesis of 6-Acyl-7-aryl-4,7-dihydrotetrazolo[1,5-<Emphasis Type="Italic">a</Emphasis>]pyrimidine-5-carboxylic acids and their methyl esters

6-Acyl-7-aryl-4,7-dihydrotetrazolo[1,5-a]pyrimidine-5-carboxylic acids and methyl 6-acyl-7-aryl-4,7-dihydrotetrazolo[1,5-a]pyrimidine-5-carboxylates were synthesized by fusion of 4-aryl-2,4-dioxobutanoic acids and their methyl esters, respectively, with 1H-tetrazol-5-amine and aromatic aldehydes. The reaction of methyl 2,4-dioxopentanoate with 1H-tetrazol-5-amine and 2-fluorobenzaldehyde in boiling acetic acid gave methyl 6-acetyl-5-hydroxy-7-(2-fluorophenyl)-4,5,6,7-tetrahydrotetrazolo[1,5-a]pyrimidine-5-carboxylate.     

Quantum chemical studies of pyrimidin-4-ones Part 6. On peculiarities of the reactions with nitrating agents of some carboxylic acids of the thieno[2,3-<Emphasis Type="Italic">d</Emphasis>]pyrimidin-4-one series and their esters

Quantum chemical calculations of the energies, electronic structures, and molecular geometries of 5-methyl-, 2,5-dimethyl-, 3,5-dimethyl-, and 2,3,5-trimethyl-4-oxothieno[2,3-d]pyrimidine-6-carboxylic acids; 5-methyland 3,5-dimethyl-2,4-dioxothieno[2,3-d]pyrimidine6-carboxylic acids; 5-methyland 3,5-dimethyl-4-oxo-2-thiothieno[2,3-d]pyrimidine-6-carboxylic acids; and their ethyl esters were performed in terms of the HF and DFT (B3LYP) approximations in the 3-21G basis set. The reactions routes with nitrating agents were examined, and the factors governing the direction of the reactions, the probability of their occurrence were determined. Selective ipso-substitution of the 5-methyl group by the nitro group at the C(5) atom of the thiophene fragment is hindered for all compounds studied. The reasons for the unfavorable ipso-substitution were discussed taking into account effects of solvents and substituents in positions 2, 3, and 6 of 6-carboxyand 6-ethoxycarbonyl-substituted thieno[2,3-d]pyrimidin-4-ones.     

Reaction of <Emphasis Type="Italic">N</Emphasis>-aryl-3-oxobutanethioamides with 2-amino-1,3-thiazole and 2-amino-1,3-benzothiazole

N-Aryl-3-oxobutanethioamides react with 2-amino-1,3-thiazole (2-amino-1,3-benzothiazole) in acetic acid to give mixtures of 7-methyl-5H-[1,3]thiazolo[3,2-a]pyrimidine-5-thione (2-methyl-4H-pyrimido-[2,1-b][1,3]benzothiazole-4-thione) and 5-arylimino-7-methyl-5H-[1,3]thiazolo[3,2-a]pyrimidines (4-arylimino-2-methyl-4H-pyrimido[2,1-b][1,3]benzothiazoles), whose ratio depends on the nature of the aryl substituent in the initial butanethioamide.     

Synthesis of Bisthiacalix[4]arene: Reaction of Piperazine with Monoacrylamide Derivative of <Emphasis Type="Italic">p</Emphasis>-<Emphasis Type="Italic">tert</Emphasis>-Butylthiacalix[4]arene

The reaction of acryloyl chloride with the monoamine derivative of p-tert-butylthiacalix[4]arene was used to synthesize p-tert-butylthiacalix[4]arene monoacrylamide in the 1,3-alternate conformation. The effect of the nature of the amine on the result of its Michael reaction with the synthesized p-tert-butylthiacalix[4]arene monoacrylamide was studied. The latter was reacted with piperazine to obtain bisthiacalix[4]arene with the macrocyclic fragments in the 1,3-alternate conformation.     

