- Ligand-Controlled Regiodivergence for Catalytic Stereoselective Semireduction of Allenamides
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Ligand-controlled regiodivergence has been developed for catalytic semireduction of allenamides with excellent chemo- and stereocontrol. This system also provides an example of catalytic regiodivergent semireduction of allenes for the first time. The divergence of the semireduction is enabled by ligand switch with the same palladium pre-catalyst under operationally simple and mild conditions. Monodentate ligand XPhos exclusively promotes selective 1,2-semireduction to afford allylic amides, while bidentate ligand BINAP completely switched the regioselectivity to 2,3-semireduction, producing (E)-enamide derivatives.
- Hajiloo Shayegan, Mojtaba,Li, Zhong-Yuan,Cui, Xin
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supporting information
(2021/12/02)
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- PLASMA KALLIKREIN INHIBITORS AND USES THEREOF
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The present invention provides compounds and compositions thereof which are useful as inhibitors of plasma kallikrein and which exhibit desirable characteristics for the same.
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Paragraph 0731; 0732
(2021/03/19)
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- Conformational control of bis-urea self-assembled supramolecular pH switchable low-molecular-weight hydrogelators
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We report the synthesis and investigation into the structure-property relationships of eight different low molecular weight hydrogelators based on a bisaromatic urea core unit, all of which form gels as the pH of the solution is lowered. The low molecular weight hydrogelators are functionalized with carboxylic acid moieties on one aromatic ring, and the other aromatic ring features a nitro functional group either in the meta- or paraposition relative to the urea linkage. Ortho-methyl substituents were installed on the aromatic rings to enforce a non-coplanar arrangement between the phenyl and urea moieties. Gel formation was triggered by the addition of a mineral acid or the ring-opening hydrolysis of glucono-δ-lactone. The low molecular weight hydrogelators were studied by a variety of analytical techniques, including NMR spectroscopy and rheology. In addition, their ability to uptake a dye, methylene blue, was determined by UV-vis spectroscopy. (Figure Presented)
- Chippindale, Ann M.,Christie, William,Gavriel, Alexander G.,German, Ian M.,Hayes, Wayne,O'Donnell, Adam D.
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- Self-Immolative System for Disclosure of Reactive Electrophilic Alkylating Agents: Understanding the Role of the Reporter Group
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The development of stable, efficient chemoselective self-immolative systems, for use in applications such as sensors, requires the optimization of the reactivity and degradation characteristics of the self-immolative unit. In this paper, we describe the effect that the structure of the reporter group has upon the self-immolative efficacy of a prototype system designed for the disclosure of electrophilic alkylating agents. The amine of the reporter group (a nitroaniline unit) was a constituent part of a carbamate that functioned as the self-immolative unit. The number and position of substituents on the nitroaniline unit were found to play a key role in the rate of self-immolative degradation and release of the reporter group. The position of the nitro substituent (meta- vs para-) and the methyl groups in the ortho-position relative to the carbamate exhibited an influence on the rate of elimination and stability of the self-immolative system. The ortho-methyl substituents imparted a twist on the N-C (aromatic) bond leading to increased resonance of the amine nitrogen's lone pair into the carbonyl moiety and a decrease of the leaving character of the carbamate group; concomitantly, this may also make it a less electron-withdrawing group and lead to less acidification of the eliminated β-hydrogen.
- Chippindale, Ann M.,Gavriel, Alexander G.,Hayes, Wayne,Khurana, Gurjeet S.,Leroux, Flavien,Lewis, Viliyana G.,Russell, Andrew T.,Sambrook, Mark R.
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p. 10263 - 10279
(2021/08/16)
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- Three-Component Ring-Opening Reactions of Cyclic Ethers, α-Diazo Esters, and Weak Nucleophiles under Metal-Free Conditions
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A protocol for three-component reactions of cyclic ethers, α-diazo esters, and weak nitrogen, oxygen, carbon, and sulfur nucleophiles (pKa = 2.2-14.8) to afford a variety of structurally complex α-oxyalkylated esters is reported. These reactions involve intermolecular activation of the cyclic ether (present in excess) by the α-diazo ester to form an oxonium ylide under metal-free conditions, followed by ring opening by the nucleophile.
