The reaction of 4-methoxycoumarins with prenyl bromide: Synthesis of 4′,4′,5′-trimethyl-dihydrofurano-coumarins and 2,2-dimethyl-chromenopyrans

The reaction of 7-hydroxy-4-methoxy- (1a), 7-hydroxy-4,5-dimethoxy-(1b) and 5-hydroxy-4,7-dimethoxy (1c) -2H-1-benzopyran-2-ones with prenyl bromide in acetone in the presence of anhydrous potassium carbonate gave the corresponding prenyloxycoumarins1d,1e, and1f. The prenyloxy coumarins1d,1e,1f onClaisen migration by refluxing inN,N-dimethyl aniline gave the corresponding 4,4,5-trimethyl-dihydrofuranocoumarins2a,2b, and3. However, the reaction of1a,1b, and1c with 3-chloro-3-methyl-but-1-yne in acetone in presence of potassium carbonate and potassium iodide gave the corresponding propargyl ethers1g,1h,1i, which on refluxing inN,N-dimethyl aniline gave the corresponding 2,2-dimethylchromenopyrans4a,4b, and5. These can also be obtained directly if the reaction is carried out in the presence of dioxan.

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Die Reaktion von 4-Methoxycumarinen mit Prenylbromid: Synthese von 4,4,5-Trimethyl-dihydro-furanocumarinen und 2,2-Dimethylchromenopyranen

Zusammenfassung Die Reaktion von 7-Hydroxy-4-methoxy-(1a), 7-Hydroxy-4,5-dimethoxy-(1b) und 5-Hydroxy-4,7-dimethoxy-2H-1-benzopyran-2-onen (1c) mit Prenylbromid in Aceton in der Gegenwart von wasserfreiem Kaliumcarbonat ergab die entsprechenden Prenylcumarine1d,1e und1f. Diese ergaben durchClaisen-Wanderung bei Rückfluß inN,N-Dimethylanilin die entsprechenden 4,4,5-Trimethyldihydrofuranocumarine2a,2b und3. Die Reaktion von1a,1b und1c mit 3-Chlor-3-methyl-1-butin in Aceton in Gegenwart von wasserfreiem Kaliumcarbonat und Kaliumjodid ergab die entsprechenden Propargylether1g,1h und1i, die ihrerseits bei Rückfluß inN,N-Dimethylanilin die jeweiligen 2,2-Dimethylchromenopyrane4a,4b und5 ergaben. Letztere können auch direkt erhalten werden, wenn die Reaktion in Gegenwart von Dioxan durchgeführt wird.

     

Synthese arylsubstituierter 2-Pyrimidinamine,Dihydro-2-pyrimidinamine und Pyrimido[1,2-a]pyrimidine durch Reaktion von Guanidin mit Chalkonen

4- and 4-methoxy-, 4-hydroxy- and 2-hydroxychalcone4 e,k,f andg, respectively, are transformed by action of guanidine in benzene to yield 4-(4-methoxyphenyl)-6-phenyl-2-pyrimidinamine (6 e=6 k) and hydroxyphenylpyrimidinamines6 f andg, respectively. In contrast, 4- and 4-chlor-, 4-brom- and 4-phenylchalcone4 h,l–n resp. react with guanidine under analogous conditions to give 4,6-diaryl-1,4-dihydro-2-pyrimidinamines5 h,l–n. The bases5 h,l–n also tend to aromatize, but they can be stabilized by transformation into salts5 h,l–n · HCl with hydrochloric acid. Heating of5 n inDMF under atmospheric oxygen yields 4-(4-biphenyl)-6-phenyl-2-pyrimidinamine (6 n). Action of guanidine on 4-nitrochalcone4 o in chloroform affords 2-amino-4-nitrophenyl-6-phenyl-tetrahydro-4-pyrimidinol8 o, which is transformed by hydrochloric acid into 6-nitrophenyl-dihydropyrimidinamine-hydrochloride5 o · HCl. Treating of the latter with sodiummethylat in methanol yields the very stable dihydropyrimidinamine5 o. Action of guanidine on 4-chlor- and 4-bromchalcone4 h andm respectively (in addition to5 h andm) yields 2,4,6,8-tetraaryl-1,4-dihydro-2H-pyrimido[1,2-a]pyrimidines7 h andm, respectively.

