- 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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- The Diels-Alder reactions of para-benzoquinone nitrogen-derivatives: An experimental and theoretical study
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An experimental and theoretical study of the comparative reactivity and selectivity of the Diels-Alder reactions of para-benzoquinones and three nitrogen derivatives have been performed. The mono-oximes derivatives do not react under the tested reaction conditions, whereas the tosylated mono-oximes react slowly. However, the mono N-tosyl imines show excellent reactivity, and superior to the parent parabenzoquinones. DFT calculations support these experimental results.
- Uliana, Marciana P.,Servilha, Bruno M.,Alexopoulos, Olga,De Oliveira, Kleber T.,Tormena, Cláudio F.,Ferreira, Marco A.B.,Brocksom, Timothy J.
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p. 6963 - 6973
(2015/11/09)
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- Pd-catalyzed [2+2+1] coupling of alkynes and arenes: Phenol diazonium salts as mechanistic trapdoors
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Alkynes and phenol diazonium salts undergo a Pd-catalyzed [2+2+1] cyclization reaction to spiro[4,5]decatetraene-7-ones. This structure was confirmed for one example by X-ray single-crystal structure analysis. The reaction is believed to proceed through oxidative addition of the phenol diazonium cation to Pd0, subsequent insertion of two alkynes, followed by irreversible spirocyclization. Copyright
- Schmidt, Bernd,Berger, Rene,Kelling, Alexandra,Schilde, Uwe
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p. 7032 - 7040
(2011/07/30)
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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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- 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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- 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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- 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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- Dialkylquinoneimine metabolites of chloroacetanilide herbicides induce sister chromatid exchanges in cultured human lymphocytes
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Some of the most widely-used herbicides are the chloroacetanilides exemplified by alachlor and butachlor (derived from 2,6-diethylaniline) and metolachlor and acetochlor (synthesized from 2-ethyl-6-methylaniline). This investigation tests the hypothesis that the previously-observed oncogenicity of these herbicides is due to genotoxic intermediates such as diethylbenzoquinoneimine, a purported alachlor metabolite. Syntheses are reported here for the corresponding 2,6-dialkylbenzoquinoneimines, selected chloroacetyldialkylbenzoquinoneimines and several other candidate or known metabolites. The possible mutagenicity of diethylbenzoquinoneimine was tested in Salmonella typhimurium strains TA98 and TA100 with a weakly-positive response in the TA100 strain indicating induction of base-pair substitution mutations. The frequency of sister chromatid exchange (SCE) in Chinese hamster ovary cells was increased by alachlor at 10 μM and diethylaniline but not ethylmethylaniline at 30 and 3 μM. Isolated and cultured peripheral lymphocytes (mostly T cells) were used from two human donors to study the effects of the chloroacetanilides and their metabolites on primary human cells. In tests at 10 μM, the SCE frequency was increased by alachlor and possibly acetochlor but not by butachlor, metolachlor, dimethachlor (a 2,6-dimethyl analog) and dimethenamid (an analog based on 2,4-dimethyl-3-thienylamine). At 0.3 μM in cultured human lymphocytes, alachlor, the corresponding chloroacetanilide (N-dealkyl-alachlor) and aniline metabolites (and their 4-hydroxy derivatives), and diethylbenzoquinone were inactive or active in only one of the two donors whereas at 0.1-0.3 μM the SCE ratio for treated cells divided by the controls was always higher for diethylbenzoquinoneimine than for ethylmethyl- and dimethylbenzoquinoneimines. All the tested compounds were toxic to lymphocytes, but the depression of the mitotic index and increased duration of the cell cycle were not directly linked with SCE induction. Previous investigations have suggested that chloroacetanilide herbicides such as alachlor derived from 2,6-dialkylanilines are metabolized to 2,6-dialkylbenzoquinoneimines and the present study provides the first direct evidence that these metabolites are genotoxic in human lymphocytes.
- Hill, Anna B.,Jefferies, Phillip R.,Quistad, Gary B.,Casida, John E.
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p. 159 - 171
(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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- Aminocoumaran derivatives, their production and use
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A novel aminocoumaran derivatives of the general formula (I): STR1 wherein R1 and R2 are a hydrogen atom, an acyl group, an alkoxycarbonyl group, an aliphatic group or aromatic group; R3 R4 and R5 are an optionally acylated hydroxyl optionally substituted amino group, alkoxy group or aliphatic group, or two of R3, R4 and R5 may be linked together to form a carbocyclic group; R6 and R7 are an aliphatic group and at least one of them has a methylene group at the α-position; R8 and R9 are a hydrogen atom or an aliphatic group or aromatic group, or a salt thereof is useful for medicines for preventing and treating various diseases such as arterial schleosis, hepatopathy, cerebrovascular diseases and the like.
