Pentafluorophenylation of Perfluorinated Benzocyclobutene,Indan, and Tetralin by Reaction with Pentafluorobenzene in SbF5

The reactivity of perfluorinated benzocyclobutene, indan, and tetralin in reaction with pentafluorobenzene in SbF₅ medium, and also the relative stability of generated therewith perfluoro-1-phenylbenzocycloalkenyl cations decrease with increasing alicyclic fragment in the benzocycloalkene. Treating the solutions of salts of the above cations with anhydrous HF results in the corresponding perfluoro-1-phenylbenzocycloalkenes, and the hydrolysis of salts furnishes their 1-hydroxy derivatives. In a reaction of 1-hydroxyperfluoro-1-phenylbenzocyclobutene, -indan, and -tetralin with SOCl₂ the hydroxy group is replaced by chlorine. Besides with indan and tetralin derivatives form respectively 7-pentafluorophenyloctafluoro-3-chlorobicyclo[4.3.0]hepta-1,4,6-triene and 7-pentafluorophenyldecafluoro-3-chlorobicyclo[4.4.0]octa-1,4,6-triene.     

Skeletal transformations of perfluoro-1-ethyl-1-phenylbenzocyclobutene in the reaction with antimony pentafluoride

Interaction of perfluoro-1-ethyl-1-phenylbenzocyclobutene with SbF₅ at room temperature gives, after treatment of the reaction mixture with H₂O, perfluoro-4-[1-(2-methylphenyl)propylidene]cyclohexa-2,5-dienone as a main product. The reaction at 90-95 °C leads, after treatment with H₂O, to a mixture of perfluorinated 9-ethyl-9-methyl-1,2,3,4-tetrahydro-9H-fluorene, 9-ethyl-4a-methyl-4,4a-dihydrofluoren-1-one, 3-ethyl-3-phenylphthalide, 1-hydroxy-2-methyl-1-phenylindan, 3-methyl-2-phenylindenone and small amounts of other products.     

Supramolecular architecture of crystals of perfluorinated 3-alkylphthalides

The molecular and crystal structures of perfluoro-3-alkylphthalides (3-hydroxyperfluoro-3-methylphthalide and its hydrate, two polymorphs of 3-hydroxyperfluoro-3-ethylphthalide and 3-hydroxyperfluoro-3-isopropylphthalide) are determined by single crystal X-ray diffraction. In the crystals, the supramolecular O–Н…O=C synthon occurs leading, except the crystallohydrate, to the formation of C₁¹ (6) hydrogen bonded chains (supramolecular 1D motifs). According to the DFT/M06-2X/TZV calculations, the interaction energy of hydrogen bonded molecular pairs increases in this series, which can be explained by additional C=O…π, O…π, and C–F…π interactions.     

Cationoid rearrangements in reactions of perfluoro-1-arylbenzocyclobutenes with antimony pentafluoride

In the presence of antimony pentafluoride at 130 °C, the four-membered ring of perfluoro-1-(2-ethylphenyl)benzocyclobutene (2) undergoes cleavage, forming perfluoro-2-ethyl-2′-methyldiphenylmethane (5). Compound 5 is converted, under the action of SbF₅ at 170 °C, to perfluoro-8,9-dimethyl-1,2,3,4-tetrahydrofluorene (8). Perfluoro-1-(4-ethylphenyl)benzocyclobutene (3) remains unchanged at 130 °C, whereas at 170 °C it gives a mixture of perfluorinated 4′-ethyl-2-methyldiphenylmethane (9), 6-ethyl-1,2,3,4-tetrahydroanthracene (11) and 2-ethyl-9,10-dihydroanthracene (12). When heated with SbF₅ at 170 °C, perfluoro-1-phenylbenzocyclobutene (1) remains unchanged. Solution of compounds 2, 3, 5 and 9 in SbF₅-SO₂ClF generated the perfluorinated 1-(2-ethylphenyl)-1-benzocyclobutenyl (29), 1-(4-ethylphenyl)-1-benzocyclobutenyl (30), 2-ethyl-2′-methyldiphenylmethyl (31) and 4′-ethyl-2-methyldiphenylmethyl (32) cations, respectively.     

