Synthesis and properties of polyimides derived from bis-(Aminophenoxy) containing naphthalene, [Phenyl] propane and [Methyl] cyclohexane segment and 4, 4′-carbonyldiphthalic anhydride

ABSTRACT

Three wholly, semi aromatic and aliphatic-aromatic polyimides containing bis(phenoxy) naphthalene, bis[(phenoxy) phenyl] propane and bis(phenoxy-methyl) cyclohexane segments by the two-step procedure from 2, 7-bis(4-aminophenoxy) naphthalene (BAPON), 2, 2-bis[4-(4-aminophenoxy)phenyl]propane (BAPOP), 1, 4-bis (4-aminophenoxy methyl) cyclohexane (BAPMC) as a diamine and 4,4′-carbonyldiphthalic anhydride (CDPA) were prepared. The first step of this procedure including ring-opening polyaddition in a polar solvent to give poly(amic-acid)s, second step containing cyclodehydration reaction to form polyimides. Synthesized monomer and polyimides were characterized by FT-IR, ¹H NMR spectroscopy and elemental analyses (CHN) that obtained results gave the most powerful evidence. The polyimide synthesized from BAPON was characterized as semi-crystalline, whereas the other polyimides showed amorphous patterns by the x-ray diffraction studies. The inherent viscosity was ranging between 0.87–1.01 dL/g. Tensile strength, initial moduli, and elongation at break of the polyimide films ranged from 88–117 MPa, 1.98–2.32 GPa, and 5–8%, respectively. Thermogravimetric analysis in nitrogen atmosphere shows that these polymers having good stability, so 10% weight will be lost in the range of 500–630°C. The point of polyimide with BAPMC segment, is “adding of good thermal stability and processability” lower moisture absorption and dielectric constant (0.75% and 2.90).     

Synthesis and structures of mercury and cadmium complexes: [Ph4Sb] 2 + [Hg2I6]2−·Ph2Hg, [Ph4Sb] 2 + [E2I6]2− (E = Hg, Cd), and [Ph4Sb] 2 + [Hg4I10]2−

The reaction of pentaphenylantimony with mercury iodide affords the ionic complex [Ph₄Sb] ₂ ⁺ [Hg₂I₆]^2?·Ph₂Hg (I). The [Ph₄Sb] ₂ ⁺ [Hg₂I₆]^2? (II) and [Ph₄Sb] ₂ ⁺ [Cd₂I₆]^2? (III) complexes are synthesized from tetraphenylantimony iodide and mercury and cadmium iodides. The [Ph₄Sb] ₂ ⁺ [Hg₄I₁₀]^2? complex (IV) is prepared from tetraphenylantimony 2,4-dimethylbenzenesulfonate and mercury iodide. According to the X-ray diffraction data, the Sb atom in the [Ph₄Sb]⁺ cations of complex I has virtually ideal tetrahedral coordination (the CSbC angles are 108.09°–109.64°). In the central square fragment Hg₂I₂ of the [Hg₂I₆]^2? anion, the Hg-I_br bond lengths are 2.825 and 3.075 Å, and the terminal iodine atoms are more strongly bonded to the mercury atoms (Hg-I_term 2.691 and 2.700 Å). The [Cd₂I₆]^2? anion in complex III has a similar structure (the Cd-I_bridg and Cd-I_term distances are 2.865, 2.872 and 2.723, 2.748 Å, respectively). The anions in complex IV are joined by I…Hg (3.651 Å) and I…I (4.058 Å) interactions into an infinite dimeric network.     

Synthesis and Complexation Properties of Novel Biscalixarene Composed of Calix[4]arene and Thiacalix[4]arene Subunits

Biscalixarenes, as examples of higher order molecular architectures than normal calixarene derivatives, were studied extensively in the recent years due to they possess two calixarene cavities which have the potential for complexing with two guests in two…     

Novel Synthesis of Pyrano[2,3-d]Thiazole,Thiazolo[3,2-a]Pyridine,and Pyrazolo [3′,4′:4,5] Thiazolo[3,2-a]Pyridine Derivatives

