Novel magnesium and zinc porphyrazines containing galactose moieties: Synthesis via click reaction and characterization

In this study, galactose conjugated new magnesium and zinc porphyrazines were synthesized by the cyclotetramerization reaction of 2,3-bis[1-(2,2,7,7-tetramethyltetra-hydro-bis[1,3]dioxolo[4,5-b;4′,5′-d]pyran-5,methyl)-1H-[1,2,3]triazol-4-yl methylsulfanyl]-but 2-enedinitrile. This substituted dicyano compound was prepared via two different routes. One started from cis-1,2-dicyano-1,2-ethylenedithiolate disodium, [1-(2, 2, 7,7-tetramethyltetrahydrobis[1,3]dioxolo[4,5-b;4′,5′-d]pyran-5-yl-methyl)-1H-[1,2,3]triazo-l-4-yl]methanol and ended in a multi-step reaction sequence via Click procedures. The other reaction was between 5-azidomethyl-2,2,7,7-tetramethyltetrahydro-bis[1,3]dioxolo[4,5-b;4′,5′-d]pyran and (2Z)-2,3-bis(prop-2-yl-1-yl-thio)but-2-enedinitrile. A very soluble galactose linked magnesium porphyrazine derivative in common polar solvents and water was achieved by the deprotected isopropylidene groups in TFA and water media. It is first time, zinc porphyrazine complex has been achieved at one-step reaction by using Zn(BuO)₂ as template agent. The new compounds have been characterized by a combination of elemental analysis, ¹H, ¹³C NMR, IR, UV–vis and MS spectral data.     

Über neue Pyrazolverbindungen. IV Darstellung und Cyclisierungsverhalten einiger akzeptorsubstituierter N-(Pyrazol-3-yl)-thioharnstoffe

New Pyrazol Derivatives. IV. Preparation and Cyclization of Some Acceptor-Substituted N-(Pyrazol-3-yl)-thioureas . 3-Aminopyrazol-4-carboxylic acid derivatives ( 1 , 2 ) were transformed by reaction with different isothiocyanates R²NCS to N-(pyrazol-3-yl)-N^. -substituted thioureas ( 5 , 6 ). Ethyl 3-amino-1-benzylpyrazol-4-carboxylate reacts with CSCl₂ to form ethyl 1-benzyl-3-isothiocyanatopyrazol-4-carboxylate ( 3 ) which yields with amines the corresponding N-(pyrazol-3-yl)-N^. -substituted thioureas ( 5 ). As a byproduct in the reaction with CSCl₂ N,N^. -di-(pyrazol-3-yl)-thiourea ( 4 ) is formed. With hydrazine or phenylhydrazine N-(pyrazol-3-yl)-thiosemicarbazides ( 7a , b ) are obtained. The thioureas ( 5 , 6 ) can be cyclized in basic solution to 4,5,6,7-tetrahydropyrazolo[3,4-d]pyrimidin-4-on-6-thiones ( 8 ) which on alkylation form 6-alkylthio-4,5-dihydropyrazolo[3,4-d]pyrimidin-4-ones ( 9 ). Methyl-N-(pyrazol-3-yl)-N^.-benzoylisothiourea ( 10 ) reacts with ethylamine to form N-benzoyl-N^. -ethyl-N^‥-(pyrazol-3-yl)-guanidine derivative ( 11 ) which on treatment with NaH in dimethylformamide yields 6-benzoylamino-5-ethyl-4,5-dihydropyrazolo[3,4-d]pyrimidin-4-one ( 12 ). By treatment with sulfuric acid the N-(pyrazol-3-yl)-thiourea derivatives ( 5 , 6 ) form new 6-amino substituted pyrazolo[3,4-d][1,3]thiazin-4-ones ( 13 ).     

