Darstellung von 2′,3′-Dideoxy-2′-hydroxymethyl-nucleosiden

Zusammenfassung Die Synthese von geschützten 2,3-Dideoxy-2-hydroxymethyl-nucleosiden wird beschrieben. Die durch ein Mehrstufenverfahren aus Isopropylidenglycerol erhaltenen Nucleoside können als Bausteine zur Darstellung von Oligonucleotiden verwendet werden, deren 2- und 5-Positionen über eine Etherbrücke verbunden sind.

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Synthesis of 2,3-dideoxy-2-hydroxymethyl nucleosides

Summary The synthesis of protected 2,3-dideoxy-2-hydroxymethyl nucleosides is presented. The nucleosides, obtained in a multi-step procedure starting from isopropylideneglycerol, may be used as building blocks for the synthesis of 2,5-ether linked oligonucleotides.

     

Etude de la séparation du thorium d'avec les terres cériques

Résumé Nous avons étudié les complexes que forment les acides éthylèneglycolbis-(-aminoéthyléther)] Sr,N-tétracétique et ,-diaminodiéthylétherN,N-tétracétique, soit avec le thorium, soit avec les terres cériques et, à la suite de cette étude, nous avons pu établir une méthode d'analyse et une séparation du thorium d'avec les terres cériques qui nous a donné satisfaction.

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Summary A study has been conducted of the complexes formed by the ethyleneglycol-bis (-amino-ethylether)-N,N-tetraacetic acid and,-diaminodiethylether-N,N-tetraacetic acid with either thorium or the ceric earths. As a result of this investigation, it was possible to set up a method of analysis and a separation of thorium from the cerium earths. These procedures have proved satisfactory.

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Zusammenfassung Die von Äthylenglykol-bis-(-aminoäthyläther)-N,N-tetraessigsäure bzw.von ,-Diaminodiäthyläther-N,N-tetraessigsäure mit Thorium bzw. mit den Cer-Erden gebildeten Komplexe wurden untersucht. Auf Grund der Ergebnisse konnte ein Analysenverfahren und eine Trennungsmethode für Thorium und Cer-Erden entwickelt werden.

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Une communication de ce travail a été faite à Graz, lors de la commémoration du centenaire de la naissance deF. Emich.     

1,1′-Disubstituted 2,2′-di(n-perfluoropropyl)-5,5′-bibenzimidazolyls

The synthesis of 4,4-di(methylamino)- and 4,4-dianilino-3,3-diaminobiphenyls is described. The condensation of the tetraaminobiphenyls mentioned with phenyl perfluorobutyrate has given, respectively, 1,1-dlmethyl- and 1,1-diphenyl-2,2-(n-perfluoropropyl)-5, 5-bibenzimidazolyls. A study of the thermal stability of the 2-perfluoroalkylbenzimidazoles has shown that the replacement of the hydrogen of the imino group in these compounds by a methyl or a phenyl radical considerably increases their heat stability.     

Zeolite Catalyzed Alkylation of Biphenyl. Where Does Shape-Selective Catalysis Occur?

