Synthesis,structure, and complexing ability of fluoroalkyl-containing 2,2′-(biphenyl-4,4′-diyldihydrazono)bis(1,3-dicarbonyl) compounds

New fluoroalkyl-containing 2,2′-(biphenyl-4,4′-diyldihydrazono)bis(1,3-diketones) and 2,2′-(biphenyl-4,4′-diyldihydrazono)bis(3-oxopropionates) were synthesized by azo coupling of the corresponding 1,3-dicarbonyl compounds with biphenyl-4,4′-bis(diazonium) dichloride. Complexing ability of the obtained bis-hydrazones was studied, and new coordination compounds of the general formula M₂L₂ [where M = Ni(II), Cu(II); L = fluoroalkyl-containing 2,2′-(biphenyl-4,4′-diyldihydrazono)bis(1,3-diketone)] were obtained.     

Synthesis and structure of 5,5′-bis(di-<Emphasis Type="Italic">iso</Emphasis>-propoxyphosphoryl)biphenyl-17-crown-5

The interaction of 5,5′-dibromophenyl-17-crown-5 with triisopropylphosphite (NiBr₂ catalysis) was employed to prepare 5,5′-bis(di-iso-propoxyphosphoryl)biphenyl-17-crown-5, its molecular structure (X-ray crystallography) being compared with the data for the unsubstituted biphenyl-17-crown-5 and an acyclic analog 2,2′-dimethoxy-5,5′-bis(di-iso-propoxyphosphoryl)biphenyl. For both crown-ethers the macrocycle shape in the crystal state is defined by mutual rotation of the benzene rings, whilst bulky isopropoxyphosphoryl groups in the 5(5′) positions gave little influence on the dihedral angle made by the aromatic cycles. The P=O bonds of these groups are pointing into opposite directions and are virtually parallel to the benzene ring planes. The 2,2′-oxygen atoms of the biphenyl fragment have the gauche orientation in all compounds studied.     

Conformational Analysis of Biphenyl-2,2′-Diacetate

Conformational analysis of biphenyl-2,2′-diacetate by dynamic NMR and UV spectra and by plots of enzyme activity vs temperature plots is described. From dynamic NMR spectra of the biphenyl-2,2′-diacetate with a chiral shift reagent, the coalescence temperature (T_c), the Gibbs energy of activation (ΔG^≠), and the rate coefficient (k) of bipbenyl-2,2′-diacetate were ?5 °C, 59.5 kJ/mol, and 13.3 s^?1, respectively. From analysis of the conformational break in the UV spectra and the discontinuity in the plots of enzyme activity vs temperature, the racemerization temperature of bipbenyl-2,2′-diacetate is about 5°C.     

Three new zinc(II) complexes constructed by biphenyl-2,2′,6,6′-tetracarboxylic acid: Effect of solvents and terminal ligands

Interaction of biphenyl-2,2′,6,6′-tetracarboxylic acid (H₄bta) and Zn(II) ions in DMF led to the formation of a one-dimensional coordination polymer, while in the presence of 1,10-phenanthroline and 1H,1′H-2,2′-biimidazole as terminal ligands in H₂O, analogous interactions induced the generation of two-dimensional layers with (6, 3) topology. The bta ligands in these three coordination polymers adopt η⁴,μ₂-tetradentate, η⁵,μ₄-pentadentate and η⁴,μ₄-tetradentate coordination modes, respectively, and the corresponding angles of two benzene rings of bta ligands are 70.52, 83.81 and 73.35°, in accordance with the coordination modes and steric hindrance effect of the terminal ligands.     

Synthesis of Macrocyclic Compounds Using Diorganotin(IV) Dicarboxylates as Covalent Templates

A series of new macrocyclic compounds have been prepared by treating di- n -butyltin(IV) dicarboxylates of diphenic acid (biphenyl-2,2′-dicarboxylic acid), thiodiacetic acid and maleic anhydride with succinyl, adipoyl and sebacoyl dichlorides. The compounds have been characterized with the help of elemental analyses and spectral data (mass, IR, ^IH and ¹³C NMR).     