Relationship Between Inhaled PAH and Urinary Excretion of Phenanthrene,Pyrene and Benzo[a]pyrene Metabolites in Coke Plant Workers

Abstract

By means of personal air samplers the exposure to polycyclic aromatic hydrocarbons (PAH) of four coke employees working at different locations was measured during 4 running days. Simultaneously the 24 hrs urines were collected. A simple, well reproducible method for the determination of 9,10-dihydroxy-9,10-dihydrobenzo[a]pyrene, 1-; 2-; 3-; 4- and 9-hydroxyphenanthrenes, 1,2-; 3,4-; and 9,10-dihydroxydihydrophenanthrenes as well as 1-hydroxypyrene and 1,2-dihydroxy-1,2-dihydropyrene was used. As expected, workers on the battery topside are most exposed and, accordingly, excrete by far the highest amount of PAH metabolites. A good correlation between the PAH inhaled during 8 hrs and the metabolites excreted in the 24 hrs urine is observed. 20% to 30% of the inhaled phenanthrene is excreted as dihydrodiols, but only 0.5% of the inhaled benzo[a]pyrene forms 9,10-dihydrodiol in the urine. The individual invariance of the metabolite profile of the isomeric phenols and dihydrodiols indicates a genetically caused enzyme pattern of oxygenases, which can or cannot be induced by exogenous factors. More investigations are necessary to clarify whether this metabolic profile may be suitable as a marker for carcinogenic risk.     

Atmospheric Distribution of Gas- and Particle-Phase Quinones in Southern California

Quinones are reactive organic compounds known to initiate reactions associated with a host of toxicological events. Their presence in different atmospheres has been demonstrated although their sources remain uncertain. As a result of their reactivity and instability during chemical analysis, only a limited number of studies have reported on atmospheric concentrations of quinones in ambient air. Furthermore, besides the limited information on quinones associated with particulate matter, no previous studies have quantified vapor-phase quinones. We report vapor- and particle-phase concentrations of 1,2- and 1,4-naphthoquinones (1,2-NQ, 1,4-NQ), 9,10-phenanthraquinone (9,10-PQ), and 9,10-anthraquinone (9,10-AQ), measured over a 5-year period in Southern California. The results showed that vapor-phase concentrations of the target quinones were in general higher than those in the particle-phase. Vapor-phase concentrations ranged from 80 pg/m ³ for the AQ to 1747 pg/m ³ for the 1,4-NQ, and the particle-phase concentrations between 13 pg/m ³ for the 1,2-NQ and 250 pg/m ³ for 9,10-AQ. The target quinones were found to be distributed between vapor- and particle-phase, with the exception of 9,10-PQ found only in the particle-phase. The differences observed in the concentrations among sites and seasons suggest different source contributions; source sites were dominated by primary sources, while downwind locations showed a high contribution from photochemical activity.     

Polycondensation of squaric acid with N-alkylcarbazoles

Summary 1,2-Dihydroxycyclobutene-3,4-dione (squaric acid) was polycondensed with N-ethyl- and N-(1-butyl)carbazole in polyphosphoric acid to give polymers having 36–43% of 1,2-oriented squarate units. The polymers are insoluble in organic solvents or sulfuric acid. Condensation of 1,2-dichlorocyclobutene-3,4-dione (squaryl dichloride) with N-1-butyl-carbazole in nitrobenzene gave 100% of 1,2-oriented squarate units. This polymer is soluble in most organic solvents, and the molecular weight (¯Mw) is 1900 (DP=6). The electrical conductivity was low, <10^–9 (ohm cm)^–1, and did not increase on treatment with iodine.     

The synthesis and characterization of novel metalloporphyrazine containing crown ether linked calix[4]arene moieties

The synthesis and characterization of novel magnesium porphyrazine, peripherally symmetrically derived from 1,3-alternate 26,28-[35,36-dicyano-34,37-dithia-29,32,40,43-tetraoxa-35-en]calix[4]arene-crown-5, were carried out. This compound was prepared starting from cis-1,2-dicyano-1,2-ethylenedithiolate and 1,3-alternate 26,28-bis(5′-chloro-3′-oxapentyloxy)calix[4]arene-crown-5. The new macrocycle was characterized using the techniques of UV–vis, ¹H, ¹³C NMR, IR, MS and elemental analysis.     

