Preparation and resolution of 2,2′-dimercapto-6,6′-dimethoxy-1,1′-biphenyl: a C2-symmetric sulfur building block

The preparation of the title dimercaptan 1 starting from 2,2′-dihydroxy-6,6′-dimethoxy-1,1′-biphenyl 2 is described. Resolution of dimercaptan 1 was performed using (−)-(1R,2S,5R)-menthyl chloroformate as a chiral resolving agent. The procedure affords dimercaptan (+)-1 and (−)-1 in 98% ee and 93% ee, respectively. A new and direct intermolecular Ullmann coupling resulting in an improved preparation of diol 2 is also reported.     

Crystal structure of 1,1′-biphenyl-2,2′,3,3′-tetracarboxylic and 1,1′-biphenyl-2,2′,3,3′,5,5′,6,6′-octacarboxylic acids: solid-state chiralization and dissociation

X-ray diffraction analysis revealed unexpected stereochemical features accompanying crystal self-assembly of the two title oligocarboxylic acids.     

Chiral nonracemic C2-symmetry biphenyls by desymmetrization of 6,6′,2,2′-tetramethoxy-1,1′-biphenyl

Regioselective bromination of the title biphenyl 1 at the 3 and 3′ positions and simultaneous desymmetrization of the biphenyl has been achieved. Metal–halide exchange at the 3,3′ positions facilitated the introduction of functional groups in good yield. Regioselective reduction was obtained by using (CH₃)₃SiI, L-Selectride and HI according to the functional groups on the biphenyls. Resolution of 6,6′,2,2′-tetramethoxy-3,3′-dimethyl-1,1′-biphenyl 3 was achieved by its conversion to the corresponding phosphorothioamidate diastereomers of the (S)-(−)-α-methylbenzylamine. The absolute configuration of (M)-(+)-3 was confirmed by X-ray analysis of the corresponding diastereomer.     

Phosphomacrocyclic systems based on 2,2′-dihydroxy-1,1′-dinaphtylmethane

For the first time phosphomacrocyclic systems were synthesized based on 2,2′-dihydroxy-1,1′-dinaphthylmethane, other aromatic diols, and phosphorous hexaethyltriamide. Spontaneous transformation of the obtained macrocycles into the more stable 1,3,2-dioxaphosphacyn and cyclobisamidophosphite was established.     

Efficient Preparative Rentes to 6,6′-Dibromo-2-2′-bipyridine and 6-Bromo-2,2′-bipyridine

The preparation of 6,6′-dibromo-2,2′-bipyridine and 6-bromo-2,2′-bipyridine are described. The dibromo compound was prepared by way of an improved cuprate synthesis resulting in a 72% yield. The monobromo species was prepared from the dibromo compound by way of metal-halogen exchange in 88% yield.     

Synthesis and Characterization of Chiral Mercury（II） and Cadmium（II） Complexes with 3,3＇-Bipyridine-5,5＇,6,6＇-tetramethyl-2,2＇-dimethoxy-1,1＇-biphenyl

Two homochiral mercury (1) and cadmium (2) complexes derived from chiral twisted biphenyl pyridine ligand (3,3'-bipyridine-5,5',6,6'-tetramethyl-2,2'-dimethoxy-1,1'-biphenyl) have been synthesized and characterized by IR, microanalysis, TGA, UV-Vis, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 2. For 1, a = 14.2038(16), b = 14.3630(17), c = 7.0257(8), V = 1433.3(3)3, Mr = 878.91, Dc = 2.037 g/cm3, μ = 7.549 mm-1, F(000) = 824, the final GOF = 1.017, R = 0.0296 and wR = 0.0645 for 2925 observed reflections with I > 2σ(I). For 2, a = 14.212(3), b = 14.392(3), c = 7.0498(14), V = 1442.0(5)3, Mr = 790.72, Dc = 1.821 g/cm3, μ = 2.924 mm-1, F(000) = 760, the final GOF = 1.075, R = 0.0340 and wR = 0.0834 for 3144 observed reflections with I > 2σ(I). The crystal structures of 1 and 2 are isostructural and each adopts a two-dimensional supramolecular network which contains the C-H···π interactions.     

1,1′,2,2′,6,6′-Hexaphenyl-4,4′-bipyridinium cation radical

Aniline reacts with 2,2,6,6-tetraphenyl-4,4-bipyrilium perchlorate to form 1,1,2,2,6,6-hexaphenyl-4,4-bipyridine perchlorate. A relatively stable cation radical is formed in the first stage of electrochemical reduction of this compound, which has been examined by ESR, where there are splittings from two nitrogen nuclei and the four protons in the 3,3,5,5 positions: a_N=0.38; a_H=0.14 mT.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, No. 1, pp. 61–64, January–February 1992.     

