Fluoroindenes

The reaction of N₂O₄, and also HNO₃ purified from oxides of nitrogen, with perfluoro-3-methylindene and perfluoro-1-methyleneindane takes place at the multiple bond of these compounds and results, after hydrolysis, in mixtures, of similar composition, of the corresponding nitro-1-hydroxy and dinitro derivatives. In contrast, whereas perfluoroindene and HNO₃ do not form perfluoro-1,2-dinitroindane, the latter is formed from N₂O₄. Furthermore, perfluoroindene reacts with HNO₃ in acetic acid in the presence of CF₃SO₃H, but there is no reaction in its absence. From these results one can apparently assume that the reaction of perfluoro-3-methylindene and perfluoro-1-methyleneindene with HNO₃ proceeds by a radical route, but that of perfluoroindene with HNO₃ is electrophilic.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 837–845, April, 1990.For previous communication, see [1].     

Reactions of 9-chloro-1,10-anthraquinone 1-dichlorophosphorylimine with N- and C-nucleophiles

9-Chloro-1,10-anthraquinone 1-dichlorophosphorylimine formed in the reaction of 1-amino-9,10-anthraquinone with PCl₅ followed by dehydrochlorination reacts with primary amines with substitution of chlorine atoms. In the case of aliphatic amines, the reaction occurs further concurrently in two directions: the addition of the amine molecule with the formation of 9,9-di(alkylamino) derivatives of the anthrone and the substitution of hydrogen atom at position 4 with the formation of 4,9-di(alkylamino) derivatives of 1,10-anthraquinone 1-imine. In the case of aromatic amines, 1-amino-9,10-anthraquinone 9-arylimines are the end products. Reactions with the anions of CH-acids containing an alkoxycarbonyl or cyano group occur with substitution in position 9 followed by intramolecular cyclization with the formation of 2-alkoxy- or 2-amino-7H-dibenzo[f,ij]isoquinolin-7-one derivatives, respectively. For preliminary communication, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1179–1184, June, 1998.     

Fluoroindenes. 10. Cyclization of difluorocarbene to perfluoro-3-methylindene and perfluoro-1-methyleneindane. Thermolysis and bromination of the resultant cyclopropane derivatives

Conclusions Upon reaction of perfluoro-3-methylindene and perfluoro-1-methyleneindane with hexafluoropropylene oxide at 225°C the corresponding cyclopropane derivatives are formed: perfluoro-la-methyl-1,1a,6,6a-tetrahydrocycloprop[a]indene and perfluorospiro[indane-1,1-cyclopropane], which are transformed during thermolysis in the presence of bromine into 1-bromo-2-difluorobromomethylperfluoro-1-methylindane and 1-bromo-1-(2-bromotetrafluoroethyl)perfluoroindane respectively, and in the absence of bromine into the starting olefins.Deceased.For previous report, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1839–1845, August, 1988.     

Reaction of perfluoro-2-methylpent-2-ene with oxygen nucleophiles

Conclusions Perfluoro-2-methyl-2-pentene reacts with alcohols to give either fluorine substitution products or addition products, depending on the amount of basic catalyst which is used. Alcohols containing branched substituents give another product in addition to those derived from substitution of a vinyl fluorine atom in perfluoro-2-methyl-2-pentene, namely isomeric vinyl ethers which are derivatives of perfluoro-2-methyl-1-pentene.Dehydrofluorination of the addition products, namely 2-hydro-3-alkoxyperfluoropentanes, leads in high yields to fluorine-containing allyl ethers containing terminal double bonds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 106–119, January, 1986.     