Cyclocondensation of 2-cyanomethyl-4-thiazolidinone (1) with tetracyanoethylene (2) furnished pyrano[2,3-d]thiazole derivative (4) . Benzo[e]pyrano[2,3-d]thiazole derivative (6) was obtained by cyclization of compound (1) with salicylaldehyde. In a similar manner, condensation of compound (1) with 2-hydroxy-1-naphthaldehyde in refluxing ethanol yielded naphtho[e]pyrano[2,3-d]thiazole derivative (7) . Interaction of compound (9) with benzylidenemalononitriles (10) (1 : 1 molar ratio) at reflux temperature in ethanol in the presence of piperidine afforded thiazolo[3,2-a]pyridines (12a-c) . Treatment of compound (12a) with hydrazines furnished pyrazolo[3′,4′:4,5] thiazolo[3,2-a]pyridines (14a,b) . The reaction of compound (1) with benzyli-denecyanoacetate (16) yielded 5-hydroxythiazolo[3,2-a]pyridine derivative (21) . Cyclization of bis(thiazolinone) (23) with benzylidenemalononitriles (10) produced bis(thiazolopyridine) derivatives (25a,b) .     

Self－assembly of Novel Hetero[3]rotaxane, [2]Rotaxanes and [2]Catenane

One linear template 13 and one cyclophane template 15, both incorporating two electron rich 1,4‐dialkoxybenzene units and one diamide unit, have been synthesized. By utilizing donor‐acceptor interaction and/or intermolecular hydrogen bonding assembling principles, one novel hetero[3]rotazane 22·4Cl, possessing one neutral and one tetracationic ring components, has been synthesized from 13, through neutral [2]rotaxane 21 as intermediate. With 15 as template, tetracationic [2]catenane 23·4PF₆ was assembled by using donor‐acceptor interaction, but no neutral [2]rotaxane could be obtained under the typical conditions of hydrogen bonding assembling principle. The interlocked supramolecular compounds have been characterized and their spectral properties are investigated.     

Design and Syntheses of Novel Calix[4]crown: Calix[4]‐Dixanthates‐Crowns

Abstract

A series of novel calix[4]‐dixanthates‐crowns were designed and synthesized by the “1 + 1 condensation” of reacting calix[4]‐1,3‐dixanthate salts derivative (4) with polyethylene glycol ditosylates in 40–60% yields. It was found that the new calixcrowns showed outstanding complexation abilities towards soft cations. Calix[4]‐dixanthate‐crown‐4 (5b) exhibited high complexation selectivity towards Ni²⁺.     

Doebner condensation in ionic liquids [Bmim]BF_4 and [Bpy]BF_4 to synthesize α,β-unsaturated carboxylic acid

Ionic liquids[Bmim]BF_4 and[Bpy]BF_4 were employed as environmentally benign media in Doebner condensation to synthesizeαβ-unsaturated carboxylic acid.The good results showed that[Bmim]BF_4 and[Bpy]BF_4 were efficient media for Doebner condensation,which could be recycled easily.The highest yields could reach 93%and 90%in[Bmim]BF_4 and[Bpy]BF_4,respectively.     

Calix[4]dithiacrown-6 and Its Platinum Complex

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Synthesis and properties of p-per fluoroalkylcalix [4]arenes

p-Perfluoroalkylealix[4]arenes were prepared readily from the reaction of calix-[4]arene with perfluoroalkyl iodides in the presence of sodium dithionite or sodium hydroxy-methanesulfinate under mild conditions,These fluorine-containing calixarenes showed bettersolubilities in common organic solvents as compared to their nonperfluoroalkylation analogand formed inclusion complexes with many neutral molecules as well as fluorocarbons.     

Synthesis and crystal structure of 15α,20α-di(4-hydroxylphenyl)calix[4]pyrroles and 10α,20β-di(4-hydroxylphenyl)calix[4]pyrroles

In the presence of methanesulfonic acid as catalyst, the condensation reactions of 5,5′-dialkyldipyrromethanes with p-hydroxyacetophenone in methanol resulted in a mixture of the unexpected polysubstituted 15α,20α-di(4-hydroxylphenyl)calix[4]pyrroles and the expected 10α,20β-di(4-hydroxylphenyl)calix[4]pyrroles in comparable lower yields. The crystal structures of the new calix[4]pyrroles and their oxyacetate derivatives were successfully determined by X-ray diffraction and the intermolecular interactions in the solid state is briefly discussed.     

