Fluorescent tricyclic β-azavinamidine–BF2 complexes

Boron trifluoride reacted with dipyrid-2-ylamine 6 , its N-methyl and 6,6′-dimethyl derivatives 8 and 10 , and 3,3′,5,5′-tetraphenyl-6-azapyrromethene 13 to give fluorescent β-azavinamidine (1,3,5-triazapenta-1,3-diene) dyes: 10-azapyridomethene–BF₂ complex 5 (λ_f 422 nm, λ_las 426 nm), its quaternary 10-methyl tetrafluoroborate and 4,6-dimethyl derivatives 9 (λ_f 362 nm) and 11 (λ_f 416 nm), and 1,3,5,7-tetraphenyl-8-azapyrromethene–BF₂ complex 17 (λ_f 696 nm). Treating 3,3′,4,4′-tetraphenyl-5,5′,6-trimethylpyrromethene (prepared in situ from ethyl 3,4-diphenyl-5-methylpyrrole-2-carboxylate in a reaction with acetyl chloride) with boron trifluoride gave 1,2,6,7-tetraphenyl-3,5,8-trimethylpyrromethene–BF₂ complex 21 . Absorption for the vinamidine chromophore differed from that for the β-azavinamidine chromophore by a hypsochromic shift of 86 nm in a comparison of pyridomethene–BF₂ complex 3 with its 10-aza derivative 5 and by a bathochromic shift of 105 nm in a comparison of the pyrromethene–BF₂ complex 20 with the 8-azapyrromethene–BF₂ complex 17 .     

Preparation and spectral properties of Zn(II) complexes with aryl-substituted dipyrrolylmethene and azadipyrrolylmethene

The homoleptic complexes of Zn(II) with 3,3′,5,5‘-tetraphenyl-2,2’-dipyrrolylmethene and 3,3′,5,5′-tetraphenyl-ms-aza-2,2′-dipyrrolylmethene [ZnL₂] have been prepared, and their spectral and luminescent properties have been studied. The complex with 3,3′,5,5′-tetraphenyl-2,2′-dipyrrolylmethene exhibited an intense fluorescence in the nonpolar medium, efficiently quenched in the polar solvents; thus, it can be used as a fluorescent sensor of the medium polarity.     

Syntheses of three naturally occurring polybrominated 3,3′-bi-1H-indoles

The naturally occurring polybrominated indoles 2,2′,5,5′-tetrabromo-3,3′-bi-1H-indole, 2,2′,6,6′-tetrabromo-3,3′-bi-1H-indole, and 2,2′,5,5′,6,6′-hexabromo-3,3′-bi-1H-indole were synthesized using a palladium catalyzed, carbon monoxide mediated, double reductive N-heterocyclization of 2,3-bis(2-nitro-4(or 5)-bromophenyl)-1,4-butadienes as the key step.     

Design of postmetallocene Schiff base-like catalytic systems for polymerization of olefins: XII. Synthesis of tetradentate bis-salicylaldehyde imine ligands

Reactions of salicylaldehyde, 3-tert-butylsalicylaldehyde, and 3,5-di-tert-butylsalicylaldehyde with 1,4-diaminobutane, 1,6-diaminohexane, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′,5,5′-tetramethyldiphenylmethane, 4,4′-diamino-5,5′-dicyclopentyl-3,3′-dimethyldiphenylmethane, 4,4′-diamino-5,5′-dicyclohexyl-3,3′-dimethyldiphenylmethane, bis(4-aminophenyl) sulfone, o,o′- and p,p′-diaminodiphenyl ethers, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and 4,4″-diamino-p-terphenyl gave a series of the corresponding Schiff bases which can be used as tetradentate ligands for the synthesis of titanium and zirconium complexes.     

Photolysis of 2,6-diphenyl-4h-pyran-4-thione and 2,6-diphenyl-4h-thiopyran-4-thione

Photolysis of 2,6-diphenyl-4H-pyran-4-thione and 2,6-diphenyl-4H-thiopyran-4-thione resulted in desulfurization and furnished 2,2′,6,6′-tetraphenyl-4,4′-di(pyranylidene) and 2,2′,6,6′-tetraphenyl-4,4′-di(thiopyranylidene) as the products. The mechanism was studied by quantum yield measurements. In dioxane, the quantum yield of di(pyranylidene) formation was concentration-dependent, while in benzene, it was independent of the concentration. The photoreaction proceeds via the triplet state of 2,6-diphenyl-4H-pyran-4-thione and 2,6-diphenyl-4H-thiopyran-4-thione and the H atom abstraction from solvents appears to be a key step in the formation ofdi(pyranylidene).     

