Intercalation of monomers into alpha tin(IV) hydrogen phosphate

Monomers which contain unsaturated linkages and amine groups have been intercalated to form either mono- or bi-layers. The monomertrans-N,N-diethyl-2-butene-1,4-diamine (NNBD) has been intercalated into -tin(IV) hydrogen phosphate. The guest molecule, NNBD, forms a monolayer (d ₀₀₁ = 1.35 nm) in which the amine groups are paired to protons on opposite faces of the phosphate layers. The resultant compound has the formula Sn(C₈H₁₈N₂)_0.73(HPO₄)₂·H₂O indicating that NNBD does not cover a large proportion of the available protons. 4-vinylpyridine slowly forms an intercalate in which the host molecule forms a bilayer (d ₀₀₁ = 1.56 nn). However, with 4-vinylpyridine there is surface modification in preference to intercalation.     

Intercalation of α,ω-Alkanediamines in Layered Aluminium Dihydrogen Triphosphate Dihydrate

Intercalation of ,-alkanediamines, NH₂(CH₂) _n NH₂ (n = 3–10), into layered aluminium dihydrogen triphosphate dihydrate, AlH₂(P₃(O₁₀... 2H₂O, was investigated by XRD, DTA-TG, elemental analysis, and solid-state ³¹P, ¹³C and ²⁷Al NMR. ,-Alkanediamines are intercalated to form a monomolecular layer in the interlayer region, in which the alkanediamines incline at 57 ± 5° to the phosphate layers, whereas n-alkylamines form a bilayer structure with the same inclination angle. Two amino groups in an ,-alkanediamine molecule bridge the layered sheets of phosphates.     

Intercalation ofn-alkylamines into α-titanium phosphate from aqueous solutions

The intercalation reactions betweenn-alkylamines and -titanium phosphate in aqueous media have been investigated. The compounds with the maximum intercalation have the formula -Ti(HOPO₃)₂ · 2 C _n H _2n+1 NH₂ · H₂O (n=1–10). Defined crystalline phases with lower amine content are described, the general formula being -Ti(HOPO₃)₂ · _m C _n H _2n+1 NH₂ ·pH₂O (m=1.0 1.3, 1.5, 1.7). Whenm=1.0 then-alkylamines form a monomolecular layer. Whenm>1.0 the layer is bimolecular. The inclination angle and the packing density of then-alkylamines in the interlayer space is determined.     

Intercalation of phenylethylamines intoα-zirconium phosphate and characterization of intercalates

The intercalation of phenylethylamines into-zirconium phosphate has been investigated by the pH titration method.dl-1-Phenylethylamine (dl-PEA) is taken up in two stages. New phases were obtained: Zr(HPO₄)₂(dl-PEA) · H2O in the first, and Zr(HPO₄)₂(dl-PEA)_/43· H₂O in the second stage. 2-Phenylethylamine (2-PEA) also is loaded in two stages, but the first end point is not observed clearly. A new phase, Zr(HPO₄)₂(2-PEA)₂ · H₂O has been formed at the second stage. The new phases have been characterized by elemental analysis, X-ray diffractometry, thermal analysis and IR spectroscopy.     

Zur Reaktion von Permethylcyclosilanen mit Halogenen

The series of ,-diiodopermethylpolysilanes, I(SiMe ₂) _n I, (n=4–6) andX(SiMe ₂)₄ X, (X=Cl, Br) has been prepared by the action of halogen on the corresponding cyclic compounds (SiMe ₂) _n . The mass spectra, NMR-, IR- andRaman-spectra of these compounds have been recorded.

Herrn Prof. Dr.Josef Schurz zum 60. Geburtstag gewidmet.     

Direct and stepwise intercalation of alkylalcohols intoα-zirconium phosphate

Intercalation of alkylalcohols into -zirconium phosphate was investigated at 25°C and/or under reflux.n-Alcohols having two to five carbons and 2-propanol were taken up at 25°C. These alcohols, andn-hexanol and heptanol, also intercalated under reflux.n-Alcohols having eight to eighteen carbon atoms intercalated when a stepwise method was employed. 2-Butanol and tertiary amylalcohols intercalated under reflux using a butanol intercalate as a starting material. Ethanol-to-butanol intercalates were unstable at room temperature, losing alcohols and changing to -zirconium phosphate. The particle size of the -zirconium phosphate did not affect the intercalation of alcohols.     

