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1.
The bulk reactions between 2,2′-bis(4,4-dimethyl-5(4H)-oxazolone) ( B3 ) or 2,2′-(1,2-ethylene)-bis(4,4-dimethyl-5(4H)-oxazolone) ( B4 ) and amine-terminated polyether (Jeffamine ED-900) have been studied by SEC, and 1H-and 13C-NMR and the resulting polymers were characterized by DSC and TGA. These chain coupling reactions have been applied to the synthesis of polyether-block-polyamides, starting from mixtures of amineterminated polyether and polyamide-12. High molar mass block copolymers were synthesized in the bulk within 1 h at 200°C and under atmospheric pressure, instead of several hours at 240°C under vacuum for the usual reaction between dicarboxy polyamides and dihydroxy polyethers. No other side reactions than the formation of a very small amount of 2-imidazolin-5-ones has been found. The DSC studies of block copolymers show the existence of a phase separation between the soft (polyether) and hard (polyamide) blocks. © 1993 John Wiley & Sons, Inc.  相似文献   

2.
2,2′-Bis(2-oxazoline) and 2,2′-bis[5,6-dihydro-(4H)-1,3-oxazine] have been used as chain coupling reagents ( CC ) and reacted in the bulk with α,ω-dicarboxy-poly(2,2′-oxydiethylene adipate) ( PS ) or with α,ω-dicarboxy-polyamide 12 ( PA ). The reactions have been followed by viscosimetry, titration of COOH groups and 1H- and 13C-NMR spectroscopy. Either with the PS/CC or PA/CC systems, or with the model system dodecanoic acid ( DA )/ CC , the reactions were fast, since in most cases 80% conversion was reached after 15 min reaction. The expected DA dimer or high molar mass PA or PS polymers were obtained. No significant side reaction has been detected. The thermal stability of the resulting polymers is higher than that of starting oligomers. Due to the introduction of CC units in the chains, the crystallinity of PA/CC is slower than that of starting PA . © 1995 John Wiley & Sons, Inc.  相似文献   

3.
The catalytic activity of a series of [Rh L-L chel]X complexes, in which we have varied the unsaturated ligand [L-L = cis, cis-cycloocta 1,5-diene(cod) or 2,5-norbornadiene(nbd) the nitrogen chelating ligand [chel = 2,2′-bipyridine(bipy), 2,2′-dipyridylamine(dipyam), 2,2′-bipyrazine (bipz), 4,4′-dimethyl-2,2′-bipyridine (4,4′-Me2bipy)] and the counter ion [X = PF6, ClO4, BPh4], has been examined in reactions with phyenylacetylene (PA). The catalytic behaviour of the [Rh(cod)Cl2],tmeda (tmeda = N,N,N′,N′tetramethylethylendiamine), [Rh(cod)Cl2],teda] (teda = triethylendiamine), of the dimer [Rh(cod)Cl]2, and the use of NaOH as cocatalyst in different reaction conditions was also examined. The influence of the ligands on the catalytic activity of these RhI complexes is discussed. 1H and 13C NMR spectra have shown that highly stereoregular polyphenylacetilene can be obtained. Conditions for homogeneous doping of PPA, to obtain materials whose conductivity varies over 10–11 magnitude orders, are proposed. The stability of the doped polymers is also discussed.  相似文献   

4.
Two new aromatic diamines, 2,2′-dimethyl-4,4′-diaminoazobenzene [benzenamine-(3,3′-dimethyl-4,4′-azobis)] and 2,2′-dichloro-4,4′-diaminoazobenzene [benzenamine-(3,3′-dichloro-4,4′-azobis)] were synthesized and their structures confirmed by IR, UV-visible, 1H-NMR, 13C-NMR, and mass spectra. With these diamines, 16 aromatic polyamides were synthesized by both low-temperature solution and phosphorylation polycondensation methods. The polymers were characterized by viscosity, solubility, IR, UV visible, TGA, and DTA studies.  相似文献   

5.
[Fe(dmbipy)Cl4][dmbipyH], 1 (dmbipy is 4,4′-dimethyl-2,2′-bipyridine), was prepared from reaction of FeCl3 · 6H2O with 4,4′-dimethyl-2,2′-bipyridine in 0.1 molar aqueous HCl. Treatment of 1 with dimethyl sulfoxide in methanol produced [Fe(dmbipy)Cl3(DMSO)], 2 (DMSO is dimethyl sulfoxide). Both complexes were characterized by IR, UV-vis, and 1H-NMR spectroscopies and their structures were studied by single crystal diffraction. Compounds 1 and 2 are high-spin with spin multiplicity of six.  相似文献   