Herrn Prof. Dr.Erwin Schauenstein mit den besten Wünschen zum 65. Geburtstag gewidmet.     

On the Interaction of Two Finite-Dimensional Quantum Systems

Interaction of quantum system S ^a described by the generalised × eigenvalue equation A| _s =E _s S ^a | _s (s=1,...,) with quantum system S ^b described by the generalised n×n eigenvalue equation B| _i = _i S ^b | _i (i=1,...,n) is considered. With the system S ^a is associated -dimensional space X ^a and with the system S ^b is associated an n-dimensional space X _n ^b that is orthogonal to X ^a . Combined system S is described by the generalised (+n)×(+n) eigenvalue equation [A+B+V]| _k = _k [S ^a +S ^b +P]| _k (k=1,...,n+) where operators V and P represent interaction between those two systems. All operators are Hermitian, while operators S ^a ,S ^b and S=S ^a +S ^b +P are, in addition, positive definite. It is shown that each eigenvalue _{k i} of the combined system is the eigenvalue of the × eigenvalue equation . Operator in this equation is expressed in terms of the eigenvalues _i of the system S ^b and in terms of matrix elements _s |V| _i and _s |P| _i where vectors | _s form a base in X ^a . Eigenstate | _k ^a of this equation is the projection of the eigenstate | _k of the combined system on the space X ^a . Projection | _k ^b of | _k on the space X _n ^b is given by | _k ^b =( _k S ^b –B)^–1(V– _k P})| _k ^a where ( _k S ^b –B)^–1 is inverse of ( _k S ^b –B) in X _n ^b . Hence, if the solution to the system S ^b is known, one can obtain all eigenvalues _{k i} } and all the corresponding eigenstates | _k of the combined system as a solution of the above × eigenvalue equation that refers to the system S ^a alone. Slightly more complicated expressions are obtained for the eigenvalues _{k i} } and the corresponding eigenstates, provided such eigenvalues and eigenstates exist.     

Synthesis and structure of tris(4-ferrocenylphenyl)boroxine and its utility in cross-coupling reaction

The reaction of 4-bromophenylferrocene with butyllithium followed by treatment of the organolithium compound with tributyl borate afforded tris(4-ferrocenylphenyl)boroxine (2). X-ray diffraction study of the solvate 2·2C₆H₆ revealed an intermolecular stacking interaction between the boroxine ring and the Cp rings in the crystal structure. Cross-coupling of compound 2 with 4-bromo-4-nitro-1,1-biphenyl produced 4-ferrocenyl-4-nitro-1,1:4,1-terphenyl (3). X-ray diffraction study of terphenyl 3 showed that this compound crystallizes in the noncentrosymmetric space group P2₁. In the crystal, molecules 3 are packed in an antiparallel head-to-tail fashion, which is unfavorable for generation of strong nonlinear optical effects.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2657–2662, December, 2004.     

Stereodifferentiation of some chiral monoterpenes using multidimensional gas chromatography

Summary Heptakis (2,3,6-tri-O-alkyl)--cyclodextrins are used as chiral stationary phases for the resolution of -pinene (1), -pinene (2), limonene (3), -terpineol (4), linalool (5) and the furanoid cis/trans linalool oxides (6) by chirospecific CGC-analysis. The first investigations on the direct chirality evaluation of the monoterpenoid grape and wine flavour compounds 4–6 are reported using enantioselective multidimensional gas chromatography (MDGC) and chiral main columns, coated with peralkylated -cyclodextrins. The fresh grape juice, the corresponding must, the young and the bottle maturated wine of muscat cultivars are investigated.     

