- DEUTERATED COMPOUNDS AS ROCK INHIBITORS
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Provided are compounds of Formular (I), or pharmaceutically acceptable salts thereof, pharmaceutical compositions comprising these compounds thereof, and use of these compounds in preparing drugs for inhibiting ROCK.
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Paragraph 105; 117
(2019/10/15)
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- Direct conversion of cellulose to high-yield methyl lactate over Ga-doped Zn/H-nanozeolite Y catalysts in supercritical methanol
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For realizing sustainable bio-based refineries, it is crucial to obtain high yields of value-added chemicals via the direct conversion of cellulose and lignocellulosic biomass. Although the conversion of cellulose using homogeneous catalysts has been demonstrated to be quite successful, low cellulose conversion and poor product selectivity have been observed using heterogeneous catalysts. In this study, for the first time, the efficient conversion of cellulose to lactic acid derivatives, which can be used as a green solvent and a potential precursor for fine chemicals and biodegradable polymers, over a Ga-doped Zn/H-nanozeolite Y (Ga-doped Zn/HNZY) catalyst is described. Under optimized conditions at 280°C in supercritical methanol, methyl lactate (ML) and methyl 2-methoxypropionate (MMP) are obtained in yields of 57.8% and 12.8%, respectively, from cellulose; these values are greater than those reported in previous studies conducted using heterogeneous catalysts. Using oakwood, ML and MMP are obtained in yields of 12.3% and 18.6%, respectively. A large external surface area of the HNZY support and the synergistic effect of Ga doping on ZnO enhance Lewis acid sites with the simultaneous decrease of the Br?nsted acid sites. This unique catalyst (Ga-doped Zn/HNZY) is beneficial for controlling the consecutive reaction pathways of the decomposition of cellulose to glucose, retro-aldol condensation to trioses, and intramolecular Cannizzaro reaction to ML.
- Verma, Deepak,Insyani, Rizki,Suh, Young-Woong,Kim, Seung Min,Kim, Seok Ki,Kim, Jaehoon
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supporting information
p. 1969 - 1982
(2017/06/09)
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- A double-nitroxide free radical preparation method and structural characterization
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The invention discloses a preparation method of a novel triazoldinitrooxy radical, and structure characterization of the novel triazoldinitrooxy radical. The structure of the triazoldinitrooxy radical [3,5-di-(4,4,5,5-tetramethylimidazoline-3-oxide-1-oxy radical)-1H-1,2,4-triazole] is shown in the specification. The above synthesis route of the dinitrooxy radical disclosed in the invention has the characteristics of simple synthesis step, easy operation, high yield and the like. The above compound is a dinitrooxy radical having potential application values, has strong ferromagnetic interaction at a low temperature, and possibly becomes a new magnetic material used in the memory equipment for making computers.
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Paragraph 0031-0036
(2017/01/19)
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- Dissolution of wood in α-keto acid and aldehydic carboxylic acids and fractionation at room temperature
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Wood pulverised using a ball mill was dissolved in an α-keto acid, pyruvic acid, and two aldehydic carboxylic acids, namely glyoxylic acid and formic acid, at room temperature. Viscosity and optical transmittance analyses revealed that the wood particles dissolved in glyoxylic acid and formic acid in several hours, while they dissolved in pyruvic acid in several days. Size exclusion chromatography demonstrated that substances with number average molecular mass exceeding 105 were present in every solution. Incubation of these carboxylic acids with methanol produced the corresponding ester and/or (hemi)acetal derivatives, suggesting that the dissolution mechanism involves the substitution of hydroxyl groups in biomass. After dissolution, all solutions demonstrated non-Newtonian fluid behaviour with a non-Newtonian index n ranging from 0.41 to 0.72. When the dissolution time increased, the non-Newtonian index of the formic acid solution increased towards the value for a Newtonian fluid (n = 1). This rise was accompanied by partial depolymerisation. Evaporation of the wood solution gave a smooth transparent film. Using the water-immiscible solvent 2-methyltetrahydrofuran (2-MeTHF), the formic acid solution was separated into cellulosic porous solids, lignin-rich 2-MeTHF-soluble fraction and other components at room temperature. The dissolution of woody biomass at room temperature creates a new biorefinery process for the conversion of wood components in various solution reactions. In particular, in this study, pyruvic acid, which plays a central role in the metabolism of living organisms, is used as a new solvent for wood, thus bridging biochemistry and wood biorefinery. This journal is the Partner Organisations 2014.
