[1,3]Dioxolo[5,6][1]benzothieno[2,3-c]-quinolin-6(5H)-ones

Summary The reaction of 3,4-methylenedioxycinnamic acid (1) with thionyl chloride resulted in the formation of 7-chlorothieno[2,3-f]-1,3-benzodioxole-6-carbonyl chloride (2) and cinnamoyl chloride (3). Subsequent reaction of the former withp-substituted anilines led to the formation of 7-chloro-N-(p-substituted phenyl)-thieno[2,3-f]-1,3-benzodioxole-6-carboxamides (4a–c) which on photocyclization afforded 2-substituted [1,3]dioxolo[5,6][1]benzothieno[2,3-c]quinolin-6(5H)-ones (5a–c) in fairly good yields and high purity. The structures have been confirmed by IR,¹H NMR, and analytical methods.Accepted for presentation at the Hong Kong International Symposium on Heterocyclic Chemistry (August 13–16, 1995)     

Synthesis of Diaminophosphonium Salts [Ph2(ArNH)2P]+Br− (Ar = o-MeC6H4, p-MeC6H4, p-Pr i C6H4, p-EtO2CC6H4, p-MeOC6H4)

The behavior of different anilines H₂NC₆H₄R (R = o-Me, p-Me, o-, m- and p? ⁱ Pr, p-OMe, p-CO₂Et) and 2,6-Me₂C₆H₃NH₂ towards trihalophosphoranes was studied. 2,6-Me₂C₆H₃NH₂ failed to form the diaminophosphonium salt [Ph₂PNH(2,6-Me₂C₆H₃)₂]Br, and the aminophosphine oxide Ph₂(2,6-Me₂C₆H₃NH)PO was the only isolated product. Both o- and p-toluidine gave the corresponding diaminophosphonium salts; however in the case of o-toluidine, the yield was low and a mixture with the respective aminophosphine oxide was observed. Anilines containing methoxy and ethoxycarbonyl groups in para-position form the diaminophosphonium salts in reasonable yields.     

Ab Initio Calculation of the Structure of 5-Chloro-1,2,4-triazole

Three tautomeric forms of 5-chloro-1,2,4-triazole were calculated using the Hartree-Fock (ab initio) and Meller-Plesset methods in the 6-31G(d) basis. The ³⁵Cl NQR parameters were calculated using the occupancies of the 3p-components of the valence p-orbitals of the chlorine atom. The structure of this triazole was derived from the data obtained.     

CHEMISTRY OF CIS- AND TRANS-9-PHENYLSELENOXANTHENE-N-ARYLSULFONYLSELENILIMINES1

Abstract

cis- and trans-9-Phenylselenoxanthene-N-(arylsulfonyl)selenilimines were synthesized and isolated. Their stereochemistry was ascertained from the NMR spectra. Cis isomers reacted with chloramine-T or -B by an S_N 2 type substitution to form trans isomers, but the reverse reaction did not take place. When trans isomers were refluxed in toluene they underwent intermolecular 1,4 rearrangement to give 9-arylsulfonamido-9-phenylselenoxanthene. The cis isomers neither rearranged nor isomerized. On treatment with DABCO, both isomers rearranged intermolecularly to 9-(N-arylsulfonamido)selenoxanthenes at room temperature. Hydrolysis of both isomers yielded trans-9-phenylselenoxanthene 10-oxide. Reactions with p-methoxyphenylmagnesium bromide or methylmagnesium iodide afforded 9-(p-methoxyphenyl)-9-phenylselenoxanthene or 9-phenylselenoxanthene as a main product, respectively.     

Synthesis of Quercetin 3-O-[6″-O-(trans-p-Coumaroyl)]-β-D-Glucopyranoside

This report describes the efficient synthesis of quercetin 3-O-[6^″-O-(trans-p-coumaroyl)]-β-D-glucopyranoside 1 (isoquercitrin coumarate), an acylated quercetin glycoside possessing antihypertensive, antidiabetic, and tyrosinase inhibitory activities. The synthesis is initiated from commercially available quercetin via regioselective benzylation of quercetin to produce 4′, 7-di-O-benzylquercetin (4). Through 4, 1 was successfully achieved via selective β-glycosylation of the 3-OH, acylation of 6^″-OH, and finally debenzylation via catalytic transfer hydrogenation.     

Tautomerism of 2-(o-hydroxyphenyl)-azines

The tautomeric properties ofo-hydroxyphenylazines have been investigated by¹⁷O NMR and UV spectroscopy. 2-(o-Hydroxyphenyl)-pyridine and itsp-nitrophenole analog II exist in chloroform or ethanol as a phenol A. In the case of 2-(2-hydroxy-5-nitrophenyl)-quinoline the NH-tautomer is realized, the content of which increases when going to the dinitro-analog IV.