苝酰亚胺衍生物的合成及光谱性能研究

以3,4:9,10-苝四酸二酐为原料,合成了两种新型的苝酰亚胺衍生物:N-(1-己基庚基)-N'-苯基-3,4:9,10-苝四酸二酰亚胺和N-(1-己基庚基)-N'-苯基-1,7-二(4-叔丁基苯氧基)-3,4:9,10-苝四酸二酰亚胺,其结构经¹H NMR和MS表征。用紫外可见吸收光谱和荧光光谱研究了它们的光学性质,研究结果表明苝核海湾区供电子基团的引入,使得苝核的最大吸收波长发生了明显的红移,Stokes位移达到了29 nm。     

Detection of Reactive Quinones in the Metabolism of Polycyclic Aromatic Hydrocarbons by the Formation of their Glutathione Conjugates

The biotransformation of polycyclic aromatic hydrocarbons to quinones by rat liver microsomes was investigated. The employment of an electrochemical detector allowed the specific detection of quinones separated by reverse phase HPLC with higher sensitivity as compared to UV detection. Microsomal incubations of benzo[a]pyrene (BP) resulted in the formation of 1,6-, 3,6- and 6,12-quinones, of naphthalene in the detection of naphthalene-1,4-quinone, whereas ortho-quinones could only be detected in trace amounts. Additional protein binding studies showed that only 9–22% of synthetic ortho-quinones could be recovered from microsomal incubations. In order to scavenge possible reactive quinone metabolites with glutathione (GSH) and to identify these metabolites, GSH-conjugates of naphthalene-1,2-quinone, naphthalene-1,4-quinone, chrysene-1,2-quinone, BP-7,8-quinone and BP-9,10-quinone were synthesized and spectroscopically characterized. After incubations of 1-naphthol or naphthalene with rat liver microsomes the GSH conjugate of naphthalene-1,2-quinone could be identified by cochromatography with the authentic reference compound.     

Synthesis and characterization of poly(tetramethylsilarylenesiloxane) derivatives bearing benzodithiophene moieties

Poly(tetramethylsilarylenesiloxane) derivatives bearing benzo[1,2-b;4,5-b′]dithiophene (P1) and benzo[2,1-b;3,4-b′]dithiophene (P2) moieties were prepared via polycondensation of the corresponding disilanol monomers, that is, 2,6-bis(dimethylhydroxysilyl)benzo[1,2-b;4,5-b′]dithiophene (M1) and 2,7-bis(dimethylhydroxysilyl)benzo[2,1-b;3,4-b′]dithiophene (M2), respectively. It was deduced that P1 is a crystalline polymer while P2 is an amorphous one from the results of differential scanning calorimetry (DSC). Bathochromic and hyperchromic effects were observed in the absorption and fluorescence spectra when dimethylsilyl substituents were introduced on the benzo[1,2-b;4,5-b′]dithiophene and benzo[2,1-b;3,4-b′]dithiophene skeletons. The fluorescence quantum yields (Φ_Fs) were not improved by the introduction of dimethylsilyl groups onto the benzo[1,2-b;4,5-b′]dithiophene and benzo[2,1-b;3,4-b′]dithiophene skeletons, whereas the improvement in the Φ_Fs was remarkable in the case of poly(tetramethylsilarylenesiloxane) derivatives that possessed the corresponding fused benzene ring systems, i.e., poly(tetramethyl-2,6-silanthrylenesiloxane) and poly(tetramethyl-1,8-silphenanthrylenesiloxane).     

Synthesis,antimicrobial, anti-inflammatory and antioxidant activity of novel Spiro (imidazo[4′,5′:4,5′]benzo[1,2-e][1, 4] thiazepine)-9,3′-indolines

An efficient synthesis of novel spiro(imidazo[4′,5′:4,5′]benzo[1,2-e][1, 4]thiazepine)-9,3′-indolines has been accomplished from 5-amino-2-mercapto benzimidazole, istains and mercapto acetic acid. Compounds 6 were characterized by IR, ¹H NMR, ¹³C NMR and mass spectral data. The title compounds 6a–6e were evaluated for their antimicrobial, anti-inflammatory and antioxidant activity. Compounds 6a–6e exhibited significant antimicrobial activity, and as potent anti-inflammatory and antioxidant activities as that shown by standard drugs.     

