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41.
Ahmad S. Shawali Abdou O. Abdelhamid Hamdi M. Hassaneen Abdelfattah Shetta 《Journal of heterocyclic chemistry》1982,19(1):73-75
Diazotized anthranilic acid and its methyl ester react with substituted phenacyl thiocyanates 3 to give in both cases the corresponding thiadiazolo[2,3-b]quinazolines 7a-e . A mechanism is proposed and it is substantiated by alternate synthesis of 7a from the hydrazidoyl chlorides 9a,b and potassium thiocyanate. 相似文献
42.
Abdou O. Abdelhamid Hamdi M. Hassaneen Ikhlass M. Abbas Ahmad S. Shawali 《Tetrahedron》1982,38(10):1527-1530
Diazotized anathranilic acid and its methyl ester react with substituted α-thiocyanatoacetoacetanilides3a–c to give in both cases the corresponding thiadiazolo [2,3-b] quinazolines6a–c, respectively. A mechanism is proposed and it is substantiated by synthesis of6a from N-(2-car?yphenyl)-C-phenylcarbamoyl hydrazidoyl chloride8a or its N-(2-methoxycarbonylcarbonylphenyl) analogue8d. 相似文献
43.
Devillers CH Dime AK Cattey H Lucas D 《Chemical communications (Cambridge, England)》2011,47(6):1893-1895
Regioselective meso-functionalization of the totally unsubstituted magnesium(II) porphine was performed by controlled potential electrolysis with pyridine and triphenylphosphine as nucleophiles leading to the original pyridinium and phosphonium substituted derivatives, respectively. The crystallographic structure of the latter is described as the only meso-phosphonium porphyrin reported to date. 相似文献
44.
A family of rigid ferrocenyl-terminated redox stars has been synthesized-by Negishi coupling, including hexa(ferrocenethynyl)benzene complexes, a dodecaferrocenyl star, and stars with extended rigid tethers-and fully characterized. Cyclic voltammetry (CV) studies of the parent complex hexa(ferrocenylethynyl)benzene, 1, show a single wave for the six-electron oxidation of 1 using Nn-Bu(4)PF(6) as the supporting electrolyte on a Pt anode in CH(2)Cl(2), whereas three distinct two-electron reversible CV waves are observed using Nn-Bu(4)BAr(F)(4) (Ar(F) = 3,5-C(6)H(3)-(CF(3))(2,)). The CV of 1,3,5-tris(ferrocenylethynyl)benzene, 11, also shows only one wave for the three-electron transfer with Nn-Bu(4)PF(6) and three one-electron waves using Nn-Bu(4)BAr(F)(4). This confirms the lack of electronic communication between the ferrocenyl groups and a significant electrostatic effect among the oxidized ferrocenyl groups. This effect is not significant between para-ferrocenyl groups in 1,4-bis(ferrocenylethynyl)benzene for which only a single wave is observed even with Nn-Bu(4)BAr(F)(4) as the supporting electrolyte. The para-ferrocenyl substituents are quite independent, which explains that two para-ferrocenyl groups are oxidized at about the same potential in a single CV wave of 1. With the additional steric bulk introduced with a methyl substituent on the ferrocenyl group, however, even the para-methylferrocenyl groups are submitted to a small electrostatic effect splitting the six-electron transfer into six single-electron waves, probably because of the overall steroelectronic constraints. Contrary to 11, 1,3-bis(ferrocenylethynyl)benzene and related complexes with a third, different substituent in the remaining meta position different from a ferrocenylethynyl only show a single two-electron wave using Nn-Bu(4)BAr(F)(4), which is attributed to the transo?d conformation of the ferricinium groups minimizing the electrostatic effect. This shows that, in 11, it is the steric frustration that is responsible for the electrostatic effect, and the same occurs in 1. In several cases, ΔE(p) is much larger than the expected 60 mV value, characterizing a quasi-reversible (i.e., relatively slow) redox process. It is suggested that this slower electron transfer be attributed to conformational rearrangement of the ferrocenyl groups toward the transo?d position in the course of electron transfer. Thus both the thermodynamic and kinetic aspects of the electrostatic factor (isolated from the electronic factor), including the frustration effect, are characterized. The distinction between the electronic communication and through-space electrostatic effect was made possible in all of these complexes in which the absence of wave splitting using a strongly ion-pairing electrolyte shows the absence of significant electronic communication, and was confirmed by the new frustration phenomenon. 相似文献
45.
We have investigated the possibility of altering the electronic configuration of the niobium oxochloride cluster compound Ti2Nb6Cl14O4 (I) by doping this material with monovalent cations that can fit into cavities present in its cluster framework. The doping of I with In+ and Tl+ ions resulted in the formation of MxTi2Nb6Cl14-xO4+x (M = In, x = 0.10, 0.20, 0.27; M = Tl, x = 0.10, 0.20) in which the M+ ions partially occupy these cavities. The crystal structure analysis indicated that the additional charge provided by M+ ions is compensated by substitution of chlorine by oxygen, which leads to the cluster electronic configuration being intact. Crystal data: In0.272Ti2Nb6Cl13.728O4.272, space group C2/c (No. 15), a = 12.679(2) A, b = 14.567(2) A, c = 12.632(3) A, beta = 95.26(2) degrees, Z = 4; Tl0.196Ti2Nb6Cl13.804O4.196, space group C2/c (no. 15), a = 12.732(1) A, b = 14.607(2) A, c = 12.662(2) A, beta = 95.28(1) degrees, Z = 4. 相似文献
46.