Cubane-Type Molybdenum-Zinc or -Cadmium Mixed-Metal Clusters with Diethyldithiophosphate or Nitrilotriacetate Ligands

The reactions of sulfur-bridged clusters, [Mo₃( ₃-S)(-S)₃(-dtp)(dtp)₃(CH₃CN)] (1) in acetonitrile or [Mo₃( ₃-S)(-S)₃(Hnta)₃]^2– (2) in pure water, with zinc or cadmium metal result in the formation of three novel molybdenum-zinc or molybdenum-cadmium mixed-metal clusters, [Zn{( ₃-S)₄Mo₃(-dtp)(dtp)₃(CH₃CN)}₂] (3), [Cd{( ₃-S)₄Mo₃(-dtp)(dtp)₃(CH₃CN)}₂] (4), and [Cd{( ₃-S)₄Mo₃(Hnta)₃}₂]^4– (5), respectively. The X-ray crystal structures of 1·H₂O(1), 3, 4, and [Co(H₂O)₆]₂ 5·22H₂O (5) were determined, and the existence of the sandwich cubane-type cores Mo₃S₄MS₄Mo⁸⁺ ₃ cores (M=Zn, Cd) in 3, 4, and 5 verified. By the change of the ligands, the peak positions at the longest wavelength in the electronic spectra are distinctly different from each other between 4 (856 nm) and 6 (1235 nm). The electronic structures of 3, 4, and 5 have been calculated by Discrete Variational (DV)-X method.     

Chemistry of Tetraosmium Carbonyl Clusters with Phenylazopyridine Ligands: Synthesis, Structure and Electrochemistry

Two new tetraosmium carbonyl clusters [Os₄(-H)₄(CO)₁₁{ ¹-NC₅H₄(N=N)C₆H₅}] (1) and [Os₄(-H)₄(CO)₁₀{ ²-NC₅H₄(N=N)C₆H₅}] (2) were synthesized from the reaction of [Os₄(-H)₄(CO)₁₂] with two equivalent of 2-phenylazopyridine ligand in dichloromethane at ambient temperature using trimethylamine-N-oxide as the decarbonylation reagent. Subsequent chromatographic purification led to the isolation of 1and 2as stable orange and blue solids in respectively 25 and 13% yields. Complex 1converted to 2in a 25% yield in refluxing chloroform. Treating a solution of [Os₄(-H)₄(CO)₁₂] in dichloromethane with two equivalent of 3-phenylazopyridine led to the formation of another two new clusters [Os₄(-H)₄(CO)₁₁{ ¹-NC₅H₄(N=N)C₆H₅}] (3) and [Os₄(-H)₄(CO)₁₀(NMe₃){ ¹-NC₅H₄(N=N)C₆H₅}] (4), which could be isolated as yellow solids in 34% and 21% yields respectively. Thermolysis of 3or 4in refluxing n-hexane gives [Os₄(-H)₃(CO)₁₀{- ³-NC₅H₃(N=N)C₆H₅}] (5) in 24 and 33% yields respectively. Their electronic absorption properties and electrochemical behavior are also reported.     

Synthesis,crystal structure,and properties of 2H-4,8-dimethylfuro[2′,3′:5,6]naphtho[1,2-b]pyran-2-one,a novel DNA intercalator

Summary The furonaphthopyrone6, a novel DNA intercalator, was synthesized in two steps (ca. 56% overall yield) starting from naphthopyrone3. The new naphthopyrone derivatives4 and6 were fully characterized and the absorption and fluorescence spectroscopic properties of6 were determined. The dark interactions of furonaphthopyrone1 and6 with DNA have been investigated by a fluorescence quenching technique and their apparentScatchard binding constants were calculated. The crystal structure of6 was determined. The planarity of6 and the geometry of the active double bond between the -pyrone and the furan moieties of6 suggest that furonaphthopyrones are efficient monofunctional DNA intercalators.