Self-assembly of chiral hydrogen-bonded grid layers from terephthalic Siamese twins

2,2′,5,5′-Tetracarboxy- and 2,2′,5,5′-tetracarbamoyl-substituted biphenyls and also the 2,2′,3,3′,6,6′-hexacarboxy-substituted analogue behave as Siamese twins of terephthalic tectons in the single crystal self-assembly, giving rise to chiral 2D grid layers. A comparison has been made with the corresponding 2,2′,6,6′-tetrasubstituted biphenyls which mimic isophthalic twins in their self-assembly.     

(Perhalogenmethylthio)heterocyclen. XXI. Reaktionen halogenierter perhalogenmethylthiopyrrole: Salz- und radikalbildung,dimerisierung

2-Chloro-3,4,5-tris(trifluoromethylthio)pyrrole ( 2a ), 3-Chloro-2,4,5-tris(trifluoromethylthio)pyarrole ( 2b ) and 3,4-dichloro-2,5-bis(trifluromoethylthio)pyrrole ( 2c ) react with silver nitrate/silver acetate in good yield to give the corresponding N-silver salts 3a-c . Compound 2b forms with an aqueous potassium hydroxide solution the N-potassium salt 4 . Compounds 3a and 3b react with iodine to give the dimeers 2,2′-dichloro-3,3,′ 4,4′5,5′-hexakis(trifluoromethylthio)-2,2′-bi-2H-pyrrolyl ( 5a ) and 3,3′-dichloro-2,2′,4,4′,5,5′-hexakis(trifluoromethylthio)-2,2′-bi-2H-pyrrolyl ( 5b ). The dimers dissociate in solution to the corresponding pyrrolayl radicals. The esr and endor spectra of 3-chloro-2,4,5-tris(trifluoromethylthio)pyrrolyl were measured; coupling constants are given. For the newly prepared substances melting-points, ¹⁹F-nmr and ir spectroscopical data are provided.     

Synthesis,spectral-luminescent properties of B(III) and Zn(II) complexes with alkyl- and aryl-substituted dipyrrins and azadipyrrins

Effect of complexing atom, molecular structure of dipyrrolylmethene and its aza analog on spectral-luminescent properties of heteroleptic boron(III) and homoleptic zinc(II) complexes with 3,3′,5,5′-tetramethyl-2,2′-dipyrrolylmethene, 3,3′,5,5′-tetraphenyl-2,2′-dipyrrolylmethene, and 3,3′,5,5′-tetraphenyl-ms-aza-2,2′-dipyrrolylmethene in organic solvent solutions was studied. The complexes were found to exhibit strong chromophore (λ = 350–690 nm, ? ～ 10⁵ L/mol cm) and fluorescent properties. Quantum yield (γ^fl) for fluoroborate complexes reaches 100% and is weakly dependent on medium nature. The value of γ^fl for phenyl- and alkyl-substituted zinc(II) dipyrrolylmethenates in nonpolar solvents is not higher 0.3 and 0.03, respectively; complete fluorescence quenching is observed in electron-donating solvents. Aza-substitution at the meso spacer causes considerable shift of electronic absorption and fluorescence spectra to the red region but completely quenches fluorescence of zinc(II) chelates and decreases γ^fl of boron(III) complex to 0.04.     

Synthesis of Novel Monodentate Phosphoramidites and Their Application in Iridium‐Catalyzed Asymmetric Hydrogenations

New monodentate H₈‐binaphthol based phosphoramidites 6 b–i have been prepared. Starting from (S)‐3,3′‐dibromo‐5,5′,6,6′,7,7′,8,8′‐octahydro‐1,1′‐binaphthyl‐2,2′‐diol 3 , a general protocol for the synthesis of ligands 6 is presented. A small ligand library bearing aryl substituents in the 3,3′‐position of the binaphthol core was synthesized and successfully tested in the iridium‐catalyzed asymmetric hydrogenation of 2‐amidocinnamates to obtain different α‐amino acid derivatives in up to 99 % ee.     

The synthesis and thermal curing parameters of a novel quinoxaline monomer with terminal ethynyl thermoset and phenylethynyl intramolecular cycloaddition postcure capability

The Synthesis of 3,3′-bis(4-[3-ethynylphenoxy]phenyl)-7,7′-bis(phenylethynyl)-2,2′-diphenyl-6,6′-biquinoxaline (I) was accomplished by the reaction of 2,2′-bis(phenylethynyl)-5,5′-diaminobenzidine (II) and 4-(3-ethynylphenoxy)benzil. Thermal analysis of I indicated a softening temperature of 107°C, followed by an exotherm above 150°C that corresponded to a independent crosslinking reaction of the terminal acetylene groups and an intramolecular cycloaddition (IMC) reaction of the 2,2′-bis(phenylethynyl)biphenyl moieties. In the synthetic work substantial improvements were made in the synthesis of II. The sample of I was cured at 200°C and the maximum partially cured transition temperature attained was 280°C. A sample of 3,3′-bis(4,[3-ethynylphenoxy]phenyl)-2,2′-diphenyl-6,6′-biquinoxaline (IV) was similarly tested as a model without IMC capability and its corresponding value was 250°C. The difference between these two values is discussed briefly.     

