50-82-8Relevant academic research and scientific papers
The effect of chlorine and fluorine substitutions on tuning the ionization potential of benzoate-bridged paddlewheel diruthenium(II, II) complexes
Kosaka, Wataru,Itoh, Masahisa,Miyasaka, Hitoshi
supporting information, p. 8156 - 8168 (2015/05/13)
A series of paddlewheel diruthenium(II, II) complexes with various chlorine-substituted benzoate ligands (Cl-series) was synthesized as tetrahydrofuran (THF) adducts [Ru2(ClxPhCO2)4(THF)2]; where ClxPhCO2- = o-chlorobenzoate, o-Cl; m-chlorobenzoate, m-Cl; p-chlorobenzoate, p-Cl; 2,3-dichlorobenzoate, 2,3-Cl2; 2,4-dichlorobenzoate, 2,4-Cl2; 2,5-dichlorobenzoate, 2,5-Cl2; 2,6-dichlorobenzoate, 2,6-Cl2; 3,4-dichlorobenzoate, 3,4-Cl2; 3,5-dichlorobenzoate, 3,5-Cl2; 2,3,4-trichlorobenzoate, 2,3,4-Cl3; 2,3,5-trichlorobenzoate, 2,3,5-Cl3; 2,4,5-trichlorobenzoate, 2,4,5-Cl3; 3,4,5-trichlorobenzoate, 3,4,5-Cl3; 2,3,4,5-tetrachlorobenzoate, 2,3,4,5-Cl4. This Cl-series and the previously synthesized F-series together with four new fluorine-substituted derivatives, [Ru2(FxPhCO2)4(THF)2] (where FxPhCO2- = 2,3-difluorobenzoate, 2,3-F2; 2,4-difluorobenzoate, 2,4-F2; 2,5-difluorobenzoate, 2,5-F2; 2,3,5-trifluorobenzoate, 2,3,5-F3), were experimentally characterized with respect to solid-state structure, magnetic properties and electrochemistry. By tuning the substituents of the benzoate ligands using chlorine or fluorine atoms, the redox potential (E1/2) for [Ru2II,II]/[Ru2II,III]+ varied over a wide range of potentials from -40 mV to 360 mV (vs. Ag/Ag+ in THF). This was dependent on (i) the number of ortho-substituents, i.e. non-, mono- and di-o-substituted groups, with quasi-Hammett parameters for ortho-Cl and -F substitutions (σo = -0.272 and -0.217, respectively) and (ii) the general Hammett constants, σm and σp, for each group. The HOMO energy level calculated on the basis of the atomic coordinates of the solid-state structure was strongly affected by Cl- and F-substitutions as well as the redox potential in solution, which emphasizes the steric contribution of ortho-substituents in the energy level giving a deviation of EHOMO 0.3 eV and 0.55 eV for the Cl- and F-series, respectively.
Anti-MRSA cephems. Part 3: additional C-7 acid derivatives.
Springer, Dane M,Luh, Bing Yu,Goodrich, Jason T,Bronson, Joanne J
, p. 281 - 291 (2007/10/03)
Twenty-seven novel cephalosporin derivatives with activity against methicillin-resistant Staphylococcus aureus (MRSA) are described. The compounds contain novel acid moieties at C-7 that were synthesized using nucleophilic aromatic substitution reactions and Stille couplings. The most interesting compound (6) displayed an MIC(90) against MRSA of 3.7 microg/mL, and an average PD(50) of 3.9 mg/kg.
Cephalosporin derivatives
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, (2008/06/13)
The present invention provides a novel series of cephem derivatives of the general formula I wherein R1, R2, R3, R5, R6, R7, A, L1, X, n and n′ are as defined herein above. The compounds of formula I are antibacterial agents useful in the treatment of infections in humans and other animals caused by a variety of gram-positive bacteria, particularly methicillin-resistant Staphylococcus aureus. Also included in the invention are processes for preparing the compounds of formula I and pharmaceutical compositions containing said compounds in combination with pharmaceutically acceptable carriers, diluents or excipients.
Electrocarboxylation of chlorinated aromatic compounds
Golinske, Dirk,Voss, Juergen,Adiwidjaja, Gunadi
, p. 862 - 880 (2007/10/03)
Chorinated benzenes (1, 4), biphenyls (6, 9), dibenzofurans (10, 15, 17, 18), 2-chlorodibenzo[1,4]dioxine (24) and 1-chloronaphthalene (26) as well as dibenzofuran (12) and naphthalene (27) themselves were transformed into carboxylic acids by galvanostatic electroreduction in the presence of carbon dioxide ("electrocarboxylation"). Dry DMF was used as solvent, zinc or stainless steel as cathode and magnesium as a sacrificial anode in an undivided cell. Hydrogenation of aromatic rings was not observed. However, reductive addition of two molecules of carbon dioxide to form dihydrodicarboxylic acids, e.g. 22 and 29, occurs in the dibenzofuran and naphthalene series.
Process for the preparation of halogenated benzoic acids
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, (2008/06/13)
A process for the preparation of halogenated benzoic acids of formula (1): STR1 in which R1, R2, R3, R4 and R5 are hydrogen, fluorine, chlorine or bromine atoms or C1 -C6 -alkyl, C1 -C6 -alkoxy, nitro, cyano, trifluoromethyl, aidehyde, C1 -C4 -alkoxycarbonyl, -SO2 -C1 -C4 -alkyl, -SO2 -phenyl, -CONH2, -CON(C1 -C4 -alkyl)2, hydroxy, carboxy, -NH2 or -N(C1 -C4 - alkyl)2 groups, at least one of the substituents R1 -R5 being one of said halogen atoms, which comprises reacting 1 mol of a benzophenone, asymmetrically substituted on the benzene rings A and B, of general formula (2): STR2 in which R1 -R10 are as defined above for R1 -R5, with about 1 to about 10 mol of an oxidizing agent selected from the group comprising hydrogen peroxide, urea/hydrogen peroxide addition product, an alkali metal peroxide, ammonium, alkali metal or alkaline earth metal peroxodisulfates, pertungstates, perborates or percarbonates, ozone, alkyl- or aryl-percarboxylic acids, alkyl- or aryl-persulfonic acids or persulfuric acid, at temperatures from about -20° to about +100° C.