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Synthese, Kristallstruktur und Eigenschaften von 2H-4,8-Dimethylfuro[2,3:5,6]naphtho[1,2-b]pyran-2-on, einem neuen DNA-Intercalator

Zusammenfassung Der neue DNA-Intercalator6 wurde, ausgehend vom Naphthopyron3, in zwei Stufen mit einer Gesamtausbeute vonca. 56% hergestellt. Die neuen Naphthopyronderivate4 und6 wurden vollständig charakterisiert; die Absorptions- und Fluoreszenzeigenschaften von6 wurden bestimmt. Die Dunkelwechselwirkungen von1 und6 mit DNA wurden mittels einer Fluoreszenzquenchtechnik untersucht; ihreScatchard-Bindungskonstanten wurden berechnet. Die Kristallstruktur von6 wurde bestimmt. Die Planarität von6 und die Geometrie der aktiven Doppelbindung zwischen dem -Pyron- und dem Furanteil von6 lassen erwarten, daß Furonaphthopyrone effiziente monofunktionelle DNA-Intercalatoren sind.

     

Über die Umsetzung von 6-Chlor-4-phenyl-3,4-dihydro-1H-2,1,3-benzothiadiazin-2,2-dioxid mit 1,4-Dijodbutan

Zusammenfassung Bei der Umsetzung des Dinatriumsalzes von 6-Chlor-4-phenyl-3,4-dihydro-1H-2,1,3-benzothiadiazin-2,2-dioxid (1) mit 1,4-Dijodbutan inDMF wurde das erwartete 1,3-Butano-derivat nich erhalten.1 wurde einerseits zu 6-Chlor-4-phenyl-1H-2,1,3-benzothiadiazin-2,2-dioxid (4) dehydriert, andrerseits traten je nach Herstellungsweise des Dinatriumsalzes Methylierungsreaktionen ein bzw. es entstanden 6-Chlor-1-(4-jodbutyl)-4-phenyl-3,4-dihydro-1H-2,1,3-benzothiadiazin-2,2-dioxid (7) und 6,6-Dichlor-4,4-diphenyl-3,3,4,4-tetrahydro-3,3-tetramethylenbis(1H-2,1,3-benzothiadiazin)-2,2,2,2-tetroxid (8).

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Reaction of 6-chloro-4-phenyl-3,4-dihydro-1H-2,1,3-benzothiadiazine-2,2-dioxide with 1,4-Diiodobutane. (Cyclic and bicyclic sulfamides III)

On reaction of the disodium salt of 6-chloro-4-phenyl-3,4-dihydro-1H-2,1,3-benzothiadiazine-2,2-dioxide (1) with 1,4-diiodobutane inDMF the expected 1,3-butano derivative was not obtained. On the one hand1 was dehydrogenated to give 6-chloro-4-phenyl-1H-2,1,3-benzothiadiazine-2,2-dioxide (4), on the other hand according to the method of preparation of the disodium salt either methylation reactions occured or 6-chloro-1-(4-iodobutyl)-4-phenyl-3,4-dihydro-1H-2,1,3-benzothiadiazine-2,2-dioxide (7) and 6,6-dichloro-4,4-diphenyl-3,3,4,4-tetrahydro-3,3-tetramethylenebis(1H-2,1,3-benzothiadiazine)-2,2,2,2-tetroxide (8) were formed.

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Herrn Prof. Dr.H. Nowotny gewidmet.     

Über spasmolytisch wirksame 1-Phenyl-isochinoline und Bis-(phenyläthyl)-amine mit Guajacyl-gruppierung

Zusammenfassung Die Synthese des 1-Phenyl-6-methoxy-7-oxy-isochinolins, des1-(3-Methoxy-4-oxy-phenyl)-6-methoxy-7-oxy-isochinolins sowie des1-(3,5-Dimethoxy-4-oxy-phenyl)-6-methoxy-7-oxy-isochinolins wird beschrieben. Als weitere Spasmolytika wurden das Bis-(3-methoxy-4-benzyloxy--phenyläthyl)-amin, dessen N-Methylderivat und das Bis-(3-Methoxy-4-oxy--phenyläthyl)-amin dargestellt. Vereinfachte Synthesen der Ausgangsprodukte, Benzylsyringasäure, Syringaaldehyd und Benzylsyringaaldehyd, wurden ausgearbeitet. K. Kratzl undG. Billek, Mh. Chem.83, 1409 (1952).     