- Nishiwaki-Akine, Yuri,Watanabe, Takashi
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p. 3569 - 3579
(2014/07/08)
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- Syntheses of 3,4-benzotropolones by ring-closing metatheses
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Ortho-lithiated styrenes or ortho-lithiated benzaldehyde dimethyl acetals were added to 2,2-dimethoxypent-4-enals 7. The resulting alcohols were carried on to the aromatic dienones 10. These were ring-closed by olefin metathesis. Hydrolysis of the dimethyl ketal moiety and enolization provided the 3,4-benzotropolones 5. Overall, this access comprises 4-6 steps and totaled a 22-81% yield.
- Arican, Deniz,Brückner, Reinhard
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supporting information
p. 2582 - 2585
(2013/07/19)
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- Conversion of levulinate into succinate through catalytic oxidative carbon-carbon bond cleavage with dioxygen
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Grand Cleft Oxo: Levulinate, available from biomass, is oxidized into succinate through manganese(III)-catalyzed selective cleavage of C-C bonds with molecular oxygen. In addition to levulinate, a wide range of aliphatic methyl ketones also undergo oxidative C-C bond cleavage at the carbonyl group. This procedure offers a route to valuable dicarboxylic acids from biomass resources by nonfermentive approaches. Copyright
- Liu, Junxia,Du, Zhongtian,Lu, Tianliang,Xu, Jie
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p. 2255 - 2258
(2014/01/06)
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- Vinylic Substitution of 1,2-Dibromo-1,2-difluoroethylene and Tribromofluoroethylene. An Intramolecular kBr/kF Element Effect and Apparent Inversion of Configuration in SNV Reactions
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The reactions of (E/Z)-1,2-dibromo-1,2-difluoroethylene(1) and of tribromofluoroethylene (2) with alkoxide ions and of 1 with p-toluenethiolate ion give multiplicity of products.The reaction of 1 with 1 equiv of NaOMe gives mainly a 2:1 mixture of the product of one bromine displacement, together with methyl dimethoxyacetate (3), methyl bromofluoroacetate (4), 1,1,2-trifluoro-2-bromoethyl ether (7), and 1,1-difluoro-1,2,2-trimethoxyethane (8).With 2 equiv of MeO(1-) 3 and 4 are the main products, and at 130 deg C, dimethyl ether 5 is also formed.With EtOCH2CH2O(1-) 1 gave 2-ethoxyethyl bromofluoroacetate (9), bis(2-ethoxyethyl) ether (10), and E/Z mixtures of the substitution products EtOCH2CH2OC(F)=C(F)Br (12) and EtOCH2CH2OC(Br)=C(F)Br (13).Reaction of 2 with excess RO(1-) (R = Me, Et) gives alkyl dibromoacetates, while with 1 equiv of RO(1-) only a bromine from the =C(F)Br carbon is displaced.Reaction of 1 with p-TolSNa in MeOH gives the reduction-substitution product p-TolSC(F)=CHF (18), together with (P-TolS)2 (16) and p-TolSMe (17).The same reaction in DMSO gives E/Z mixtures of the product of displacement of one bromine (19) or two bromines (20).Formation of the products is rationalized by an initial nucleophilic attack on the vinylic carbon followed by leaving group expulsion, giving, e.g., 12, 13, 19, or 20.Hydrolysis of the intermediate or addition of HF to the initial substition product gives saturated products, e.g., 3, 4, 7, or 8, while SN2 reactions on the ether oxygen give ethers 5 and 10.A bromophilic reaction gives the reduction-substitution product 18, while hydrolysis-decarboxylation leads to 17.The regiospecificity of the nucleophilic addition is due to polar and hyperconjugative effects.An intramolecular element effect kBr/kF of > 10 is reported for the first time in the reaction of 1 with EtOCH2CH2O(1-).This value and the absence of such effects in other reactions are consistent with a much higher nucleofugality from a (1-)CC(F)Br system of Br(1-) compared with F(1-).The E/Z compositions of 18-20 indicates an apparent inversion in their formation, but it is not known whether these compositions are thermodynamically or kinetically controlled.