A new stable perfluoroalkyl radical

Conclusions The radiolysis of perfluoro-4-methyl-2-pentene gives a stable radical whose ESR spectrum corresponds to (CF₃)₂CFFCF(CF₃)₂.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1667–1669, July, 1985.The authors express their gratitude to Yu. L. Bakhmutov for assistance in this work.     

Reaction of perfluoro-1-methylindan with SiO2-SbF5

The reaction of perfluoro-1-methylindan with SiO₂-SbF₅ depending on the amount of SiO₂ led to the formation after hydrolysis of the reaction mixture of perfluoro-3-methylindan-1-one, perfluoro-4-methylisochromen-1-one, 6-(1-carboxy-2,2,2-trifluoro-ethyl)-2,3,4,5-tetrafluoro-benzoic and 6-(carboxymethyl)-2,3,4,5-tetrafluorobenzoic acids. Heating in the SbF₅ medium perfluoro-1-methylindan in a glass ampoule at 130°C, or perfluoro-3-methylindan-1-one at 70°C provided a solution of a perfluoro-4-methylisochromenium salt that on treating with anhydrous HF was converted into perfluoro-4-methyl-1H-isochromen, and on hydrolysis, into perfluoro-4-methylisochromen-1-one.     

Skeletal reactions of perfluoromethylethyl- and perfluorodiethylbenzocyclobutenes with 1,1- and 1,2-alkyl groups in SbF5

Taking perfluoro-1,1-dialkylbenzocyclobutenes as examples, it has been shown to be possible to enlarge the four-membered ring in polyfluorobenzocyclobutenes to five-membered in the presence of SbF₅, by cleavage of the four-membered ring followed by cyclization of the resulting polyfluorostyrene to the polyfluoroindane, which then undergoes further reactions. Perfluoro-1-methyl-1-ethylbenzocyclobutene isomerizes at 50°C in the presence of SbF₅ to perfluoro-,-o -trimethylstyrene, which is reversibly converted at 130°C into perfluoro-1,2-dimethylindane. Perfluoro-l,l-diethylbenzocyclobutene isomerizes at 130°C in the presence of SbF₅ to give perfluoro- -ethyl-,o -dimethylstyrene, which at 170°C gives perfluoro-2-methyl-3-ethylindene- and perfluoro-2-methyl-3-ethyl-4,5,6,7-tetrahydroindene. The last two compounds, together with perfluoro-o-dipropylbenzene, are obtained from per fluoro-1,2-diethylbenzocyclobutene-with SbF₅ at 170°C. From perfluoro-1-methyl-2-ethylbenzocyclobutene with SbF₅ at 95°C there is obtained perfluoro-1-ethylindane, while at 130°C, in addition to the latter compound, there are obtained perfluorinated 1,1-dimethylindane, 1,2-dimethylindane, ,,o-trimethylstyrene, 2,3-dimethylindene, and 2,3-dimethyl-4,5,6,7-tetrahydroindene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1114–1120, May, 1990.     

Expansion of the pentafluorobenzene ring of perfluoro-1,2-diethyl-1-phenylbenzocyclobutene under the action of SbF5

Perfluoro-1,2-diethyl-1-phenylbenzocyclobutene under the action of SbF₅ gives, after treatment of the reaction mixture with water, perfluoro-4-[1-(6-propyl-phenyl)-propylidene]cyclohexa-2,5-dienone along with the products of unusual pentafluorobenzene ring expansion - perfluorinated 4b,10-diethylbenzo[a]azulen-7(4bH)-one and 10-ethylbenzo[a]azulen-6(10H)-one.     