6.
Two substituted 2,2′-bipyridine lead(II) complexes, [Pb(5,5′-dm-2,2′-bpy)(tfac)2] n (1) (5,5′-dm-2,2′-bpy?=?5,5′-dimethyl-2,2′-bipyridine and tfac?=?trifluoroacetate) and [Pb2(4,4′-dmo-2,2′-bpy)2(ftfa)4] (2) (4,4′-dmo-2,2′-bpy?=?4,4′-dimethoxy-2,2′-bipyridine and ftfa?=?furoyltrifluoroacetonate), have been synthesized and characterized by elemental analysis, IR, 1H NMR, and 13C NMR spectroscopies, thermal behavior, and X-ray crystallography. Complexes 1 and 2 are 1D coordination polymer and dinuclear complex, respectively. The supramolecular features in these complexes are guided by weak directional intermolecular interactions.  相似文献   

7.
Two lead(II)-thiocyanato coordination polymers with 5,5′-dimethyl-2,2′-bipyridine (5,5′-dm-2,2′-bpy) and 4,4′-dimethoxy-2,2′-bipyridine (4,4′-dmo-2,2′-bpy) as chelating ligands were synthesized and characterized by elemental analysis, IR and 1H-NMR spectroscopy, thermal behavior, and X-ray crystallography. These complexes have formulas [Pb(5,5′-dm-2,2′-bpy)(NCS)2] n (1) and [Pb(4,4′-dmo-2,2′-bpy)(NCS)2] n (2). The coordination numbers of PbII in 1 and 2 are four, PbN4, with “stereo-chemically active” electron pairs and hemidirected coordination spheres. Considering Pb···S as weak bonds, 1 and 2 are 1- and 2-D coordination polymers, respectively. The supramolecular features in these complexes are guided/controlled by weak directional intermolecular interactions.  相似文献   

8.
《Journal of Coordination Chemistry》2012,65(16-18):2632-2645
Abstract

By changing the ancillary ligands, three new zinc-based coordination polymers (CPs), {[Zn(4,4′-bpy)(H2O)4]·(TDC)·(H2O)}n (1), [Zn(2,2′-dmbpy)(TDC)]n (2), and [Zn2(3,3′-dmbpy)(TDC)2]n (3) (H2TDC =2,5-thiophenedicarboxylic acid, 4,4′-bpy =4,4′-bipyridine, 2,2′-dmbpy =2,2′-dimethyl-4,4′-bipyridine, 3,3′-dmbpy =3,3′-dimethyl-4,4′-bipyridine) have been synthesized under the same reaction conditions (H2O, pH =7–8, and 140°C) and were structurally characterized. 1 is a linear chain structure and further connected into a 3-D structure through hydrogen bonds. 2 shows a 2-D (4,4) network when the dinuclear [Zn2(COO)4N2] building unit is regarded as a six-connected node. 3 has a twofold-interpenetrating 3-D zinc-organic framework pcu topology. Furthermore, 1–3 show strong photoluminescence at room temperature in the solid state, and the catalytic activities of 1–3 for degradation of methyl orange in a Fenton-like process have been investigated. The results suggest that the ancillary ligands influence the final resulting CPs.  相似文献   

9.
1,6-Dialkoxy-3,4-diones 3 are easily accessible by acylation of enol ethers 1 with oxalyl chloride and subsequent elimination of hydrogen chloride using triethylamine. The open-chain 2,5-dimethyl derivative 3b is converted with amidines 4a-c and S-methylisothiourea (4d) , respectively, to give 2,2′-disubstituted 5,5′-dimethyl-4,4′-bipyrimidines 5a-d . The dihydrofuran and dihydropyran derivatives 3c and 3d , however, react with benzamidine (4c) in dimethylformamide only in the presence of calcium hydride as condensation agent yielding 5,5′-bis(2-hydroxyethyl)- and 5,5′-bis(3-hydroxypropyl)-2,2′-diphenyl-4,4′-bipyrimidine 6a and b.  相似文献   

10.
Treatment of several substituted benzils [3,3′- and 4,4′-dimethyl-; 2,2′-, 3,3′- and 4,4′-dichloro-; 3,3′-dibromo-; 4-(N,N-dimethylamino)-] with an excess of chlorosulfonic acid gave the corresponding 3-chloro-2-phenylbenzofuran disulfonyl dichlorides. Disubstitution was confirmed by microanalytical and spectral data for the corresponding bis(N,N-dimethylaminsulfonamides). The positions of electrophilic substitution were not confirmed with 3,3′-dimethyl-, 2,2′- and 3,3′-dichlorobenzils. With 4,4′-dichlorobenzil, a smaller amount of chlorosulfonic acid enabled the isolation of 3,6,4′-trichloro-2-phenylbenzofuran-5-sulfonyl chloride, which was identified by X-ray analysis of the N,N-dimethylsulfonamide. The cyclisation failed with 3,3′-dimethoxy-, and 3,3′- and 4,4′-dinitrobenzils. The results have been interpreted mechanistically.  相似文献   