Conjugate halo- and mercuroazidation of 1-phenyltricyclo-[4.1.0.0<Superscript>2.7</Superscript>]heptane. Synthesis of a conformationally rigid α-amino acid with a bicyclo[3.1.1]heptane skeleton

1-Phenyltricyclo[4.1.0.0^2.7]heptane reacted with N-bromo-, N-chloro-, and N-iodosuccinimides and with mercury(II) acetate in the presence of sodium azide as external nucleophile to give conjugate addition products to the central C¹–C⁷ bicyclobutane bond with a norpinane structure, where the azido group and the phenyl were attached to the same carbon atom (C⁶). The bromo- and chloroazidation showed anti-stereo-selectivity, and the iodoazidation, moderate syn-stereoselectivity; the mercuroazidation afforded exclusively the corresponding syn-addition product. Hydro-, bromo- and chlorodemercuration of the mercury adduct with sodium tetrahydridoborate and elemental bromine and chlorine, respectively, did not involve the azido group, and the original configuration was retained. The reduction of the hydrodemercuration product with LiAlH₄ gave 6-exo-phenylbicyclo[3.1.1]heptan-6-amine which was transformed in three steps into conformationally rigid 6-endo-(acetamido)bicyclo[3.1.1]heptane-6-carboxylic acid.     

Copper,cobalt, and nickel complexes of azomethine compounds containing phenylazo group in the amine fragment: Syntheses,structures, and magnetic properties

The Cu, Ni, and Со complexes based on the following new azomethine compounds containing azobenzene groups in the ortho- or para-positions of the amine fragment are synthesized: 2-allyl-6-[(E)-[4-(E)-phenylazophenyl]iminomethyl]phenol (HL¹), 2-allyl-6-[(E)-[4-methyl-2-[(E)-phenylazo]-p-tolylazo] iminomethyl]phenol (HL²), 5-methoxy-2-[(E)-[4-[(E)-phenylazo]phenyl]iminoethyl]phenol (HL³), and 5-methoxy-2-[(E)-[4-methyl-2-[(E)-p-tolylazo]phenyl]iminomethyl]phenol (HL⁴). The structures of the complexes are determined by the data of IR and ¹Н NMR spectroscopy (for the azomethine compounds), X-ray absorption spectroscopy, and magnetochemistry. The coordination centers of all Cu complexes have a distorted square structure. A direct dependence of the geometry of the coordination polyhedron on the position of azobenzene groups in the amine fragments of the ligands is found for the Ni and Co complexes. The octahedral environment of the nickel and cobalt ions takes place in the case of the ortho-position of the amine fragment, whereas the square environment for the Ni complexes or the tetrahedral environment for the Co complexes is observed at the para-position. The molecular structures of two azomethines HL¹ and HL⁴ are determined by X-ray diffraction analysis (CIF files CCDC nos. 1552836 (HL¹) and 1552837 (HL⁴)).     

Study of reaction of reformatsky reagent prepared from methyl bromocyclopentanecarboxylate and zinc with 2-oxochromen-and 6-bromo-2-oxochromen-3-carboxylic acids <Emphasis Type="Italic">N</Emphasis>-arylamides

Reformatsky reagent prepared from methyl 1-bromocyclopentanecarboxylate and zinc reacted with 2-oxochromen-and 6-bromo-2-oxochromen-3-carboxylic acids N-arylamides yielding 3-aryl-1,1-tetramethylene-and 3-aryl-9-bromo-1,1-tetramethylene-2,3,4,4a,5,10b-hexahydro-1H-chromeno[3,4-c]pyridine-2,4,5-triones as single diastereomers.     

