2,3- and 3,4-Bis(diethoxyphosphorylmethyl)-5-tert-butylfurans

Reduction of 2-, 4-acetoxymethyl derivatives of 5-tert-butylfuran-3-carboxylic acid leads to the corresponding bis(hydroxymethyl)furans. Bis(chloromethyl)furans prepared from the latter were involvedin reaction with sodium diethyl phosphite. In the presence of two equivalents of a phosphorus-containing nucleophile, bis(phosphonomethyl)furans are formed. One equivalent of sodium diethyl phosphite reacts with 3,4-bis(chloromethyl)furan to give a mixture of 3-and 4-phosphorylated products in a 4.5:1 ratio in a low yield. The revealed difference in reactivity between the 3- and 4-chloromethyl groups demonstrates the importance of shielding of the chloromethyl group by the neighboring tert-butyl substituent. Examination of the ¹H NMR spectra of 3,4-bis(hydroxymethyl)-, 3,4-bis(chloromethyl)-, 3,4-bis(diethoxyphosphorylmethyl)-5-tert-butylfurans, and also specially prepared 5-tert-butyl-3-(diethoxyphosphorylmethyl)-4-(ethoxymethyl)-2-methylfuran established that the signal of the substituent neighboring to the tert-butyl group is always shifted downfield.     

Synthesis of pyrazine acetals by the biased reaction of symmetric 2,5-bis(chloromethyl) or 2,3,5,6-tetrakis(chloromethyl) substituents on pyrazine ring with sodium alkoxides

2,5-Bis(chloromethyl)pyrazine reacted with sodium alkoxide to give unexpected 2-dialkoxymethyl-5-methylpyrazine along with normal substitution product, 2,5-bis(alkoxymethyl)pyrazine. The reaction of 2,3,5,6-tetrakis(chloromethyl)pyrazine with sodium alkoxide afforded similar results to yield 2,6-bis(dialkoxymethyl)-3,5-dimethylpyrazine along with other alkoxymethylpyrazines. The ratio of products depended on the solvent and alkoxide used. A general discussion of the mechanism of such a pyrazine acetal synthesis in the basic conditions is given.     

Synthesis and characterization of new soluble fluorinated seco-porphyrazines

Magnesium porphyrazinate substituted with eight 3,5-bis(trifluoromethyl)phenyl groups on the peripheral positions has been synthesized by the cyclotetramerization of 3,4-[3,5-bis(trifluoromethyl)phenyl]pyrroline-2,5-diimine in the presence of magnesium butanolate. Acid-mediated demetallation of the magnesium porphyrazine resulted in peripheral oxidation of one pyrrole ring to reveal the seco-porphyrazine, octakis[3,5-bis(trifluoromethyl)phenyl]-2-seco-porphyrazine-2,3-dione. Further reaction of this product with copper (II) acetate, zinc (II) acetate and cobalt (II) acetate has led to the metallo-derivatives, {octakis[3,5-bis(trifluoromethyl)phenyl]-2-seco-2,3-dioxoporphyrazinato} M(II) [M = Cu(II), Zn(II), Co(II)]. These new soluble complexes were characterized by elemental analysis, together with FT-IR, ¹H NMR, ¹³C NMR, ¹⁹F NMR, UV-Vis and mass spectral data.     

Molecular structure of (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide. Synthesis of (3,5-diallylisocyanuratomethyl)phosphine sulfides

X-Ray study of the (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide showed that the phosphorylmethyl group is bonded to the nitrogen atom of the cycle. Reaction of the tris(chloromethyl)phosphine sulfide with sodium diallylisocyanurate gave (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide, and treatment of the tris(3,5-diallylisocyanuratomethyl)phosphine oxide with phosphorus pentasulfide gave a tris(3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1446–1448, August, 1993.     

