- Synthesis of Substrates for Aldolase-Catalysed Reactions: A Comparison of Methods for the Synthesis of Substituted Phenylacetaldehydes
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Methods for the synthesis of phenylacetaldehydes (oxidation, one-carbon chain extension) were compared by using the synthesis of 4-methoxyphenylacetaldehyde as a model example. Oxidations of 4-methoxyphenylethanol with activated DMSO (Swern oxidation) or manganese dioxide gave unsatisfactory results; whereas oxidation with 2-iodoxybenzoic acid (IBX) produced 4-methoxyphenylacetaldehyde in reasonable (75%) yield. However, Wittig-type one-carbon chain extension with methoxymethylene-triphenylphosphine followed by hydrolysis gave an excellent (81% overall) yield of 4-methoxyphenylacetaldehyde from 4-methoxybenzaldehyde (a cheap starting material). This approach was subsequently used to synthesise a set of 10 substituted phenylacetaldehydes in good to excellent yields.
- Al-Smadi, Derar,Enugala, Thilak Reddy,Norberg, Thomas,Kihlberg, Jan,Widersten, Mikael
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supporting information
p. 1187 - 1190
(2018/03/26)
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- Maleimide-assisted anti-Markovnikov Wacker-type oxidation of vinylarenes using molecular oxygen as a terminal oxidant
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Arylacetaldehydes were successfully synthesized by the anti-Markovnikov Wacker-type oxidation of vinylarenes using 1 atm O2 as a terminal oxidant under mild conditions. Electron-deficient alkenes, such as maleic anhydride and maleimides, were effective additives and would operate as ligands to stabilize the Pd(0) species during the reaction.
- Nakaoka, Sonoe,Murakami, Yuka,Kataoka, Yasutaka,Ura, Yasuyuki
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supporting information
p. 335 - 338
(2016/01/09)
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- Catalysed anti-Markovnikov oxidation of terminal aryl alkenes to aldehydes and transformation of methyl aryl tertiary amines to formamides with H2O2 as a terminal oxidant
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Anti-Markovnikov oxidation of terminal aryl alkenes to aldehydes and transformation of N-methyl aryl tertiary amines to formamides with H2O2 as a terminal oxidant under mild conditions have been achieved with moderate to good product yields using [FeIII(TF4DMAP)OTf] as catalyst. This journal is
- Du, Yi-Dan,Tse, Chun-Wai,Xu, Zhen-Jiang,Liu, Yungen,Che, Chi-Ming
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supporting information
p. 12669 - 12672
(2015/05/20)
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- PHARMACEUTICAL COMPOUNDS
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The invention provides a compound of the formula (1): or a salt, N-oxide or tautomer thereof; wherein R1 is cyano or C1-4 alkyl; R2 is hydrogen or C1-4 alkyl; R3 is hydrogen or C1-4 alkyl; R4 and R5 are the same or different and each is selected from hydrogen, saturated C1-4 hydrocarbyl and saturated C1-4 hydrocarbyloxy; R6 and R7 are the same or different and each is selected from hydrogen, halogen, CN, C1-4 alkyl and C1-4 alkoxy wherein the C1-4 alkyl and C1-4 alkoxy are each optionally substituted with hydroxy, C1-2 alkoxy or by one or more flourine atoms; R8 is hydrogen or C1-4 alkyl; Q is an alkylene chain of 1 to 4 carbon atoms in length between the moiety Ar and the nitrogen atom N, wherein one or more of the 1 to 4 carbon atoms of the alkylene chain may optionally be substituted with one or two C1-4 alkyl groups, or wherein one carbon atom of the 1 to 4 carbon atoms of the alkylene chain may optionally be substituted with a group -CH2CH2- which together with the said one carbon atom forms a cyclopropyl group; m is 1, 2, 3 or 4; n is 0 or 1; and Ar is a monocyclic or bicyclic aryl or heteroaryl group of 5 to 10 ring members containing 0, 1, 2, 3 or 4 heteroatom ring members selected from O, N and S, the aryl or heteroaryl group being optionally substituted with one to four substituents R13 as defined in the claims. The compounds are inhibitors of Chk-1 kinase and are active against cancers.
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Page/Page column 105-106
(2011/12/02)
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- Novel process for ropinirole preparation
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A method for producing compounds of the formula: Wherein R2 is selected from the group consisting of amino, lower alkylamino, di-lower alkylamino, allylamino, diallylamino, N-lower alkyl-N-allylamino, benzylamino, dibenzylamino, phenethylamino, diphenethylamino, 4-hydroxyphenethylamino or di-(4-hydroxyphenethylamino); comprising: a) reacting with Wittig Reagent to produce wherein R1 is alkoxyl; f) hydrolyzing compound II under acidic conditions to produce g) subjecting compound III to reduction and amination to produce the tertiary amine wherein R2 is as defined above; h) reacting compound IV with 4-chlorophenoxyacetonitrile to create nucleophilic substitution to produce the nitrile compound wherein R2 is as defined above; and i) effecting reduction and hydrolysis in the same step with palladium/C and sodium hydroxide to produce wherein R2 is as defined above.
