Phthalocyanines and related compounds: XLIII. Synthesis of poly[phenyl(alkyl)sulfanyl]-substituted phthalonitriles and some phthalocyanines based thereon

Nucleophilic substitution of chlorine atoms in tetrachlorophthalonitrile by benzene- and alkanethiols in the presence of a base was studied at different reactant ratios. The substitution is characterized by complete regioselectivity: the chlorine atom in position 4 of tetrachlorophthalonitrile is replaced first; next follows replacement of the 5-chlorine atom. The reactions of tetrachlorophthalonitrile with nucleophiles at ratios of 1:2 and 1:4 lead to the formation of the corresponding 3,6-dichloro-4,5-bis[phenyl(alkyl)sulfanyl]- and tetrakis[phenyl(alkyl)sulfanyl]phthalonitriles. The latter were converted into metal complexes of [phenyl-(alkyl)sulfanyl]-substituted phthalocyanines which absorb in the red and near-IR regions of the electronic spectra.     

Phthalocyanines and related compounds: XLV. Nucleophilic substitution of chlorine in tetrachlorophthalonitrile: Synthesis of aryloxy-aubstituted phthalonitriles and phthalocyanines derived from them

Nucleophilic substitution of chlorine in tetrachlorophthalonitrile by the reaction with aryloxy anions is studied. Depending on the reactant ratio, the products of substitution of one, two, and/or three chlorine atoms are formed. Their tetramerization gives aryloxychloro-substituted phthalocyanines having the absorption band in the near-IR range.     

Synthesis of 5-(5-amino-3,6-dichloro-1,4-benzoquinon-2-yl)-2-dimethylaminothiazoles and their properties

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.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 410–415, March, 1991.     

Azaindole derivatives. 67. Synthesis of N-substituted 1-benzyl-4-methyl-5-cyano-6-amino-7-azaindoles

N-substituted 1-benzyl-4-methyl-5-cyano-6-amino-7-azaindoles have been synthesized from the respective 1-benzyl-4-methyl-5-cyano-6-chloro(and 6-hydroxy)-7-azaindoles. The effect of the 5-cyano group on the oxidation-reduction processes accompanying nucleophilic replacement of chlorine in 6-chloro-7-azaindoles by primary and secondary amines has been considered. 7-Azaindoline compounds were dehydrogenated by chloranil to N-substituted 1-benzyl-4-methyl-5-cyano-6-amino-7-azaindoles.For communication 66, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 91–96, January, 1986.     

Erbium and ytterbium complexes with the phtalocyanines with aryloxy and chlorine substituents

By nucleophilic substitution of chlorine atoms in tetrachlorophthalonitrile by phenoxy- or 1-naphthyloxy groups aryloxychlorophthalonitriles were synthesized and on this basis respective substituted erbium and ytterbium phthalocyanines with chloro-, acetate- or acetylacetonate anions as extra ligands. The compounds obtained were characterized by elemental analysis, chromato-mass spectrometry, IR, ¹³C NMR, and electronic spectroscopy.     

Synthesis of the Substituted 3‐Cyclobutene‐1,2‐diones

A convenient synthesis of the novel squaric acid derivatives is reported. Unsymmetrically substituted 3,4‐diamino‐3‐cyclobutene‐1,2‐diones and 3‐amino‐4‐hydroxy‐3‐cyclobutene‐1,2‐diones were prepared by interaction of diethyl squarate with different nucleophilic reagents such as alkali, primary and secondary amines and amino acids. Substituted 3‐amino‐4‐aryl‐3‐cyclobutene‐1,2‐diones were synthesized by interaction of squaryl dichloride with different arenes followed by arylsquarylation of amines. Efficient procedures were developed for consequent substitution of ethoxy groups in diethyl squarate and chlorine atoms in squaryl dichloride. The synthesized compounds have a great potential of bioactivity and are useful objects for biomedicinal screening.     

Reactions of 4-chloro-6-oxo-2,3-dihydro-5-azabenzofurans with amines

The reaction of 7-nitro- and 7-unsubstituted 4-chloro-6-oxo-2,3-dihydro-5-azabenzofurans with primary and secondary amines proceeds with substitution of the chlorine atoms by amine residues and with recyclization of the compounds to 5- and 7-azaindoline derivatives.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No, 10, pp. 1311–1313, October, 1973.We thank Yu. N. Sheinker, E. M. Peresleni, L. M. Alekseeva, N. A. Zosimova, and Yu. I. Pomerantsev for their assistance in conducting the spectral investigations.     