Reactivity of 3,5-bis-(4-amino-1,2,5-oxadiazol-3-yl)-1,2,4-triazole

Alkylation of 3,5-bis(4-amino-1,2,5-oxadiazol-3-yl)-1,2,4-triazole with haloalkanes afforded N-CH₂R derivatives, and nitration furnished the corresponding bis-N-nitramine isolated as a trisodium salt. Treatment of the latter with CH₃I resulted in denitration. Diazotization and oxidation of 3,5-bis(4-amino-1,2,5-oxadiazol-3-yl)-1,2,4- triazole, its N-methyl and N-carboxy derivatives gave rise to the corresponding azido and nitro derivatives. Salts of 3,5-bis(4-amino-1,2,5-oxadiazol-3-yl)-1,2,4-triazol-5-acetic acid with nitrogen-containing bases were synthesized. It was established that the character of reaction products of 3,5-bis(4-amino-1,2,5-oxadiazol-3-yl)-1,2,4-triazole with formaldehyde depended on the acid-base properties of the medium.__________Translated from Zhurnal Organicheskoi Khirmii, Vol. 41, No. 2, 2005, pp. 270–276.Original Russian Text Copyright © 2005 by Sergievskii, Romanova, Mel’nikova, Tselinskii.     

Synthesis and several transformations of sulfides of the thiophene series

Several new N-substituted 2,5-bis(mercapto)-3,4-bis(iminomethyl)thiophenes, which are new tetradentate ligands of the thiophene series, were obtained by the reaction of primary amines with the product formed during the successive action of four equivalents of sodium in liquid ammonia and HCl on the tetraethylacetal of 2,5-bis(methylmercapto)-3,4-thiophenedialdehyde.For Communication XXII, see [4].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1323–1325, October, 1970.     

Reaction of 2,4-Difunctional Esters of 5-tert-Butylfuran-3-carboxylic Acid with Nucleophilic Reagents

Ethyl 5-tert-butyl-4-(chloromethyl)-2-methylfuran-3-carboxylate was brominated with N-bromo-succinimide to obtain the corresponding 2-bromomethyl derivative. The latter is selectively phosphorylatedwith trimethyl, triethyl phosphites by the bromomethyl group. The resulting [4-(chloromethyl)furyl]methyl-phosphonates in the presence of secondary amines and sodium butanethiolate behave as alkylating agents,while sodium phenolate causes their decomposition. 4-Acetoxymethyl- and 4-phenoxymethyl derivatives of the starting product are also selectively brominated with N-bromosuccinimide by the 2-methyl group. The first of the 2-(bromomethyl)furans formed is smoothly phosphorylated with trimethyl phosphite, while the second one under the action of triethyl phosphite gives a mixture of phosphorylation and debromination products. In all the cases, an additional electron-acceptor group in position 4 of alkyl 2-(bromomethyl)-5-tert-butylfuran-3-carboxylate considerably accelerates the Arbuzov reaction.     

Oxidation of 2-Chloro-1-phenylethane-1,1-dithiol

Oxidation of 2-chloro-1-phenylethane-1,1-dithiol with bromine, iodine, and elemental sulfur, as well as under UV irradiation, leads to formation of 1,4-bis(chloromethyl)-1,4-diphenyl-2,3,5,6-tetrathiane in 50–95% yield. Oxidation of the same substrate with selenium dioxide gives 1,5-bis(chloromethyl)-1,5-diphenyl-2,4-dithia-3-selenapentane-1,5-dithiol. On heating to 60°C, the latter loses selenium to afford 1,4-bis-(chloromethyl)-1,4-diphenyl-2,3-dithiabutane-1,4-dithiol.     

Synthesis of 3,4-Disubstituted Phosphorus-containing Furans with Free 2 and 5 Positions

A synthetic approach to -(chloromethyl)furans with free 2, 5 positions is developed. It isshown that these compounds enter the Michaelis-Becker reaction to form usual phosphorylation products.With 3,4-bis(diethoxyphosphorylmethyl)furan, two conformers with different chemical shifts of phosphorus nuclei and PCH₂ protons were detected.     

(3,5-Diallylisocyanuratomethyl)phosphine oxides and some of their properties

Reaction of sodium diallylisocyanurate with tris(chloromethyl)-, bis(chloromethyl)phenyl-, and (chloromethyl)diphenylphosphine oxides yields, depending on the stoichiometric ratio of the reagents, mono-, bis-, and tris(3,5-diallylisocyanuratomethyl)phosphine oxides.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan, Tatarstan, Russia. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2773–2777, December, 1992.     

