- Hydroxylation of aromatic amines with dioxygen in photooxidation sensitized by substituted phthalocyanines
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Photooxidation of aniline and its methyl and chloro derivatives with dioxygen sensitized by substituted zinc (PcZn) and palladium (PcPd) phthalocyanines in solution and on the carrier surface upon visible light irradiation affords selectively the corresponding p-aminophenols. Active and the most stable PcPd derivative adsorbed on Amberlite XAD 7HP provides conversion of 2,6-dimethylaniline with selectivity over 90% without the loss of sensitizer activity at least in 8 repeated cycles, the overall turnover number of the sensitizer being greater than 25,000.
- Fedorova, Tatyana M.,Derkacheva, Valentina M.,Shevchenko, Ekaterina N.,Luk'yanets, Evgeny A.,Bordaev, Eduard B.,Kaliya, Oleg L.
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- Method for synthesizing 4-amino-3-chlorophenol by means of multiple-temperature-zone continuous flow microchannel reactor
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The invention relates to a method for synthesizing 4-amino-3-chlorophenol by means of a multiple-temperature-zone continuous flow microchannel reactor, which belongs to the field of organic synthesisof anti-cancer drugs, and solves the problems in the prior art that in a process of synthesizing 4-amino-3-chlorophenol, the product yield is low, the purity is low, the cost is high and the safety property of the product is poor and the like as raw materials are not easily available, the catalyst is high in cost and the synthesized intermediate product is unstable in diazonium salt. By means of the microchannel reactor, sulfanilic acid is taken as an initial raw material, a target product 4-amino-3-chlorophenol is obtained by three steps of diazotization, coupling of diazonium salt and reduction of an azoic compound. The method provided by the invention can be applied to large-scale production of 4-amino-3-chlorophenol.
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Paragraph 0039; 0044; 0045; 0050; 0051; 0052; 0057; 0058
(2018/04/03)
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- TYROSINE KINASE INHIBITOR AND PHARMACEUTICAL COMPOSITION COMPRISING SAME
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The present invention relates to a tyrosine kinase inhibitor and a pharmaceutical composition comprising same. The tyrosine kinase inhibitor of the present invention has the structures as shown in the following formula (I) or (II):
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Paragraph 0342; 0343
(2018/03/25)
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- Synthesis method of important pharmaceutical and chemical intermediate 4-amino-3-chlorophenol
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The present invention discloses a synthesis method of important pharmaceutical and chemical intermediate 4-amino-3-chlorophenol, and the method comprises the following steps: acetylation of p-aminophenol, triethylamine and an acylating agent to obtain 4-acetamino phenyl acetate shown as a formula I; chlorination of the formula I compound and a chlorinated reagent to obtain 4-acetamino-3-phenyl chloroacetate shown as a formula II; and reaction of the formula II compound and an alkali at 80-120 DEG C to obtain the 4-amino-3-chlorophenol. The preparation method has the advantages of easy availability of raw materials, low cost, mild condition, high process operability and controllability, high yield and no need of complex post-treatment to obtain the high-purity 4-amino-3-chlorophenol.
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Paragraph 0038
(2017/08/29)
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- One step hair coloring compositions using salts
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A hair coloring composition comprising the following two compositions which are mixed just prior to application to the hair: (a) a composition comprising a water-soluble peroxygen oxidizing agent; and (b) a composition comprising one or more oxidative hair coloring agents selected from the group consisting of an aromatic diamine, an amino phenol, a naphthol, a polyhydric phenol, a catechol and mixtures thereof; wherein the composition comprising one or more oxidative hair coloring agents further comprises al least one water soluble carbonate releasing salts; and optionally a water soluble ammonium salt, is described.
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- Transition metal complexes as dye forming catalysts in hair coloring compositions
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A hair coloring composition comprising a first composition which comprises: (a) a dye forming transition metal salt or complex; which is first applied to the hair; and a second composition which comprises the following two compositions which are mixed just prior to application to the hair: (a) a composition comprising a water-soluble peroxygen oxidizing agent; and (b) a composition comprising one or more oxidative hair coloring agents selected from the group consisting of an aromatic diamine, an aminophenol, a polyhydric phenol a catechol and mixtures thereof.
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- Enhanced color deposition for hair with sequestering agents
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Hair coloring compositions which comprise: (A) non-nitrogenous chelating agents from the group consisting of polyphosphate; phosphonates; hydroxycarboxylates; polyacrylates; zeolite; and mixtures thereof; (B) an oxidative dye primary intermediate; and (C) an oxidative dye coupler; (D) and water are described. The present invention also relates to a method for coloring hair which comprises contacting said hair with a hair coloring composition as described above.