Reaktionen mit phosphororganischen Verbindungen, 48. Mitt.

Reaction of the vicinal diols of steroids1, 5, 7, 10, 13, and16 with TPP/DEAD yields both regio-and stereospecifically the oxosteroids2, 6, 8, 11, 14, and15 by displacement of an axial hydrogen and extrusion ofTPPO besides the cholest-4-en-6-ols9 and12 and the cyclic carbonate3. 16, 17-androstandiol16 gives only the cyclic carbonate17. The different structures of the carbohydrates withcis-diol arrangement19 and21 lead exclusively to cyclic carbonates20 and22 in moderate yields. Treatment of1 with TPP/DEAD/HN₃ affords 3-azido-2-hydroxycholestane4 in addition to the above mentioned2.

     

Zur Chemie des „Dinaphthyldichinhydron”

Dinaphthyldiquinhydrone (4) first obtained byStenhouse andGroves ² reacts as well as 4,4-bi-(1,2-naphthoquinone)¹ with aniline and substituted anilines to give anilinoquinones2 a-h. However, yields of2 are considerable higher if4 is used. The IR-Spectrum of4 is very similar to that of 2,11-dihydroxy-3,10-perylenquinone, therefore we suggest for4 a the structure of a 3,3-dihydroxy-4,4-dioxo-1,1, 4,4-tetrahydro-1,1-binaphthylidene, at least in the solid state.

Herrn Prof. Dr.G. Zigeuner in traditionsverbundener Freundschaft zum 60. Geburtstag gewidmet.     

Influence of the β-substitution on the photochemistry of α,2-diacetoxystyrenes. Irradiation of phenyl,vinyl, and benzyl derivatives

Summary -Substitution shows a pronounced influence on the photochemistry of ,2-diacetoxystyrenes. As in the case of the parent compound, intramolecular cyclization with participation of the neighbouring 2-acetoxy group takes place upon irradiation of the enol esters4a–c; however other processes are also observed, depending on the substrate. The phenyl derivative4a gives theE isomer7a and the phenanthrene9. The vinyl derivative4b also undergoescis-trans isomerization and/or photooxidation, to afford7b and10. Finally, a 1,4-acyl migration occurs in the benzyl derivative4c, whereby the 1,4-diketone12 is formed.

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Einfluß der -Substitution auf die Photochemie von ,2-Diacetoxystyrolen. Bestrahlung von Phenyl-, Vinyl- und Benzylderivaten

Zusammenfassung Bei ,2-Diacetoxystyrolen haben die -Substituenten einen deutlichen Einfluß auf das photochemische Verhalten. Wie im Fall der Stammverbindung erfolgt bei der Bestrahlung der Enolester4a–c intramoleukulare Cyclisierung unter Einbeziehung der benachbarten 2-Acetoxygruppe; jedoch werden je nach Substrat auch andere Reaktionen beobachtet. Das Phenylderivat4a liefert dasE-Isomer7a und das Phenanthren9. Das Vinylderivat4b erfährt ebenfallscis/trans-Isomerisierung zu7b und/oder Photooxidation zu10. Beim Benzylderivat4c tritt eine 1,4-Acylverschiebung zum 1,4-Diketon12 auf.

     

Synthesis of obtusinin and 7-(3′-hydroxymethylbut-2′-enyloxy)-6-methoxy-2H-1-benzopyran-2-one

Obtusinin (1) has been synthesised by the reaction of 6-methoxy-7-(3-methylbut-2-enyloxy)-2H-1-benzopyran-2-one (3) with OsO₄. Synthesis of 7-(3-hydroxymethylbut-2-enyloxy)-6-methoxy-2H-1-benzopyran-2-one (2) has been achieved by the regiospecific oxidation of3 with SeO₂ followed by reduction of the formed aldehyde with KBH₄.