Intercalation of Cyclic Amines into α-Titanium Phosphate

The intercalation of some amines (aniline, benzylamine, cyclohexylamine,piperidine, pyridine, pyrazine and piperazine) into -titaniumphosphate, Ti(HPO₄)_2×H₂O,has been investigated by the batch method and/or by exposing the host to thevapour of the amines. The changes in the interlayer distance of the solidduring the intercalation process was followed by X-ray powder diffraction.The new intercalates were characterised by chemical and thermal analysis.Materials with a monolaminar and/or bilaminar arrangement of amine moleculesin the phosphate interlayer region are obtained depending on the nature ofthe amine. Due to steric hindrance, saturated phases are not obtained forall amines studied. The thermal decomposition of the intercalates (nitrogenatmosphere), takes place in three stages: dehydration, removal of amines andcondensation of the hydrogenphosphate to pyrophosphate groups.     

Studies of the energy spectrum of α, ω- substituted polymethine chains. II. Polymethine chains with odd number of methine groups

The analysis of the experimental data for the energy of the longest wavelength optical transitions _n,opt of substituted polymethines X (CH)_2n+1 X shows that in the asymptotic case (n) _,opt does not tend to zero, as it follows from the empirically established correlations, but has a finite, non-zero value. It is shown that the energy gap of odd polymethines is the same as that of the even polymethines - the polyenes (E 2 eV). The substituents (X N, O, B) are responsible for the appearance of levels in the gap. These, depending on the substituent character, are vacant (X B) or occupied (X N, O). The transition from or to such a level determines the longest wavelength optical transition energy of polymethines.     

Convergent synthesis of 2′,3′-dideoxy-3′-mercapto nucleosides — Potential anti-HIV agents

Summary Methyl 3-benzoylthio-5-O-tert-butyldiphenylsilyl-2,3-dideoxy--D-erythro-pentofuranoside (4) and its corresponding anomer5 were synthesized in four steps from 2-deoxy-D-ribose and used as substrates for the synthesis of nucleosides by condensation with silylated thymidine and N⁶-isobutyryladenine. The nucleosides were deprotected by treatment with Bu₄NF inTHF followed by reaction with MeONa in MeOH to give 3-deoxy-3-mercaptothymidine (8), 2,3-dideoxy-3-mercaptoadenosine (15) and its corresponding anomer16. In the latter reactions it was important to use degassed solvents to minimize formation of the corresponding disulfides of purine nucleosides. Using Bu₄NF, without subsequent reaction with MeONa in the deprotection reaction, resulted in intermolecular transesterification reactions.On leave from Chemistry Department, Faculties of Science and Education, Tanta University, Tanta, Egypt     

XPS characterization ofγ-zirconium phosphate and of some of its intercalation compounds. A comparison with the α-zirconium phosphate analogues

An X-ray photoelectron spectroscopic investigation of-Zr (HP0₄)₂·2 H₂O and its intercalation compounds with 1,10-phenanthroline, Co²⁺-phenanthroline and Cu²⁺-phenanthroline is described. The analysis of theNls spectra of the compound containing only phenanthroline clearly shows that, on average, more than one nitrogen atom of the diamine interacts with the acid groups of the host, giving protonated species. XPS also provides evidence of the coordination of Co²⁺ and Cu²⁺ ions after their diffusion in the phenanthroline--zirconium phosphate intercalation compound. They form mixed N-and O-coordinated species with the diamine and the oxygens of the interlayer region, but the presence of the characteristic peaks of uncoordinated phenanthroline, even at low intensity, shows that the diamine molecules anchored to the host are still present.A comparison is made with the analogous derivatives of -Zr (HPO₄)₂·H₂O and the differences between the two series of compounds are discussed.     