- Shainyan, Bagrat A.,Rappoport, Zvi
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p. 3421 - 3428
(2007/10/02)
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- Bis-trimethylsilylacetamide: A reagent for the control of Friedel-Crafts alkylation reactions using methyl chloromethoxyacetate
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The Friedel-Crafts alkylation reactions of electron rich aromatic compounds using methyl α-chloro-α-methoxyacetate and Lewis acids leads predominantly to the formation of diarylacetic acid derivatives in which the second stage of the sequence is favoured by the presence of hydrogen chloride generated in the first step; effective control can be achieved in a number of cases by the addition of bis-trimethylsilylacetamide.
- Earle, Martyn J.,Fairhurst, Robin A.,Heaney, Harry
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p. 6171 - 6174
(2007/10/02)
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- 3-(2-Pyrrolidinyl)-2,4-furandione Analogs
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The reaction of 4,4-dimethyl-3-oxobutanoic (or pentanoic) acid esters with the lactim ether of 2-pyrrolidone in the presence of 2-hydroxypyridine produces condensation products 4 in 57-72percent yield.Acidic hydrolysis of 4 affords the furandione system 5 in 75-81percent yield.
- Coppola, Gary M.,Damon, Robert E.
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p. 815 - 817
(2007/10/02)
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- Ozonolyse von Olefinen, III: Saeurekatalysierte Ozonolyse von 3-Hexen-1,6- und 2-Penten-1,5-dicarbonylderivaten
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The ozonolysis of mono-unsaturated compounds containing the structural element =CH-CH2-R was investigated.Reductive ozonolysis of (E)-3-hexene-1,6-dioic acid gives methyl 3,3-dimethoxypropanoate (2), whereas ozonolysis of dimethyl (E)-3-hexene-1,6-dioate (1a) and (Z)-1,1,6,6-tetramethoxy-3-hexene (1b) in a methanolic solution of HCl leads to a mixture of 2, dimethyl malonate (3a) and 1,1,3,3-tetramethoxypropane (3b).The homologuos derivatives, dimethyl glutaconate (4a) and 1,1,5,5-tetramethoxy-2-pentene (4b), were ozonized to give mixtures of 2, 3, dimethyl oxalate (5), methyl 2,2-dimethoxyacetate (6a), and 1,1,2,2-tetramethoxyethane (6b).The ratios of the various reaction products were determined by gas chromatography.In each case the formation of the bifunctional derivatives 2 and 6a was favoured.
- Poklukar, Norbert,Mittelbach, Martin
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p. 203 - 207
(2007/10/02)
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- Acid-catalyzed hydrolysis of tetramethoxyethene in aqueous solution. Initial state stabilization by the methoxy groups
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The acid-catalyzed hydrolysis of tetramethoxyethene to methyl dimethoxyacetate in aqueous solution at 25 deg C was found to occur with the hydronium-ion coefficient kH+ = 0.454 M-1s-1, to give the solvent isotope effect kH+/kD+ = 3.15, and to provide a Bronsted relation based upon six carboxylic acids with the exponent α = 0.42.These data indicate that the reaction proceeds via rate-determining proton transfer from the catalyzing acid to an olefinic carbon atom of the substrate.They also show tetramethoxyethene to be 1.0 * 1E6 times less reactive than 1,1-dimethoxyethene (ketene dimethyl acetal), a rate retardation 600 times greater than that expected from initial state stabilization by the two additional methoxy groups in tetramethoxyethene; possible causes of this disparity are discussed.
- Kresge, A. J.,Leibovitch, M.,Kopecky, K. R.
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p. 1786 - 1790
(2007/10/02)
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- About the Ozone Cleavage of Chloroprene and of 2-Chloro-3-methyl-1,3-butadiene in Methanol
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Monoozonolyses of chloroprene (1a) and of 2-chloro-3-methyl-1,3-butadiene (1b) in methanol occur with more than 90percent at the non-chlorinated double bonds to afford the corresponding α,β-unsaturated oxo compounds 2 with selectivities of 96 and 80percent respectively.The latter subsequently react with methanol, and 2a also with the complementary fragment methoxymethyl hydroperoxide (5).The α,β-unsaturated methoxy hydroperoxides 3 which have also been obtained, are less stable than similarly structured, non-α-chlorinated methoxy hydroperoxides.Diozonolyses of 1a and 1b in methanol afforded in 50-60percent the corresponding α-oxocarboxylates (21) and/or the corresponding ketals.In addition, anomalous products were obtained viz. ca. 15percent of methyl hydroxyacetate (12d) from 1a and 1b, as well as ca. 30percent of dimethyl oxalate (27b) from 1a and ca. 35percent of methyl acetate (13) from 1b.The modes of formation of these products have been postulated according to model reactions.