Liquid-phase alkylation of biphenyl (BP) was studied over large-pore zeolites. Selective formation of the least bulky products, 4,4-diisopropylbiphenyl (4,4-DIPB) occurred only in the isopropylation of BP over one- or two-dimensional zeolites, H-mordenite (HM), ZSM-12, SSZ-24, SAPO-5, SSZ-31, and CIT-5. These shape-selective catalyses are ascribed to steric restriction of transition state and to easiness of the substrates to enter into the pores. HM gave the highest selectivity among them. The dealumination of HM enhanced catalytic activity and the selectivity for 4,4-DIPB because of the decrease of coke deposition. Non-regioselective catalysis occurs on external acid sites over HM with the low SiO₂/Al₂O₃ ratio because severe coke deposition deactivates the acid sites inside the pores by blocking pore openings. The selectivity of DIPB isomers was changed with propylene pressure and/or with reaction temperature. Selective formation of 4,4-DIPB was observed at moderate temperatures such as 250°C, whereas the decrease of the selectivity of 4,4-DIPB occurred at higher temperatures as 300°C. 4,4-DIPB yielded selectively under high propylene pressure (<0.3 MPa) at 250°C, while the selectivity of 4,4-DIPB decreased under low propylene pressure as 0.2 MPa. However, 4,4-DIPB was almost exclusive isomer in the encapsulated DIPB isomers inside the pores under every temperature and pressure. The decrease of the selectivity of 4,4-DIPB is due to the isomerization of 4,4-DIPB on the external acid sites. The deactivation of external acid sites of HM was examined by the modification with cerium and other rare earth metal oxide on HM. Selectivities of 4,4-DIPB were improved over modified HM even at high temperatures because of the suppression of non-regioselective alkylation and isomerization at the external acid sites. The ethylation of BP to ethylbiphenyls (EBPs) and diethylbiphenyls (DEBPs) was non-regioselective. The ethylation of BP to EBPs was controlled kinetically. However, there was difference in reactivities of EBPs and DEBPs for their further ethylation. 4-EBP was ethylated preferentially among the isomers, although the formation of 4,4-DEBP was less selective. 4-EBP and 4,4-DEBP have the highest reactivities among EBPs and DEBPs for the ethylation to polyethylbiphenyls (PEBPs). These results show that the environments of HM pores are too loose for shape-selective formation of the least bulky isomers, 4-EBP and 4,4-DEBP, in the ethylation of BP, and that HM pores have enough space for the further ethylation of 4,4-DEBP.     

7-Azaindole derivatives

A study is made of new synthetic routes, based on accessible 3-formyl-7-azaindoles, to 3-substituted 7-azaindole. 2-Phenyl-4-(1-phenyl-4-methyl-7-azaindolyl-3-rnethylene)-1, 3-oxazol-5-one is synthesized, and it is converted to 1-phenyl-4-methyl-7-azatryptophane, 1-phenyl-4-methyl-7-azaindolyl-3-acetic acid,1-phenyl-3-(,-dihydroxypropyl)-4-methyl-7-azaindole, and 1-phenyl-4-methyl-7-azaindolyl-3-pyrotartaric acid.For Part XVIII see [1].     

Spaltungen mittels Diazoniumverbindungen und Chinonimidchlorid, 2. Mitt.: Über die Reaktion von 4,4′-Dihydroxydiphenyl-äthan- und-propanderivaten mit Diazoniumsalzen und Chinonimidchlorid

Zusammenfassung 4,4-Dihydroxydiphenyl-äthan (I) und 4,4-Dihydroxydiphenyl-propan (II) geben beim Kuppeln mit p-Nitrobenzoldiazoniumchlorid die o-Kernkupplungsprodukte (III, IV, V) und reagieren mit Chinonimidchlorid nicht. Dagegen werden 2,4,6-Trimethylphenol (Mesitol), 4,4-Dihydroxy-3,5,3,5-tetramethyldiphenyl-äthan (VI) und 4,4-Dihydroxy-3,5,3,5-tetramethyldiphenyl-propan (VII) von p-Nitrobenzoldiazoniumchlorid zu 4-Hydroxy-3,5-dimethyl-4-nitroazobenzol und von Chinonimidchlorid zum 4-Hydroxy-3,5-dimethylphenolindophenol (IX) zum Teil gespalten. Der Reaktionsmechanismus wird diskutiert.Als erste Mitteilung dieser Reiho gilt: Mh. Chem.93, 1 (1962).     

Electronic structure and models of receptor of monooxygenase inductors from a number of polychlorinated polycyclic compounds. IV. MNDO calculations of halogen-substituted azobenzenes

The electron and geometric structures of the cis and trans isomers of 3,3,4,4-tetrachloroazobenzene (3,3,4,4-TCAB) and the trans isomers of 3,3,5,5-TCAB and 3,3-dichloro-4,4-difluoroazobenzene were calculated by the MNDO method. It was established that the trans isomer, which has a planar structure, is most stable for 3,3,4,4-TCAB. Change in the position of the Cl atoms in the azobenzene, i.e., the transition from 3,3,4,4-TCAB to 3,3,5,5-TCAB, does not lead to appreciable change in the formation energy, the position of the electronic levels, the nature of the frontier orbitals, or the charge distribution in the molecules. This gives reason to suggest that the biological activity of 3,3,4,4-TCAB is due to the metabolism products and not to the action of the substrates themselves.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1797–1801, August, 1990.     