Synthesis of poly-3,3-bis(chloromethyl)-oxacyclobutane (penton) derivatives

The derivatives of poly-3,3-bis(chloromethyl)oxacyclobutane were prepared by the reaction of the chloromethyl group with organic alkali salts at 100–130°C. in dimethyl sulfoxide. Various reagents were used, including sodium cyanide, sodium acetate, sodium thiophenolate, sodium phenolate, sodium methoxide, sodium diethyl malonate, and potassium phthalimide. For all the substitution reactions, the infrared spectra and elementary analyses substantiated the structures of the designated products. The intrinsic viscosities of the derivatives decreased with increasing the reaction time. It was found that the ions of these salts are strong nucleophiles in dimethyl sulfoxide.     

New Morpholine Derivatives

A study was carried out on the reaction of morpholine with 2,5-di(chloromethyl)-p-xylene, 4,6-di(chloromethyl)-m-xylene, 4,5-di(chloromethyl)-o-xylene, 4,4′-bis(chloromethyl)diphenyl, 4,4′-bis-(chloromethyl)diphenyl ketone, and 4,4′-bis(chloromethyl)diphenyl sulfide. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1691–1692, November, 2005.     

Electrolytic methoxylation of 3,4-bis(hydroxymethyl) furan and synthesis of 4,5-bis-(hydroxymethyl) pyridazine

3,4-Bis(hydroxymethyl)furan was electrolytically methoxylated during intense cooling. 4,5-Bis(hydroxymethyl)pyridazine was obtained by reaction of the methoxylation product — 2,5-dimethoxy-3,4-bis (hydroxymethyl)-2,5-dihydrofuran — with hydrazine hydrate.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1306–1307, October, 1970.     

Photochemical heterolysis of 3,5-bis(dimethylamino)benzyl alcohols and esters: generation of a benzyl cation with a low-energy triplet state

An earlier computational study (CASPT2/pVDZ) by Winter et al. predicts the 3,5-bis(dimethylamino)benzyl cation to have nearly degenerate singlet and triplet states. Through product studies it is demonstrated that photolysis of 3,5-bis(dimethylamino)benzyl alcohol and its corresponding acetate and phenylacetate esters in alcoholic solvents produces a solvent incorporated adduct, 3,5-bis(dimethylamino)benzyl ethers, and 3,5-bis(dimethylamino)toluene.     

1-alkyl 3,5-diallyl isocyanurates as synthetic building blocks for sulfur-containing macroheterocycles

2-Sulfanylethanol was added to readily available 1-alkyl 3,5-diallyl isocyanurates to obtain 1-alkyl 3,5-bis[3-(2-hydroxyethylsulfanyl)propyl] isocyanurates. Treatment of the products with thionyl chloride gave 1-alkyl 3,5-bis[3-(2-chloroethylsulfanyl)propyl] isocyanurates whose reaction with thiourea followed by hydrolysis resulted in preparation 1-alkyl 3,5-bis[3-(2-sulfanylethylsulfanyl)propyl] isocyanurates. Oxiative cyclization of the latter gave macrocyclic disulfides in 56–75% yields. The composition and structure of the macrocyclic disulfides were established on the basis of the elemental and X-ray diffraction analyses, ¹H and ¹³C NMR and IR spectra, as well as MALDI-TOF and electron impact mass spectra.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004, pp. 1368–1376.Original Russian Text Copyright © 2004 by Fattakhov, Shulaeva, Saifina, Efremov, Rizvanov, Soloveva, Nafikova, Azancheev, Gubaidullin, Litvinov, Reznik.This revised version was published online in April 2005 with a corrected cover date.     