The alicyclic ring contraction of perfluoro-1-phenyltetralin in reaction with antimony pentafluoride

Perfluoro-1-phenyltetralin (1) heated with antimony pentafluoride at 130 °C, then treated with water, gave a mixture of perfluorinated 3-methyl-2-phenylindenone (3), 3-methyl-2-phenylindene (4), 3-hydroxy-1-methyl-3-phenylindan (5), 1-methyl-3-phenylindan (6), 9-methyl-1,2,3,4,5,6,7,8-octahydroanthracene (7), and 1,9-dimethyl-5,6,7,8-tetrahydro-β-naphthindan (8). When heated with SbF₅ in the presence of HF, then treated with water, compound 1 is transformed to a mixture of products 3-6. The reaction at 170 and 200 °C forms compounds 3-6 together with perfluoro-2-(cyclohexen-1-yl)-3-methylindene (10).     

Synthesis and biological activity of new 2-amino-4-[3-methyl-3-(5,6,7,8-tetrahydro-2-naphthyl)cyclobutyl]thiazole derivatives

2-Amino-4-[3-methyl-3-(5,6,7,8-tetrahydro-2-naphthyl)cyclobutyl]thiazole was synthesized by reaction of 1-methyl-1-(5,6,7,8-tetrahydro-2-naphthyl)-3-chloroacetylcyclobutane with thiourea in ethanol, and its subsequent transformations afforded new derivatives which were tested in vitro for antibacterial activity against some bacteria using the disk diffusion technique.__________From Zhurnal Organicheskoi Khimii, Vol. 40, No. 12, 2004, pp. 1861–1865.Original English Text Copyright © 2004 by Koparr, Cansz, Ahmedzade.The original article was submitted in English.     

Metal complexes of 1-hydroxy-2,3-dimethyl-4-(3′-methyl-4′-amino-5′-mercapto-1′, 2′, 4′-triazole)-1,4-diaza-1, 3-butadiene with manganese(II), cobalt(II), nickel(II) and copper(II)

Summary Binuclear metal complexes of the type [M(HDDB)-(H₂O)₂]₂: where HDDB=1-hydroxy-2,3-dimethyl-4-(3-methyl-4-amino-5-mercapto-1, 2, 4-triazole)-1,4-diaza-1, 3-butadiene and M=manganese(II), cobalt(II), nickel(II) and copper(II), have been prepared and characterised by elemental and thermal analyses, magnetic measurements, electronic and i.r. spectra. Octahedral geometry around the metal(II) ions is proposed and the crystal field parameters of the cobalt(II) and nickel(II) complexes are also calculated. Fungicidal screening of the complexes has been made aginstHelminthosporium oryzae andFusarium oxysporium.     

α-Oxides in reaction with N-H acids of the heterocyclic series

Anumber of 1-methyl-4-(2-hydroxyalkyl)-3-nitro-1,2,4-triazol-5-ones and their derivatives were obtained by reaction of 1-methyl-3-nitro1,2,4-triazol-5-one with -epoxides. The fact of intramolecular nucleophilic substitution of the nitro group in hydroxy derivatives of 3-nitro-1,2,4-triazol-5-one with cyclization to 2-methyl-3-oxo-5,6-dihydrooxazolo[3,2-b]-1,2,4-triazoline was established.See [1] for communication III.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1407–1410, October, 1977.     

Heterocyclic analogs of pleiadiene

1-Methylperimidine adds phenylsodium and phenyllithium to the C=N bond to give 1-methyl-2-phenyl-2, 3-dihydroperimidines. However, if benzophenone is present in the reaction mixture, a mixture of 1-methyl-2-phenylperimidine and l-methyl-2, 4-diphenylperimidine (when phenylsodium is used) or l-methyl-2-phenyl-4-(-hydroxybenzhydryl)perimidine (when phenyllithium is used) is formed. It is assumed that the formation of products involving substitution in the naphthalene ring is associated with the participation of C₆H₅ and (C₆H₅)₂C-O^– radical particles that are formed on reaction of the phenylmetallic compound with benzophenone.See [1] for communication XXIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 697–701, May, 1976.     