- Lu, Lin,Chen, Chuwei,Jiang, Huanfeng,Yin, Biaolin
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p. 14385 - 14395
(2018/11/27)
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- Method and using tracer charged ion channel
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The invention provides compounds, compositions, methods, and kits for the treatment of pain, itch, and neurogenic inflammation.
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Paragraph 0422; 0424; 0425-0427
(2018/08/20)
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- Development of 2, 4-diaminoquinazoline derivatives as potent PAK4 inhibitors by the core refinement strategy
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Upon analysis of the reported crystal structure of PAK4 inhibitor KY04031 (PAK4 IC50?=?0.790?μM) in the active site of PAK4, we investigated the possibility of changing the triazine core of KY04031 to a quinazoline. Using KY04031 as a starting
- Hao, Chenzhou,Huang, Wanxu,Li, Xiaodong,Guo, Jing,Chen, Meng,Yan, Zizheng,Wang, Kai,Jiang, Xiaolin,Song, Shuai,Wang, Jian,Zhao, Dongmei,Li, Feng,Cheng, Maosheng
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- NOVEL KCNQ POTASSIUM CHANNEL AGONIST, AND PREPARATION METHOD THEREFOR AND USE THEREOF
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The present invention provides a compound represented by general formula I or a pharmaceutical acceptable salt thereof, the preparation method therefor and the use thereof in preparing a medicine for treating a neurological disease, such as epilepsy, conv
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Paragraph 0040; 0041
(2017/03/21)
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- Enhancing the Gas Permeability of Tr?ger's Base Derived Polyimides of Intrinsic Microporosity
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A series of four novel Tr?ger's base (TB) derived polyimides of intrinsic microporosity (PIM-TB-PI) is reported. The TB diamine monomer (4MTBDA) possesses four methyl groups in order to restrict rotation about the C-N imide bonds in the resulting polymers
- Lee, Michael,Bezzu, C. Grazia,Carta, Mariolino,Bernardo, Paola,Clarizia, Gabriele,Jansen, Johannes C.,McKeown, Neil B.
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p. 4147 - 4154
(2016/07/06)
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- Nickel-catalyzed monoarylation of ammonia
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Structurally diverse (hetero)aryl chloride, bromide, and tosylate electrophiles were employed in the Ni-catalyzed monoarylation of ammonia, including chemoselective transformations. The employed JosiPhos/[Ni(cod)2] catalyst system enables the use of commercially available stock solutions of ammonia, or the use of ammonia gas in these reactions, thereby demonstrating the versatility and potential scalability of the reported protocol. Proof-of-principle experiments established that air-stable [(JosiPhos)NiCl2] precatalysts can be employed successfully in such transformations. Lighten Up: The substrate scope of the title reaction includes (hetero)aryl chloride, bromide, and tosylate electrophiles. The versatility and potential scalability of the reported method is demonstrated by the use of either commercially available stock solutions of ammonia or ammonia gas.
- Borzenko, Andrey,Rotta-Loria, Nicolas L.,Macqueen, Preston M.,Lavoie, Christopher M.,McDonald, Robert,Stradiotto, Mark
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p. 3773 - 3777
(2015/03/18)
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- Tosyl oxygen transfer and ion-neutral complex mediated electron transfer in the gas-phase fragmentation of the protonated N-phenyl p-toluenesulfonamides
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In this work, an interesting oxygen transfer reaction in the gas phase dissociation of N-phenyl p-toluenesulfonamides has been explored by combination of the ESI-MS techniques and theoretical calculations. The protonated molecules underwent dissociation reactions, upon collisional activation, to give the [tosyl cation/aniline] ion-neutral complex (INC), in which the coupling reactions subsequently occurred to afford an ionic species of toluenesulfinate. The subsequent reactions of the toluenesulfinate species resulted in generation of the protonated 6-iminocyclohexa- 2,4-dienone or the 2-aminophenol radical cation, via cleavage of the SO bond. The above processes involved the tosyl oxygen transfer, and calculation results indicated that both the ortho- and the para- positions at the aniline ring are favorite for the tosyl oxygen transfer, and formation of radical cation involved an INC mediated electron transfer. The isomeric N-methylphenyl p-toluenesulfonamides behaved significant difference in the CID-MS spectra, indicating that the three isomers can be distinguished by ESI-MS.