Activation parameters and excitation yields of 1,2-dioxetanes of photogenotoxic interest

The chemiluminescent decomposition of functionalized 1,2-dioxetanes was examined in toluene solution. Activation energies were measured by isothermal and nonisothermal kinetic methods. Quantum efficiencies were determined by Stern-Volmer kinetics, using the fluorescers 9,10-dibromo- and 9,10-diphenylanthracene for the triplet and singlet excitation yields. The derivatives of 3-hydroxymethyl-3,4,4-trimethyl-1,2-dioxetane ( 1a ) have free energies of activation (ΔG^≠) of ca. 25 kcal/mol, but the ΔG^≠ values of the annelated benzofuran-type dioxetanes ( 5 ) are ca. 1 kcal/mol lower. There exists a reasonable correlation between the free energies of activation (ΔG^≠) for the thermal decomposition of the dioxetanes and their triplet excitation flux (E_p^T).     

Synthesis and characterization of thieno[3,4-c]pyrrole-4,6-dione and pyrrolo[3,4-c]pyrrole-1,4-dione-based random polymers for photovoltaic applications

New random poly{benzo[1,2-b:4,5-b']dithiophene-thieno[3,4-c]pyrrole-4,6-dione-pyrrolo[3,4-c]pyrrole-1,4-dione} (PBDT-TPD-DPP) based on benzo[1,2-b:4,5-b']dithiophene (BDT) as donor and thieno[3,4-c]pyrrole-4,6-dione (TPD, 60–90%), pyrrolo[3,4-c]pyrrole-1,4-dione (DPP, 10–40%) as acceptors were synthesized through Stille coupling reaction. The photophysical, electrochemical and photovoltaic properties of random polymers were investigated. The random polymers with high molecular weight (M_n = 33.5–41.7 kDa) exhibited broad and strong absorption covering the spectra range from 350 nm up to 922 nm with absorption maxima at around 700 nm, the relatively deep highest occupied molecular orbital (HOMO) energy levels vary between ?5.25 and ?5.42 eV and suitable lowest unoccupied molecular orbital (LUMO) energy levels ranging from ?3.85 to ?3.91 eV. Polymer solar cells (PSC) based on these new random polymers were fabricated with device structures of ITO/PEDOT: PSS/random polymers: PC₇₁BM (1:2, w/w)/Ca/Al. The photovoltaic properties of random polymers were evaluated under AM 1.5G illumination (100 mW/cm²). Devices based on the random polymers showed open circuit voltage (V_oc) of 0.71–0.83 V, and power conversion efficiency (PCE) of 0.82–1.80%.     

Synthesis,Structural Characterization,Spectroscopic Properties,and Theoretical Investigations of Aminoacridine Derivatives

Synthesis of four N-(heterocyclic)-9-aminoacridine derivatives was investigated. The synthesized compounds, N-thiazolyl-9-aminoacridine (AC1), N-(1,3,4-thiadiazolyl)-9-aminoacridine (AC2), N-(5-methyl-1,3,4-thiadiazolyl)-9-aminoacridine (AC3), and N-(5-phenyl-1,3,4-thiadiazolyl)-9-aminoacridine (AC4) were characterized by FT-IR, ¹H NMR, mass-spectral, and elemental analysis. Amine-imine tautomerism was suggested by density functional theory (DFT) calculations. The optimized structures were obtained using B3LYP/6–311++G(d,p) level of theory. The UV–Vis absorption spectra were measured in various organic solvents. The synthesized compounds AC1–AC4 exhibit absorption spectra characteristic of typical donor–acceptor compounds. The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) analysis have been used to explain the internal charge transfer (ICT) phenomena within the molecules. Also, simulated UV spectra were calculated using TD-DFT (B3LYP/6–311++G(d,p) and the results were compared with the experimental values.     