Untersuchungen an Stickstoff-Chlor-Verbindungen. VII. Neue N-Perchlorylverbindungen durch Ammono- und Aminolyse von Dichlorheptoxid

Studies on Nitrogen Chlorine Compounds. VII. New N-Perchloryl Compounds by Ammono- and Aminolysis of Dichlorine Heptoxide The reaction of dichlorine heptoxide with ammonia, primary and secondary amines leads to compounds belonging to the class of amides of perchloric acid. The remaining acidic hydrogen atoms on nitrogen could be replaced by metal cations. The compounds were characterized as far as possible by analysis, IR and ¹H-NMR spectroscopy. The changing of the bond character between nitrogen and chlorine depending on the substituents on nitrogen is discussed.     

Electrochemical Reduction of Pyridinic Herbicides Picloram and Clopyralid on a Mercury Pool Electrode

This paper presents the identification by GC/MS of the products obtained after the total reduction of picloram and clopyralid on a mercury pool electrode. The products found in the strongly acidic media reduction of picloram are 4‐amino‐3,5,6‐trichloro‐2‐pyridinecarboxaldehyde, 4‐amino‐3,5,6‐trichloro‐2‐pyridinecarbinol and 4‐amino‐3,5‐dichloro‐2‐pyridinecarboxylic acid; at pH 3–4 the first compound is substituted by 4‐amino‐3,5‐dichloro‐2‐pyridinecarboxaldehyde. For clopyralid 3,6‐dichloro‐2‐pyridinecarbinol was detected. Under the light of such products the overall reduction processes are discussed showing the partial reductive cleavage of chlorine atoms in both cases.     

Reactions of pyranylidenemethylpyrylium salts with ammonia and amines

Pyranylidenemethylpyrylium salts (1) react with ammonia to give pyranylidenepyridines as a result of the replacement of one of the oxygen atoms of 1 by nitrogen. Aliphatic primary amines react with 1 by replacing both of the oxygen atoms by nitrogens. Aniline and 1 give the monoreplacement product. Pyranylidenemethylthiopyrylium salts have only the oxygen atom replaced by reaction with primary aliphatic amines.     

2,4,6-trichloropyrimidine. Reaction with ethanolamine and diethanolamine

2,4,6-Trichloropyrimidine, 1, reacts with neutral nucleophiles, such as ethanolamine and diethanolamine, to produce both mono- and disubstituted derivatives resulting from replacement of either one (2 and 3) or two (4) chlorine atoms. The third chlorine could not be replaced by these nucleophiles. Failure of this final step was attributed to intramolecular hydrogen bonding of the nucleophiles.     

Polyfunctional imidazoles: VII. 1-aryl-4-chloro-5-[hydroxy(halo)methyl]-1H-imidazoles and their derivatives

The reduction of 1-aryl-4-chloro-1H-imidazole-5-carbaldehydes with sodium tetrahydridoborate gave 1-aryl-4-chloro-1H-imidazol-5-ylmethanols which were converted into 5-chloromethyl and 5-fluoromethyl derivatives. 1-Aryl-4-chloro-5-chloromethyl-1H-imidazoles reacted with sodium azide, secondary amines, thiols, and triphenylphosphine to produce the corresponding products of chlorine replacement in the 5-chloromethyl group.     

Synthesis of 2-methyl-3,5,6-trichloro-4-pyridyl vinyl sulfone and its reactions with nucleophilic reagents

The reaction of excess primary aliphatic amines and mercaptans with 2-methyl-3,5,6-trichloro-4-pyridyl vinyl sulfone gives products of addition to the double bond.     

Phosphorheterocyclen aus 2-Mercaptophenol

Phosphorus-Heterocycles of 2-Mercaptophenol Phosphorus trihalides react with 2-mercaptophenols 1 to 2-halogeno-benzo-1,3,2-oxathiaphospholenes 2 , which yield after reacting with alcohols, phenols, thiophenol and secondary amines substituted benzo-1,3,2-oxathiaphospholenes 3 . Phosphorus pentachloride react with 2-mercaptophenols, the chlorine atoms being substituted step by step, so pentacoordinated phosphorus compounds 4 , 5 and 6 . 4 can also be obtained by chlorination of 2 .     