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Die Tautomerie von 2-(o-Hydroxyphenyl)-azinen (Kurze Mitteilung)

Zusammenfassung Es wurden die tautomeren Eigenschaften vono-Hydroxyphenylazinen mittels¹⁷O-NMR und UV-Spektroskopie untersucht. 2-(o-Hydroxyphenyl)-pyridin und seinp-Nitrophenol-Analog II existieren in Chloroform und Ethanol als Phenol A. Das 2-(2-Hydroxy-5-nitrophenyl)-chinolin liegt als NH-Tautomer vor, dessen Anteil im Dinitro-Analog IV noch steigt.

     

Tricarbonylchromium complexes with phenalene. Synthesis, structure, and thermal rearrangements

The reaction of phenalene with Cr(CO)₃Py₃/BF₃·OEt₂ afforded a mixture of two isomeric complexes, tricarbonyl(6a,7-9,9a,9b-·⁶-phenalene)chromium (1) and tricarbonyl(3a,6a,9b,4-6-·⁶-phenalene)chromium (2). Deprotonation of the mixture of compounds1 and2 followed by treatment with MeI, BuⁿI, or D₂O gave complexesexo-1-R-1 (3–5: R=Me (3), Buⁿ (4), or D (5)). The molecular geometry of complex3 was established by X-ray structural analysis. Heating of complex5 in toluene or C₆F₆ at 90–110 °C resulted in redistribution of deuterium among positionsexo-1,endo-1, and 3 in the resulting complexes of types1 and2 via sigmatropic shifts of the H _exo and H _endo atoms in the nonaromatic ring as well asvia inter-ring migrations of the tricarbonylchromium group. In the case of3, the methyl label is distributed among positionsexo-1 and3 to form isomeric complexes with similar structures (exo-1-Me-2 (6), 3-Me-2 (7), and 3-Me-1 (8), respectively)via processes analogous to those observed in the case of isomerization of compound5 (except for migration of the H _exo atom). The mechanisms of these rearrangements are discussed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1863–1880, October, 1997.     

Azocalixarenes. 6: Synthesis, complexation, extraction and thermal behaviour of four new azocalix[4]arenes

Four new azocalix[4]arenes {5,11,17,23-tetrakis[(2-hydroxy-5-tert-butylphenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (1), 5,11,17,23-tetrakis[(2-hydroxy-5-nitro phenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (2), 5,11,17,23-tetrakis[(2-amino-5-carboxylphenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (3) and 5,11,17,23-tetrakis[(1-amino-2-hydroxy-4-sulfonicacidnapthylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (4)} have been synthesized from p-tert-butylphenol, p-nitrophenol, p-aminobenzoic acid and 1-amino-2-hydroxy-4-sulphonic acid by diazo coupling reaction with p-aminocalix[4]arene. The resulting ligands (1–4) were treated with three transition metal salts (e.g., CuCl₂·2H₂O, NiCl₂·6H₂O or CoCl₂·6H₂O). Cu(II), Ni(II) and Co(II) complexes of the azocalix[4]arene derivatives were obtained and characterized by UV-vis, IR, ¹H-NMR spectroscopic techniques and elemental analysis. All the complexes have a metal:ligand ratio of 2:1. The Cu(II) and Ni(II) complexes of azocalix[4]arenes are square-planar, while the Co(II) complexes of azocalix[4]arenes are octahedral with water molecules as axial ligands. The solvent extraction of various transition metal cations from the aqueous phase to the organic phase was carried out by using azocalix[4]arenes (1–4). It was found that, azocalix[4]arenes 1, 2 and 3 examined selectivity for transition metal cations such as Ag⁺, Hg⁺ and Hg²⁺. In addition, the thermal stability of metal:azocalix[4]arene complexes were also reported. Dedicated to Prof. Dr. Mustafa Yılmaz on the occasion of his 50th birthday     

Analysis of the Rydberg structure in the vapor-phase electronic absorption spectrum of (η7-cycloheptatrienyl)(η5-cyclopentadienyl) chromium