- Wang, Shanshan,Guo, Cheng,Zhang, Ningwen,Wu, Yanqing,Zhang, Huarong,Jiang, Kezhi
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- Tosyl oxygen transfer and ion-neutral complex mediated electron transfer in the gas-phase fragmentation of the protonated N-phenyl p-toluenesulfonamides
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In this work, an interesting oxygen transfer reaction in the gas phase dissociation of N-phenyl p-toluenesulfonamides has been explored by combination of the ESI-MS techniques and theoretical calculations. The protonated molecules underwent dissociation reactions, upon collisional activation, to give the [tosyl cation/aniline] ion-neutral complex (INC), in which the coupling reactions subsequently occurred to afford an ionic species of toluenesulfinate. The subsequent reactions of the toluenesulfinate species resulted in generation of the protonated 6-iminocyclohexa- 2,4-dienone or the 2-aminophenol radical cation, via cleavage of the SO bond. The above processes involved the tosyl oxygen transfer, and calculation results indicated that both the ortho- and the para- positions at the aniline ring are favorite for the tosyl oxygen transfer, and formation of radical cation involved an INC mediated electron transfer. The isomeric N-methylphenyl p-toluenesulfonamides behaved significant difference in the CID-MS spectra, indicating that the three isomers can be distinguished by ESI-MS.
- Wang, Shanshan,Guo, Cheng,Zhang, Ningwen,Wu, Yanqing,Zhang, Huarong,Jiang, Kezhi
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- Natural Indian Natrolite zeolite-supported Cu nanoparticles: A new and reusable heterogeneous catalyst for N-arylation of sulfonamides with boronic acids in water under ligand-free conditions
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We report here on the preparation of primary sulfonamides and efficient, easily recoverable and reusable copper nanoparticles supported on natural Indian Natrolite zeolite as a catalyst for arylation of sulfonamides with arylboronic acids in water. The catalyst was characterized using the powder XRD, SEM, EDS and FT-IR spectroscopy. The significant advantages of this methodology are high yields, elimination of organic solvents, and simple work-up procedure. The catalyst was easily isolated from the reaction mixture and reused with no significant loss in its activity.
- Azarifar, Davood,Soleimanei, Fatemeh
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p. 12119 - 12126
(2014/03/21)
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- Ultrasound-promoted green approach for the synthesis of sulfonamides using natural, stable and reusable Natrolite nanozeolite catalyst at room temperature
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Natural Natrolite nanozeolite has been investigated as an efficient and reusable catalyst for the N-sulfonylation of amines under ultrasound irradiation at room temperature. Compared with traditional methods, the significant advantages for method are green solvent, milder and cleaner conditions, higher purity and yields, shorter reaction time, easier work-up procedure and the lower generation of waste or pollutions. The catalyst can be recovered and reused several times without significant loss of its catalytic activity.
- Nasrollahzadeh, Mahmoud,Ehsani, Ali,Rostami-Vartouni, Akbar
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p. 275 - 282
(2013/10/01)
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- Palladium-catalyzed regiocontrolled domino synthesis of N-sulfonyl dihydrophenanthridines and dihydrodibenzo[c, e]azepines: Control over the formation of biaryl sultams in the intramolecular direct arylation
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A palladium-catalyzed domino N-benzylation/intramolecular direct arylation involving sulfonanilides and 2-bromobenzyl bromides has been developed for the first time, providing a workable access to N-sulfonyl dihydrophenanthridines in good to excellent yields. Under the optimized conditions, the formation of 5,6-dihydrophenanthridines was largely controlled over the formation of biaryl sultams containing a seven member ring. The optimized condition was found extendable to the regiocontrolled domino formation of N-sulfonyl-6,7-dihydro-5H-dibenzo[c,e]azepines over the biaryl sultam formation. Using an appropriate substrate, a biaryl sultam has been obtained exclusively.