Fluoroindenes. 13. Transformations of polyfluorinated indenes and 1-alkylideneindans in the H2O2-HF-SbF5 system

The reaction of perfluorinated indene, 3-methylindene, and 1-methylene- and 1-ethylideneindans with hydrogen peroxide in the hydrogen fluoride—antimony pentafluoride medium takes place at the multiple bond of the substrate and leads to the oxo derivatives of indan. The process probably takes place through the electrophilic addition of HO⁺. The C=C bond in perfluoro-3-methylindenone is not affected. In this compound and also in perfluoro-2-indanone and perfluoro-1-methyl-2-indanone the carbonyl group is involved in reaction with hydrogen peroxide in the HF-SbF₅ system, and six-membered oxygen-containing heterocyclic compounds are formed.For Communication 12, see [1].Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 630090 Novosibirsk. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1412–1419, June, 1992.     

Geminal systems. 16. Reactions of N-chloro-N-alkoxy-N-alkylamines with amines

Conclusions The reactions of N-chloro-N-alkoxy-N-tert-alkylamines with amines are characterized by nucleophilic substitution at the nitrogen atom with formation of the corresponding N-alkoxyhydrazines which are stable in the case of ethyleneimine and pyridine; give diazenes as in the case of MeNH₂, EtNH₂, and Me₂ or yield products of further transformations as in the case of NH₃, Me₂NH, and MeO(Me)NH. Nucleophilic substitution is repressed in the reaction with Et₂NH and Et₃ N by one-electron reduction with the formation of azoxy compounds.For Communication 15, see previous article [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2327–2334, October, 1981.     

The generation of polyfluoroindenyl cations : On the aromaticity of polyfluoroindenyl cations

A number of polyfluoroindenyl cations has been generated by the interaction of polyfluoroindenes with SbF₅. In particular perfluoro-2-methylindenyl cation has been generated from perfluoro-2-methylindene (“open-chain” perfluoro-2-indenylmethyl ion has not been fixed). On this basis it has been proposed, that perfluoro-2-methylindenyl cation has an aromatic character (according to the Dewar and Breslow's criterion of the aromati-city).     

Synthesis of 5-Amino-1-aryl-4-(4-aryl-1,3-thiazol-2-yl)- 2,3-dihydro-1H-pyrrol-3-ones*

Reactions of 2-(4-aryl-1,3-thiazol-2-yl)-3-oxo-4-chlorobutyronitriles with primary aromatic amines result in nucleophilic substitution of the chlorine atom by amino group, followed by intramolecular addition of the secondary amino group to the cyano group. The products are 5-amino-1-aryl-4-(4-aryl-1,3-thiazol-2-yl)- 2,3-dihydro-1H-pyrrol-3-ones which are structurally related to the known antiischemic drugs.     

Thermolytic transformations of polyfluoroorganic compounds

The reaction of α,α-dichlorooctafluoroethylbenzene with tetrafluoroethylene as a source of difluorocarbene has been studied. The copyrolysis of these compounds gave not only the expected products, decafluoro-α-methylstyrene and α-chloroheptafluorostyrene, but also noticeable amounts of perfluoro-1-methylindan and perfluoro-7-methylbicyclo[4.3.0]nona-1,4,6-triene along with perfluoro-3-methylindene and octafluorostyrene. It has been suggested that indan and the triene are formed with the participation of the C₆F₅CCICF₃ radical through sigmatropic shifts of fluorine atoms in the intermediate bicyclic compounds. The reaction of α,α-dichlorodecafluoropropylbenzene with tetrafluoroethylene afforded α-chloroheptafluorostyrene as the main product.     

Trifluoromethyl phosphaalkenes of the type F3CPC(OR)NR2: Synthesis,spectroscopic investigations,and ligand properties [1]

The one-pot reaction of the alcohol adducts F₃CP(H)CF₂OR of perfluoro-2-phosphapropene with secondary amines in a 1:3 molar ratio affords the stable phosphaalkenes F₃CPC(OR)NR₂ (R = Me, Et) 1–4 in yields of 58%. NMR and He(I) PE spectroscopic investigations show that the lone pair electrons on nitrogen and oxygen participate in n/π conjugation. In contrast to typical low-coordinated double bonds the new derivatives do not react with alcohols, amines, and 1,3-dienes. The derivatives are more closely related to the phosphaalkenes F₃C(F)NR₂ than to perfluoro-2-phosphapropene. The reaction of F₃C(OEt)NMe₂ ( 3 ) with Cr(CO)₅THF yields the η¹(P) complex Cr(CO)₅[F₃CPC(OEt)NMe₂] ( 7 ) with an unusually long sp² PC bond (1.809 Å).     