Parameters of the Rydberg transitions in the vapor-phase absorption spectrum of (η⁷-C₇H₇)(η⁵-C₅H₅)Cr were analyzed in detail. A correspondence between the three Rydberg series in the short-wavelength region of the spectrum and low-frequency Rydberg bands was established. Vibronic structure of the observed transitions to the lowest Rydberg s, p _x,y , p _z , and d _xz,yz levels was interpreted. The long-wavelength and short-wavelength series, respectively characterized by quantum defect (σ) values of 1.26 and 0.82, were unambiguously assigned to the Rydberg p _x,y and d _xz,yz excitations, respectively. Transitions from the 3d _z 2 orbital to theR(n−1)f,Rnd _z 2, andRnp _z levels can contribute to the series characterized by a σ value of 1.04. The assignment was made of Rydberg bands in the spectral region corresponding to the principal quantum number (n) values of 5, 6, and 7 (in this region, interpretation of the spectral pattern is complicated because of the band shifts and broadening). Atn>5, changes in the σ values of the Rydberg excitations with increase in then value are due to configuration interaction. The electronic-excited states, which can be responsible for the observed changes in the Rydberg parameters, were determined. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1677–1684, September, 1999.     

Umsetzung von 1,5-Dimethyl-2,3,3,4-tetrachlor-1,5,2,4-diazadiphosphorinan-6-on mit Anilinderivaten,Heptamethyldisilazan und tert.-Butylamin: Oxidative Addition von Tetrachlor-o-benzochinon an einige P(III)-haltige Produkte

The reaction of the title compound 1 with the p-R-aniline derivatives (R═H, F, OCH₃, NO₂, and NH₂) led to the formation of the aza-2σ³,4σ³-diphosphetidines 2a– 2e, whereas 2-trimethylsiloxyaniline furnished the azadiphosphetidine 2f. The reaction of the sterically crowded 2,6-dimethylaniline with 1 furnished the disubstituted derivative 3. The tricyclic compound 5 was formed during the reaction of 1,2-phenylenediamine with 1. Heptamethyldisilazane formed the aza-2σ ³ ,4σ ³ -diphosphetidine 6 on reaction with 1. The bulkier tert.-butylamine formed with 1 a mixture of the aza-2,4-diphosphetidine 7a and the disubstituted derivative 7b, which could not be separated. The reaction of 2b and 6 with tetrachloro-o-benzoquinone resulted in the formation of the bis-spirophosphoranes 8 and 9b, respectively. The formation of the monospirophosphorane 9a was observed in the ³¹P NMR spectrum. The characterization of compounds is based in particular on NMR investigations (¹H, ¹³C, ³¹P). 2a was characterized by a single-crystal X-ray structure analysis. The dimethylurea fragment is planar; the four-membered ring is folded about the P···P vector by 38.7°.     

1,3-Dipolar cycloaddition of diazomethane and diazocyclopropane to 2-fluoro-3-methylbutadiene and thermal transformations of fluorine-containing vinylpyrazolines and vinylcyclopropanes

Reactions of 2-fluoro-3-methylbuta-1,3-diene with diazomethane in ether at 15 °C and with diazocyclopropane generated in situ by decomposition of N-cyclopropyl-N-nitrosourea in the presence of K₂CO₃ in CH₂Cl₂ at –10 °C selectively involve the double bond at the methyl group to give 3-(1-fluorovinyl)-3-methylpyrazolines. Thermal dediazotization of the latter at 250 °C yields 1-(1-fluorovinyl)-1-methylcyclopropane and -spiropentane 5, which are capable of isomerizing, under more severe conditions (400—600 °C), into 1-fluoro-2-methylcyclopent-1-ene and 5-fluoro-4-methylspiro[2.4]hept-4-ene (7), respectively. Spiropentane derivative 5 partially isomerizes into 1-fluoro-2-methyl-3-methylidenecyclohex-1-ene. In a similar way, thermolysis of 6-(2,3,3-trifluorocyclobut-1-enyl)-4,5-diazaspiro[2.4]hept-4-ene at 400 °C gives a mixture of 1-(spiropentyl)-2,3,3-trifluorocyclobut-1-ene and 2,3,3-trifluoro-1-(2-methylidenecyclobutyl)cyclobut-1-ene. Thermolysis of 1-cyclopropyl-2,3,3-trifluorocyclobut-1-ene at 550—620 °C affords a mixture of 1-(trifluorovinyl)cyclopentene and 2,3-difluorotoluene.     

Acetyl ketene aminals in Nenitzescu reaction

Nenitzescu reaction of acetyl ketene aminals (N,N-acetals) was investigated. The interaction of 2-acetyl-1-amino-1-anilinoethene with benzoquinone gave 3-acetyl-2-amino-7a-hydroxy-1-phenyl-5,7a-dihydro-1H-indol-5-one, which was then transformed into 3-acetyl-2-amino-6-chloro-5-hydroxy-1-phenylindole. The reaction of benzoquinone with 2-acetyl-1-amino-1-benzoylaminoethene led to the corresponding hydroquinone-adduct which was oxidized to 4-acetylamino-5-(2,5-dihydroxyphenyl)-2-phenyloxazole. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 160–165, January, 1999.     