Turn-on circularly polarized luminescent (CPL) molecular system realized by thermo-driven Newman–Kwart rearrangement reaction from CPL-silent O- to CPL-active S-thiocarbamate groups at peripheral position of 1,1′-binapthyl rings

Although chiral 1,1′-binaphthalene-2,2′-diyl-O,O-bis(N,N-dimethylthiocarbamate) (1) revealed no circularly polarized luminescence (CPL) signals, Newman–Kwart rearrangement of O-thiocarbamate groups at 1 yielded clear CPL signals from 1,1′-binaphthalene-2,2′-diyl-S,S-bis(N,N-dimethylthiocarbamate) (2), which acts as a CPL-gen molecule.     

Preparation and properties of aromatic polyimides from 2,2′-bis(p-aminophenoxy)biphenyl or 2,2′-bis)p-aminophenoxy)-1,1′-binaphthyl and aromatic tetracarboxylic dianhydrides

New aromatic polyimides containing a biphenyl-2,2′-diyl or 1,1′-binaphthyl-2,2′-diyl unit were prepared by a conventional two-step method starting from 2,2′-bis(p-aminophenoxy) biphenyl or 2,2′-bis(p-aminophenoxy)-1,1′-binaphthyl and aromatic tetracarboxylic dianhydrides. The polyimides having inherent viscosities of 0.69–0.99 and 0.51–0.59 dL/g, respectively, were obtained. Some of these polymers were readily soluble in a variety of organic solvents including N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide, and pyridine. Transparent, flexible, and pale yellow to brown films of these polymers could be cast from the DMAc or NMP polyamic acid solutions. These aromatic polyimides containing biphenyl and binaphthyl units had glass transition temperatures in the range of 200–235 and 286–358°C, respectively. They began to lose weight around 380°C, with 10% weight loss being recorded at about 470°C in air. © 1993 John Wiley & Sons, Inc.     

Preparation and properties of new soluble aromatic polyimides from 2,2′-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride and aromatic diamines

A new aromatic tetracarboxylic dianhydride having a crank and twisted noncoplannar structure, 2,2′-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, was synthesized by the reaction of 4-nitrophthalonitrile with biphenyl-2,2′-diol, followed by hydrolysis and cyclodehydration. The biphenyl-2,2′-diyl-containing aromatic polyimides having inherent viscosities up to 0.66 dL/g were obtained by the conventional two-step procedure starting from the dianhydride monomer and various aromatic diamines. Most of the polyimides were readily soluble in amide-type solvents such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone. The aromatic polyimides had glass transition temperatures in the range of 205–242°C, and began to lose weight around 415°C, with 10% weight loss being recorded at about 500°C in air. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2021–2027, 1998     

Enantioselective cyanoformylation of aldehydes mediated by BINOLAM–AlCl as a monometallic bifunctional catalyst

BINOLAM–AlCl's, binaphthoxide aluminium chloride species generated in situ from either (R)- or (S)-3,3′-bis(diethylaminomethyl)-2,2′-dihydroxy-1,1′-binaphthalene (BINOLAM) behave as Lewis acid–Lewis base (LA-LB) catalysts in the enantioselective addition of methyl cyanoformate to aldehydes at room temperature, thereby leading to the asymmetric synthesis of (S)- or (R)-O-methoxycarbonyl cyanohydrins, respectively.     

Synthesis,characterization, and crystal structures of two Ag (I) coordination polymers based on biphenyl-2,2′,4,4′-tetracarboxylate

In this article, [Ag₈(btc)₂(2,2′-bpy)₂] _n (1) and [Ag₄(btc)(phen)₂] _n (2) (H₄btc?=?biphenyl-2,2′,4,4′-tetracarboxylic acid, 2,2′-bpy?=?2,2′-bipyridine, phen?=?1,10-phenanthroline) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectra, thermogravimetric analyses, and single-crystal X-ray diffraction. Complex 1 shows a 3-D framework containing a 2-D bilayer network constructed from (btc)^4? with Ag (I), whereas 2 features a 2-D supramolecular bilayer network. The differences of the two complexes demonstrate that nitrogen-containing chelating ligands have a significant effect on the formation and structure of the resulting complexes. Electrochemistry properties of 1 were also studied.     

Convenient Preparation of Chiral trans-9,10-Dihydrophenanthrene-9,10-diamine

Chiral trans-9,10-dihydrophenanthrene-9,10-diamine was conveniently prepared from biphenyl-2,2′-dialdehyde using intramolecular imino pinacol coupling and oxidative cleavage of aminoalcohol as key steps.     