Purines,pyrimidines and condensed systems based on them. 10. Reactivity of 1,3-dimethyl-6-chlorolumazine with respect to amines: Competition of aminodechlorination and aminodehydrogenation reactions

1,3-Dimethyl-6-chlorolumazine reacts with secondary alkylamines and hydrazine to form 1,3-dimethyl-6-amino(hydrazino) derivatives in good yields. At the same time, 6-chloro-7-amino-1,3-dimethyllumazines are formed by the action of primary amines and liquid ammonia, in addition to the nucleophilic substitution products of chlorine.Article for Communication 9, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1202–1207, September, 1992.     

Alkylation of 3-aminoisocarbostyryl derivatives

The alkylation of derivatives of 3-aminoisoquinolin-1(2H)-one in the presence of NaH may proceed in three directions: 1) at the carbonyl group oxygen atom, 2) at the nitrogen atom N-2, and 3) at the 3-amino group. The reaction of equivalent amounts of the reagents gives predominantly products of substitution at the 3-amino group. Repeated alkylation proceeds at the lactam fragment to give a mixture of O-alkyl and N-alkyl derivatives. Acylation of 3-dialkylamino- and 3-alkylanilinoisoquinolin- 1(2H)-ones in the presence of NaH gave derivatives of 3-amino-1-isoquinolinyl 4-ethoxybenzoate.     

Amination of 5-azacinnoline. instances of facile nucleophilic substitution of the hydrogen atom by an amino group

Direct nucleophilic substitution of the hydrogen atom by an amino group was observed in the case of 5-azacinnoline. The reaction with amines in the presence of an oxidizing agent under mild conditions leads to 4-amino-5-azacinnoline derivatives. Both electronic and steric factors affect the trend of the reaction. In the case of reactive amines the yields of the final products are close to quantitative. The formation of 4,4-bis-5-azacinnolyl was observed in the absence of oxidizing agents. A probable scheme for the process that takes into account both possible reaction pathways is proposed. The structures of the products were proved by a combination of physicochemical methods and the results of elementary analysis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1554–1560, November, 1977.     

Pyrolysis of tetradecafluorotricyclo [6,2,2,0]dodeca-2,6,9-triene and related compounds. Thermal isomerizations involving fluorine shifts

The vacuum pyrolysis of tetradecafluorotricyclo-[6,2,2,0^2,7]dodeca-2,6,9-triene (6) results in initial isomerization to perfluorotricyclo[8,2,0,0^2,7]dodeca-2,6,8-triene (7) followed by elimination of tetrafluoroethylene and formation of perfluoro-1,2-dihydronaphthalene (8), perfluoro-1,4-dihydronaphthalene (9), perfluoroindene (10) and perfluoro-(2 3)-methylindene (11); the expected primary product of elimination of tetrafluoroethylene from (6) or (7), namely perfluoro-2,3-dihydronaphthalene, was not detected. The formation of the observed products can be accounted for in terms of fluorine migrations, further examples of such migrations are described.     

Synthesis and Reactivity of Azidoximes: III. 1-Azido(4-amino-1,2,5-oxadiazol-3-yl)aldoxime in the Cycloaddition Reaction

By 1,3-dipolar addition of 1-azido(4-amino-1,2,5-oxadiazol-3-yl)aldoxime to propargyl alcohol and phenylacetylene bicyclic 4-amino-1,2,5-oxadiazol-3-yl(4-R-1,2,3-triazol-1-yl)ketoximes were obtained which in reaction with acetic anhydride afforded the corresponding O-acyl derivatives. Diazotization of 4-amino-1,2,5-oxadiazol-3-yl(4-R-1,2,3-triazol-1-yl)ketoximes furnished 4-azido derivatives. The treatment of 4-amino-1,2,5-oxadiazol-3-yl(4-hydroxymethyl-1,2,3-triazol-1-yl)ketoxime with SOCl₂ resulted in 4-amino-1,2,5-oxadiazol-3-yl(4-chloromethyl-1,2,3-triazol-1-yl)ketoxime, whose chlorine atom was readily replaced by azide ion affording 4-amino-1,2,5-oxadiazol-3-yl(4-azidomethyl-1,2,3-triazol-1-yl)ketoxime.     