Di- and tetranulcear Ru complexes of phenylene-1,4-diaminotetra(phosphonite), p-C6H4[N{P(OC6H4OMe-o)2}2]2 and their catalytic investigation towards transfer hydrogenation reactions

The stoichiometric reaction of phenylene-1,4-diaminotetra(phosphonite), p-C₆H₄[N{P(OC₆H₄OMe-o)₂}₂]₂ (P₂NФNP₂) (1) with [RuCl₂(p-cymene)]₂ in acetonitrile produces cis,cis-[{RuCl₂(CH₃CN)₂}₂(P₂NФNP₂)] (2), whereas the similar reaction of 1 with [RuCl₂(p-cymene)]₂ in THF medium affords a tri-chloro-bridged tetrametallic complex, [{(η⁶-p-cymene)Ru₂(μ₂-Cl)₃Cl}₂(P₂NФNP₂)] (3) irrespective of the stoichiometry and reaction conditions. The formation and structure of complexes 2 and 3 are assigned through various spectroscopic and micro analysis data. The molecular structure of 2 is confirmed by single crystal X-ray diffraction study. The catalytic activities of complexes 2 and 3 have been investigated in transfer hydrogenation reactions.     

4a,6-Bis-(N-methlanilino)-7-hydroxy-2,3,8-trimethyl-4a,9a-dihydro-xanthen-1,4-dion: Ein thermolyseprodukt von 6-(N-methylanilino)-7a-methyl-3a,7a-dihydroindazol-4,7-dion

Summary 4a,6-Bis-(N-methylanilino)-7-hydroxy-2,3,8-trimethyl-4a,9a-dihydro-xanthene-dione (4) was obtained by thermolysis of 6-(N-methylanilino)-7a-methyl-3a,7a-dihydroindazol-4,7-dione (1) The structure was determined on basis of 1D- and 2D-NMR techniques.Herrn Prof. Dr. G. Zigeuner zum 70. Geburtstag gewidmet     

Crystal structure and synthesis of benzimidazole substituted acrylonitriles and benzimidazo[1, 2-a]quinolines

The benzimidazole compounds and benzoannulated cyclic benzimidazole analogues, such as benzimidazo[1,2-a]quinolines, are a part of our wider investigation on biologically active compounds, potential antitumor drugs. Here, we present the synthesis of two compounds, [2-(1H-benzimidazol-2-yl)-3-(4-bromophenyl)-acrylonitrile, 5] and [2-bromo-benzimidazo[1,2-a]quinoline-6-carbonitrile, 7] and their crystal structures revealed by X-ray single crystal diffractometry. We also report the molecular and crystal structures of two additional compounds [2-(1H-benzimidazol-2-yl)-3-(4-cyanophenyl)-acrylonitrile, 4] and [benzimidazo[1,2-a]quinoline-2,6-dicarbonitrile, 6], whose synthesis and spectroscopic characterization have been published earlier by us too (Hranjec and Karminski-Zamola, Molecules 12:1817, 2007). The compounds 4 and 5 crystallize as monohydrates. The dihedral angles calculated between phenyl and benzimidazole ring reflect not significant deviation from molecular planarity in the crystalline state for 4 and 5, while benzoannulated cyclic benzimidazole derivatives 6 and 7 are essentially planar. The crystal structures of 4 and 5 are characterized by O–H···N and N–H···O hydrogen bonds between water molecule of crystallization and imidazole NH group as well as CN group, while in 6 and 7 only weak C–H···N intermolecular hydrogen bonds exist. Although, crystal packings are analogous in 4 and 5, the molecular conformations differ slightly. In 6 there is one C–H···N hydrogen bond that do not exist in 7.     

Water-soluble para-Sulfonated 1,2;3,4-Calix[4]arene-biscrowns in the 1,2-Alternate Conformation

The preparation of a series of p-sulfonated 1,2;3,4-calix[4]arene-biscrowns in the 1,2-alternate conformation is reported. These compounds are of two types:symmetrical p-sulfonated 1,2;3,4-calix[4]arene-biscrowns in which the two crown loops are the same and unsymmetrical p-sulfonated1,2;3,4-calix[4]arene-biscrowns in which the two crown loops are different. The X-ray structures of two synthetic intermediates are given. Preliminary complexation studies showed the ligands to present pronounced Cs⁺/Na⁺ selectivities.     