Homolytic addition of polyhaloalkanes to α-vinyloxy-ω-trialkylstannoxy-alkanes as a new route to 2-perhaloalkylmethyl-substituted 1,3-dioxacyclanes

Photoinduced reactions of -vinyloxy--trialkylstannoxyalkanes, CH₂=CHO(CH₂) _n OSnEt₃ (n = 2 to 4), with polyhaloalkanes result in 2-perhaloalkylmethyl-substituted 1,3-dioxacyclanes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1824–1826, September, 1995.     

2,2′-Diphenyl-Δ3,3′-bi-3H-indole-1,1′-dioxide: Molecular interactions and crystal structure

The Dinitrone 2,2-diphenyl-^3,3-bi-3H-indole-1,1-dioxide acts as a demethylating and dehydrogenating agent. The mechanism of interaction of the dinitrone with donors and acceptors does not involve intermediate charge-transfer complexes probably due to a self association between dinitrone molecules (as supported by X-ray determinations). The crystal structure of the dinitrone was obtained by direct methods;a=9.967 (2),b=19.817 (3),c=10.875 (2) Å, =111.2 (2)°, space group P2₁/n. The finalR andR _w were 0.089 and 0.063 for all measured reflexes.

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2,2-Diphenyl-^3,3-bi-3H-indol-1,1-dioxid: Molekulare Wechselwirkungen und Kristallstruktur

Zusammenfassung Das Dinitron 2,2-Diphenyl-^3,3-bi-3H-indol-1,1-dioxid wirkt als Demethylierungs- und Oxydationsmittel. Die Wechselwirkung des Dinitrons mit Elektronen-Acceptoren und Elektronen-Donatoren geht wegen der Selbstassoziation zwischen den Dinitron-Molekülen ohne die dazwischenliegende Bildung eines Charge-Transfer-Komplexes vor sich; das wird auch von Röntgenstrukturuntersuchungen gestützt. Die Kristallstruktur wurde mit direkten Methoden ermittelt:a=9.967 (2),b=19.817 (3),c=10.875 (2) Å; =111.2 (2)°. P2₁/n. Die endgültigen WerteR undR _w waren 0.089 und 0.063 für alle gemessenen Reflexe.

     

Glykosylazide als Ausgangsbasis zur Gewinnung von Nucleosidanalogen, 3. Mitt. Synthese von Alkylaminotetrazol- und Uretidinonnucleosiden

The -ribofuranosylazide1 is transformed after usual derivatization by suitable protecting groups into the P–N-ylid2, which gives the corresponding N-Glykosyl-N-alkylcarbodiimides4 and a small amount of the glykosylisocyanatde-rivative3 by reaction with alkylisocyanates. The carbodiimides4 were reacted with hydrazoic acid to give the alkylaminotetrazolnucleosides5 and finally the free nucleosidanalogs6. In the case of5 c the 5-aziridinyltetrazolnucleosid5 h was formed by an usual neighbouring group reaction. In addition the compound1 is transformed into the 3,5-diprotected anchor derivative7 by reaction withTIPSCl₂. The latter could be transformed by usual steps into the alkylaminotetra-zolnucleosides8 with a free 2-OH group. In the next step the 2-p-tolylthiocarbo-nates9 were prepared followed by transformation to the 2-desoxynucleosides10 by means of tributyltinhydride. Finally the free 2-desoxynucleosides11 were prepared. By reacting the carbodiimides4 with phenylisocyanate a mixture of the two possible regiouretidinonnucleosidderivatives12 and13 are formed. In the case of the N-glykosyl-N-allylcarbodiimide4 d only the one isomer13 d arises.

Herrn Prof. Dr.A. Neckel mit den besten Wünschen zum 60. Geburtstag gewidmet.     

Reactions of dodecacarbonyltriruthenium with α,β-unsaturated ketones. Crystal and molecular structures of two reaction products

The thermal reactions of Ru₃(CO)₁₂ with RCOCH=CHPh (R=Me, p-MeC₆H₄) in hydrocarbon solvents lead to the formation of a series of complexes, several of which have been isolated as individual compounds by chromatography. The dinuclear complex Ru₂(-H)(CO)₆(-MeCOCH=CPh) and the tetranuclear complex Ru₄(-H)(-CO)(CO)₇(p-MeC ₆H₄ COCH=CPh)(-p-MeC₆H₄COCH=CPh)(₄-p-MeC₆H₃COCH=CHPh) are characterized by an X-ray structural study. The structures of other reaction products are discussed on the basis of spectral data. The reactions are accompanied by reduction of the starting enones to the corresponding unsaturated ketones.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1285–1293, July, 1993.     

