4445-59-4Relevant academic research and scientific papers
Diphosphametacyclophanes: Structural and electronic influences of substituent variation within a family of bis(diketophosphanyl) macrocycles
Pearce, Kyle G.,Crossley, Ian R.
, p. 14697 - 14707 (2020/11/20)
The condensation of MeP(SiMe3)2 with a series of 5-substituted isophthaloyl chlorides (5-R′C6H3-2,6-{C(O)Cl}2) affords the diphosphametacyclophanes m-{-C(O)-C6H3-5-R′-(C(O)PMe)}2 (R′ = I, Me, tBu, Ph, and p-NCC6H4); the analogues m-{-C(O)-C5H3N-(C(O)PMe)}2 and m-{-C(O)-C6H4-(C(O)PPh)}2 are similarly obtained in preference to higher oligomers, in contrast to precedent reports. The cyclophanes all adopt butterfly-like conformations in the solid state with the P-organyl substituents adopting mutually exo arrangements. Structural and computational data suggest the nature of the 5-R substituent is key in directing the inter-ring angle and the extent of LUMO stabilization about the diketophophanyl scaffold. The latter is substantiated by UV/vis spectroscopy and cyclic voltammetry, which demonstrate these cyclophanes to be appreciably comparable to the diketophosphanyl systems commonly explored in the context of organic electronic materials; intriguingly, the distinct dikeophosphanyl moieties within the macrocycles appear effectively “insulated” by the macrocycle geometry, rather than acting as a through-conjugate.
Divergent pathways to isophthalates and naphthalate esters from methyl coumalate
Yu, Huangchao,Kraus, George A.
supporting information, p. 4008 - 4010 (2018/10/04)
Methyl coumalate readily reacts with enamines at ambient temperature to give lactones, which can be further transformed into isophthalates and tetrahydronaphthoates. Both cyclic and acyclic enamines show good reactivity. Dehydrogenation of tetrahydronaphthoate 4a was achieved on a hundred-gram scale.
Design and Synthesis of an MOF Thermometer with High Sensitivity in the Physiological Temperature Range
Zhao, Dian,Rao, Xingtang,Yu, Jiancan,Cui, Yuanjing,Yang, Yu,Qian, Guodong
, p. 11193 - 11199 (2015/12/17)
An important result of research on mixed-lanthanide metal-organic frameworks (M′LnMOFs) is the realization of highly sensitive ratiometric luminescent thermometers. Here, we report the design and synthesis of the new M′LnMOF Tb0.80Eu0.20BPDA with high relative sensitivity in the physiological temperature regime (298-318 K). The emission intensity and luminescence lifetime were investigated and compared to those of existing materials. It was found that the temperature-dependent luminescence properties of Tb0.80Eu0.20BPDA are strongly associated with the distribution of the energy levels of the ligand. Such a property can be useful in the design of highly sensitive M′LnMOF thermometers.
A Highly Stable Nanotubular MOF Rotator for Selective Adsorption of Benzene and Separation of Xylene Isomers
Huang, Wei,Jiang, Jun,Wu, Dayu,Xu, Jun,Xue, Bing,Kirillov, Alexander M.
supporting information, p. 10524 - 10526 (2015/11/27)
A remarkably stable tubular 3D Zn-MOF with hexagonal channels and a rare ptr topology was prepared under solvothermal conditions for liquid and vapor phase adsorption and separation of the C6-8 aromatic compounds. The material showed preferential affinity for benzene and can effectively separate benzene from its organic analogues under ambient conditions in both vapor and liquid phases. Furthermore, it exhibited preferable uptake of p-xylene over other C8 xylenes.
Process For Production of 5-Phenylisophthalic Acid
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Page/Page column 6, (2009/07/03)
The present invention provides an industrially advantageous process for producing 5-phenylisophthalic acid, which process attains excellent selectivity and yield and also realizes recovery and reuse of a catalyst. The process for producing 5-phenylisophthalic acid represented by formula (1) is characterized in that the process includes the following steps (A) to (C): (A) reacting m-xylene with cyclohexene in the presence of hydrogen fluoride and boron trifluoride, to thereby produce 1-cyclohexyl-3,5-dimethylbenzene;(B) dehydrogenating the 1-cyclohexyl-3,5-dimethylbenzene produced in step (A) in the presence of a dehydrogenation catalyst, to thereby produce 3,5-dimethylbiphenyl; and(C) dissolving the 3,5-dimethylbiphenyl produced in step (B) in a solvent and oxidizing the 3,5-dimethylbiphenyl in the co-presence of an oxidation catalyst, to thereby produce 5-phenylisophthalic acid.
PROCESS FOR PRODUCTION OF 5-PHENYLISOPHTHALIC ACID
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Page/Page column 9, (2009/01/24)
The present invention provides an industrially advantageous process for producing 5-phenylisophthalic acid, which process attains excellent selectivity and yield and also realizes recovery and reuse of a catalyst. The process for producing 5-phenylisophthalic acid represented by formula (1) is characterized in that the process includes the following steps (A) to (C): (A) reacting m-xylene with cyclohexene in the presence of hydrogen fluoride and boron trifluoride, to thereby produce 1-cyclohexyl-3,5-dimethylbenzene; (B) dehydrogenating the 1-cyclohexyl-3,5-dimethylbenzene produced in step (A) in the presence of a dehydrogenation catalyst, to thereby produce 3,5-dimethylbiphenyl; and (C) dissolving the 3,5-dimethylbiphenyl produced in step (B) in a solvent and oxidizing the 3,5-dimethylbiphenyl in the co-presence of an oxidation catalyst, to thereby produce 5-phenylisophthalic acid.
Electron deficient dienes. 4.1 A synthetic equivalent of 4-methyleneglutaconic acid, its mono and diethyl esters and their use in a concise general synthesis of isophthalic acids and isophthalates
Bodwell, Graham J.,Hawco, Krista M.,Satou, Teizi
, p. 879 - 881 (2007/10/03)
Reaction of a series of 2′-hydroxybenzophenone-3-carboxylic acid ethyl esters under Dakin reaction conditions affords isophthalic acid monoethyl esters, which can be converted into the corresponding diethyl isophthalates (6 examples) and isophthalic acid (1 example) by esterification and hydrolysis, respectively. This transformation renders the direct precursor of the benzophenones a synthetic equivalent of 4-methyleneglutaconic acid (4-methylenepent-2-enedioic acid) and its mono and diethyl esters.
Formation of cyclopent[a]indene and acenaphthylene from allyl esters of biphenyl mono- and di-carboxylic acids and from biphenyl dicarboxylic anhydrides on flash vacuum pyrolysis at 1000-1100°C
Bapat, Jayant B.,Brown, Roger F.C.,Bulmer, Glenn H.,Childs, Trevor,Coulston, Karen J.,Eastwood, Frank W.,Taylor, Dennis K.
, p. 1159 - 1182 (2007/10/03)
Flash vacuum pyrolysis at 1000-1100°C of the allyl esters of the three isomeric biphenylcarboxylic acids, of the allyl esters of the 12 biphenyldicarboxylic acids and of the three biphenyldicarboxylic anhydrides gave pyrolysates which were examined by 1H n.m.r. spectroscopy at temperatures below -50°C. In all cases the spectra showed the presence of cyclopent[a]indene and acenaphthylene together with other products. Possible mechanisms for these ring contraction and cyclization processes are discussed and the results of pyrolyses of [2,3-13C2]biphenyl-2,3-dicarboxylic anhydride, and [3,4-13C2]-and (2-2H1)-biphenyl-3,4-dicarboxylic anhydrides are reported.