Condensation of 2-(3,4-dihydro-6-methoxy-1-naphthyl)-ethenol acetate with 3,5-dimethyl-3-cyclopentene-1,2-dione

Summary The diene condensation of 2-(3,4-dihydro-6-methoxy-1-naphthyl)ethenol acetate (I) with 3,5-dimethyl-3-cyclopentene-1,2-dione (II) goes structurally specifically with formation of an adduct of the steroid type with functional groups in normal positions and an angular methyl group.We are deeply grateful to Prof. Buchta (Erlangen University) for the provision of a sample of 2-ethyl-7-methoxy-1-methylphenanthrene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1051–1058, June, 1965     

Ring inversion in 5,5-disubstituted 1,3-dioxanes

The conformational mobility was studied by dynamic PMR and the free energies of activation of the conformational transitions of 5,5-bis(chloromethyl)-, 5,5-bis(iodomethyl)- and 2,3-pentamethylene-bis-5,5-bis(chloromethyl)-1,3-dioxanes were determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 607–608, May, 1987.     

C,O-dialkylation of Meldrum's acid: synthesis and reactivity of 1,3,7,7-tetramethyl-4H,10H-6,8,9-trioxa-2-thiabenz[f]azulen-5-one

Reaction of Meldrum's acid with 3,4-bis(chloromethyl)-2,5-dimethylthiophene (1) or 3,4-bis(bromomethyl)-2,5-dimethylthiophene (2) produces the kinetically favored C,O-dialkylation product, 1,3,7,7-tetramethyl-4H,10H-6,8,9-trioxa-2-thiabenz[f]azulen-5-one (4). Recrystallization of 4 from refluxing methanol results in the methanolysis product 5-(4-methoxymethyl-2,5-dimethylthiophen-3-ylmethyl)-2,2-dimethyl[1,3]dioxane-4,6-dione (5). Attempts to isomerize 4 to the thermodynamically favored C,C-dialkylation product, 1,3-dimethyl-5,6-dihydro-4H-cyclopenta[c]thiophene(2-spiro-5)2,2-dimethyl-4,6-dione (8), result in the formation of 1,3-dimethyl-7,8-dihydro-4H-thieno[3,4-c]oxepin-6-one (6). The transformation occurs via a retro-Diels-Alder elimination of acetone followed by hydrolysis and decarboxylation of the resulting ketene. The ketene is trapped by tert-butyl alcohol, furnishing 1,3-dimethyl-6-oxo-7,8-dihydro-4H,6H-thieno[3,4-c]oxepine-7-carboxylic acid tert-butyl ester (7). All compounds are characterized spectroscopically as well as by X-ray crystallography of products 4-7.     

Reaction of Malonic Acid Derivatives with Acetylenic Diphosphonates

The primary addition products in the reactions of malonic esters, cyanoacetic esters, and malononitrile with acetylenediphosphonates in acetonitrile in the presence of anhydrous potassium carbonate are potassium derivatives, viz. esters and nitriles of the corresponding 2-alkoxycarbonyl(or 2-cyano) -3,4-bis(di-alkoxyphosphinoyl)-2-potassiobut-3-enoic acid. Further hydrogen replacement for potassium in the nitriles is accompanied by isomerization involving double-bond shift and geometry change. (E)- and (Z)-3,4-bis(dial-koxyphosphinoyl)-2-cyano-2-potassiobut-3-enenitriles (the alkoxy groups are CH₃O and C₂H₅O) are crystalline compounds; they were isolated and characterized.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 1, 2005, pp. 11–20.Original Russian Text Copyright © 2005 by Shekhadeh, Didkovskii, Dogadina, Ionin.     

Condensation of 1,2-dihydro-7-methoxy-4-vinylnaphthalene with 3,5-dimethyl-3-cyclopentene-1,2-dione

Summary Unlike 2-(3,4-dihydro-6-methoxy-1-naphthyl)ethenol acetate (I) [4-(2-acetoxyvinyl)-1,2-dihydro-7-methoxy-naphthalene], the diene of analogous structure -1,2-dihydro-7-methoxy-4-vinylnaphthalene (III)-in condensation with 3,5-dimethyl-3-cyclopentene-1,2-dione (II) forms an adduct (IV) which contains a 15- and not a 17-keto group. The orientation in the diene condensation is determined by the presence, or absence, of an electronegative substituent in the 1-position of the diene of type (III).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1058–1061, June, 1965