2,2′,3,3′,5,5′-Hexaphenyl-[1,1′-biphenyl]-4,4′-diols as Monomer Units for Redox Polymers: Synthesis and Polymerization Strategies

Abstract

2,2′,3,3′,5,5′-Hexaphenyl-[1,1′,-biphenyl]-4,4′-diol (Ib), which is prepared by the oxidative coupling of 2,3,6-triphenylphenol, and its oxidized form (IIIb) constitute a powerful oxidation-reduction system. The oxidative coupling reaction is carried out in the presence of molecular oxygen with copper(I) chloride as a catalyst and butyronitrile as ligand and solvent. An approach to the incorporation of such biphenols into an oxidation-reduction polymer is presented.     

A highly efficient method for the resolution of 8,8′-dihydroxy-1,1′-binaphthyl

The diastereomeric mixture of monoesters of racemic 8,8′-dihydroxy-1,1′-binaphthyl and N-CBZ-l-proline was easily separated. Each diastereomer gave enantiomerically pure (R)- or (S)-8,8′-dihydroxy-1,1′-binaphthyl in good yields after hydrolysis.     

Synthesis of chiral 3,3′-disubstituted 1,1′-binaphthyl-2,2′-disulfonic acids

A convenient synthesis of chiral 3,3′-disubstituted 1,1′-binaphthyl-2,2′-disulfonic acids (BINSA, 1) was developed. The key was directed ortho-lithiation of BINSA methyl ester 2 with n-BuLi and subsequent reaction with an electrophile. Electrophiles such as Br₂, I₂, Me₃SiOTf, and i-PrOB(Pin) reacted smoothly with 3,3′-dilithiated BINSA methyl ester, and the corresponding 3,3′-dihalo-, 3,3′-bis(trimethylsilyl)-, and 3,3′-diboryl-BINSA derivatives were obtained in yields of 21–78%. This simple synthetic method is highly attractive since the ability to prepare 3,3′-disubstituted BINOLs in advance can be useful.     

A New and Efficient Method for the Synthesis of 2,2′-Dibromo-1,1′-binaphthyl Under Microwave Irradiation

Abstract

A very simple and efficient method to prepare 2,2′-dibromo-1,1′-binaphthyl via two-step procedure from β-naphthol in good yield under microwave irradiation is described.     

Spectroscopic and electrochemical properties of cyclopalladated complexes of 2,3-diphenylquinoxaline and 2,2′,3,3′-tetraphenyl-6,6′-biquinoline

Comparative study of cyclopalladated ethylenediamine complexes of 2,3-diphenylquinoxaline (Hdphqx) [Pd(dphqx)En]ClO₄ and 2,2′,3,3′-tetraphenylbiquinoline (H₂tphbq) [(PdEn)₂(μ-tphbq)](ClO₄)₂, and the free heterocyclic ligands was performed by means of ¹H NMR spectroscopy, electronic absorption and emission spectroscopy, and cyclic voltammetry. It was shown that cyclopalladation gives rise to a long-wave absorption band in the visible spectrum, a batochromic shift of the vibrationally structured phosphorescence band, and an anodic shift of the ligand-centered reduction potential of the complexes com-pared to free ligands.     

New Chiral Ligand N-Toluenesulfonyl-2,2′-dimethoxy-6,6′-diaminobiphenyl for Catalytic Asymmetric Transfer Hydrogenation of Ketones

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4-Hydroxy-2-quinolones 146. Synthesis and structure of 1,1′-diallyl-4,4′-dihydroxy-1H,1′ H-[3,3′]biquinolinyl-2,2′-dione

The methyl ester of N-allyl-2-methoxycarbonylsuccinanilic acid is partially converted to 1,1′-diallyl-4,4′-dihydroxy-1H,1′H-[3,3t′]biquinolinyl-2,2′-dione in refluxing toluene in the presence of metallic sodium. A possible mechanism for the occurrence of these chemical processes is discussed. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1033–1038, July, 2008.     

Toxicokinetics and metabolic study of 2,2′-dihydroxy-4,4′- dimethoxybenzophenone

2,2′-Dihydroxy-4,4′-dimethoxybenzophenone (UV-D) is one of the benzophenones, which is widely used as UV filter to protect industrial and commercial products from light. This compound is suspected as a kind of endocrine-disrupting chemical, which might interfere with hormonal signaling pathways, and have potential adverse effects on human health. Thus, toxicity and metabolism of it could be important to know its biological effect. As little is known about the toxicokinetics and metabolism of UV-D, herein, the related study was performed on rats by orally administrating with UV-D. UV-D was found to be promptly metabolized to five main metabolites, which were further identified by high-performance liquid chromatography–quadrupole time-of-flight mass spectrometry. Demethylation, hydroxylation, sulfonation, and glucuronidation were the main metabolic pathways for UV-D.     