- Laha, Joydev K.,Dayal, Neetu,Jain, Roli,Patel, Ketul
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p. 10899 - 10907
(2015/01/08)
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- Half-sandwich scorpionates as nitrene transfer catalysts
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Scorpionate complexes of the middle to late 3d transition metals [(L)M(NCMe)3](BF4)n (M = Mn, Fe, Co, Ni: 1 M, L = tris(3,5-dimethylpyrazol-1-yl)methane, TpmMe,Me, n = 2; 2M, L = tris(3-phenylpyrazol-1-yl)methane, TpmPh, n = 2; 3M except 3Mn, L = hydrotris(3,5-dimethylpyrazol-1-yl) borate, [TpMe,Me]-, n = 1; 4M, L = hydrotris(3-phenyl-5-methylpyrazol-1-yl)borate, [TpPh,Me] -, n = 1) were examined as catalysts for styrene aziridination and THF amination using phenyl-N-tosyliodinane as a nitrene donor. [(Tpm Me,Me)Fe(NCMe)3](BF4)2 (1 Fe) was identified as the most active catalyst, giving nearly quantitative nitrene transfer yields at 5 mol % loadings. The reactivity of 1Fe with a wider range of organic substrates was also explored, and a striking observation was strong selectivity for aromatic rather than benzylic amination for alkylaromatic substrates.
- Liang, Shengwen,Jensen, Michael P.
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p. 8055 - 8058
(2013/02/22)
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- Highly diastereo- And enantioselective aldol reactions in common organic solvents using N-arylprolinamides as organocatalysts with enhanced acidity
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A broad set of N-arylprolinamides 1-8 with increasing NH acidity and steric crowding has been synthesized and its catalytic activity explored for enantioselective aldol reactions. In DMF containing 10 mol-% of TFA, all arylamides are found to catalyze the reaction between cyclohexanone and a variety of electrophilic aldehydes leading to aldols in excess of 90% yield and >95 % enantioselectivity. The per-fluorophenyl catalyst 8 is found to perform best with a broad substrate scope as compared to all other N-arylamides 1-7. It is shown that 8 can indeed be employed in highly nonpolar as well as polar solvents including brine to afford high yields of aldols with excellent diastereo- as well as enantio-selectivity. The results observed for 8 are amongst the best reported so far for prolinamides that do not contain additional stereogenic center(s) and hydrogen-bonding site(s). The molecular structures of 7 and 8, determined by X-ray crystallography and presumed to reflect the most stable conformations, reveal a notable difference in the conformations of the N-aryl rings; the aryl ring exhibits tendency to lie coplanar with the amide functionality in the case of 7, while the per- fluorophenyl ring twists almost orthogonally with respect to the plane of the amide of functionality in 8. The superior performance of the latter is attributed to, in addition to the enhanced NH acidity, the tendency of the perfluorophenyl ring to lie orthogonally to the amide group, which may facilitate a stronger binding of the electrophilic aldehyde via hydrogen bonding in the transition state.
- Moorthy, Jarugu Narasimha,Saha, Satajit
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supporting information; experimental part
p. 739 - 748
(2009/07/19)
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- 2,6-Dimethyl-4-nitrobenzoic anhydride (DMNBA): An effective coupling reagent for the synthesis of carboxylic esters and lactones
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Various carboxylic esters are obtained at room temperature in excellent yields with high chemoselectivities from nearly equimolar amounts of carboxylic acids and alcohols using 2,6-dimethyl-4-nitrobenzoic anhydride with triethylamine by the promotion of 4-(dimethylamino)pyridine. The efficiency of the esterification is compared to those of other dehydrations using substituted benzoic anhydrides as coupling reagents. This method was successfully applied to the synthesis of threo-aleuritic acid lactone and the desired 17-membered ring compound was prepared in high yield at room temperature from the corresponding free trihydroxycarboxylic acid using 2,6-dimethyl-4-nitrobenzoic anhydride in the presence of 4-(dimethylamino)pyridine.