Prediction of retention indexes. I. Structure-retention index relationship on apolar columns

A simple method is reported for predicting the retention index (RI) of a chemical compound from the number of carbon and carbon equivalent atoms in the molecule, the RI increment for atom addition and the group retention factors (GRFs) for substituents and functional groups. Atoms other than carbon such as oxygen, nitrogen, sulfur, chlorine, bromine and iodine are assigned carbon atom equivalency of approximately 1, 1, 2, 2, 3 and 4, respectively and are counted for their contribution towards RI prediction. The GRFs of substituents and functional groups are derived from the RIs of reference compounds and series of homologues. Ring structures, ring fusion, ring connection, iso- and neo-carbons, chain branching and unsaturation are also assigned GRFs. The predicted RIs of a number of alicyclic, aliphatic and aromatic hydrocarbons, primary, secondary and tertiary alcohols, phenols, aliphatic amines, aromatic amines, heterocyclics, carboxylic acids, acid esters, aldehydes, ketones, and halogenated compounds, are found to be within +/- 3% of the observed values. The structure-retention index relationship thus developed is extremely useful in the tentative identification of radioactive side products formed in tritium labeling by radiation-induced methods.     

Electron transfer and paramagnetic products of reactions of haloquinones with aliphatic amines

The reactions of chloranil (Cl₄Q) and bromanil (Br₄Q) with aliphatic amines in a DMF : H₂O (5 : 1, vol/vol) mixture were studied. The radical anions of 2,5-didimethylamino-3,6-chloro-p-benzoquinone and 2,5-didimethylamino-3,6-bromo-p-benzoquinone were identified by ESR spectra. The reaction rate constant of the replacement of two chlorine atoms by the amino groups in the radical anion of Cl₄Q at 288 K was estimated.     

Synthesis and structure of amino esters of menthol

The conditions for the acylation of (?)-menthol with monochloroacetyl chloride have been studied. Amino esters of (?)-menthol have been obtained by the nucleophilic replacement of the chlorine in (?)-menthol monochloroacetate by residues of secondary amines. Their properties and their mass, IR, and¹³C NMR spectra are described.     

Reactions of tetrachloropyridazine with aliphatic nitrogen nucleophiles

Nucleophilic aromatic substitution reactions of tetrachloropyridazine with a series of aliphatic primary and secondary amines led selectively to products arising from replacement of chlorine at the 4‐position in all cases. The structures of the products were unambiguously confirmed by X‐ray crystallography. Substitution occurs at the most activated site para to ring nitrogen, despite the possible steric hindrance to substitution by adjacent chlorine atoms, reflecting the activating influence of ring nitrogen meta to the site of attack. N,N′‐Dimethylethylene diamine gave a mixture of [6,6] ring fused products following initial substitution at the 4‐position.     

Reactions of the trimer of phosphonitrile chloride

Replacement of the chlorine atoms of the trimer of phosphonitrile chloride by piperidine has yielded derivatives with a degree of replacement ranging from one to six chlorine atoms. In the case of the replacement of two and four chlorine atoms, isomeric di- and tetrapiperidino derivatives of the trimer of phosphonitrile chloride have been isolated.For part IV, see [6].     

Three ways of reactions of 5-(3,5-dimethyl-1<Emphasis Type="Italic">H</Emphasis>-pyrazol-1-yl)-2-phenyl-1,3-oxazole-4-carbonitrile and its analogs with nitrogen-containing bases

Substituted 5-(3,5-dimethyl-1H-pyrazol-1-yl)-1,3-oxazole-4-carbonitrile differently react with nitrogen bases having different numbers of labile hydrogen atoms. Treatment of the title compounds with secondary amines or morpholine results in nucleophilic replacement of the pyrazolyl substituent at C⁵, the ozaxole ring remaining unchanged. Their reactions with primary amines are accompanied by cleavage of the oxazole ring with formation of the corresponding enamino nitriles. Hydrazine hydrate acts in a similar way, but enehydrazino nitriles thus formed undergo fast cyclization to give new 4,5-diaminopyrazole derivatives. The latter can be converted into substituted pyrazolo[1,5-a]pyrimidines whose structure has been proved by X-ray analysis.