A New Trifluoromethylating Agent: Synthesis of Polychlorinated (Trifluoromethyl)benzenes and 1,3-Bis(trifluoromethyl)benzenes and Conversion into Their Trichloromethyl Counterparts and Molecular Structure of Highly Strained Polychloro-m-xylenes
Castaner, J.,Riera, J.,Carilla, J.,Robert, A.,Molins, E.,Miravitlles, C.
, p. 103 - 110 (2007/10/02)
Mixtures of CCl3F and AlCl3 replace CF3 for H in polychlorobenzenes.Thus, by treatment of a solution of the suitable polychlorobenzene in CCl3F with AlCl3, the following compounds can be prepared: pentachloro- (2), 2,3,4,5-tetrachloro- (5), 2,3,4,6-tetrachloro- (8), 2,3,5,6-tetrachloro- (11), 2,3,4-trichloro- (14), 2,4,5-trichloro- (17), and 2,4,6-trichloro-1-(trifluoromethyl)benzene (20), as well as 4,5,6-trichloro- (31) and 2,4,6-trichloro-1,3-bis(trifluoromethyl)benzene (32).The reaction of the above-mentioned trifluoromethylated compounds with AlCl3 in CS2 yieldstheir trichloromethyl counterparts: 3, 6, 9, 12, 15, 18, 21, 34, and 36.The chlorination of 32 or 36 by means of Silberrad's reagent (SO2Cl2, AlCl3, and S2Cl2) affords perchloro-m-xylene (38), a new highly strained chlorocarbon whose synthesis was attempted repeatedly in the past. 9, 15, 17, and 21, when treated with oleum and then with water, are converted into 2,3,4,6-tetrachloro- (22), 2,3,4-trichloro- (23), 2,4,5-trichloro- (24), and 2,4,6-trichlorobenzoic acid (25), respectively; under similar treatment, 34, 36, and 38 give 4,5,6-trichloro- (33), 2,4,5-trichloro- (35), and tetrachloroisophthalic acid (39), respectively.The formation of the (trifluoromethyl)benzenes is discussed, and in this connection it has been found that CCl3F solutions of 3 and 18 in the presence of AlCl3 give back 2 and 17, respectively.Molecular structures of highly strained m-xylenes 36 and 38, as well as that of the much less strained 34, ascertained by X-ray analysis, are reported and commented.IR, UV, and NMR spectral data of the compounds synthesized are presented.The interesting UV spectrum of 21 is discussed.
METABOLISM OF CHLOROPHENYLALANINES IN CROP AND WEED PLANTS IN RELATION TO THE FORMATION OF POTENTIAL HERBICIDAL END PRODUCTS
Taylor, David C.,Wightman, Frank,Kazakoff, Clem W.
, p. 51 - 72 (2007/10/02)
Metabolism of 12 synthetic D,L-chlorophenylalanines has been examined in several crop and weed plants.Twenty-five gram samples of excised shoots or leaves of bushbean, soybean, corn, pigweed, lambsquarters, and giant foxtail were allowed to metabolize 10-4 M solutions of the D,L-chlorophenylalanines for 24 hr in continuous light.The plant samples were then extracted in 80percent methanol and the soluble acidic metabolites fractionated into ether.Each ether concentrate was partially purified by fractional elution from a PrepSep C18 coloumn and then analysed by HPLC.Collected fractions were esterified with pentafluorobenzylbromide and examined by GC-MS to demonstrate the presence of PFB-esters of chlorophenylacetic, chlorobenzoic and/or chlorocinnamic acids.Since certain of these metabolites are known to be potent plant growth-regulators and herbicides, the results are discussed in relation to the potantial herbicidal action of certain chlorophenylalanines by the mechanism of 'lethal synthesis'.Key Word Index - Phaseolus vulgaris; Glycine max.; Leguminosae; Zea mays; Amaranthus retroflexus; Chenopodium album; Setaria faberii; metabolism; D,L-chlorophenylalanines; chlorophenylacetic acids; chlorobenzoic acids; chlorocinnamic acids; growth regulators.
Annelations with Tetrachlorothiophene 1,1-Dioxide
Raasch, Maynard S.
, p. 856 - 867 (2007/10/02)
Tetrachlorothiophene 1,1-dioxide is a reactive, cheletropic Diels-Alder reagent.It has been used to annelate, with loss of sulfur dioxide, a large variety of olefinic compounds to form 1,2,3,4-tetrachloro-1,3-cyclohexadiene derivatives.Dehydrochlorination of these forms 1,2,4-trichloro aromatic compounds.Both double bonds in thiophene and N-methylpyrrole are annelated.Addition of tetrachlorothiophene dioxide to acyclic 1,5-dienes, which may contain a heteroatom, provides a facile synthesis of tetrachloroisotwistenes (51) and heteroisotwistenes (56) by a double Diels-Alder reaction.Acyclic 1,6-dienes lead to tetrachlorohomoisotwistene (59) and heterohomoisotwistenes (61).By use of 1,5-cyclooctadiene, sym-dibenzocyclooctatetraene, and 1,5-cyclononadiene, the more complex carbocycles 62, 65, and 66 are generated.Tetrabromothiophene dioxide reacts like the tetrachloro compound.