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Synthese von Obtusinin und 7-(3-Hydroxymethylbut-2-enyloxy)-6-methoxy-2H-1-benzopyran-2-on

Zusammenfassung Obtusinin (1) wurde über 6-Methoxy-7-(3-methylbut-2-enyloxy)-2H-1-benzopyran-2-on (3) mit OsO₄ synthetisiert. Die Darstellung von 7-(3-Hydroxymethylbut-2-enyloxy)-6-methoxy-2H-1-benzopyran-2-on (2) wurde mittels regioselektiver Oxidation von3 mit SeO₂, gefolgt von Reduktion des gebildeten Aldehyds mit KBH₄, bewerkstelligt.

     

1-Aryl-6-azauracile, 5. Mitt.: Die Synthese von 1-(β-Pyridyl)-6-azauracil-5-carbonsäure und einiger ihrer Derivate

Zusammenfassung Analog wie in vorherigen Mitteilungen^1–4 wurden -Pyridyl-hydrazono-cyanacetylcarbamidsäureäthylester (1), 1-(-Pyridyl)-5-cyan-6-azauracil (2), 1-(-Pyridyl)-6-azauracil-5-carbonsäure (3), deren Thioamid (4), und Amidoxim (5), welches in 1-(-Pyridyl)-5-[5-methyl-1,2,4-oxdiazolyl(3)]-6-azauracil (6) überge-führt wurde, hergestellt.

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-Pyridylhydrazono-cyanacetylcarbamic acid ethyl ester (1), l-(-pyridyl)-5-cyano-6-azauracil (2), 1-(-pyridyl)-6-azauracil-5-carboxylic acid (3), its thioamide (4) and amidoxime (5) were prepared as described in preceding communications. (5) was converted into l-(-pyridyl)-5-[5-methyl-1,2,4-oxdiazolyl(3)]-6-azauracil (6).

     

Transformations of 1-azinyl-4-ethoxycarbonyl thiosemicarbazides. The synthesis of 3-ethoxycarbonylamino-s-triazolo[4,3-x]azines

1-Azinyl-4-ethoxycarbonyl thiosemicarbazides4,5, and12 and 1-azinyl-4-ethoxycarbonylmethyl thiosemicarbazide17, prepared from the corresponding heterocyclic hydrazino compounds and ethoxycarbonyl isothiocyanate or ethoxycarbonylmethyl isothiocyanate, were converted by oxidation with bromine in acetic acid into derivatives of fused 3-ethoxycarbonylamino-s-triazolo[4,3-a]pyridine6, -pyridazine7, and -pyrazine13,18 and20. The thiosemicarbazide derivative8 was transformed at 0 °C into bis-s-triazolo[4,3-b:34-f]pyridazine derivative9, while at room temperature 6-bromo-s-triazolo[4,3-b]pyridazine (10) was obtained. Further transformations of 8-substituted 3-ethoxycarbonylamino-s-triazolo[4,3-a]pyrazines13 and14 afforded derivatives of bis-s-triazolo[4,3-a:3,4-c]pyrazine15 and s-triazolo[4,3-a]tetrazolo[1,5-c]pyrazine16.

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Transformation von 1-Azinyl-4-ethoxycarbonylthiosemicarbaziden. Die Synthese von 3-Ethoxycarbonylamino-s-triazolo[4,3-x]azinen

Zusammenfassung Die aus den entsprechenden heterocyclischen Hydrazinverbindungen und Ethoxycarbonylmethylisothiocyanaten hergestellten 1-Azinyl-4-ethoxycarbonylthiosemicarbazide4,5 und12 und 1-Azinyl-4-ethoxycarbonyl-methylthiosemicarbazid17 wurden mittels Oxidation mit Brom in Essigsäure in die kondensierten Produkte 3-Ethoxycarbonylamino-s-triazolo[4,3-a]pyridin6, -pyridazin7 und -pyrazine13,18 und20 übergeführt. Das Thiosemicarbazidderivat8 wurde bei 0 °C in das Bis-s-trazolo[4,3-b:3,4-f]pyridazin-Derivat9 transformiert, währenddessen bei Raumtemperatur 6-Brom-s-triazolo[4,3-b]pyridazin (10) erhalten wurde. Weitere Transformationen der 8-substituierten 3-Ethoxycarbonylamino-s-triazolo[4,3-a]pyrazine13 und14 ergaben Derivate von Bis-s-triazolo[4,3-a:3,4-c]pyrazin15 und s-Triazolo[4,3-a]tetrazolo[1,5-c]pyrazin (16).