Synthesis of 6-acylpyrido[2,3-<Emphasis Type="Italic">d</Emphasis>]pyrimidine derivatives from 5-acetyl-4-aminopyrimidine hydrochlorides

Reaction of 2,6-disubstituted 5-acetyl-4-aminopyrimidine hydrochlorides with acetylacetone or benzoylacetone afforded new substituted 6-acylpyrido[2,3-d]pyrimidines. The reaction of these hydrochlorides with ethyl acetoacetate also proceeds according to the classical version of the Friedländer condensation to form the corresponding pyrido[2,3-d]pyrimidine-6-carboxylic acid esters.     

Reactions of Bi-, Tri-, and tetracyclic amines with succinic anhydride

Succinic anhydride reacted with cage-like amines {bicyclo[2.2.1]hept-5-en-exo-and-endo-2-yl-methanamines, 2-(bicyclo[2.2.1]hept-5-en-endo-2-yl)ethanamine, exo-5,6-epoxybicyclo[2.2.1]heptan-exo-2-yl-methanamine, tetracyclo[6.2.1.1^3,6.0^2,7]dodec-9-en-endo-4-ylmethanamine, 1-(bicyclo[2.2.1]heptan-2-yl)ethanamine, and 4-azatricyclo[5.2.1.0^2,6]dec-8-ene} to give the corresponding amido acids having a cage-like fragment. The latter were converted into carboximides by the action of hexamethyldisilazane in boiling benzene in the presence of zinc(II) chloride and then into epoxy derivatives. The structure of the newly synthesized compounds was confirmed by IR and NMR spectroscopy.     

Electrophilic heterocyclization of 6-alken(yn)ylsulfanyl-pyrazolo[3,4-<Emphasis Type="Italic">d</Emphasis>]pyrimidin-4(5<Emphasis Type="Italic">H</Emphasis>)-ones

6-Allylsulfanyl-1-arylpyrazolo[3,4-d]pyrimidin-4(5H)-ones react with iodine and sulfuric acid to give angular pyrazolothiazolopyrimidine derivatives. The reaction of 6-(prop-2-yn-1-ylsulfanyl)-1-(4-tolyl)-pyrazolo[3,4-d]pyrimidin-4(5H)-one with sulfuric acid gives angularly fused pyrazolo[4,3-e][1,3]thiazolo-[3,2-a]pyrimidin-4-one, whereas in the reaction with sodium methoxide linearly fused pyrazolo[3,4-d][1,3]-thiazolo[3,2-a]pyrimidin-4-one was formed. Linearly fused pyrazolo[3′,4′:4,5]pyrimido[2,1-b][1,3]thiazole derivatives were also obtained by reaction of 1-aryl-6-(3-phenylprop-2-en-1-ylsulfanyl)pyrazolo[3,4-d]pyrimidin-4(5H)-ones with sulfuric acid.     

Synthesis of fullerene C<Subscript>60</Subscript> monoadducts. Cyclopropanation of C<Subscript>60</Subscript> with sulfonium ylides

3′H-Cyclopropa[1,9](C₆₀-I_h)[5,6]fullerene-3′-carboxylic acid can be synthesized in a good yield by cyclopropanation of fullerene C₆₀ with 2-(dimethyl-λ⁴-sulfanylidene)acetates provided that the ester residue is readily hydrolyzable in acid medium.     

4-aryl-2-hydroxy-4-oxobut-2-enoic acids <Emphasis Type="Italic">N</Emphasis>-(2-pyridyl)amides in reactions with diazo compounds

Reactions of 4-aryl-2-hydroxy-4-oxobut-2-enoic acids N-(2-pyridyl)amides with diazomethane, diazoethane, diaryldiazomethanes, and diazofluorene lead to the formation of 2-alkoxy-4-aryl-4-oxobut-2-enoic acids N-(2-pyridyl)amides, 3-aroyl-5-methylpyrazole-4-carboxylic acids N-(2-pyridyl)amides, and 3-alkoxy-3-(2-aryl-2-oxoethyl)-2,3-dihydro-2-oxoimidazo[1,2-a]pyridines. The composition and structure of compounds obtained depend on the nucleophilic nature of the diazo compound and on the character of substituents in the aryl and pyridine parts of the substrate.