Design and Synthesis of 3, 4-Dihydropyrrolo[2, 1-c][1, 4]oxazin-l-one and its 7-Acyl Derivatives

Starting from 1H-pyrrole, unreported 3, 4-dihydropyrrolo[2, 1-c][1, 4]oxazin-1-one 4, 7-(4-chlorobenzoyl)-3, 4-dihydropyrrolo[2, 1-c][1, 4]oxazin-1-one 5 and 7-benzoyl-3, 4-dihydro-pyrrolo [2, 1-c][1, 4]oxazin-1-one 9 were designed and synthesized. They may have antipyretic and analgesic activities.     

Synthesis of dialkyltetrahydrobenz[f]iso-indoline,dialkyl-4-δ′-cyclohexenylbenz[f]iso-indoline,and dimethyl-4-alkenylnaphth[f]iso-indolive salts through base-catalyzed intramolecular cyclization of quaternary ammonium salts

Dialkylpropargyl(3-,-cyclohexenylpropargyl)amrnonium salts are cyclized in the presence of a base catalyst to give dialkyltetrahydrobenzlfliso-indoline salts in high yields. When the 3--cyclohexenylpropargyl and 3 phenylpropargyl groups are both present in the ammonium salt molecule, cyclization proceeds in more than one direction. Salts which contain both the 3-a-naphthylpropargyl and 3-alkenylpropargyl groups are also cyclized in two possible ways.Institute of Organic Chemistry, Republican Academy of Sciences, Armenia, Yerevan. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 328–332, March, 1996. Original article submitted September 30, 1995.     

Phase Transfer Catalyzed Synthesis of 1, 2-Bis[（3-aryl）-s-triazolo- [3, 4-b]-[1, 3, 4]thiadiazole-6-yl]ethanes

s-Triazolo[3, 4-b]-[1, 3, 4]thiadiazole derivatives have been paid attractive attention due to their significantly biological activities1-5, including antibacterial, antifungal, anticancer, relaxing vascular activities. They are highly important heterocyc…     

Synthesis of Some New Thieno[2,3-b]pyridines,Pyrimidino[4′,5′:4,5]thieno[2,3-b]-pyridines,and 2,3-Dihydro-1,3,4-thiadiazoles

Thieno[2,3-b]pyridines were synthesized from 6-benzofuran-2-yl-4-phenyl-2-sulfanylpyridine-3-carbonitrile and each of chloro acetone, ethyl chloroacetate, ω -bromoacetophenone, and chloroacetonitrile. These compounds were conveniently converted into novel pyrido[4′,5′:4,5]thieno[3,2-d]pyrimidines. Also, 2,3-dihydro-1,3,4-thiadiazole was synthesized from hydrazonoyl halides and 2-benzofuran-2-yl-3-(phenylamino)-3-thioxopropanenitrile. The structures of the products have been elucidated by elemental analyses, spectral data studies, and alternative syntheses whenever possible. The newly synthesized compounds were tested towards microorganisms.     

The unusual stability of [NpO2Cl4]2−: Synthesis and characterisation of [NpO2(DPPMO2)2Cl]2[NpO2Cl4] and [Ph3PNH2]2[NpO2Cl4]

The [NpO₂(DPPMO₂)₂Cl][NpO₂Cl₄] complex (where DPPMO₂ = bis(diphenylphosphino)methanedioxide) contains the linear neptunyl group, {NpO₂}²⁺, with two bidentate P=O donor ligands. Coordinating anion Cl^? fills the fifth equatorial coordination site yielding a complex of general formula [NpO₂(DPPMO₂)₂X]₂[Y] (1) (where X = Cl^? and Y = [NpO₂Cl₄]^2?. Reaction between our newly prepared neptunium starting material [NpO₂Cl₂(thf)]_n and phosphinimine ligand produced crystals of [Ph₃PNH₂]₂[NpO₂Cl₄] (2). Compounds 1 and 2 have been structurally characterised.     

Erratum to: “Asymmetric Calix[4]-thiacalix[4]arene Tubes: Synthesis and Ionophore Properties”

Russian Journal of Organic Chemistry -     

Heterocyclizations of Di- and Tricarbonyl Indole Derivatives. Synthesis of β-Carbolines, 3H-[1,2,5]Triazepino-[5,4-a]indol-4(5H)-one,and 5,10-Dihydro[1,2]diazepino-[4,5-b]indol-4(3H)-one

Russian Journal of Organic Chemistry - A synthetic approach to β-carbolines has been proposed on the basis of heterocyclization of ethyl 2-(2-benzoyl-1H-indol-3-yl)acetate with...     

