- FRIES REACTION AND DAKIN REARRANGEMENT IN BENZO-2,1,3-THIADIAZOLES
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The Fries rearrangement of 4- and 5-acetoxybenzo-2,1,3-thiadiazoles has given 4-hydroxy-7-acetyl- and 5-hydroxy-4-acetylbenzo-2,1,3-thiadiazoles, which on oxidation afford mixtures of 5-chloro-4,7-dioxo- and 5,6-dichloro-4,7-dioxobenzo-2,1,3-thiadiazole and of 6-chloro-4,5-dioxo- and 6,7-dichloro-4,5-dioxobenzo-2,1,3-thiadiazole.Reaction of 6,7-dichloro-4,5-dioxobenzo-2,1,3-thiadiazole with ortho-phenylenediamine gives 4,5-dichloro-2,1,3-thiadiazolophenazine.
- Belen'kaya, I. A.,Krokhina, G. P.,Sirik, S. A.,Andronati, S. A.
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- Method for preparing 2,3-dichloro-1,4-naphthoquinone from wastes in production process of 2-chloro-1,4-naphthoquinone
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The invention discloses a method for preparing 2,3-dichloro-1,4-naphthoquinone from wastes in the production process of a 2-chloro-1,4-naphthoquinone in the technical field of chemical industry. The method for preparing the 2,3-dichloro-1,4-naphthoquinone from the wastes in the production process of 2-chloro-1,4-naphthoquinone comprises the following specific steps: (S1) metering the wastes accumulated in production and feeding the wastes into a reaction kettle; (S2) feeding washed, centrifuged and dried materials into the reaction kettle again for discoloring treatment; (S3) carrying out detection through a GS gas chromatography analysis method; (S4) feeding pretreated tailings to the reaction bottle; (S5) adding industrial sodium acetate; and (S6) naturally cooling and stirring for about 30 minutes and then removing excessive chlorine. The 2,3-dichloro-1,4-naphthoquinone is prepared from waste residues generated in the production process of 2-chloro-1,4-naphthoquinone as a starting material through pretreatment and deep chlorination, so that the problem of waste residue emission is solved, the environment pressure is relieved, the environmental pollution is avoided and the production cost is reduced.
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- Synthesis, cytotoxic activities and structure-activity relationships of topoisomerase I inhibitors: Indolizinoquinoline-5,12-dione derivatives
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A series of indolizinoquinoline-5,12-dione derivatives (IQDs) are synthesized and evaluated for their cytotoxic activities toward human lung adenocarcinoma (GLC-82), large-cell lung carcinoma (NCI-H460), promyelocytic leukemia (HL-60) and breast carcinoma (MCF-7) cells by MTT method. Most of the IQDs show significant cytotoxic potency. In addition, the evaluation of structure-activity relationships indicated that the incorporation of electron-withdrawing substituents at the C or D ring will enhance the activities of the target compounds distinctly. The topoisomerase I inhibitory activity is also measured.
- Cheng, Yu,An, Lin-Kun,Wu, Ning,Wang, Xiao-Dong,Bu, Xian-Zhang,Huang, Zhi-Shu,Gu, Lian-Quan
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p. 4617 - 4625
(2008/12/20)
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- Reaction of semiquinoid compounds derived from N-arylsulfonyl-p-quinonemono- and diimines with tosylhydrazine
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Reaction of 4-arylsulfonylimino-2,3,5,6,6-pentachloro-2-cyclohexen-1-ones with tosylhydrazine gives rise to N-arylsulfonyl-N-p-tolylsulfonyl-2,3,5,6-tetrachloroaminophenols. With 4-arylsulfonylimino-2,2,3-trichloro-1,2,3,4-tetrahydronaphthalen-1-ones and 4-arylsulfonylimino-2-dihalo-1,2,3,4-tetrahydronaphthalen-1-ones reaction products are 4-arylsulfonylamido-2,3-dichloro-4-p-tolylsulfonylhydrazido-1,4-dihydronaphthalen-1-ones and 2-p-tolylsulfonyl-1,4-naphthoquinone-4-diazide respectively. First stage of the processes consists in dehydrohalogenation yielding the corresponding N-arylsulfonyl-p-quinonimines.
