- TRANSITION METAL FREE METHODS OF SYNTHESIS OF BIARYL COMPOUNDS
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The present disclosure provides methods of preparing biaryl compounds which do not require transition metal catalysts. In yet another aspect, the present disclosure provides pharmaceutical compositions comprising compounds as described herein and pharmaceutically acceptable carriers.
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Page/Page column 74; 75
(2017/06/21)
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- Symmetry in Cascade Chirality-Transfer Processes: A Catalytic Atroposelective Direct Arylation Approach to BINOL Derivatives
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Herein we disclose a scalable organocatalytic direct arylation approach for the regio- and atroposelective synthesis of non-C2-symmetric 2,2′-dihydroxy-1,1′-binaphthalenes (BINOLs). In the presence of catalytic amounts of axially chiral phosphoric acids, phenols and naphthols are coupled with iminoquinones via a cascade process that involves sequential aminal formation, sigmatropic rearrangement, and rearomatization to afford enantiomerically enriched BINOL derivatives in good to excellent yields. Our studies suggest that the (local) symmetry of the initially formed aminal intermediate has a dramatic impact on the level of enantioinduction in the final product. Aminals with a plane of symmetry give rise to BINOL derivatives with significantly lower enantiomeric excess than unsymmetrical ones featuring a stereogenic center. Presumably asymmetric induction in the sigmatropic rearrangement step is significantly more challenging than during aminal formation. Sigmatropic rearrangement of the enantiomerically enriched aminal and subsequent rearomatization transfers the central chirality into axial chirality with high fidelity.
- Wang, Jin-Zheng,Zhou, Jin,Xu, Chang,Sun, Hongbin,Kürti, László,Xu, Qing-Long
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supporting information
p. 5202 - 5205
(2016/05/19)
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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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- 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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- 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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- 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 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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- 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 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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- 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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- Substituted ortho-aminophenols, process for preparing them and their use for the oxidatin dyeing of keratinous fibres
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5-Substituted ortho-aminophenols of formula: STR1 in which: R1 denotes a hydrogen atom, an alkyl radical having 1 to 4 carbon atoms or a hydroxyalkyl radical having 1 to 4 carbon atoms; and R2 denotes, independently of R1, an alkyl radical having 1 to 4 carbon atoms, an alkoxy radical having 1 to 4 carbon atoms or a benzyl radical; the addition salts with an acid and the phenates, and dyeing composition containing a compound of formula (I) or a salt or a phenate of such a compound. The 5-substituted ortho-aminophenols enable hair to be dyed in a rich spectrum of hues having good durability.
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- Nitrated coupler compounds useful in direct dyeing and simultaneous oxidation and direct dyeing of keratinic fibers
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A cosmetic composition for application to the hair contains either (a) at least one compound having the formula STR1 wherein: R is hydrogen, alkyl or halogen; and R' is hydrogen, alkyl, hydroxyalkyl, carbamylalkyl, mesylaminoalkyl, aminoalkyl, acylaminoalkyl, monoalkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, carbamoyl, acyl or carbalkoxy; or (b) at least one of said compounds having formula I above and at least one benzene or heterocyclic oxidation base. The invention also relates to new couplers of formula I as well as to new indo compounds which result from the coupling of said compounds with an oxidation base. These cosmetic compositions for application to the hair are useful in direct dyeing, oxidation dyeing or simultaneous oxidation and direct dyeing of said hair.
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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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