Synthesis and Antibacterial Activity of 8-Substituted Phenyl-1-pyridin-3-yl-5H-bis[1, 2, 4]triazolo[3, 4-b； 4＇, 3＇-d][1, 3, 4] thiadiazines

To find new structural leading compounds for the research of the multidrug resistant of antibacterial agents, five novel 8-substituted phenyl-l-pyridin-3-yl-5H-bis[1, 2, 4] triazolo[3, 4-b;4‘,3‘-d] thiadiazines were prepared from the corresponding intermediates of 3-(5-substituted phenyl[1,3,4]oxadiazol-2-ylmethylsulfanyl)-5-pyridin-3-yl-[1,2,4]triazol-4-ylamines via intramolecular cyclization and the antibacterial activity in vitro against Gram-postive (G^ ) and Gramnegatiye (G) bacteria was primarily evaluated.     

Total synthesis of [Ψ[C(═S)NH]Tpg4]vancomycin aglycon, [Ψ[C(═NH)NH]Tpg4]vancomycin aglycon, and related key compounds: reengineering vancomycin for dual D-Ala-D-Ala and D-Ala-D-Lac binding

The total synthesis of [Ψ[C(═S)NH]Tpg(4)]vancomycin aglycon (8) and its unique AgOAc-promoted single-step conversion to [Ψ[C(═NH)NH]Tpg(4)]vancomycin aglycon (7), conducted on a fully deprotected substrate, are disclosed. The synthetic approach not only permits access to 7, but it also allows late-stage access to related residue 4 derivatives, alternative access to [Ψ[CH(2)NH]Tpg(4)]vancomycin aglycon (6) from a common late-stage intermediate, and provides authentic residue 4 thioamide and amidine derivatives of the vancomycin aglycon that will facilitate ongoing efforts on their semisynthetic preparation. In addition to early stage residue 4 thioamide introduction, allowing differentiation of one of seven amide bonds central to the vancomycin core structure, the approach relied on two aromatic nucleophilic substitution reactions for formation of the 16-membered diaryl ethers in the CD/DE ring systems, an effective macrolactamization for closure of the 12-membered biaryl AB ring system, and the defined order of CD, AB, and DE ring closures. This order of ring closures follows their increasing ease of thermal atropisomer equilibration, permitting the recycling of any newly generated unnatural atropisomer under progressively milder thermal conditions where the atropoisomer stereochemistry already set is not impacted. Full details of the evaluation of 7 and 8 along with several related key synthetic compounds containing the core residue 4 amidine and thioamide modifications are reported. The binding affinity of compounds containing the residue 4 amidine with the model D-Ala-D-Ala ligand 2 was found to be only 2-3 times less than the vancomycin aglycon (5), and this binding affinity is maintained with the model d-Ala-d-Lac ligand 4, representing a nearly 600-fold increase in affinity relative to the vancomycin aglycon. Importantly, the amidines display effective dual, balanced binding affinity for both ligands (K(a)2/4 = 0.9-1.05), and they exhibit potent antimicrobial activity against VanA resistant bacteria ( E. faecalis , VanA VRE) at a level accurately reflecting these binding characteristics (MIC = 0.3-0.6 μg/mL), charting a rational approach forward in the development of antibiotics for the treatment of vancomycin-resistant bacterial infections. In sharp contrast, 8 and related residue 4 thioamides failed to bind either 2 or 4 to any appreciable extent, do not exhibit antimicrobial activity, and serve to further underscore the remarkable behavior of the residue 4 amidines.     

Synthesis and Fluorescence of alt-Copoly[1, 4-divinylenebenzene／1, 4-bis（dimethylsilylene）benzene]

Silicon inserted n conjugated copolymer was synthesized by Heck reaction with moderate molecular weight. This silicon containing copolymer is thermally stable to 400℃, while emission of this polymer is blue-shifted compared with polyphenylenevinylene greenish emission. It shows potential application as organic emitter in OLED.