11.
New complexes,of bis(2,2'-diamino-4,4'-bithiazole)sulfate nickel(Ⅱ) and bis(2,2'-diami-no-4,4'-bithiazole)sulfate cobalt(Ⅱ),have been prepared.The complexes were characterized by infrared and UV-Vis spectroscopy,1H NMR,elemental analyses and molar conductivity.The effect of these complexes on the DNA synthesis of sarcoma 180 cells has been studied by the technique of isotopic liquid scintillation.The results indicated that complexes show ability to inhibit DNA synthesis of the tumor cells.In order to provide a molecular basis for understanding the biological effects,the probe,[trana-en2Os(η2-H2)](CF3SO3)2 (en,ethylenediamine) as a monitor was first used to explore interaction of the complexes with 2'-deoxyguanosine-5'-monophosphate (dGMP).  相似文献   

12.
Poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3a ), poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐4,4′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3b ), and poly{bis(2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3c ) were synthesized by the Suzuki coupling reaction. The alternating structure of the copolymers was confirmed by 1H and 13C NMR and elemental analysis. The polymers showed, by ultraviolet–visible, the π–π* absorption of the polymer backbone (320–380 nm) and at a lower energy attributed to the d–π* metal‐to‐ligand charge‐transfer absorption (450 nm for linear 3a and 480 nm for angular 3b ). The polymers were characterized by a monomodal molecular weight distribution. The degree of polymerization was approximately 8 for polymer 3b and 28 for polymer 3d . © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2911–2919, 2004  相似文献   

13.
The reaction of lead(II) nitrate with 4,4′‐bipyridine (4,4′‐bpy) and 4,4′‐dimethyl‐2,2′‐bipyridine (4,4′‐dm‐2,2′‐bpy) or 5,5′‐dimethyl‐2,2′‐bipyridine (5,5′‐dm‐2,2′‐bpy) resulted in the fomation of single crystals of [Pb2(4,4′‐bpy)(5,5′‐dm‐2,2′‐bpy)2(NO3)4] ( 1 ) and [Pb3(4,4′‐bpy)2(4,4′‐dm‐2,2′‐bpy)2(NO3)6] ( 2 ). The new compounds have been characterized by single‐crystal X‐ray diffraction structure analysis as well as through elemental analysis, IR, 1H‐NMR and 13C‐NMR spectroscopy and their stability has been studied by thermal analysis. In the crystal structure of ( 1 ) formula‐like dimers are further connected to a 2‐D network through the auxiliary nitrate ligands. The crystal structure of ( 2 ) exhibits two crystallographically independent PbII central atoms (in a ratio of 1:2). With the aid of the 4,4′‐bpy and the nitrate ions, a 3‐D polymeric structure is achieved.  相似文献   

14.
The composition, structure, and properties of a series of Au(III) complexes with heterocyclic diimine ligands [Au(N^N)Cl2]+, where (N^N) = 2,2′-bipyridine (Bipy), 4,4′-dimethyl-2,2′-bipyridine (DmBipy), 2,2′-biquinoline (Bqx), 1,10-phenanthroline (Phen), 2,9-dimethyl-1,10-phenanthroline (DmPhen), and 4,7-diphenyl-1,10-phenanthroline (DphPhen), were characterized by 1H NMR, electronic absorption, and emission spectroscopy and also by cyclic voltammetry. The influence of donor and acceptor substituents on the spectroscopic and electrochemical properties of the Au(III) complexes was revealed.  相似文献   

15.
[{CuCl(dm4bt)}2 μ-Cl)2] (1) (dm4bt = 2,2′-dimethyl-4,4′-bithiazole) was prepared from the reaction of CuCl2 · 2H2O with 2,2′-dimethyl-4,4′-bithiazole in methanol; [Cu(dm4bt)2NO3](NO3) (2) was prepared from the reaction of Cu(NO3)2 · 3H2O with 2,2′-dimethyl-4,4′-bithiazole in methanol. Both complexes were characterized by IR, UV–Vis spectroscopy, and single-crystal structure. The structure of 1 consists of centrosymmetric dimeric [{CuCl(dm4bt)}(μ-Cl)], in which two chloro ligands bridge the coppers forming a four-membered ring; a terminal chloride and a bidentate chelating bithiazole complete five coordination at each Cu(II) in a highly distorted trigonal-bipyramidal geometry. The mononuclear structure 2 consists of a Cu(II), two 2,2′-dimethyl-4,4′-bithiazoles, one monodentate nitrate and one uncoordinated nitrate in a highly distorted square pyramid.  相似文献   