- Avdeenko,Zhukova
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p. 816 - 819
(2007/10/03)
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- Kinetics of oxidation of hydroquinones by molecular oxygen. Effect of superoxide dismutase
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The kinetics of the autoxidation of sixteen hydroquinones (QH2) (substituted 1,4-hydroquinones and 1,4-dihydroxynaphthalenes as well as 9,10-dihydroxyphenanthrene) were studied using the Clark electrode technique in aqueous solution, pH 7.40, at 37°C both with and without added superoxide dismutase (SOD). QH2 oxidation occurs typically with a self-acceleration. A maximum rate of oxidation, RMAX, was found to be the most indicative parameter characterizing QH2 oxidizability. A kinetic scheme of QH2 autoxidation was developed; computer simulations carried out on the basis of this scheme reproduce the main kinetic features of the studied process. QH2 autoxidation is suggested to be a free-radical chain process with semiquinone (Q-) and superoxide (O2-) as chain-carrying species. The oxidation is initiated by reaction (1) Q + QH2→2Q- + 2H+. The addition of SOD results in two main effects: shifting the equilibrium (2) Q- + O2?Q + O2- (K2) to the right and suppressing reaction (3) QH2 + O2-→Q- + H2O2. The net effect of SOD depends basically on K2. When K2 2 > 0.1, the more SOD inhibits the oxidation, the higher K2. The concentration of SOD causing the 50%-effect on RMAX ([SOD]50), both inhibitory and stimulatory, decreases dramatically when K2 increases. At [SOD] ? [SOD]50 the rate of QH2 autoxidation is definitively determined by the rate of reaction (1). For the majority of QH2, [SOD]50 is significantly less than the physiological values of [SOD] and thus QH2 autoxidation in biological environment is expected to occur in the above kinetically simple mode.
- Roginsky, Vitaly,Barsukova, Tatyana
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p. 1575 - 1582
(2007/10/03)
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- The treatment of pests using substituted naphthoquinones
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Naphthoquinone compounds of the formula I wherein R1 and R2 are each, independently, selected from H and OH and R3 and R4 are each, independently, selected from H, halo and 1-4C alkyl groups, provided that when R1 and R2 are each H, R3 and R4 cannot both be H, have use as pesticides particularly in the treatment of acarids and insects. A pesticidal composition comprises at least one compound of the formula I together with an inert carrier.
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- Solid-state organic reactions proceeding by pulverization: Oxidation and halogenation with iodosobenzene and inorganic solid-supports
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Pulverization-activation method was employed to accelerate solid-state organic reactions. Crushing and grinding of solid mixtures of hydrogen halide-treated silica gels, iodosobenzene and organic substrates in the absence of a solvent brought about smooth and rapid reactions to give halogenated and/or oxidized products in good yields. Various sulfides were smoothly converted to sulfonyl chlorides in one step in excellent yields. The surface of silica gel activated by pulverization serves as a reaction field on which reagent molecules can effectively encounter with each other.
- Sohmiya, Hajime,Kimura, Takahide,Fujita, Mitsue,Ando, Takashi
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p. 13737 - 13750
(2007/10/03)
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- Use of thiazyl chlorides, alkyl carbamates, and thionyl chloride to fuse 1,2,5-thiadiazoles to quinones and to oxidize, chlorinate, and aminate them
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Thiazyl chlorides in a simple one-step procedure fuse 1,2,5-thiadiazole rings to quinones. So do alkyl carbamates mixed with excess thionyl chloride and pyridine. Evidence is put forward to support the hypothesis that NSCl or a related thiazyl derivative is the reactive species that brings about the transformations. Selenoyl chloride mixed with an alkyl carbamate, pyridine, and quinones similarly gives 1,2,5-selenodiazoloquinones. Thionyl chloride in pyridine chlorinates quinones and oxidizes hydroquinones. 2,3-Dichloro-1,4-quinones with S4N4 or with alkyl N-sulfinylcarbamates give 1,2,5-thiadiazoloquinones. Quinones and their 2,3-dichloro derivatives with TsNSO in pyridine give betaine derivatives of 2,3-diaminoquinones, which pyrrolidine converts into 2-amino-3-(tosylamino)quinones. A unified set of mechanisms is presented that accounts for these transformations.