Oxidative polymerization of aniline on the surface of silica in the presence of poly(sulfonic acids) as a method of preparing efficient biosorbents

Polyaniline coatings on the surface of the macroporous silica have been prepared by oxidative polymerization via protonation of aniline by poly(sulfonic acids): poly(p,p′-(2,2′-disulfonic acid)diphenyle-neisophthalamide and poly(p,p′-(2,2′-disulfonic acid)diphenyleneterephthalamide. Two variants of modification have been studied: namely, the polymerization of aniline carried out in the presence of the preliminarily silaminated glass covered by poly(sulfonic acid) and the modification of silaminated glass by preformed complexes of poly(p,p′-(2,2′-disulfonic acid)diphenylenephthalamide-polyaniline. In both cases, the even polyaniline-containing polymer coating with a thickness of ～3 nm is formed on the support surface. Sorbents containing the poly(p,p′-(2,2′-disulfonic acid)diphenylenephthalamide-polyaniline complex are efficient for isolation of DNA from mixtures of biopolymers.     

Improved syntheses of Ru(CO)2 (O3SCF3)2 (bidentate) complexes and their conversion into new [Ru(CO)2 (bidentate)2]2+ complexes

Reaction of the complexes Ru(CO)₂Cl₂L [L = 2,2′-bipyridyl (bpy) or 1,10-phenanthroline (phen)] with trifluoromethanesulphonic acid under carefully controlled conditions yields Ru[cis-(CO)₂] [cis-(O₃SCF₃)₂] (bidentate complexes. From reactions of the trifluoromethanesulphonates with the appropriate bidentate ligands, the new complexes [cis-Ru(CO)₂-L(L′)]²⁺ (L as above; L′ = 4,4′-dimethyl-2,2′-bipyridyl or 4,4′-diisopropyl-2,2′-bipyridyl) as well as the known [_cis-Ru(CO)₂L₂]²⁺ and [cis-Ru(CO)₂bpy(phen)]²⁺ have been prepared.     

Preparation and properties of polyarylates both from 2,2′-bibenzoyl chloride and bisphenols and from biphenyl-2,2′-diol and aromatic dicarboxylic acid chlorides

Polyarylates having inherent viscosities up to 1.02 dL/g were synthesized both by the phase-transfer catalyzed two-phase polycondensation of 2,2′-bibenzoyl chloride with various bisphenols and by the high-temperature solution polycondensation of biphenyl-2,2′-diol with aromatic dicarboxylic acid chlorides. All the polyarylates were amorphous and soluble in a variety of organic solvents including N,N-dimethylformamide, N-methyl–2-pyrrolidone, chloroform, m-cresol, and pyridine. Transparent and flexible films of these polymers could be cast from the chloroform solutions. These polyarylates had glass transition temperatures in the range of 120–250°C and began to lose weight at around 380°C in air. © 1992 John Wiley & Sons, Inc.     

2,4,8,10-TETRASUBSTITUTED DIBENZO[d,f][1,3,2]DIOXAPHOSPHEPINS

Abstract

The synthesis of the dibenzo[d,f][1,3,2]dioxaphosphepin ring system from substituted biphenyl-2,2′-diols and alkylphosphonous dichlorides is described. The NMR spectral data are consistent with either rapidly interconverting ring conformers or a static non-planar ring conformation.     

A crystalline paradise – three substances exhibiting the following crystallization modes: (1) conglomerate,kryptoracemic and unbalanced (2) conglomerate and kryptoracemic

The compound bis(ethylenediamine-N,N′)-(oxalato-O,O′)-cobalt biphenyl-4,4′-disulfonate hydrate, refcode TIQHOR, crystallizes with four Co(III) cations in the asymmetric unit. Another pair of compounds, rac-bis(ethylenediamine-N,N′)-(oxalato-O,O′)-cobalt(III) l-hydrogenaspartate, refcode VAGBOU, and tetra-ammine-(N-benzylethanediamine)-cobalt(III) trinitrate sesquihydrate, refcode ZIFHEB crystallize both as conglomerates and kryptoracemates. Their stereochemical characteristics are described, and the fact that they display more than one mode of crystallization in a single lattice, is illustrated numerically and visually.     