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- Process for dyeing keratinous fibers combining isatin or its derivatives with a tri-, tetra- or pentasubstituted aniline or with a bisphenylalkylenediamine, and dyeing agents
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The invention relates to a process for dyeing keratinous fibres, comprising the simultaneous or sequential application of a component (A) containing at least one compound of formula (I): STR1 in which: R1 denotes hydrogen, alkyl, acetyl, benzoyl, phenyl or C1 -C4 carboxyalkyl, R2 and R3 denote hydrogen, alkyl, alkoxy, hydroxyalkyl, amino, halogen, nitro, alkylphenyl, phenyl, alkylamino or hydroxyalkylamino, and a component (B) containing at least (i) a compound of formula (II): STR2 in which: Y denotes OH or NR8 R9, R8 and R9, which are identical or different, denote hydrogen, aminoethyl, hydroxyethyl or C1 -C4 alkyl, R4 to R7 independently of each other denote a hydrogen atom, a C1 -C4 alkyl, a chlorine, a C1 -C4 alkoxy, an acetylamino, an aryloxy, not more than two of the groups R4 to R7 denote a hydrogen atom, excluding 2,5-dimethoxy-1,4-diaminobenzene, and the cosmetically acceptable salts, or (ii) a bisphenylalkylenediamine. It also relates to the dyeing agents for implementing it.
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- Synthesis of 1,4-Benzoquinone Derivatives Having Two Side-Armed Polyethers and Crown Ethers, and Their Electrochemical Study in the Presence of Alkali Metal Cations (Na+ and K+)
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Several crown ethers and two side-armed polyethers which have reducible quinonoid groups were prepared.Some of them, 7a, 7b, and 7d, showed highly enhanced cation-binding properties for the Na+ cation upon electrochemical reduction.
- Togo, Hideo,Hashimoto, Kiichi,Morihashi, Kenji,Kikuchi, Osamu
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p. 3026 - 3028
(2007/10/02)
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- Substituent Effects on Solvent Dependence of the Bandshape of Charge-Transfer Transitions in N-Pyridinium Phenolates
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The solvatochromic absorption bands for "betaine-1", "betaine-22", and "betaine-29" (2,4,6-triphenyl-N-(4-hydroxyphenyl)-, 2,4,6-triphenyl-N-(2,6-dimethyl-4-hydroxyphenyl)- and 2,4,6-triphenyl-N-(3,5-dodecamethylene-4-hydroxyphenyl)pyridinium ions, respectively) in a range of polar, apolar, protic, aprotic solvents have been investigated.The bands can be accurately fitted by a single harmonic high-frequency mode Franck-Condon envelope of Gaussian solvent-broadened sub-bands.Multiphonon band analysis including both molecular modes and the solvent dynamics indicates that the solvent broadening for betaine-29 in polar solvents correlates well with εo-1 - εs-1, εo being the optical and εs the static dielectric constant, not only for aprotic solvents but also for normal alcohols.This is different from the behavior of 2,4,6-triphenyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)pyridinium ion ("betaine-26") for which the high-frequency solvent vibrational spectral part was previously found to be important.Bands for apolar solvents are independent of the solvent and are much wider than what corresponds to a structureless dielectric medium, pointing to other than purely electrostatic coupling mechanisms.Both the molecular frequencies and coordinate displacements are largely independent of the solvent, emphasizing their molecular character, and the frequency value of about 1600 cm-1 suggests that C-O or C-N stretching is involved.Spectral data for "betaine-1" and "betaine-22" could also be obtained for alcohol solvents and chloroform.The C-O/C-N mode at 1600 cm-1 can also be identified for these compounds.In addition, the band features suggest that coupling both to O-H stretching modes and to less isotope sensitive solvent modes is important.
- Kjaer, A. M.,Ulstrup, J.
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p. 3874 - 3879
(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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- Studies on the mechanism of toxicity of acetaminophen. Synthesis and reactions of N-acetyl-2,6-dimethyl- and N-acetyl-3,5-dimethyl-p-benzoquinone imines
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N-Acetyl-2,6-dimethyl-p-benzoquinone imine and N-acetyl-3,5-dimethyl-p-benzoquinone imine were prepared from 2,6-dimethylacetaminophen and 3,5-dimethylacetaminophen by oxidation with lead tetraacetate. Reaction of N-acetyl-2,6-dimethyl-p-benzoquinone imine with hydrochloric acid gave 3'-chloro-2',6'-dimethyl-4'-hydroxyacetanilide, whereas ethanethiol, aniline, and ethanol gave tetrahedral adducts resulting from addition to the imine carbon. Water gave 2,6-dimethyl-p-benzoquinone. With N-acetyl-3,5-dimethyl-p-benzoquinone imine, water and aniline gave substitution on the imine carbon, yielding 2,6-dimethyl-p-benzoquinone and 3,5-dimethyl-N-phenyl-p-benzoquinone imine, respectively. Ethanethiol gave 3',5'-dimethyl-2'-(ethylthio)-4'-hydroxyacetanilide. The toxicity of 2,6-dimethylacetaminophen and 3,5-dimethylacetaminophen was examined histologically in mice and rats. 3,5-Dimethylacetaminophen was slightly more nephrotoxic but showed a similar hepatotoxicity to acetaminophen. 2,6-Dimethylacetaminophen, like N-methylacetaminophen, showed very little tissue damage.
- Fernando,Calder,Ham
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p. 1153 - 1158
(2007/10/02)
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