Calculation of the electron structures and electronic spectra of 3-chloro- and 3-amino-1,2,4-triazole derivatives

3-Chloro- and 3-amino-1,2,4-triazole derivatives were subjected to a theoretical study by means of quantum-chemical calculation by the Pariser-Parr-Pople method. The experimentally observed electron transitions were assigned. The Cl atom and the NH₂ group in the 3 position of 1,2,4-triazole subject the electron system of the heteroring to substantial perturbation.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 698–700, May, 1977.     

Stereochemical characteristics of the ammonia reaction with perfluoro-2-methyl-2-pentenethiocyanate-3: The defining role of the steric factor determined by geometric modeling

Geometric modeling has been used to analyze the stereochemical characteristics of the ammonia reaction with perfluoro-2-methyl-2-pentenethiocyanate-3. This reaction is stereospecific because it results in only one E stereoisomer of 2-aminoperfluoro-4,4-dimethyl-4,5-dihydro-5-ethylidene-1,3-thiazole (3). It is shown that such stereospecificity is determined by a lower steric hindrance in the anion from which the E isomer is formed as compared to that in the anion from which a Z isomer would be formed. Strong steric hindrances associated with the amino group attached to a double bond exclude the heat-dependent cyclization of E-2,4-diaminoperfluoro-4-methyl-2-pentenethiocyanate-3 (4), which would result in the formation of a thiazole ring. The substitution of the fluorine atom at the double exocyclic bond in thiazoline E-3 by an amino group does not occur because of the electron destabilization of the transition state resulting from the repulsion of the unshared electron pairs of the carbanion and the sulphur atom .A. N. Nesmeyanov Institute of Heteroorganic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 343–349, February, 1992.     

Acyl chlorides of 2,2,5,5-tetramethyl-3-imidazolin-1-oxyl-4-0-acylhydroximic acids

Acylation of nitroenamine derivatives of imidazolidin-1-oxyl with carboxylic acid chlorides leads to 0-acylhydroximic acid chloride derivatives of 3-imidazolin-1-oxyl. The reaction proceeds apparently through a nitrile oxide. It was shown for the 0-benzoyl derivative that reaction of the obtained acyl chlorides with nucleophilic reagents usually gives products of chlorine atom substitution with simultaneous cleavage of the acyl group.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 444–450, February, 1991.     

Purines, pyrimidines, and condensed systems based on them. 17. Reactions of 6,8-dimethyl-3-chloropyrimido-[4,5-c]pyridazin-5,7(6H,8H)dione with C-nucleophiles

6,8-Dimethyl-3-chloropyrimido-[4,5-c]pyridazin-5,7(6H,8H)dione reacts with malonodinitrile, cyanoacetic ester, and nitromethane in the presence of bases to give products of nucleophilic substitution of the chlorine atom. The products containing the cyanoacetic ester and nitromethane residues exist exclusively in the chelated methylidene form in CHCl₃ and DMSO solutions. Reactions of pyridazinouracil with methylmagnesium chloride and butyllithium gave products of nucleophilic addition at C₍₄₎.For Comuunication 16, see [1].Rostov State University, Rostov-on-Don 344090, Russia Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1113–1118, August, 2000.     

Synthesis and properties of 2-amino-1-thio-4-chromone derivatives

2-Amino-1-thio-4-chromone was synthesized and its substitution reactions at the N and C₃ atoms were studied. The mass spectrometric behavior of the synthesized 2-amino-1-thio-4-chromone derivatives was studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 182–185, February, 1978.