The well-known Jones matrix formalism, which can be directly applied to the propagation of the polarization of fundamental (TEM(00)) laser resonator modes, has to be modified for higher-order transverse modes. It is shown that this can be done in straightforward manner by using N x N matrices instead of the 2 x 2 Jones matrices, where N denotes the number of orthogonal polarization states of the transverse mode under consideration. The most common case of TEM(01) Hermite-Gaussian modes, where N is four, is discussed in detail. 相似文献
47.
The high conformational flexibility of triphenyl phosphite (TPP) is investigated by density functional theory (DFT) calculations. First, through a scan of the molecular potential energy surface, we bring to light a new stable conformation of an isolated molecule, not yet encountered in the crystal states of TPP. Different relevant conformations of the TPP monomer in the gas state are further presented and discussed in terms of molecular structure, relative energy, and dipole moments. Second, we considered dimer and trimer of TPP starting from their structural topology within the hexagonal crystal, which is characterized by the existence of molecular rods. It is shown that weak C-H...O intermolecular hydrogen bonds in TPP cannot definitely be excluded, and finally this point is discussed in the scope of the glacial state problem. 相似文献
48.
Pyrazolo[4,3‐d]pyrimidines, pyrazolo[4,3‐d]triazolino[4,3‐a]pyrimidines, 3‐(2‐thiazolyl)thiophenes, thiazolo[3,2‐a]pyridine and pyrazolo[1,5‐a]pyrimidines were synthesized from 2‐[4‐(3‐oxobenzo[f]‐2H‐chromen‐2‐yl)‐1,3‐thiazol‐2‐yl]ethanenitrile. The newly synthesized compounds were elucidated by elemental analysis, spectral data, chemical transformation and alternative synthesis route whenever possible. 相似文献
49.
Three novel coordination polymers built of octahedral niobium cyanochloride clusters [Nb6Cl12(CN)6] and alkaline earth metal complexes have been prepared by reaction of aqueous solutions of (Me4N)4Nb6Cl18 and KCN with solutions of alkaline earth metal salts and 1,10-phenanthroline (phen) (1:2 molar ratio) in H2O/EtOH. The structures of [Ca(phen)2(H2O)3]2[Nb6Cl12(CN)6] x (phen)(EtOH)1.6 (1), [Ca(phen)2(H2O)2]2[Nb6Cl12(CN)6] x (phen)2 x 4H2O (2), and [Ba(phen)2(H2O)]2[Nb6Cl12(CN)6] (3) were determined by single-crystal X-ray diffraction. The three compounds were found to crystallize in the monoclinic system (space group Pn) with a = 11.5499(6) A, b = 17.5305(8) A, c = 21.784(1) A, beta = 100.877(1) degrees for 1; triclinic system (P1) with a = 12.609(4) A, b = 13.262(4) A, c = 16.645(5) A, alpha = 69.933(6) degrees, beta = 68.607(6) degrees, gamma = 63.522(5) degrees for 2; and a = 16.057(1) A, b = 16.063(1) A, c = 16.061(1) A, alpha = 86.830(1) degrees, beta = 64.380(1) degrees, gamma = 67.803(1) degrees for 3. Compounds 1 and 2 are built of cluster anions [Nb6Cl12(CN)6]4- trans-coordinated by two Ca2+ complexes via CN ligands to form neutral macromolecular units [Ca(phen)2(H2O)3]2[Nb6Cl12(CN)6] in 1 and [Ca(phen)2(H2O)2]2[Nb6Cl12(CN)6] in 2. Water of coordination and cyanide ligands form hydrogen bonded 3D and 2D frameworks for 1 and 2, respectively. The structure of 3 consists of [Nb6Cl12(CN)6]4- cluster anions and [Ba(phen)2(H2O)]2+ complexes linked through bridging cyanide ligands to form a neutral three-dimensional framework in which each barium complex is bound to three neighboring Nb6 clusters and each Nb6 cluster is linked to six Ba complexes. 相似文献
50.
Ahmad M. Farag Abdelgawad A. Fahmi Abdou O. Abdelhamid Ahmad S. Shawali Mohamed S. Algharib 《Journal of heterocyclic chemistry》1987,24(5):1341-1344
The reaction of diazotized 3-phenyl-5-aminopyrazole with phenacyl thiocyanate 1a and phenacyl selenocyanate 1b afforded directly 2-imino-3-(3-phenyl-5-pyrazolyl)-5-benzoyl-2,3-dihydro-1,3,4-thiadiazole monohydrate 9a and 2-imino-3-(3-phenyl-5-pyrazolyl)-5-benzoyl-2,3-dihydro-1,3,4-selenadiazole monohydrate 9b , respectively. The products 9a and 9b were also obtained from the reaction of C-benzoyl-N-(3-phenyl-5-pyrazolyl)formohydrazidoyl bromide 10 with potassium thiocyanate and potassium selenocyanate, respectively. Acetylation, benzoylation, and nitrosation of 9 afforded the corresponding diacetyl, dibenzoyl, and nitroso derivatives 11-13 , respectively. Cyclization of C-benzoyl-N-(3-phenyl-5-pyrazolyl)-nitrilimine 6 was shown to give the pyrazolo [5,1-d]triazole 8 and not the pyrazolo[5,1-c]-as-triazine derivative 7 , as previously reported. 相似文献