Synthesis and Catalytic Properties of Di- and Trinuclear Palladium Complexes with PCP-Pincer Ligands

Linear and branched conjugated pincer ligands having Ph₂P groups were synthesized: 3,3',5,5'- tetrakis(diphenylphosphinomethyl)diphenylacetylene, 3,3',5,5'-tetrakis(diphenylphosphinomethyl)diphenyldi- acetylene, 1,3,5-tris[3,5-bis(diphenylphosphinomethyl)phenylethynyl]benzene, and hexakis[3,5-bis(diphenylphosphinomethyl)phenylethynyl]benzene. Palladation of these ligands by heating with Pd(BF₄)₂(MeCN)₄ in boiling acetonitrile gave the corresponding di- and trinuclear ionic pincer palladium complexes. No individual complex was obtained from hexakis[3,5-bis(diphenylphosphinomethyl)phenylethynyl]benzene. The ionic com- plexes were converted into the corresponding chloride complexes by treatment with sodium chloride in a mixture of water with methylene chloride. The structure of the ionic palladium complex with 3,3',5,5'-tetrakis(diphenylphosphinomethyl)diphenylacetylene was established by X-ray analysis. The obtained palladium complexes exhibited a considerable catalytic activity in the Heck reaction of iodobenzene with ethyl acrylate and in the Michael addition of ethyl cyanoacetate with methyl vinyl ketone. The catalytic activity per palladium atom decreases as the number of palladium atoms in the complex increases.     

6,6′‐Dimethoxygossypolone

6,6′‐Dimethoxygossypolone (systematic name: 7,7′‐dihydroxy‐5,5′‐diisopropyl‐6,6′‐dimethoxy‐3,3′‐dimethyl‐1,1′,4,4′‐tetraoxo‐2,2′‐binaphthalene‐8,8′‐dicarbaldehyde), C₃₂H₃₀O₁₀, is a dimeric molecule formed by oxidation of 6,6′‐dimethoxygossypol. When crystallized from acetone, 6,6′‐dimethoxygossypolone has monoclinic (P2₁/c) symmetry, and there are two molecules within the asymmetric unit. Of the four independent quinoid rings, three display flattened boat conformations and one displays a flattened chair/half‐chair conformation. The angles between the planes of the two bridged naphthoquinone structures are fairly acute, with values of about 68 and 69°. The structure has several intramolecular O—H...O and C—H...O hydrogen bonds and several weak intermolecular C—H...O hydrogen bonds, but no intermolecular O—H...O hydrogen bonds.     

天然产物Angustifolin D中间体的合成

以3,4,5-三甲氧基苯甲酸为原料,经6步反应以23％总收率完成了Angustifolin D关键中间体--6,6′-2［(Z)-2-碘代-1-丙烯基］-2,2′,3,3′,4,4′-六甲氧基-1,1′-联苯(7)的合成,其结构经¹H NMR, ¹³C NMR, IR和MS确证。其中关键步骤联苯偶连反应采用了廉价易得的铜试剂(CuBr·SMe₂)作为催化剂。     

Pyrylium salts in the synthesis of redoxites

Redoxites poly(2,6-diphenyl-4-vinylpyran), poly(2,6-diphenyl-4-vinylpyrylium perchlorate), poly-(2,6-diphenyl-4-vinylpyridine) and poly(2,2′,6,6′-tetraphenyl-γ,γ′-dipyridine) were obtained based on pyrylium salts. Poly(2,2′,6,6′-tetraphenyl-γ,γ′-dipyridine) was transformed into the polyene to improve its film-forming and conducting properties. Electrochemical properties of polyviologen and conductive properties of the obtained polymers were studied.     

Polymerization by oxidative coupling. II. Co-redistribution of poly(2,6-diphenyl-1,4-phenylene ether) with phenols

Poly(2,6-diphenyl-1,4-phenylene ether) reacts with phenols in the presence of an initiator to form a mixture of low molecular weight hydroxyarylene ethers. Although the reaction is similar to the equilibration of poly(2,6-dimethyl-1,4-phenylene ether) with phenols, higher reaction temperatures and larger initiator concentrations are required. Compounds as 3,3′,5,5′-tetraphenyl-4,4′-diphenoquinone, tert-butyl perbenzoate, and benzoyl peroxide are active initiators. The structure of the polymer affects the extent to which the polymer equilibrates.     