- Griesbaum, Karl,Meister, Martin
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p. 1573 - 1580
(2007/10/02)
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- Formation of 4,6-Dinitro-2-nitrosoaniline by Intramolecular Redox Reaction of Esters and Amides of 2-(2,4,6-Trinitroaniline) Carboxylic Acids
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The reaction of methyl and ethyl esters of N-(2,4,6-trinitrophenyl)glycine and N-(2,4,6-trinitrophenyl)-α-alanine (3a-d) with methoxide ion in methanol produces 4,6-dinitro-2-nitrosoaniline (4).N-(2,4,6-Trinitrophenyl)glycine methylamide (1d) gives, under the same conditions, the nitroso compound (4) in addition to 12percent of the spiro adduct (2d).A reaction mechanism is suggested, and the influence of the side chain on the reaction kinetics has been studied.
- Machacek, Vladimir,Hassanien, Makky M.M.,Sterba, Vojeslav,Lycka, Antonin
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p. 867 - 874
(2007/10/02)
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- Acetaldehyde process
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A process for the production of an aldehyde at high selectivity and rate by the reaction of an inorganic or organic ester with carbon monoxide or synthesis gas in contact with a catalyst system containing cobalt, rhodium or ruthenium atoms and lithium iodide and, optionally, an organic ligand.
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- Etude de la composition de solutions aqueuses d'acide glyoxylique en RMN de 13C
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In order to determine the composition of aqueous solutions of glyoxylic acid, we studied the 13C nmr spectra of variously concentrated solutions (20 to 60 percent).The two well-separated regions (acids and esters on one side, acetals, hemiacetals and hydrates on the other) display not directly related intensities owing to the relaxation times of carbonyl carbons.Nevertheless, by plotting the relative intensity of each line in its own region, we were able to associate signals coming from the same species.Aside from the two prominent lines of monomeric hydrate, we identified two other pairs with intensity increasing with total concentration.Apart from a small line due to glyoxal and some other very small lines, we observed four lines of equal and slightly increasing intensity, three of acetal type and one of acid or ester type.In order to establish the structures of the species present, we determined the chemical shifts of a series of related molecules to be used as models (reported on table 2): first esters, acids, acetals, hemiacetals and hydrates of monomeric strukture, then dimers and trimers of acetaldehyde, ethyl glyoxylate and glyoxal.We were thus able to establish increments and correlations which allowed us to estimate the values of chemical shifts for possible dimers and trimers of glyoxylic acid: it was easy to see that two of the entities present in the solution are dimeric hemiacetals-acids, the erythro and threo isomers (figure 3).The fourth species is necessarily a combination of acid with glyoxal and the inspection of models led us to identify it as dihydroxy-4,5 dioxolan-1,3 carboxylic acid (figure 4).Its concentration was shown to increase with that of glyoxal in glyoxylic acid, and furthermore, some of its derivatives could be isolated.The acetalization and esterification of glyoxylic acid by ethanol in acidic medium, effected with remowal of water, provided a mixture of esters-acetals which was analysed by coupled VPC-mass spectrometry and VPC-chemical ionization (with ammonia).The analysis confirmed the existence of the above monomer and dimers in proportions related to the composition of the aqueous solution; moreover a small amount of a cyclic dimer is observed.No more than 5 percent of higher oligomers was evidenced.As for the combinations between glyoxal and glyoxylic acid, the principal one can be accompanied by many others, of various stoechiometries, when more glyoxal is initially present in the glyoxylic acid solution.Thus it is shown that glyoxylic acid in aqueous solution is mostly in the form of monomeric hydrate (69 to 88 percent)) and dimeric hemiacetals-acids (2,5 to 12 percent).Higher oligomers never exceed 5 percent in concentrated solutions, but glyoxal, if present, easily combines with glyoxylic acid, to form various compounds, the major one accounting for up to 12 percent of the material in some concentrated mixture of glyoxal and glyoxylic acid.