- Shi,Katz,Yang,Liu
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p. 1285 - 1297
(2007/10/02)
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- Method for dyeing keratinous fibres using an aminoindole in combination with a quinone derivative
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Method for dyeing keratinous fibres, characterized in that at least one composition (A) containing at least one aminoindole in a medium appropriate for dyeing is applied to these fibres, the application of the composition (A) being preceded or followed by the application of a composition (B) containing, in a medium appropriate for dyeing, at least one quinone derivative chosen from ortho- or para-benzoquinones, ortho- or para-benzoquinone monoimines or diimines, 1,2- or 1,4-naphthoquinones, ortho- or para-benzoquinone sulphonimides, α,ω-alkylene-bis-1,4-benzoquinones, or 1,2- or 1,4-naphthoquinone monoimines or diimines, the aminoindoles and the quinone derivatives being chosen such that the difference in redox potential ΔE between the redox potential Ei of the aminoindoles, determined at pH 7 in a phosphate medium on a vitreous carbon electrode by voltametry, and the redox potential Eq of the quinone derivative, determined at pH 7 in a phosphate medium by polarography on a mercury electrode relative to the saturated calomel electrode, in such that
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- METHOD FOR TREATING DISEASE STATES IN MAMMALS WITH NAPHTHALENE LIPOXYGENASE-INHIBITTNG AGENTS
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Psoriasis in mammals is relieved by topically administering naphthalenes of the formula: wherein: R1 is lower alkoxy or optionally substituted phenoxy, R2 is the same as R1, or R2 is hydrogen, lower alkyl, optionally substituted phenyl or optionally substituted phenylalkyl, R3 is hydrogen, lower alkyl, lower alkoxy, halo, optionally substituted phenyl, optionally substituted phenyl-lower-alkyl or optionally substituted phenyl-lower-alkoxy, and m is 1 or 2; both X groups are the same and X is either -C(O)OR4 or -C(O)NR5R6 , wherein R4 is alkyl, phenyl or benzyl optionally substituted with one or two lower alkyl groups, lower alkoxy groups or halo; and R5 and R6 are independently hydrogen, lower alkyl, cycloalkyl or phenyl optionally substituted with one or two lower alkyl groups, lower alkoxy groups or halo. The compounds of this invention are also useful for the treatment of disease-states caused by lipoxygenase activity in mammals, particularly 5-lipoxygenase activity, when administered systemically.
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- CHLORINATION OF N-ARYLSULFONYL-1,4-AMINONAPHTHOLS AND N-ARYLSULFONYL-1,4-NAPHTHOQUINONE 4-IMINES
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The final products from the chlorination of N-arylsulfonyl-1,4-aminonaphthols and N-arylsulfonyl-1,4-naphthoquinone 4-imines are 4-arylsulfonylimino-1-oxo-2,2,3,3,-tetrachloro-1,2,3,4-tetrahydronaphthalenes.
- Avdeenko, A. P.,Velichko, N. V.,Romanenko, E. A.,Pirozhenko, V. V.
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p. 1535 - 1543
(2007/10/02)
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- Process for dyeing keratinous fibres with a hydroxyindole in combination with a quinone derivative; and novel 1,4-benzoquinones
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Process for dyeing keratinous fibres, comprising the step of applying to these fibres at least one composition A containing, in a medium appropriate for dyeing, at least one mono- or di-hydroxyindole the application of the composition A being preceded or followed by the application of a composition B containing, in a medium appropriate for dyeing, at least one quinone derivative chosen from ortho- or para-benzoquinones, monoimines or diimines of ortho- or para-benzoquinones, 1,2- or 1,4-naphthoquinones, sulphonimides of ortho- or para-benzoquinones, α, ω-alkylene-bis-1,4-benzoquinones, or 1,2- or 1,4-naphthoquinone-monoimines or -diimines; the mono- or di-hydroxyindoles and the quinone derivatives being chosen such that the oxidation-reduction potential difference ΔE between the oxidation-reduction potential Ei of the mono- or di-hydroxyindoles, determined at pH 7 in a phosphate medium on a vitreous carbon electrode by voltametry, and the oxidation-reduction potential Eq of the quinone derivative determined at pH 7 in a phosphate medium by polarography on a mercury electrode and relative to a saturated calomel electrode is such that
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- N-alkyl-2,6-dimethylmorpholinocarboxamide salts, compositions and their use as fungicides
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Novel N-alkyl-2,6-dimethylmorpholinocarboxamide salts of the general formula I, STR1 processes for their preparation, and their use as fungicides for controlling pathogenic fungi. The agents according to the invention additionally possess plant growth-regulating properties. The meanings of R1, R2, R3, R4 and X- are given in the description. (Formula I)
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- Electron Donor-Acceptor Complex Formation Involving 2,3-Dichloro-1,4-naphthoquinone and Aromatic Amines
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Spectrophotometric studies of donor-acceptor (D-A) equilibria involving 2,3-dichloro-1,4-naphthoquinone (DCINQ) and several aromatic amines have shown that they do not conform to 1:1 equilibria alone in dichloromethane solution.It is suggested that the results can be explained on the basis of formation of 1:2 (AD2), in addition to 1:1 (AD) complexes.The formation constants for both AD and AD2 complexes and their molar absorptivities have been evaluated by a computer analysis of the data.The calculated values of the oscillator strengths and transition moments confirm this suggestion.
- Jayadevappa, E. S.,Bundi, M. L.