Chemical properties of marine terpenoids. 1. Some reactions of (6S,10R)-10-bromo-3,11,11-trimethyl-7-methylidenespiro[5,5]undec-2-en-4-one,a sesquiterpenoid from the sea hare Aplysia dactylomela

The structures of products obtained by reductive debromination and CF₃COOH- and KOH-induced transformations of natural chamigrane-type sesquiterpenoid (6S,10R)-10-bromo-3,11,11-trimethyl-7-methylidenespiro[5,5]undec-2-en-4-one (dactylone) isolated from the sea hare Aplysia dactylomela were analyzed. The absolute configurations of the reaction products were established by CD spectra taking into account the configuration of the starting dactylone.     

Synthese und Eigenschaften einigerp-tolyl-phenylsubstituierter Di- und Trisilane und von 1,1,1,3,3,3-Hexaphenyltrisilan

The synthesis and properties of [Ph ₂ p-TolSi]₂, [Ph ₂ p-TolSi]₂SiPh ₂, [Ph ₃ Si]₂Si(p-Tol)₂, [Ph ₂ p-TolSi]₂Si(p-Tol)₂ and (SiPh ₃)₂SiH₂ are described. The silanes are identified using IR,Ra- and²⁹Si-NMR-spectroscopy.

     

1H, 13C, 15N NMR and 13C, 15N CPMAS studies of cobalt(III)-chloride-pyridine complexes, spontaneous py → Cl substitution in trans-[Co(py)4Cl2]Cl, and a new synthesis of mer-[Co(py)3Cl3]

trans-[Co(py)₄Cl₂]Cl·6H₂O, mer-[Co(py)₃Cl₃] and mer-[Co(py)₃(CO₃)Cl] were studied by UV-Vis, far-IR and ¹H, ¹³C, ¹⁵N NMR. The formation of Co-N bonds lead to variable in sign and magnitude changes of ¹H NMR chemical shifts, heavily dependent on proton position, coordination sphere geometry and character of auxiliary ligands. ¹³C nuclei were deshielded upon Co(III) coordination, while ¹⁵N NMR studies exhibited ca. 85–110 ppm shielding effects (ca. 15–25 ppm more expressed for nitrogens trans to N than trans to Cl or O). ¹³C and ¹⁵N CPMAS spectra revealed a slight inequivalency of formally identical Co-py bonds in trans-[Co(py)₄Cl₂]Cl·6H₂O and mer-[Co(py)₃Cl₃], suggesting for the latter complex an existence of distortion isomers. In chloroform, a spontaneous trans-[Co(py)₄Cl₂]Cl → mer-[Co(py)₃Cl₃] + py reaction was monitored by ¹H NMR and UV-Vis. This process of py → Cl substitution allowed the design of a more convenient and efficient method of mer-[Co(py)₃Cl₃] preparation.      

New polyhydroxysteroids and steroid glycosides from the far east starfishCeramaster patagonicus

Two new polyhydroxysteroids and five new glycosides were isolated from the starfishCeramaster patagonicus and their structures were elucidated: 5α-cholestane-3β,6α,15β,16β,26-pentol, (22E)-5α-cholest-22-ene-3β,6α,8,15α,24-pentol, (22E)-28-O-[O-(2-O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-galactofuranosyl]-24-hydroxymethyl-5α-cholest-22-ene-3β,4β, 6α,8,15β,16β,28-heptol (ceramasteroside C₁), (22E)-28-O-[O-(2,4-di-O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-galactofuranosyl]-24-hydroxymethyl-5α-cholest-22-ene-3β, 6α,8,15β,16β,28-hexol (ceramasteroside C₂), (22E)-28-O-[O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-galactofuranosyl]-24-hydroxymethyl-5α-cholest-22-ene-3β,6α,8,15β,16β 28-hexol (eramasteroside C₃), (22E)-28-O-[O-(2-O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-galactofuranosyl]-24-methyl-5α-cholest-22-ene-3β,4β,6α,8, 15β, 26-hexol (ceramasteroside C₄), and (22E)-28-O-[O-(2-O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-xylopyranosyl]-5α-cholest-22-ene-3β,6α,8,15β,24-pentol (ceramasteroside C₅)). Three known polyhydroxysteroids (24-methylene-5α-cholestane-3β,6α,8,15β,16β,26-hexol, 5α-cholestane-3β,6α,8,15β,16β,26-hexol, and 5α-cholestane-3β,6β,15α,16β,26-pentol) were also isolated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 190–195, January, 1997.