Bisindoles. 26. Synthesis of 7,7-dichlorobis (5-indolyl) methane

7,7-Dichloro-2,2-dicarbethoxybis (5-indolyl) methane has been synthesized by cyclization of the 3,3-dichloro-4,4-diphenylmethanedihydrazone of ethyl pyruvate. Subsequent hydrolysis and decarboxylation of the corresponding diacid gave the unsubstituted 7,7-dichlorobis (5-indolyl) methane. The syn-syn, syn-anti, and anti-anti forms of 3,3-dichloro-4,4-diphenylmethanedihydrazone of ethyl pyruvate have been separated and characterized.For Communication 25, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1062–1065, August, 1988.     

Organodimagnesium derivatives of thiophene. 3. Synthesis of an organodimagnesium derivative of hexabromo-2,2′-dithienyl and its reaction with oxalic acid esters

It was established that the reaction of hexabromo-2,2-dithienyl with magnesium in the presence of ethyl bromide gives an organodimagnesium derivative, which reacts with oxalic acid esters to give 3,3,4,4-tetrabromo-5,5-dithienyl-diglyoxalic acid esters. Reduction of the latter with ethylmagnesium bromide leads to 3,3,4,4-tetrabromo-5,5-dithienyl-2,2-diglycolic acid esters.See [1] for Communication 2.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 468–470, April, 1981.     

Synthesis and oxidative polycondensation of 4, 4−diethynylbiphenyl

Summary 4,4-Diethynylbiphenyl was synthesized. By polycondensing it an oligomer with alternating biphenyl (-4,4) and diacetylene chains was obtained.     

Spaltungen mittels Diazoniumverbindungen und Chinonimidchlorid, 6. Mitt.: Über Hydroxychalkone

Zusammenfassung Es wird über die Reaktion verschieden methylsubstituierter 4-Hydroxychalkone mittels Chinonimidchlorid berichtet und gezeigt, daß die Ausbeute an 2,6-Dimethylphenol-indophenol bei der Spaltung von 4,4-Dihydroxy-3,5,3-trimethylchalkon (VII) am RingB dreimal so groß ist als beim 4,4-Dihydroxy-3,3,5-trimethylchalkon (III) am RingA.

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The reaction between several methyl-4-hydroxy-chalkones and p-benzoquinone-monochloroimine has been studied. It has been shown that the yield of 2.6-dimethylphenol-indophenol from the cleavage of 4.4-dihydroxy-3.5.3-trimethyl-chalkon (VII) at ringB is three times the yield resulting from the cleavage of 4.4-dihydroxy-3.3.5-trimethylchalkon (III) at ringA.

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Herrn Prof. Dr.H. Bretschneider zum 60. Geburtstag gewidmet.     

Reactions of the 2,2′,6,6′-tetra-tert-butyl-4,4′-bispyrylium cation with bases

From 2,2,6,6-tetra-tert-buty1-4,4-bispyrylium perchlorate by the action of aqueous solutions of sodium acetate or caustic soda we have obtained a spiran containing pyran and dihydrofuran rings the structure of which has been established by the x-ray structural method. It has been shown that under the same conditions sodium sulfide reduces the bispyrylium salt to 2,2,6,6-tetra-tert-butyl-4,4-bispyranylidene. For the product of the interaction of the bispyrylium salt with aqueous ammonia the structure of an unsaturated tetraketone is suggested. Possible mechanisms of the formation of the compounds mentioned are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 461–467, April, 1980.     

Synthesis, Spectral and Structural Study of N-[1-(N,N,N′,N′-Tetramethylphosphoramidoyl)- 1H-Benzimidazol-2-yl]-Propionimidic Ethyl Ether

The preparation of N-[1-(N,N,N,N-tetramethylphosphoramidoyl)-1H-benzimidazol-2-yl]-proponimidic ethyl ester 2 has been achieved by the reaction of N-(1H-benzimidazol-2-yl)-proponimidic acid ethyl ester 1 with N,N,N,N-tetramethylchlorophosphoramide. The structure of compound 2 has been determined by X-ray diffraction. The results of (¹H, ¹³C, ³¹P) NMR, IR, EI-MS spectral data are consistent with those obtained from the X-ray diffraction. The compound crystallizes in the triclinic system, following the EsZ conformation. In the crystal, there are two weak C3–H3s1 and C15–H15sO1 intermolecular hydrogen bonds.     