     

NMR study of the sigmatropic [1,3]-B shift in 7,8-dipropyl-7-borabicyclo[4.2.2]deca-2,4,9-triene

Activation parameters of the interconversion of geometric isomers6a and6b were determined by a complete lineshape analysis of the temperature-dependent¹³C NMR spectra of 7,8-dipropyl-7-borabicyclo[4.2.2]deca-2,4,9-triene (6). For the reaction6a 6b, G ₂₉₈ = 52.2±0.1 kJ mol^–1, H = 27.9±0.5 kJ mol^–1, S = –82±8 J mol^–1 K^–1; For the reaction6b 6a, G ₂₉₈ = 52.6±0.1 kJ mol^–1, H = 24.7±0.5 kJ mol^–1, S = –93±10 J mol^–1 K^–1. The interconversion of deuteropyridine complexes9a and9b proceedsvia their dissociation, which indicates that the rearrangement of borane6 occurs according to the [1,3]-B shift mechanism.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2243–2250, September, 1996.     

peri-Naphthylenediamines. 33. Further studies of the reactions of 1,8-bis(dimethylamino)naphthalene with trifluoroacetic anhydride

The reaction of 1,8-bis(dimethylamino)naphthalene (1) (proton sponge) with a large excess of trifluoroacetic anhydride in the absence of a solvent afforded a complex mixture of products among which were trans- (2) and cis-diols (3) of the naphtho[1,8-c,d]pyran series, the double proton sponge (4), its di- (5) and tetrafluoroacetyl (6) derivatives, and compound 7. These results differ substantially from those obtained previously in the reactions performed in various solvents. Some conversions of compounds 4 and 7 were investigated. The ¹⁹F NMR spectra of the compounds synthesized are discussed.     

Synthesis of New Cyclophane Host Molecules and Crystal Structures of Their Compounds with Hydrocarbon Guests

Three new cyclophane host molecules 2, 4, and 6 are prepared by connecting the oxygen atoms of two ,'–di(4-hydroxyphenyl)-1,4-diisopropylbenzene units with two di-, tetra-, and hexamethylene spacers, respectively. Solid-state structures are determined for host 2 with a hexane guest, host 4 with a toluene guest and a solvating toluene molecule, host 4 with a p-xylene guest,and host 6 with two p-xylene guests.     

Intramolecular O→Te and N→Te coordination bonds in molecules of β-tellurocyclohexenals and their nitrogen analogs

The structures of -tellurocyclohexenals and their nitrogen analogs, viz., -methyltellurocyclohexenal (6), -(4-ethoxyphenyltelluro)cyclohexenal (7), di(2-formylcyclohexen-1-yl) telluride (8), -(4-ethoxyphenyltelluro)cyclohexenylidene(4"-methylaniline) (9), -bromotellurenylcyclohexenylidene(4"-methylaniline) (10), and -bromotellurenylcyclohexenal (4-methylbenzoyl)hydrazone (11), were studied by X-ray diffraction analysis. Compounds 6—11 have a Z configuration at the double bond, which provides the formation of intramolecular OTe or NTe coordination bonds. The bonds about the Te atom have a T-shaped configuration. There is only one of two possible OTe coordination bonds in dialdehyde 8 and, consequently, this compound belongs to the 10-Te-3-tellurane structural type. Hydrazone 11 possesses both NTe and OTe intramolecular coordination bonds. Taking into account these interactions, the coordination polyhedron of the tellurium atom can be considered as a trigonal bipyramid. The intramolecular OTe or NTe coordination bond lengths in compounds 6 (2.692 ), 7 (2.657 ), 8 (2.657 ), and 9 (2.690 ) are 0.9—1.0 smaller than the sums of the van der Waals radii of the corresponding atoms. These bond lengths in compounds 10 (2.170 ) and 11 (2.203 ) are almost equal to the standard covalent bond length.