Die Dissoziationskonstanten von 2,2′-Dihydroxydiphenylmethanderivaten

The pK-values of the first and second degree of dissociation of 2.2-dihydroxy-5-methyl-3.5-dinitro-diphenylmethane, 2.2-dihydroxy-5-methyl-5-nitro-diphenylmethane and 2.2-dihydroxy-5.5-dimethyl-3-nitro-diphenylmethane were determined in aqueous solution at 25°C spectrophotometrically. Comparing the observed pK-values with those of 2-methyl-4.6-dinitrophenol, 2-methyl-4-nitrophenol, 2.4-dimethyl-6-nitro-phenol and 2.4-dimethylphenol, we found a decrease of the values of pK ₁ and an increase of pK ₂. We explain this by the formation of an intramolecular hydrogen bridge which stabilizes the anion of the half dissociated form. This assumption is supported by the UV spectra.

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Mit 3 Abbildungen     

Reaction ofβ,β -dimethyldivinyl ketone with 2,5-dimethyl- and 1,2,5-trimethyl-4-piperidones

1-(3-Oxo-5-methyl-4-hexen-1-yl)-2,5-dimethyl-4-piperidone, 5-(3-oxo-5-methyl-4-hexen-1-yl)-2, 5-dimethyl-4-piperidone, and 5-(3-oxo-5-methyl-4-hexen-1-yl)-1,2,5-trimethyl-4-piperidone were synthesized. In the absence of a catalyst,-dimethyldivinyl ketone adds to 2,5-dimethyl-4-piperidone at the 1-position, while in the presence of alkali it adds at the 5-position.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 350–351, March, 1971.     

Rearrangement of the carbon skeletion of perfluorinated 1-isopropyl-, 1-methyl-1-isopropyl-, and 1-methyl-2-isopropylbenzocyclobutenes by the action of antimony pentafluoride

Perfluorinated 1-isopropyl-, 1-methyl-1-isopropyl-, and 1-methyl-2-isopropylbenzocyclobutenes isomerize under the influence of antimony pentafluoride to perfluorinated alkylstyrenes and alkylindans. The process may be accompanied by dealkylation and also by fluorination and defluorination of the products. With antimony pentafluoride at 50°C perfluoro-1-methyl-1-isopropylbenzocyclobutene gives perfluoro-,,,o-tetramethylstyrene, which isomerizes under the influence of antimony pentafluoride at 130°C into perfluoro-1,2,2-trimethylindan, and the latter forms perfluoro-2,3-dimethylindene under the reaction conditions. Perfluoro-1-methyl-2-isopropylbenzocyclobutene is not changed in the presence of antimony pentafluoride at 50°C but isomerizes to perfluoro-1-isopropylindan at 90°C. The latter is transformed under these conditions into the above-mentioned tetramethylstyrene. Perfluoro-1-isopropylbenzocyclobutene does not react with antimony pentafluoride at 130°C, but at 170°C it gives a mixture of perfluorinated 2,2-dimethylindan, 2,3-dimethylindene, 2,3-dimethyl-4,5,6,7-tetrahydroindene, and 2-isobutyltoluene, which is converted into perfluoro-o-xylene under the reaction conditions.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 630090 Novosibirsk. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1419–1424, June, 1992.     