Electronic structure and models of monooxygenase inductor receptor from a number of polychlorinated polycyclic compounds. 5. MNDO calculations of halogen derivatives of azoxybenzenes

The MNDO method has been used to calculate the electronic and geometric structure of 3,3,4,4-tetraehloroazoxybenzene (TCAOB), 3,3,4,4-tetrachloro-6-hydroxyazobenzene (TCHAB), and 2,3,7,8-tetrachlorodibenzofuran (TCDF). The TCAOB exists in the gas phase in the form of two configurations, one nonplanar and one nearly planar. The latter is approximately 4 kcal/mole less stable than the first. The oxidation of 3,3,4,4-tetrachloroazobenzene (TCAB) to TCAOB is endothermic only in the case of the acton of hydrogen peroxide, not molecular oxygen. The isomerization of TCAOB to TCHAB proceeds with a gain in energy (–62 kcal/mole); however, the reaction from the ground state of the TCAOB molecule is symmetry-forbidden and is possible only from an excited state of the TCAOB. The process of oxidation of TCAOB and TCHAB by molecular oxygen to form TCDF or 2,3,7,8-tetrachlorobenzo-p-dioxin is energy-favorable; this is important in judging the biological action of TCAOB.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 101–105, January, 1991.     

Synthesis of benzotristriazole. 4-nitrobenzo[1,2-d:3,4-d′] bistriazole and 4,4′-dicarboxy-5,5′-1H-1,2,3-triazole

The treatment of 2,5,8-tri(2,4-dinitrophenyl)benzotristriazole, 2,7-di(2,4-dinitrophenyl)-4-nitrobenzo[1,2-d3,4-d]bistriazole, and 4,4-dicarboxy-5,5-bis[2- (2,4-dinitrophenyl)-2H-1,2,3-triazole with sodium methylate leads to loss of the 2,4-dinitrophenyl group as 2,4-dinitroanisole and formation of benzotristriazole, 4-nitrobenzo[1,2-d3,4-d]bistriazole, and 4,4-dicarboxy-5,5-bis-1H-1,2,3-triazole, respectively, in good yields.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1364–1367, October, 1993.     

The preparation by a solid-solid interaction route of aromatic polyamide materials containing sulphone, ether and ketone linkages

The polycondensation reactions between 4,4-[sulphonyl bis(p-benzoyl)(p-phenyleneoxy)]dibenzoic acid (I) andp-phenylenediamine (II), 1,5-diaminonaphthalene (III), 4,4-sulphonyldianiline (IV), 4,4-diaminodiphenylsulphide (V) 4,4-methylenedianiline (VI) and 4,4-oxydianiline (VII) to form aromatic polyamides containing sulphone, ether and ketone linkages were attempted by a solid-solid interaction route. A stoichiometric 11 molar ratio of solid reactants was dynamically heated directly in a TG/DSC apparatus, and simultaneous TG/FT-IR was performed to interpret the mechanism of reaction. The results suggest that the polycondensation is dependent on the diamine used. The formation of polyamide was successful when I interacted with II, III, VI and VII. The interaction with IV and V was in part successful because partial decarboxylation of the diacid, made unstable by the diamine, occurred before the condensation reaction.     

Complexes of some bivalent cobalt,nickel, copper,zinc, cadmium and monovalent silver salts with 4,4′-BipyridylN,N′-dioxide

Summary Coordination compounds have been prepared from 4,4-hipyridylN,N-dioxide (4,4-BipyO₂) and some hivalent metal halides, nitrates and thiocyanates as well as silver(1) nitrate.viz., Co(4.4-BipyO₂)₂Cl₂, Co(4.4-BipyO₂)Br₂, Co(4,4-Bi-pyO₂)(NO₃)₂. Co(4,4-BipyO₂)₂(NCS)₂. Ni(4.4-BipyO₂)₂Cl₂. Ni(4,4-BipyO₂)(NO₃)₂, Ni₂(4.4-BipyO₂)₃(NSC)₄. Cu(4,4-BipyO₂)(NO₃)₂. Zn(4,4-BipyO₂(NO₃)₂, Zn,(4.4-BipyO₂)₃-(NCS)₄. Cd(4.4-BipyO₂)(NO₃)₂, Cd(4.4-BipyO₂)₂(NCS)₂ and Ag(4,4-BipyO₂)(NO₃). The products were characterized by magnetic susceptibility. electronic and i.r. spectral measurements down to 200 cm^–1. Tentative stereochemistries for the complexes isolated in the solid state are proposed. The ligand field parameters 111 Dy. B. j3. )., and calculated for the cobalt. nickel and copper complexes are consistent with these stereochemistries.     