The synthesis of some phthalocyanines derived from bulky substituted phthalonitriles

Phthalocyanine precursors were prepared by displacement of the –CH proton in 1-chloro-3,4-dicyano-6-(1,1-dicarbethoxymethyl) benzene with 1-(chloromethyl)-2-methyl benzene and 1-(chloromethyl)-4-methyl benzene. Metallo-phthalocyanines were obtained by cyclotetramerization in the presence of template metal salts {Zn(CH₃COO)₂, CoCl₂, CuCl₂, and Pb(CH₃COO)₂·3H₂O} that possessed substituents to enhance the solubility of the macrocycle and reduce its propensity to aggregate in solution. The structures of the newly synthesized molecules were proposed according to elemental analysis and ¹H NMR, FT-IR, Micro-TOF mass, MALDI-TOF mass and UV–vis spectral data.     

Isolation of unsaturated diols after oxidation of conjugated linoleic acid with peroxygenase

Oat seeds are a rich source of peroxygenase, an iron heme enzyme that participates in oxylipin metabolism in plants. An isomer of CLA, 9(Z), 11(F)-octadecadienoic acid (1), believed to have anticarcinogenic activity, was used as a substrate for peroxygenase in an aqueous medium using t-butyl hydroperoxide as the oxidant. After acidification of the reaction medium, the products were extracted with ethyl ether, converted to their methyl esters, and characterized using HPLC. Major products after reaction for 24 h showed resonances from ¹H NMR spectroscopy that were further downfield than the expected epoxides and were thought to be diol hydrolysis products. However, analyses by HPLC with atmospheric pressure chemical ionization MS (APCI-MS) of the putative allylic diols or their bis-trimethylsilyl ether derivatives gave incorrect M.W. The M.W. of the diols could be obtained by APCI-MS after removal of unsaturation by hydrogenation or by EI-MS after conversion of unsaturation by hydrogenation or by EI-MS after conversion of the allylic 1,2-diols to cyclic methyl boronic esters. Data from MS in conjunction with analyses using ¹H and ¹³C NMR showed that the methylated products from 1 were methyl 9,10(threo)-dihydroxy- 11(E)-octadecenoate, methyl 9,10(erythro)-dihydroxy-11(E)-octadecenoate, methyl 9,12(threo)-dihydroxy-10(E)-octadecenoate. Solid-phase extraction without prior acidification and conversion of the products to methyl esters allowed identification of the following epoxides: methyl 9,10(Z)-epoxy-11(E)-octadecenoate (6M), methyl 9,10(E)-epoxy-11(E)-octadecenoate, and methyl 11,12(E)-epoxy-9(Z)-octadecenoate. At times of up to at least 6h, 6M accounted for approximately 90% of the epoxide product. Product analysis after the hydrolysis of isolated epoxide 6M showed that hydrolysis of epoxide 6 could largely account for the diol products obtained from the acidified reaction mixtures.     

Addition of alkyllithiums to 3H-quinazoline-4-thione and various substituted quinazoline derivatives; application in synthesis

Reaction of 3H-quinazoline-4-thione (1) with two mole equivalents of an alkyllithium (t-BuLi, n-BuLi or MeLi) at?78 ^°C in dry THF gave the corresponding 2-alkyl-1,2-dihydro-3H-quinazoline-4-thione (4, 5 or 6) in high yield. Similarly, reactions of 4-(methylthio)quinazoline (7), 4-(ethylthio)quinazoline (8) and 4-methoxyquinazoline (9) with alkyllithiums (one mole equivalent) gave the corresponding 4-substitued 2-alkyl-1,2-dihydroquinazolines 11–18. On the other hand, blocking position 2 with a phenyl group in 4-(methylthio)-2-phenylquinazoline (20) and 4-methoxy-2-phenylquinazoline (21) resulted in reaction with two mole equivalents of alkyllithiums to give 4,4-dialkyl-2-phenyl-3,4-dihydroquinazolines 22–24.     