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- Hair colouring and conditioning compositions
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A hair colouring and conditioning composition comprising: (a) a hair colouring agent; and (b) a hair conditioning agent; wherein the composition provides an Average Combing Index Value of greater than 1.2 as measured by the Combing Technical Test Method. The products can provide excellent hair colouring together with excellent conditioning, reduced hair damage, brittleness and dryness, and is convenient and easy to use.
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- Hair conditioning compositions and their use in hair colouring compositions
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The present invention relates to a hair care composition comprising a aminofunctional polysiloxane having a specified average effective particle size which provides improved durable conditioning particularly when utilised in conjunction with a hair colouring composition.
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- HAIR COLORING COMPOSITIONS
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A hair coloring composition comprising: (a) from about 0.0003 moles (per 100 g of composition) to less than about 0.09 moles (per 100 g of composition) of an inorganic peroxygen oxidizing agent; and (b) an oxidative hair coloring agent; wherein the pH of each of (a) and (b) is in the range of from about 1 to about 6 and wherein the combined mixture of (a) and (b) has a pH in the range of from about 1 to about 6. The products can provide excellent hair coloring and in-use efficacy benefits including excellent initial color and good wash fastness in combination with reduced hair damage at low pH.
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- HAIR COLORING COMPOSITIONS
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A hair coloring composition comprising: (a) a preformed organic peroxyacid oxidising agent; and (b) an oxidative hair coloring agent; wherein the pH of each of components (a) and (b) is in the range of from about pH 1 to less than about pH 7 and wherein the pH of the composition is in the range of from about pH 1 to less than about pH 7. The products can provide excellent hair coloring and in-use efficacy benefits including excellent initial color and good wash fastness in combination with reduced hair damage at low pH.
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- Methods for dyeing keratinous fibers with compositions which contain aminoindole couplers, oxidation dye precursors, and oxidizing agents at acid pHs
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A method for dyeing keratin fibers, wherein a composition is applied to said fibers which contains, in a suitable dyeing medium, at least one coupler having formula (I) STR1 wherein R1 is hydrogen or alkyl; R2 and R3 are hydrogen, alkyl, COOR', where R' is alkyl or hydrogen; R4 is hydrogen, hydroxyalkyl, alkyl, polyhydroxyalkyl or acetyl or aminoalkyl wherein the amine may be mono- or disubstituted by alkyl; Z1 and Z2 are hydrogen, alkyl, hydroxy, halogen, alkoxy or a salt thereof; at least one precursor of an oxidation hair dye; and at least one oxidizing agent, the pH of the composition applied to the fibers being less than 7.
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- Mechanism of the benzidine disproportionation of (arylhydrazo)pyridines. The reactions of 4-(4-chlorophenylazo)pyridine and -hydrazo)pyridine in acid media
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A kinetic and product analysis study of the reactions of 4-(4- chlorophenylhydrazo)pyridine (1) and 4-(4-chlorophenylazo)pyridine (2) in acid media is reported. The disproportionation of two moles of 1 in aqueous sulfuric acid gives one mole of the oxidized product 2, and one mole each of the reduced products 4-chloroaniline and 4-aminopyridine. The azo compound 2, a product of the reaction of 1, undergoes a slower hydroxylation reaction in acid media, and this process was also investigated. The first-formed product in the reaction of 2 is probably 4-(4-hydroxyphenylazo)pyridine, the 4- chlorine being displaced. At the low substrate concentrations used for the kinetic measurements both reactions are straightforward, but at the much higher concentrations used for product isolation studies a complex product mixture results, one of the products being a dimer. The complexity is increased because 1 had to be used as its hydrochloride salt for reasons of stability, and the chloride ion can also react with the diprotonated substrates; chloride ion also accumulates in the system as it is displaced from 2 during the hydroxylation. Thus chloride ion competes with bisulfate ion (present in large excess) for the diprotonated substrates. Nevertheless, complete mechanistic schemes accounting for all of the observed products, including the dimer, could be derived and are presented. Values of pK(BH22+) for 2 and two of the azo products, needed for the kinetic analysis, were measured using the excess acidity equilibrium method. The nucleophile reacting with protonated 2 in the rate-determining step of the hydroxylation was positively identified as being bisulfate ion by an excess acidity analysis. A comparison of the reaction of 1 with the equivalent reactions of two previously studied 4-(arylhydrazo)pyridines, 9 and 10, reveals that the benzidine disproportionation of these molecules is an A1 process with the second protonation being a pre-equilibrium; pK(BH22+) values for the hydrazo compounds could not be measured as they react too quickly, but they could be determined from the kinetic data, using the excess acidity method. The rate-determining step is a thermally allowed 10-electron electrocyclic process of the diprotonated substrate, giving rise to an intermediate that undergoes fast reaction with a molecule of protonated substrate in a thermally allowed 14-electron electrocyclic process to give the observed products.