1,1′,2,2′,6,6′-Hexaphenyl-4,4′-bipyridinium cation radical

Aniline reacts with 2,2,6,6-tetraphenyl-4,4-bipyrilium perchlorate to form 1,1,2,2,6,6-hexaphenyl-4,4-bipyridine perchlorate. A relatively stable cation radical is formed in the first stage of electrochemical reduction of this compound, which has been examined by ESR, where there are splittings from two nitrogen nuclei and the four protons in the 3,3,5,5 positions: a_N=0.38; a_H=0.14 mT.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, No. 1, pp. 61–64, January–February 1992.     

Nitration,amination, and halogenation of Di-O-methylphloracetophenone

Chlorination of the title compound gave 5- and 3-chloro-2-hydroxy-4,6-dimethoxyacetophenone. The nitration of its acetate, followed successively by reduction, diazotization, and reaction with cuprous chloride, gave the 3-substituted series, 2-acetoxy-4,6-dimethoxy-3-nitroacetophenone, 3-amino-2-hydroxy-4,6-dimethoxyacetophenone, and 3-chloro-2-hydroxy-4,6-methoxyacetophenone, respectively. The orientation of substituents in the products was proved. The amino and chloro members of the isomeric 5-substituted series were availablevia 2-hydroxy-4,6-dimethoxy-5-phenylazoacetophenone, the product of the reaction of the title compound with benzenediazonium chloride.

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Nitrierung, Aminierung und Halogenierung von Di-O-methylphloracetophenon

Zusammenfassung Chlorierung der Titelverbindung gab 5- und 3-Chlor-2-hydroxy-4,6-dimethoxyacetophenon. Die Nitrierung des Acetats, gefolgt von Reduktion, Diazotierung und Reaktion mit CuCl ergab die 3-substituierte Reihe: 2-Acetoxy-4,6-dimethoxy-3-nitroacetophenon, 3-Amino-2-hydroxy-4,6-dimethoxyacetophenon und 3-Chlor-2-hydroxy-4,6-dimethoxyacetophenon. Die Orientierung der Substituenten wird diskutiert. Die Amino- und Chlorderivate der isomeren 5-substituierten Reihe sind über 2-Hydroxy-4,6-dimethoxy-5-phenylacetophenon zugängig, dem Produkt der Reaktion der Titelverbindung mit Phenyldiazoniumchlorid.

     

Untersuchungen an 4-Hydroxy-1-thiacumarinen, 3. Mit.: Reaktionen des 4-Hydroxy-1-thiacumarins mit aliphatischen und aromatischen Aldehyden und Dehydratation ihrer Kondensationsprodukte

Es wird die Darstellung einer Anzahl von 3,3-Methylen-bis-(4-hydroxy-1-thiacumarinen), von 3,3-Aryliden-bis-(4-hydroxy-1-thiacumarinen) mit verschiedenen Substituenten im aromatischen Ring und einiger 3,3-Aryliden-4,4-epoxydithiacumarine beschrieben. Die Bildung von Anhydroverbindungen bei Verwendung von Salicyladehyd als Aldehydkomponente bei derartigen Kondensationen wird diskutiert.The synthesis of a number of 3,3-methylene-bis-(4-hydroxy-1-thiacumarins), 3,3-arylidene-bis-(4-hydroxy-1-thiacumarins) carrying various substituents in the arylidene nucleus as well as that of the corresponding 3,3-arylidene-4,4-epoxydithiacumarins is described. The formation of anhydrocompounds when salicylaldehyde is the aldehyde component in such condensations is discussed.

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Teil der DissertationP. S. J. zur Erlangung der Würde eines Ph. D. der Karnatak University.