An Efficient One‐Pot Synthesis of Bis Butenolides

3,3′,4,4′‐Tetramethyl‐5,5′‐dioxo‐2,2′‐bifuran‐2,2′(5H,5′H) diyl diacetate was obtained from the reaction between 2,3‐dimethyl maleic anhydride and acetic anhydride in the presence of zinc in toluene. This easy synthetic route gave bis butenolide in excellent yield.     

Improved synthesis of 2,2'-bipyrimidine

A high-yield synthesis was developed for the preparation of 2,2'-bipyrimidine (1) using the Ullmann coupling of 2-iodopyrimidine. The new procedure was also used for the preparation of 4,4',6,6'-tetramethyl-2,2'-bipyrimidine (2) and 5,5'-dibromo-2,2'-bipyrimidine (3).     

Reactivity of Organolithium Reagents to 2,3,4,5-Tetraphenylcyclopentadienone and Crystal Structures of Addition Products

The conjugate addition reactions of four organolithium reagents to 2,3,4,5-tetraphenylcyclopentadienone (tetracyclone) were investigated to reveal the reactivity of organolithium reagents to tetracyclone. The results show that 1,2-addition products 2,3,4,5-tetraphenyl-1-(2-thienyl)-2,4-cyclopentadien-1-ol(1), 1-n-butyl-2,3,4,5-tetraphenyl-2,4-cyclopentadien-1-ol(2) and 1,2,3,4,5-pentaphenyl-2,4-cyclopentadien-1-ol(3) were synthesized in excellent yields while tetracyclone reacted with 2-thienyllithium, n-butyllithium and phenyllithium, respectively. Interestingly, three 1,2-, 1,4- and 1,6-addition isomers 1-tert-butyl-2,3,4,5-tetraphenyl-2,4-cyclopentadien-1-ol(4), 4-tert-butyl-2,3,4,5-tetraphenyl-2-cyclopenten-l-one(5) and 2-tert-butyl-2,3,4,5-tetraphenyl-3-cyclopenten-l-one(6), were simultaneously obtained by the conjugate addition reaction of tert-butyllithium with larger steric hindrance to tetracyclone. Compounds 1-6 were characterized by ¹H and ¹³C NMR spectra, Fourier transform infrared(FTIR) spectra and mass spectra(MS). The crystal and molecular structures of compounds 1, 2 and isomers 5, 6 were determined by X-ray single crystal diffraction technique. The results imply that the steric hindrance of tert-butyllithium probably play a key role in controlling the conjugate addition reaction. The conjugate addition mechanism of organolithium reagents to tetracyclone was proposed.     

Reactions of 2,2′,5′,2′-terfuran

Formylation of 2,2′,5′,2′-terfuran ( 1 ) with N-methylformanilide and phosphorus oxychloride gave 5-formyl-2,2′,5′,2′-terfuran ( 2 ) and 5,5′-diformyl-2,2′5′,2′-terfuran ( 3 ). Reduction of 2 and 3 afforded 5-hydroxymethyl-2,2′,5′,2′-terfuran ( 4 ) and 5,5′ dihydroxymethyl-2,2′,5′,2′-terfuran ( 5 ), respectively. Terfuran 1 reacted with phenylmagnesium bromide to give 5-(phenylhydroxymethyl)-2,2′,5′,2′-terfuran ( 6 ), and was carbonated to 5-carboxy 2,2′,5′,2′-terfuran ( 7 ) and 5,5′-dicarboxy-2,2′,5′,2′-terfuran ( 8 ). Bromination of 1 with N-bromosuccinimide gave 5,5′-dibromo 2,2′,5′,2′-terfuran ( 9 ).     

Bidirectional racemic synthesis of the biologically active quinone cardinalin 3

Readily available 2,2',6,6'-tetramethoxy-1,1'-biphenyl was transformed in 14 synthetic steps into the natural product cardinalin 3 using a bidirectional approach. One of the key steps was the formation of the cis-1,3-dimethylnaphtho[2,3-c]pyran ring. (+/-)-1,1'-[6,6'-Diallyl-5,5'-bis(benzyloxy)-1,1',3,3'-tetramethoxy-2,2'-binaphthalene-7,7'-diyl]diethanol was treated with O(2) in the presence of CuCl(2) and catalytic PdCl(2) to afford 5,5'-bis(benzyloxy)-7,7',9,9'-tetramethoxy-1,1',3,3'-tetramethyl-1H,1'H-8,8'-bibenzo[g]isochromene. Hydrogenation of this compound afforded 7,7',9,9'-tetramethoxy-cis-1,3-cis-1',3'-tetramethyl-3,3',4,4'-tetrahydro-1H,1'H-8,8'-bibenzo[g]isochromene-5,5'-diol in quantitative yield, which was converted in 3 steps to cardinalin 3.