Über die stereoisomeren α-Phenyläthylamide der Biphenyl-2,2′,6,6′-tetracarbonsäure,Molekeln der Punktsymmetrie D2, S4, C2 und C1

All four possible diastereomeric α-phenylethylamides of biphenyl-2,2′, 6,6′-tetra-carboxylic acid (point symmetries D₂, S₄, C₂ and C₁) have been prepared and their properties investigated. Both enantiomers of the C₂-diastereomer have been synthetized along stereospecific routes which determine their absolute configurations. Specification of molecular chirality and pseudoasymmetry of compounds with axial chirality in two and three dimensional space is discussed.     

New chiral lithium aluminum hydrides based on biphenyl-2,2′-bisfenchol (BIFOL): structural analyses and enantioselective reductions of aryl alkyl ketones

A series of new chiral lithium aluminum hydrides based on BIFOL (biphenyl-2,2′-bisfenchol) and various alkyl alcohols (i.e., methanol, n-butanol, tert-butanol yielding BIFAl-H's) was synthesized and characterized by single crystal X-ray analyses. These investigations point to alkoxide redistribution for BIFAl-H-(O-tBu) (biphenyl-2,2′-bisfenchol aluminum hydride) species. The new BIFAl-H reagents are suitable to reduce aryl alkyl ketones with up to 62% ee. Computational transition structure analyses help to explain the experimentally observed enantioselectivities.     

Investigation of reactions postulated to occur during inhibition of ribonucleotide reductases by 2′-azido-2′-deoxynucleotides

Model 3′-azido-3′-deoxynucleosides with thiol or vicinal dithiol substituents at C2′ or C5′ were synthesized to study reactions postulated to occur during inhibition of ribonucleotide reductases by 2′-azido-2′-deoxynucleotides. Esterification of 5′-(tert-butyldiphenylsilyl)-3′-azido-3′-deoxyadenosine and 3′-azido-3′-deoxythymidine (AZT) with 2,3-S-isopropylidene-2,3-dimercaptopropanoic acid or N-Boc-S-trityl-L-cysteine and deprotection gave 3′-azido-3′-deoxy-2′-O-(2,3-dimercaptopropanoyl or cysteinyl)adenosine and the 3′-azido-3′-deoxy-5′-O-(2,3-dimercaptopropanoyl or cysteinyl)thymidine analogs. Density functional calculations predicted that intramolecular reactions between generated thiyl radicals and an azido group on such model compounds would be exothermic by 33.6–41.2 kcal/mol and have low energy barriers of 10.4–13.5 kcal/mol. Reduction of the azido group occurred to give 3′-amino-3′-deoxythymidine, which was postulated to occur with thiyl radicals generated by treatment of 3′-azido-3′-deoxy-5′-O-(2,3-dimercaptopropanoyl)thymidine with 2,2′-azobis-(2-methyl-2-propionamidine) dihydrochloride. Gamma radiolysis of N₂O-saturated aqueous solutions of AZT and cysteine produced 3′-amino-3′-deoxythymidine and thymine most likely by both radical and ionic processes.     

Preparation and properties of aromatic polyamides from 2,2′-bis(p-carboxyphenoxy) biphenyl or 2,2′-bis(p-carboxyphenoxy)-1,1′-binaphthyl and aromatic diamines

New aromatic dicarboxylic acids having kink and crank structures, 2,2′-bis(p-carboxyphenoxy) biphenyl and 2,2′-bis(p-carboxyphenoxy)-1,1′-binaphthyl, were synthesized by the reaction of p-fluorobenzonitrile with biphenyl-2,2′-diol and 2,2′-dihydroxy-1,1′-binaphthyl, respectively, followed by hydrolysis. Biphenyl-2,2′-diyl-and 1,1′-binaphthyl-2,2′-diyl-containing aromatic polyamides having inherent viscosities of 0.58–1.46 dL/g and 0.63–1.30 dL/g, respectively, were obtained by the low-temperature solution polycondensation of the corresponding diacid chlorides with aromatic diamines. These polymers were readily soluble in a variety of organic solvents including N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide, m-cresol, and pyridine. Transparent, pale yellow, and flexible films of these polymers could be cast from the DMAc or NMP solutions. These aromatic polyamides containing biphenyl and binaphthyl units had glass transition temperatures in the range of 210–272 and 260–315°C, respectively. They began to lose weight around 380°C, with 10% weight loss being recorded at about 450°C in air. © 1993 John Wiley & Sons, Inc.