Synthesis of coumarin derivatives by palladium complex catalyzed intramolecular Heck reaction: Preparation of a 1,2-cyclobutadiene-substituted CpCoCb diphosphine chelated palladium complex

A cobalt-sandwich diphosphine chelated palladium complex 2, [(η⁵-cyclopentadienyl)(η⁴-1,2-diphenyl-3,4-bis(diphenylphosphino-κP)cyclobutadiene)cobalt(I)]palladium(II)dichloride, was prepared from the reaction of a cyclobutadiene-substituted CpCoCb diphosphine 1, (η⁵-cyclopentadienyl) (η⁴-1,2-diphenyl-3,4-bis-diphenylphosphinocyclobutadiene)cobalt(I), with one molar equivalent of Pd(COD)Cl₂. Both compounds were characterized by spectroscopic means as well as single-crystal X-ray diffraction methods. Application of purified 2 as the catalytic precursor in intramolecular Heck cyclization reaction on 4-hydroxycoumarin resulted in the formation of several derivatives with intensity enhanced fluorescence property.     

Synthesis and characterization of a new zinc phthalocyanine containing macrobicyclic moieties

Novel zinc phthalocyanine (ZnPc) containing symmetrically eight triaza-tetraoxa macrobicycles on peripheral positions has been synthesized in a multistep reaction sequence. The cyclotetramerization reaction was accomplished with 4,5-bis[2-(4,7,13,16-tetraoxa-1,10,22-triazabicyclo[8.8.7]pentacosane-22-yl)ethylthio]phthalonitrile (6) which was prepared by the reaction of 1,2-bis(2-iodoethoxy)-4,5-dicyanobenzene (5) and 4,7,13,16-tetraoxa-1,10,22-triazabicyclo[8.8.7]pentacosane (4). The novel compounds were characterized by a combination of elemental analysis, ¹H and ¹³C NMR, IR, UV–vis and MS spectral data.     

Synthesis,spectroscopic characterization and DFT studies on the novel indeno-thiazolopyrimidine heterocyclic system

4-Phenyl-2-thioxo-3,4-dihydro-1H-indeno[1,2-d]pyrimidin-5(2H)-one 2, obtained by stirring a mixture of indane-1,3-dione, benzaldehyde and thiourea in acetic acid at room temperature for 12 h, on reaction with chloroacetic acid and 1,2-dibromoethane furnish compounds 3 (or 6) and 4 (or 7), respectively. The regiochemistry of the cyclized products and their structure is established by an elemental analysis, ¹H NMR, ¹³C NMR, IR and mass spectral data. Density functional theory calculations have been carried out for compounds 3 and 4 and their isomers 6 and 7 with Jaguar version 6.5112 using the B3LYP density functional method and LACVP* basis set. ¹H and ¹³C NMR of compounds 3, 4, 6 and 7 have been calculated. 2-Arylidene derivatives of 3 were obtained by two routes and their structure was established by spectral data.     

Cyclodehydration reactions of methyl 9,10-; 10,12-; and 9,12-dioxostearates with 1,2-diaminoethane under ultrasonic irradiation

Reaction of methyl 9,10-dioxostearate (1) and 9,12-dioxostearate (2) with 1,2-diaminoethane under concomitant ultrasonic irradiation (10–15 min, 60°C) in water furnished the corresponding 2,3-dihydropyrazine (4, 79%) and 1,2,3,4-tetrahydro-1,4-diazocine (5, 70%) derivatives, respectively. Reaction of methyl 10,12-dioxostearate (3) with 1,2-diaminoethane was successful only when glacial acetic acid was used instead of water under ultrasonic irradiation (4×10 min, 70°C) to give a 2,3-dihydro-1H-1,4-diazepine (6, 95%) derivative. The structures of these novel six-membered (4), seven-membered (6), and eight-membered (5) N-heterocyclic fatty ester derivatives were confirmed by a combination of infrared, nuclear magnetic resonance spectroscopic and mass spectral analyses.