Synthesis of γ-zirconium phosphate by the fluoro-complex method and the intercalation behavior of some α-diimines

The ammonium form of -zirconium phosphate has been synthesized by the direct precipitation method from fluorozirconate solution in the presence of ammonium dihydrogen phosphate. The hydrogen form Zr(HPO₄)₂ · 2H₂O, was obtained by acid treatment of the ammonium form -Zirconium phosphate , Zr(HPO₄)₂ · H₂O, with a relatively large particle size resulted from fluorozirconate solution in the presence of concentrated orthophosphoric acid. The intercalation behavior of such -diimines as 2,2-bipyridine (bpy) and 1,10-phenanthroline (phen) toward -zirconium phosphate was investigated, and it was found that about 0.2 mol of bpy and 0.5 mol of phen have been incorporated respectively per one mol of the host, with the expansion of interlayer distances. Further incorporation of Cu(H) ions into the interlayer space of these intercalates was possible. The bpy intercalate took up more Cu(II) ions than -zirconium phosphate, indicating that effective pillars are constructed between layers and the ion exchange of Cu(II) ions is facilitated thereby.     

Intercalation of ferrocene and dimethylaminomethylferrocene into α-Sn(HPO4)2 · H2O and α-VOPO4 · 2H2O

The intercalation of ferrocene and dimethylaminomethylferrocene into -tin(IV) hydrogen phosphate (SnP) and -vanadyl phosphate has been investigated. Successful intercalation of 0.81 mol of dimethylamino-methylferrocene into -SnP by an acid-base reaction in aqueous medium to form a bilayer of protonated amines was achieved. However, ferrocene was not intercalated under the same conditions. Intercalation of -vanadyl phosphate by 0.11 mol of ferrocene in acetonic medium at room temperature was effected by a redox topotactic reaction. The voluminous dimethylaminomethylferrocene was not intercalated into -vanadyl phosphate.     

Effect of fusion conditions ofβ-polypropylene on the new crystallization

The new crystallization of -modification of polypropylene (-PP) was studied after melring as a function of the final temperature of fusion (T _F ). The new crystallization, thermal characteristics, polymorphic composition, and structure of recrystallized samples were highly influenced by theT _F level. As a function ofT _F , three characteristic regions were outlined: Region I below the melting point of -modification, region II between the melting points of - and -modifications, and region III above the melting point of -modification. In the vicinity of the melting points of both modifications, two narrow transition regions are observed where the crystallization and structural characteristics changed abruptly withT _F . AtT _F values in region I, recrystallization of -modification proceeded without any change in the modification. IfT _F fell in region II, the sample crystallized newly into -modification. The optically negative -ring-spherulites were replaced by positive microclusters of -modification and a marked structural memory effect was observed. In region III, the above characteristic became invariant withT _F (region of blank melt). These observations may be interpreted by the role of self nuclei.     

Synthesis of 2′,3′-dideoxynucleosides from 5-alkoxymethyluracils

Summary A modified synthesis of protected 2,3-dideoxyribose5 starting fromL-glutamic acid (1) is described. Reaction of5 with silylated 5-hydroxymethyluracil7 a and 5-alkoxymethyluracils7 b–e in the presence of trimethylsilyl triflate afforded an anomeric mixture of 2,3-dideoxyuridine derivatives8 a–e and9 a–e. Deprotection with methanolic ammonia and separation by chromatography gave the corresponding nucleosides10 a–e and11 a–e. Treatment of9 b–e with tri(1H-1,2,4-triazol-1-yl)phosphine oxide and subsequent reaction of12 b–e with ammonia in dioxane afforded the cytosine derivatives13 b–e which on treatment with methanolic ammonia gave the corresponding 2,3-dideoxycytidine derivatives14 b–e and15 b–e. In contrast with the parent compounds, these alkoxymethyl derivatives had no appreciable activity against human immunodeficiency virus (HIV-1).