Synthesis,resolution and application of 2,2′-bis(di-2-furylphosphino)-1,1′-binaphthalene

A six step synthesis and resolution of (±)-2,2′-bis(di-2-furylphosphino)-1,1′-binaphthalene 4 (TetFuBINAP) is described along with its use in asymmetric inter- and intramolecular Heck reactions.     

2,2′-Dipyridyl-6,6′-dicarboxylic acid diamides: Synthesis,complexation and extraction properties

New ligands for complexing of the post-transition metals – diamides of 2,2′-bipyridyl-6,6′-dicarboxylic acid were developed, synthesised and characterised. They were proposed to be effective extractants towards americium. The structures of the amides were studied in solid as well as in solution. The extraction of Am and lanthanides depending on diamide structure, chlorinated cobalt dicarbollide (CCD) – diamide ratio, type of diluent was studied. The optimal conditions for Am/REE separation were determined. The properties of new potentiometric sensors on the base of 2,2′-dipyridyl-6,6′-dicarboxylic acid diamides were studied. The correlation structure vs. properties of ionophores (i.e. extractants), their sensitivity and selectivity in sensor analysis and extraction are discussed.     

Molecular recognition and supramolecular self-assemblies of (±)-2,2′-dihydroxy-1,1′-binaphthyl with aromatic aza compounds

Abstract  (±)-2,2′-dihydroxy-1,1′-binaphthyl (binol) co-crystallized with 1,10-phenanthroline-5,6-dione and acridine to afford co-crystals (Binol)·(1,10-phenanthroline-5,6-dione) 1 and (Binol)·(acridine)₂ 2, respectively. Co-crystal 1 crystallizes in space group P-42(1)c, with a = 14.9921(4), b = 14.9921(4), c = 20.8102(12) ?. Co-crystal 2 crystallizes in space group P2/c, with a = 17.8004(19), b = 10.0093(11), c = 19.393(2) ?, and α = γ = 90°, β = 103.187(2)°. In co-crystal 1, the components form an infinite 1D polar array; whereas in 2, the components form discrete three-component aggregates. Graphical abstract   Molecular recognition and supramolecular self-assemblies of (±)-2,2′-dihydroxy-1,1′-binaphthyl with aromatic aza compounds Baoming Ji, Shaobin Miao, Dongsheng Deng As a result of mutual recognition, (±)-binol with 1,10-phenanthroline-5,6-dione and acridine afforded co-crystals 1 and 2, respectively. In 1 the components form an infinite 1D polar array, whereas in 2 the components form discrete three-component aggregates.      

Preparation and Characterization of Methyl Substituted 2,2′-Dipyridyl Diselenides and -Ditellurides: X-ray Structure of 6,6′-Dimethyl-2,2′-dipyridyl Diselenide

A convenient method for the preparation of various methyl substituted 2,2'-dipyridyl diselenides and -ditellurides by the aerial oxidation of lithium 2-pyridylselenolate/tellurolate, prepared from the lithium-halogen exchange between n-butyllithium and 2-bromo methyl substituted pyridines is reported. All the compounds prepared are new and have been characterized by elemental analysis, IR, 1 H, 13 C, 11 Se NMR, and mass spectral studies. Crystal structure of 6,6'-dimethyl-2,2'-dipyridyl diselenide has been determined.     

Hydrothermal Synthesis and Crystal Structure of a Manganese(II) Coordination Polymer with 1,1′-Biphenyl-2,2′,6,6′-tetracarboxyl Acid and 2,2′:6,2′′-Terpyridine Ligands

The title compound {[Mn(H2BPTC)(tpy)(H2O)]·(H2O)3}n (1, H4BPTC = 1,1′- biphenyl-2,2′,6,6′-tetracarboxylic acid, tby = 2,2′:6,2′′-terpyridine) has been synthesized by the hydrothermal reaction, and its structure was determined by X-ray diffraction and characterized by elemental analysis, IR spectrum and thermogravimetric analysis. The crystal is of monoclinic, space group P21/c with a = 10.971(2), b = 20.776(4), c = 14.332(3) , β = 109.25(3)o, MnC31H27N3O12, Mr = 688.50, V = 3084.1(10) 3, Dc = 1.483 g/cm3, F(000) = 1420, μ = 0.498 mm-1, S = 1.066 and Z = 4. The final refinement gave R = 0.0447 and wR = 0.1103 for 5107 observed reflections with I > 2σ(I). The title complex has a {[Mn(H2BPTC)(tpy)(H2O)]}n chain structure, and the hydrogen bonding interactions make it more stable. Each chain is further connected to the adjacent ones through π···π, C-H···π and rich hydrogen bonds to form a metal-organic coordination polymer.