- Cox, Robin A.,Cheon, Kap-Soo,Keum, Sam-Rok,Buncel, Erwin
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p. 896 - 906
(2007/10/03)
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- Halide ion trapping of nitrenium ions formed in the Bamberger rearrangement of N-arylhydroxylamines. Lifetime of the parent phenylnitrenium ion in water
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The data of p-aminophenol, the product of Bamberger rearrangement, Were analyzed by a mechanism involving rate-limiting formation of the appropriate arylnitrenium ion followed by product-determining steps in involving trapping by the solvent or by the added halide. The possibility that a portion of the halide-trapped products were derived from a pre-association mechanism was also include. Kinetic analyses then produced kBr:kw and kCl:kw ratios for two limiting cases, one involving pre-association with an equilibrium constant Kas = 0.3, and one ignoring pre-association. From an azide:water ratio (kAz:kw) previously determined for the 2,6-dimethylphenylnitrenium, kBr was concluded to lie in the range (4-5) × 109 M-1 s-1 for all of the nitrenium ions of this study. This range for kBr then led to kw values of (1-2) × 109 s-1 (2,5-Me2), (2-3) × 109 s-1 (2-Me), and (4-8) × 109 s-1 (parent and 2-Cl), where the ranges reflect uncertainties in the exact value of kBr and in the contribution from pre-association. The lifetime of the parent phenylnitrenium ion in water at one molar ionic strength is concluded to lie in the range 125-250 ps.
- Fishbein,McClelland
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p. 1321 - 1328
(2007/10/03)
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- Process for dyeing keratinous fibers with 2,4-diamino-1,3-dimethoxybenzene at an acid ph and compositions employed
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Process for dyeing keratinous fibres, especially human keratinous fibres such as the hair, characterised in that a composition containing, in a medium suitable for dyeing, at least 2,4-diamino-1,3-dimethoxybenzene as a coupler; an oxidation dye precursor; and an oxidising agent; is applied to these fibres, the pH of the composition applied to the fibres being less than 7.
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- Acid-catalyzed amino-migration of O-phenylhydroxylamines
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The mechanism of amino-migration of O-phenylhydroxylamine (1a) was studied. It was found that 1 rearranges to give 2-aminophenol (50%) and 4-aminophenol (7%) in trifluoroacetic acid (TFA). The predominance of the ortho rearrangement of 1 clearly distinguishes this process from the Bamberger rearrangement. From cross-coupling experiments employing stable isotopes, it was clarified that the ortho rearrangement proceeds intramolecularly and the para rearrangement involves both intra- and intermolecular processes. Good first-order kinetics were obtained for the rearrangement. The Hammett plot (σ+) with a large negative slope (ρ = -7.8) indicates that initial heterolytic N-O bond cleavage of 1 occurs and generates a positive charge on the oxygen atom with considerable delocalization into the aromatic ring. An ion-molecule pair involving a phenoxenium ion and an ammonia molecule as an intermediate rationalizes all of the results. In this pair, intramolecular combination to the ortho position proceeds preferentially over that to the para position. Formation of catechol and hydroquinone can be explained in terms of nucleophilic attack of TFA on the phenoxenium ion in a solvent-separated pair.
- Haga, Naoki,Endo, Yasuyuki,Kataoka, Ken-Ichiro,Yamaguchi, Kentaro,Shudo, Koichi
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p. 9795 - 9806
(2007/10/02)
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- Kinetics and Mechanism of the Bamberger Rearrangement. Part 4. Rearrangement of Sterically Hindered Phenylhydroxylamines to 4-Aminophenols in Aqueous Sulphuric Acid Solution
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The rates of the Bamberger rearrangement of sterically hindered phenylhydroxylamines have been determined in aqueous sulphuric acid solution and the substituent effects (in particular, the steric effects) are discussed.The rate constants for phenylhydroxylamines with 2-substituents (Me, Cl, I) satisfied the Taft equation: log krel = ρ*?* - δES with ρ*-1.93 and δ-1.16.The result shows that steric hindrance of the substituents, in addition to the electron-donating effect, has an accelerating effect on the rates of the Bamberger rearrangement.The rate constants for 3-substituted 2-methylphenylhydroxylamines were generally greater than those for 5-substituted 2-methylphenylhydroxylamines.The difference was attributed to the 'buttressing effect' of neighbouring 3-substituents.This is the first example of steric acceleration of the Bamberger rearrangement.
- Sone, Takaaki,Hamamoto, Kazuhiro,Seiji, Yoshiyuki,Shinkai, Seiji,Manabe, Osamu
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p. 1596 - 1598
(2007/10/02)
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