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- Modification of a Platinum Oxide Electrode by a Naphthoquinone Capable of Functioning in Bacterial Photosynthetic Reaction Centres
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The chemical modification of platinum oxide electrodes by naphthoquinone derivatives capable of replacing the original ubiquinone in bacterial photosynthetic reaction centres is described.The electrochemical properties of the modified electrode have been investigated by the potentiodynamic method.It has been established that the quinone immobilised as a 1E-10 mol cm-2 monolayer undergoes quasi-reversible reduction in the course of many hundreds of electron transfer cycles.However, the low rate constant for the electrochemical process (0.5-1.4 s-1) limits the possibilities for the effective use of the electrode jointly with the reaction centres for the transformation of light energy.
- Kats, E. Yu.,Shkurapatov, A. Ya.,Vagabova, O. I.,Shuvalov, V. A.
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p. 1582 - 1585
(2007/10/02)
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- Topical Nonsteroidal Antipsoriatic Agents. 1. 1,2,3,4-Tetraoxygenated Naphthalene Derivatives
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On the basis of previous observations that both 2,3-dihydro-2,2,3,3-tetrahydroxy-1,4-naphthoquinone (oxoline, 1) and 6-chloroisonaphthazarin (2) had demonstrated antipsoriatic activity in vivo, a series of structural derivatives of 2 were prepared and examined in the Scholtz-Dumas topical psoriasis bioassay.Of these six (5, 6, 9a, 10, 11a, 11b), the most effective compound was found to be 6-chloro-1,4-diacetoxy-2,3-dimethoxynaphthalene (RS-43179,lonapalene, 11a).An extensive series of 1,2,3,4-tetraoxygenated naphthalenes (16-74) incorporating variations of the ester, eth er and aryl substituents were prepared as analogues of 11a to examine the structural requirements for activity and were screened in vivo as inhibitors of arachidonic acid induced mouse ear edema, a topical bioassay capable of detecting 5-lipoxygenase inhibitors.Net lipophilicity, hydrolytic stability, and ring substitution play significant roles in determining the observed in vivo activity.Lonapalene (11a) is currently in clinical development as a topical applied nonsteroidal antipsoriatic agent.
- Jones, Gordon H.,Venuti, Michael C.,Young, John M.,Murthy, D.V. Krishna,Loe, Brad E.,et al.
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p. 1504 - 1511
(2007/10/02)
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- Electron Affinities from Electron-Transfer Equilibria : A(-) + B = A + B(-)
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Determination of the equilibrium constants K1 for gas-phase electron-transfer equilibria with a pulsed electron beam high ion source pressure mass spectrometer led to the electron affinities of 34 compounds with EA's between 0.5 and 3eV.The compounds are mostly substituted nitrobenzenes, substituted quinones, and conjugated molecules containing oxygen atoms.The EA of smaller molecules like SO2, NO2, CS2, and CH3NO2 also were determined.The method is very well suited for rapid, accurate, routine determinations of electron affinities.A comparison with EA's determined with other gas-phase methods and EA's evaluated from polarographic half-wave reduction potentials and charge-transfer spectra in solution is made.The rate constants for a number of exothermic electron-transfer reactions were determined.Most of these proceed at near collision rates.Electron-transfer reactions involving perfluorinated compounds like perfluoromethylcyclohexane, perfluorocyclohexane, and sulfurhexafluoride do not follow this behavior.While the perfluoro compounds have high thermal electron capture cross sections, they do not accept electrons from A(-) of compounds A with lower electron affinity.The perfluoro anions do transfer electrons to compounds A with higher electron affinity, and the rate constants increase with EA(A) - EA(perfluoro compound).
- Grimsrud, Eric P.,Caldwell, Gary,Chowdhury, Swapan,Kebarle, Paul
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p. 4627 - 4634
(2007/10/02)
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- Triazolylthiophosphoric acid esters
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Triazolylthiophosphonic esters corresponding to the formula SPC1 Wherein R1 represents a phenyl radical which is substituted by one or more fluorine, bromine and/or iodine atoms, by lower alkyl, lower alkoxy, lower alkylthio, lower trihalogenoalkyl, lower alkyl-SO, lower alkyl-SO2 or O2 N groups, which may be the same or different, or by at least one chlorine and at least one fluorine, bromine or iodine atom, one lower alkyl, lower alkoxy, lower alkylthio, lower trihalogenoalkyl, lower alkyl-SO, lower alkyl-SO2 or O2 N group, or represents an unsubstituted or halogenated and/or alkoxylated phenyl-lower alkyl radical or diphenylmethyl, and one of the symbols R2 and R3 represents hydrogen or a lower alkyl radical and the other represents the radical EQU1 wherein R4 represents a lower alkyl radical or the phenyl radical and R5 represents a lower alkyl radical their manufacture and their use in pest control.
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- Condensation products
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Formamidine compounds of the formula EQU1 or WHEREIN R1 represents a substituted or unsubstituted phenyl radical, R2 represents hydroogen, alkyl, alkenyl or alkinyl and R3 represents acyl their manufacture and their use in pest control.
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