- Chastrette, Francine,Bracoud, Corinne,Chastrette, Maurice,Mattioda, Georges,Christidis, Yani
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- Absolute Rates for Dimerization of Capto-dative Substituted Methyl Radicals in Solution: Absence of Kinetic Stabilization
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For three capto-dative substituted methyl radicals, t-butoxy(cyano)methyl radical (1), t-butylthio(cyano)methyl radical (2), and methoxy(methoxycarbonyl)methyl radical (3), absolute rates for dimerization have been measured by e.s.r. spectroscopy and substantiated by product analysis.Values for the rate constants of 1.0E8 - 1.5E9 l mol-1s-1 in the temperature range -60 to +60 deg C support the diffusion-controlled nature of the dimerization.The comparison of Arrhenius activation parameters for dimerization with those for the bulk viscosity of the solutions does not provide evidence for noticeable intrinsic barriers to recombination, indicating the absence of kinetic stabilization for capto-dative substituted methyl radicals.
- Korth, Hans-Gert,Sustmann, Reiner,Merenyi, Robert,Viehe, Heinz Guenther
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- Synthesis of 1-Alkylthiovinyl- and 1-Arylthiovinyl-phosphonium Salts and Their Use in the Formation of Cyclopentanes
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The synthesis of 1-methylthiovinyltriphenyl- and 1-phenylthiovinyltriphenyl-phosphonium salts (1; R = SMe and R = SPh) by introduction of a methylene group α- to the phosphonium centre in Ph3P+-CH2SR is described.The scope and limitations of the method are indicated.The salts (1; R = SMe and R = SPh) are used in the formation of highly functionalised cyclopentanes via an intramolecular Wittig reaction.
- Cameron, Andrew G.,Hewson, Alan T.
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p. 2979 - 2983
(2007/10/02)
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- ELECTROCHEMICAL OXIDATION OF ALKYL-SUBSTITUTED ALLENES IN METHANOL
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Mono-, di- and tri-alkyl-substituted allenes were potentiostatically oxidized in methanol at graphite and Pt anodes.At the former electrode, α-methoxylated ketones (due to 4F/mole electricity consumption) and esters (6F/mole) were the major products.At a Pt anode, intermediate products such as vinyl-ether derivatives (2F/mole) were characterised too.Unlike the anodic oxidation of alkenes and alkynes previously reported in the literature, dimerisation is not a typical process in the allenes' oxidation, since of all the products obtained only a sole dimer has been observed.The mechanism for the formation of most products is discussed.
- Becker, James Y.,Zinger, Baruch
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p. 1677 - 1682
(2007/10/02)
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- 4-β-D-RIBOFURANOSYL-1,2,4-TRIAZIN-3,5(2H,4H)-DIONE AND 4-β-D-RIBOFURANOSYL-6-METHYL-1,2,4-TRIAZIN-3,5(2H,4H)-DIONE
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4-β-D-Ribofuranosyl-1,2,4-triazin-3,5(2H,4H)-dione (IX) and 4-β-D-ribofuranosyl-6-methyl-1,2,4-triazin-3,5(2H,4H)-dione were prepared by cyclization of (Z)-4-β-D-ribofuranosylsemicarbazones of methyl glyoxylate (VI) and methyl pyruvate (VIII) in the methanolic solution of sodium methoxide.A mixture of (E)- and (Z)-ribosylsemicarbazones III and IV was prepared by condensation of the ribosylsemicarbazide I with methyl dimethoxyacetate and a mixture of (E)- and (Z)-isomers V and VIII was obtained on condensation of I with methyl pyruvate.The (Z)-isomer VI was prepared on acid-catalyzed isomerization of (E)-isomer III while the (Z)-isomer VIII was obtained on the UV-irradiation of isomer V.
- Hrebabecky, Hubert
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p. 994 - 999
(2007/10/02)
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- Cephalosporin compounds
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Novel 7-azido-3-cephem compounds are prepared via α-amino-phosphonoacetate esters. The cephem compounds are intermediates for the preparation of novel and known useful antibiotic cephalosporins.
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