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Page/Page column 3; 4
(2009/03/07)
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- Activated iodosylbenzene monomer as an ozone equivalent: Oxidative cleavage of carbon-carbon double bonds in the presence of water
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Reported here for the first time are the developments of an efficient method for oxidative cleavage of carbon-carbon double bonds yielding carbonyl compounds by using aryl-λ3-iodanes, which involve a combination of iodosylbenzene and HBF4 in the presence of water. The method serves as a safety alternative to ozonolysis. The oxidative cleavage of olefins probably involves the hitherto unknown direct vicinal dihydroxylations of double bonds with aryl-λ3-iodanes and the subsequent oxidative glycol fissions. Cyclic (cyclopentenes, cyclohexenes, etc.) and acyclic olefins are cleaved smoothly under our conditions. In the reaction of electron-deficient styrenes such as m-nitrostyrene, intermediate formation of the corresponding epoxide was detected. A variety of aryloxiranes also undergo an oxidative cleavage of the epoxide rings under our conditions, and aromatic aldehydes were obtained in good yields. Copyright
- Miyamoto, Kazunori,Tada, Norihiro,Ochiai, Masahito
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p. 2772 - 2773
(2007/10/03)
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- Kinetics and mechanism of oxidation of chalcones by trichloroisocyanuric acid [TCICA] in HOAc-HCIO4 medium
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The kinetics and mechanism of oxidation of chalcone and some substituted chalcones by trichloroisocyanuric acid (TCICA) has been investigated at 313 K in HOAc-HCIO4 medium. The reaction has been found to be first order each in [TCICA] and [Chalcone] and fractional order in [H+]. There is no kinetic or spectral evidence for the formation of complex between TCICA and Chalcone. The rate increases with increase in percentage of acetic acid and [CF]. The products of oxidation have been identified as phenyl acetaldehyde and benzoic acid. The reactive species of oxidant have been established as HOCl and H2OCI+. The rate increases with electron releasing groups in the benzaldehyde moety and vice versa with a Hammett's p value of -0.45. A suitable mechanism involving the chalcone molecule and the reactive species of TCICA in the rate determining step has also been proposed.
- Kumar, J. Anil,Sondu
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p. 1792 - 1795
(2008/03/15)
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- Novel anti-Markovnikov regioselectivity in the Wacker reaction of styrenes
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The Wacker reaction is one of the longest known palladium-catalysed organic transformations, and in the vast majority of cases proceeds with Markovnikov regioselectivity. Palladium(II)-mediated oxidation of styrenes was examined and in the absence of reoxidants was found to proceed in an anti-Markovnikov sense, giving aldehydes. Studies on the mechanism of this unusual transformation were carried out, and indicate the possible involvement of a η4-palladium-styrene complex. With a heteropolyacid as the terminal oxidant, oxidation of styrene to give the anti-Markovnikov aldehyde as the major product was found to be catalytic.
- Wright, Joseph A.,Gaunt, Matthew J.,Spencer, Jonathan B.
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p. 949 - 955
(2007/10/03)
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- Substituted thiophene compounds as modulators of protein tyrosine phosphatases (PTPases)
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The present invention provides novel compounds of formula 1a, novel compositions, methods of their use, and methods of their manufacture, where such compounds are pharmacologically useful inhibitors of Protein Tyrosine Phosphatases (PTPase's) such as PTP1B, CD45, SHP-1, SHP-2, PTPα, LAR and HePTP or the like. The compounds are useful in the treatment of type I diabetes, type II diabetes, impaired glucose tolerance, insulin resistance, obesity, immune dysfunctions including autoimmunity diseases with dysfunctions of the coagulation system, allergic diseases including asthma, osteoporosis, proliferative disorders including cancer and psoriasis, diseases with decreased or increased synthesis or effects of growth hormone, diseases with decreased or increased synthesis of hormones or cytokines that regulate the release of/or response to growth hormone, diseases of the brain including Alzheimer's disease and schizophrenia, and infectious diseases.
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- Diphenylurea compounds
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wherein: R1, R2, R3 and R4 independently represent hydrogen, halogen, or alkyl, alkoxy, hydroxy, cyano, optionally substituted amino, nitro, carboxy, alkoxycarbonyl, optionally substituted aminocarbonyl or carba
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- MODULATORS OF PROTEIN TYROSINE PHOSPHATASES (PTPASES)
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The present invention provides novel compounds, novel compositions, methods of their use, and methods of their manufacture, where such compounds are pharmacologically useful inhibitors of Protein Tyrosine Phosphatases (PTPase's) such as PTP1B, CD45, SHP-1, SHP-2, PTPα, LAR and HePTP or the like. The compounds are useful in the treatment of type I diabetes, type II diabetes, impaired glucose tolerance, insulin resistance, obesity, immune dysfunctions including autoimmunity diseases with dysfunctions of the coagulation system, allergic diseases including asthma, osteoporosis, proliferative disorders including cancer and psoriasis, diseases with decreased or increased synthesis or effects of growth hormone, diseases with decreased or increased synthesis of hormones or cytokines that regulate the release of/or response to growth hormone, diseases of the brain including Alzheimer's disease and schizophrenia, and infectious diseases.