16.
[Cu(II)(4,4′-dimethyl-2,2′-bipyridine)3](PF6)2 ( 2 ) and [Cu(II) (5,5′-dimethyl-2,2′-bipyridine)3](PF6)2 ( 4 ) were used together with aluminium isopropoxide and (1-bromoethyl)benzene in the controlled radical polymerization of styrene resulting in polystyrenes with predetermined molecular weight and narrow molecular weight distribution. The received polymers are colorless with a content of copper lower than 210 ppm. The substitution pattern at the bipyridine ligands has a distinct influence on the polymerization. The rate of polymerization of styrene using 2 /[(CH3)2CHO]3Al/C6H5CH(CH3)Br is two times larger than utilizing 4 /[(CH3)2CHO]3Al/C6H5CH(CH3)Br.  相似文献   

17.
A high molar extinction coefficient charge transfer sensitizer tetrabutylammonium [Ru(4,-carboxylic acid-4′-carboxylate-2,2′-bipyridine)(4,4′-di-(2-(3,6-dimethoxyphenyl)ethenyl)-2,2′-bipyridine)(NCS)2], is developed which upon anchoring onto nanocrystalline TiO2 films exhibit superior power conversion efficiency compared to the standard sensitizer bistetrabutylammonium cis-dithiocyanatobis(4,4′-dicarboxylic acid-2,2′-bipyridine)ruthenium(II) (N719). The new sensitizer anchored TiO2 films harvest visible light very efficiently over a large spectral range and produce a short-circuit photocurrent density of 18.84 mA/cm2, open-circuit voltage 783 mV and fill factor 0.73, resulting remarkable solar-to-electric energy conversion efficiency (η) 10.82, under Air Mass (AM) 1.5 sunlight. The Time Dependent Density Functional Theory (TDDFT) excited state calculations of the new sensitizer show that the first three HOMOs have ruthenium t2g character with sizable contribution coming from the NCS ligands and the π-bonding orbitals of the 4,4′-di-(2-(3,6-dimethoxyphenyl)ethenyl)-2,2′-bipyridine. The LUMO is a π* orbital localized on the 4,4′-dicarboxylic acid-2,2′-bipyridine ligand.  相似文献   

18.
Reactions of 3-(Dimethylamino)-2,2-dimethyl-2H-azirines with Barbituric-Acid Derivatives The reaction of 3-(dimethylamino)-2,2-dimethyl-2H-azirine ( 1 ) and 5,5-disubstituted barbituric acids 5 in i-PrOH at ca. 70° gives 2-[5-(dimethylamino)-4,4-dimethyl-4H-imidazol-2-yl]alkanamides of type 6 in good yields (Scheme 1). The formation of 6 proceeds with loss of CO2; various reaction mechanisms with a zwitterionic 1:1 adduct B as common intermediate are discussed (Schemes 2 and 5). Thermolysis of product 6 leads to 2-alkyl-5-(dimethylamino)-4,4-dimethyl-4H-imidazoles 8 or the tautomeric 2-alkylidene derivatives 8 ′ via elimination of HNCO (Scheme 3). The latter undergoes trimerization to give 1,3,5-triazine-2,4,6-trione. No reaction is observed with 1,5,5-trisubstituted barbiturates and 1 in refluxing i-PrOH, but an N-alkylation of the barbiturate occurs in the presence of morpholine (Scheme 4). This astonishing reaction is explained by a mechanism via formation of the 2-alkoxy-2-(dimethylamino )aziridinium ion H which undergoes ring opening to give the O-alkylated 2-amino-N1,N1-dimethylisobutyramide I as alkylating reagent (Scheme 4).  相似文献   

19.
4,4′‐hexafluoroisopropylidene‐2,2‐bis‐(phthalic acid anhydride) (1) was reacted with L ‐methionine (2) in acetic acid and the resulting N,N′–(4,4′‐hexafluoroisopropylidenediphthaloyl)‐bis‐L ‐methionine (4) was obtained in high yield. The direct polycondensation reaction of this diacid with several aromatic diols such as bisphenol A (5a), phenolphthalein (5b), 1,4‐dihydroxybenzene (5c), 4,4′‐dihydroxydiphenyl sulfide (5d), 4,6‐dihydroxypyrimidine (5e), 4,4′‐dihydroxydiphenyl sulfone (5f) and 2,4′‐dihydroxyacetophenone (5g) was carried out in a system of thionyl chloride and pyridine. Expecting that the reaction with thionyl chloride in pyridine might involve alternative intermediates different from an acyl chloride, the polycondensation at a higher temperature favorable for the reaction of the expected intermediate with nucleophiles was attempted, and a highly thermally stable poly(ester‐imide) was obtained by carrying out the reaction at 80°C. All of the above polymers were fully characterized by 1H‐NMR, 19F‐NMR FT‐IR spectroscopy, elemental analysis and specific rotation. Some structural characterization and physical properties of these optically active poly(ester‐ imide)s are reported. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   

20.
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.  相似文献   

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