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Synthese von 2,3-Dideoxynucleosiden aus 5-Alkoxymethyluracilen

Zusammenfassung Ausgehend vonL-Glutaminsäure (1) wird eine modifizierte Synthese von geschützter 2,3-Dideoxyribose (5) beschrieben. Reaktion von5 mit silyliertem 5-Alkoxymethyluracilen7 b–e in Gegenwart von Trimethylsilyltriflat ergab anomere Mischungen der 2,3-Dideoxyuridinderivate8 a–e und9 a–e. Abspaltung der Schutzgruppe mit methanolischen Ammoniak und chromatographische Trennung ergab die entsprechenden Nucleoside10 a–e und11 a–e. Behandlung von9 b–e mit Tri(1H-1,2,4-triazol-1-yl)phosphinoxid und nachfolgende Reaktion von12 b–e mit Ammoniak in Dioxan ergab die Cytosinderivate13 b–e, welche nach Behandlung mit methanolischem Ammoniak die entsprechenden 2,3-Dideoxycytidinderivate14 b–e und15 b–e ergaben. Im Gegensatz zur Stammverbindung hatten diese Alkoxymethylderivate keine nennenswerte Wirksamkeit gegen den menschlichen Immunschwächevirus (HIV-1).

     

Transition Metal Halide Salts of 1,3-bis(4-Pyridyl)propane: Synthesis and Structural Characterization

The resulting salts of (H₂bpp)MX₄ · n H₂O (M = Zn, X = Cl, n = 1, 1; M = Cd, X = Br, n = 0, 2; M = Hg, X = Cl, n = 1, 3; M = Cu, X = Cl, n = 0, 4; M = Cu, X = Br, n = 1, 5; M = Pt, X = Cl, n = 1, 6) were crystallized from the reaction mixture prepared by adding MX₂ to the HX solution of 1,3-bis(4-pyridyl)propane (bpp), while the salt of colorless (H₂bpp)SnCl₆, 7, was crystallized from the reaction mixture prepared by adding SnCl₂ to the HCl solution of bpp. Their structures have been determined by X-ray crystallography. All the compounds show supramolecular structures in the solid state by intermolecular hydrogen bondings and aromatic – interactions. The H₂bpp²⁺ cations in these metal salts adopt the gauche–gauche and anti–anti conformations with different dihedral angles for the two pyridyl rings.     

Synthesis of 5′-amino- and 5′-azido-2′,5′-dideoxy nucleosides from thieno[2,3-d]pyrimidine-2,4(1H,3H)-dione

Summary Thieno[2,3-d]pyrimidine-2,4(1H,3H)-dione (4) was silylated and condensed with methyl 5-azido-2,5-dideoxy-3-O-(4-methylbenzoyl)-D-erythro-pentofuranoside (2) in the presence ofTMS triflate to afford the corresponding protected nucleoside6 and acyclic nucleoside7. Deprotection of6 with MeONa/MeOH at room temperature gave 1-(5-azido-2,5-dideoxy--D-erythro-pentofuranosyl)-thieno[2,3-d]pyrimidine-2,4(1H,3H)-dione (8) and the corresponding anomer9, whereas compound7 yielded 5-azido-2,5-dideoxy-1-(2,4-dioxo-1,2,3,4-tetrahydrothieno[2,3-d]pyrimidin-1-yl)-1-O-methyl-D-erythro-pentitol (10) under the same reaction conditions. 1-(5-Amino-2,5-dideoxy--D-erythro-pentofuranosyl)thieno[2,3-d]pyrimidine-2,4(1H,3H)-dione (11) was obtained on treating9 with Ph₃P in pyridine followed by hyrolysis with NH₄OH. The anomeric nucleosides14 and15 and the corresponding acyclic nucleoside16 were obtained when4 was trimethylsilylated and condensed with methyl 2-deoxy-3,5-di-O-(4-methylbenzoyl)-D-erythro-pentofuranoside (3) followed by deprotection with MeONa in MeOH. Compounds8 and9 were also obtained when the anomeric mixture14/15 was treated with a mixture of NaN₃, Ph₃P, and CBr₄ in dryDMF at room temperature.On leave from Chemistry Department, Faculty of Science, Tanta University, Tanta, Egypt