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- Nitric acid in dichloromethane solution. Facile preparation from potassium nitrate and sulfuric acid
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Pure dry HNO3 can be liberated from KNO3 with 96% H2SO4 directly into CH2Cl2 to yield solutions of variable concentration for use in a number of organic reactions. The present method efficiently replaces the employment of 100% HNO3 in some synthetic applications, avoiding the problems associated in storage and handling the acid.
- Strazzolini, Paolo,Giumanini, Angelo G.,Runcio, Antonio
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p. 1387 - 1389
(2007/10/03)
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- Substituted hydrochromenopyrroles
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Compounds of formula (I): STR1 wherein: m is 0 to 3 inclusive, n is 0 to 3 and 2≤m+n≤3, p is 1 to 6 inclusive, X represents cyano or --CO--NR4 R5, R4 and R5 being selected from hydrogen, linear or branched (C1 -C6)-alkyl, (C3 -C7)-cycloalkyl, and aryl, R1 and R2 each independently represent hydrogen or linear or branched (C1 -C6)-alkyl, R3 represents hydrogen, optionally substituted phenyl, naphthyl or heteroaryl, or aryloxy or arylthio, or aryl or heteroaryl substituted by A'-Cy, A' and Cy being as defined in the description, and medicinal products containing the same which are useful as D3 receptor ligands.
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- Experiments on the Chaperon effect in the nitration of aromatics
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A nitro group may be effectively delivered to the ortho position of alkylbenzenes, provided that a suitable chaperon function is located in α- position and a dilute of HNO3 in CH2Cl2 is used. The carbonyl function of an aldehyde or ketone is the best choice, but a carboxyl, alkoxycarbonyl, and amide groups all work well. The ether function showed a less pronounced ortho orientation effect, whereas the hydroxyl group was too prone to oxidation. Side reactions were minimal under the conditions employed. A para chaperon effect was seemingly at work in the CH2Cl2 nitration of benzenepropanenitrile. All the results were compared with the corresponding classical nitration in H2SO4.
- Strazzolini, Paolo,Giumanini, Angelo G.,Runcio, Antonio,Scuccato, Massimo
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p. 952 - 958
(2007/10/03)
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- Kinetics of Ru(III)-catalysed Oxidation of Chalcones by Acid Bromate in H2SO4-HOAc Medium
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Kinetics of Ru(III) chloride catalysed oxidation of chalcone and some substituted chalcones by acid bromate have been studied in acetic acid-sulphuric acid medium in the temperature range 303-318 K.The reaction is first order each in and and zero order each in and .The rate increases with increase in the persentage of acetic acid and the plot of log k0 versus 1/D is linear with a positive slope indicating the positive ion-dipole nature of the reaction.The order of reactivities of various substituted chalcones with substituents in phenyl ring is: p-CH3 > m-CH3 > H > p-Cl > m-NO2 > p-NO2.A radical mechanism involving the chalcone and Ru(III) in the slow step followed by oxidation of Ru(II) by BrO3(-) to Ru(III) in the fast step is proposed.
- Narasimha Char, P.,Sondu, S.,Sethuram, B.,Navaneeth Rao, T.
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- Kinetics and Mechanism of Acid Bromate Oxidation of Phenyl Styryl Ketone and Its Derivatives
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Oxidation of phenyl styryl ketone (chalcone) and some substituted ketones by acid bromate in aqueous acetic acid-H2SO4 medium is first order each in and and second order in .H2BrO3(+) has been established as the reactive oxidant species from the effect of varying and on rate.The products of oxidation are benzoic acid and phenylacetaldehyde.Substituents with electron-releasing groups increase the rate and the Hammett's plot is linear with ρ = -1.10.A plausible mechanism involving the attack of oxidant on non-bonded electrons of carbonyl oxygen is proposed.
- Char, P. Narasimha,Sondu, S.,Sethuram, B.,Rao, T. Navaneeth
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p. 749 - 751
(2007/10/02)
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- Reaction of Phenyl Styryl Ketone and Its Substituted Analogues with Ce(IV) in H2SO4-HOAc Mixtures: A Kinetic Study
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Kinetics of oxidation of chalcone (phenyl styryl ketone) and its substituted analogues by Ce(IV) in H2SO4-HOAc mixtures has been investigated in the temperature range 40 deg-60 deg C.The rate law is found to be -d/dt = k''.The rate increases with the increase in at constant ionic strength, but decreases with increase in and percentage of acetic acid at constant .The effect of various substituents in the phenyl ring, directly attached to the double bond, on rate is in the order: p-Me > m-Me > p-Cl > H > m-Cl > m-NO2 >p-NO2.A mechanism in which the cleavage of carbon-carbon single bond, forming styryl carbonium ion and benzoyl radical, occurs in the rate-determining step is proposed.Activation parameters are also presented and discussed.
- Sondu, S.,Sethuram, B.,Rao, T. Navaneeth
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p. 883 - 885
(2007/10/02)
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