Synthesis,crystal structure and spectroscopic characterization of a hydrogen-bonded 1D copper(II) complex

Novel 1:2 and 1:1 (M:L) copper(II) complexes have been prepared from the tridentate ligand 2-(1-methyl-2-aza-5-oxapentyl)phenol (H₂L¹). The crystal structure of [Cu(HL¹)₂] (1) exhibits a noncentrosymmetric square-planar geometry with a slightly tetrahedral distortion. The Cu^II atom is coordinated by two amino N and two phenoxo O atoms of two (HL¹)^– ligands. The phenoxo and the alkoxy groups are involved in two strong intramolecular hydrogen bonds. The coordination moieties are further connected to a 1D linear structure by the action of intermolecular hydrogen bonds between the alkoxyl and the amino groups. The importance of steric hindrance introduced by the methyl group in the molecular structure and the packing of the complex molecules has been demonstrated. The e.p.r. parameters of (1) have been obtained: g = 2.231, g = 2.005, g _iso = 2.080, A = 185.0 G, A _iso = 86.5 G, A = (3A _iso – A )/2 = 37.3 G. These results confirm a distorted square planar stereochemistry with a ( )¹ ground state.     

On the mechanism of the Fe(CO)5-catalyzed Kharasch reaction

Regioselectivity and diastereoselectivity of the addition of BrCCl₃ to (R)-3-(E)-cinnamoyl-4-phenyloxazolidin-2-one (1) and (R)-3-(E)-acryloyl-4-phenyloxazolidin-2-one (2) catalyzed by Fe(CO)₅ or initiated with benzoyl peroxide were investigated. Stereochemistry of the reaction of BrCCl₃ with the a-complexes (4R,S,S)-²-(3-(E)-cinnamoyl-4-phenyl-oxazolidin-2-one)irontetracarbonyl (3a) and (4R,R)-²-(3-acryloyl-4-phenyloxazolidin-2-one)irontetracarbonyl (4b) was also studied. The results obtained allow the following conclusions to be drawn: (1) the thermal Kharasch reaction catalyzed by Fe(CO)₅ proceeds by a redox catalysis mechanism; (2) iron (in any of its oxidation states) is not coordinated to olefins in the transition state of the reaction; (3) the transfer of the halogen atom on the radical adduct probably occurs inside a radical-iron cation pair.Yu. T. Struchkov is deceasedTranslated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 640–648, March, 1996.     

Vinyl Ethers Containing an Epoxy Group: XXI. Synthesis and Acid-Catalyzed Cyclization of 1-[ω-(Vinyloxy)alkoxy]-3-(2-propynyloxy)-2-propanols- A Simple Route to 2-Propynyloxymethyl-Substituted Cyclic Polyethers

Base-catalyzed reaction of 2-[-(vinyloxy)alkoxy]methyloxiranes with 2-propynyl alcohol (3 wt % of t-BuOK, 60-85°C, 3-12 h) afforded first reperesentatives of the 1-[-(vinyloxy)alkoxy]-3-(2-propynyloxy)-2-propanol series in up to 99% yield. Treatment of 1-[2-(vinyloxy)ethoxy]- and 1-[2-(vinyloxy)ethoxyethoxy]-3-(2-propynyloxy)-2-propanols with trifluoroacetic acid (0.5 wt. %) in dry diethyl ether resulted in cyclization with formation of up to 96% of (2-methyl-1,3,6-trioxocan-4-yl)methyl- and (2-methyl-1,3,6,9-tetraoxacycloundecan-4-yl)methyl 2-propynyl ethers.     

Synthesis,structure, and carbamoylation of 5-alkyl-N(1)-(β-hydroxyethyl)-4,5-dihydro-1,2,4-triazin-6-ones

The condensation of methyl -(dimethylaminomethyleneamino)alkanoates with -hydroxyethylhydrazine gave the isomeric N₍₁₎- and N₍₂₎-(-hydroxyethyl)-5-alkyl-4,5-dihydro-1,2,4-triazin-6-ones. It was shown by IR spectroscopy that the products exist in the form of betaines both in solution and in the crystalline state. The reaction of the N₍₁₎ isomers with alkyl and aryl isocyanates leads to the formation of mono- or dicarbamoyl-substituted triazines. The preferred reaction path involves carbamoylation of the -hydroxyethyl group.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1237–1242, September, 1992.