- Shiina, Isamu,Miyao, Ryo
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experimental part
p. 1313 - 1328
(2009/07/05)
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- Substituent effects on aromatic stacking interactions
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Synthetic supramolecular zipper complexes have been used to quantify substituent effects on the free energies of aromatic stacking interactions. The conformational properties of the complexes have been characterised using NMR spectroscopy in CDCl3, and by comparison with the solid state structures of model compounds. The structural similarity of the complexes makes it possible to apply the double mutant cycle method to evaluate the magnitudes of 24 different aromatic stacking interactions. The major trends in the interaction energy can be rationalised using a simple model based on electrostatic interactions between the π-faces of the two aromatic rings. However, electrostatic interactions between the substituents of one ring and the π-face of the other make an additional contribution, due to the slight offset in the stacking geometry. This property makes aromatic stacking interactions particularly sensitive to changes in orientation as well as the nature and location of substituents. This journal is The Royal Society of Chemistry.
- Cockroft, Scott L.,Perkins, Julie,Zonta, Cristiano,Adams, Harry,Spey, Sharon E.,Low, Caroline M. R.,Vinter, Jeremy G.,Lawson, Kevin R.,Urch, Christopher J.,Hunter, Christopher A.
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p. 1062 - 1080
(2007/12/27)
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- Palladium-catalyzed silane/siloxane reductions in the one-pot conversion of nitro compounds into their amines, hydroxylamines, amides, sulfonamides, and carbamates
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A combination of palladium(II) acetate, aqueous potassium fluoride, and polymethylhydrosiloxane (PMHS) facilitates the room-temperature reduction of aromatic nitro compounds to anilines. These reactions tend to be quick (30 min), high-yielding, and tolerate a range of other functional groups. Replacement of PMHS/KF with triethylsilane allows for the reduction of aliphatic nitro compounds to their corresponding hydroxylamines. Depending on the substrate, both conditions can allow for the in situ conversion of the product amines into amides, sulfonamides, and carbamates. Georg Thieme Verlag Stuttgart.
- Rahaim Jr., Ronald J.,Maleczka Jr., Robert E.
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p. 3316 - 3340
(2008/09/17)
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- Reductive deprotection of allyl, benzyl and sulfonyl substituted alcohols, amines and amides using a naphthalene-catalysed lithiation
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The reaction of different protected alcohols, amines and amides with lithium and a catalytic amount of naphthalene (4 mol %) in THF at low temperature leads to their deprotection under very mild reaction conditions, the process being in many cases chemoselective.
- Alonso, Emma,Ramon, Diego J.,Yus, Miguel
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p. 14355 - 14368
(2007/10/03)
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- PROTON TRANSFER REACTIONS BETWEEN ORTHO-METHYL SUBSTITUTED DERIVATIVES OF 4-NITROPHENYLPHENYLCYANOMETHANE AND NITROGEN BASES IN ACETONITRILE SOLVENT
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Equilibrium constants, rate constants, primary deuterium isotope effects, and activation parameters have been measured for the proton transfer reactions in acetonitrile solvent of 4-nitrophenylphenylcyanomethane and 2-methyl-4-nitrophenylphenylcyanomethane with tetramethylguanidine base and for the reactions of 2-methyl-4-nitrophenylphenylcyanomethane and 2,6-dimethyl-4-nitrophenylphenylcaynomethane with 1,5-diazabicycloundec-7-ene base.Introduction of the ortho-methyl groups in the substrate molecule caused significant reductions in the equilibrium and the rate constants.The expected rise in the kinetic primary deuterium isotope effect was not observed when the first ortho-methyl group was introduced, but a 20percent increase did accompany the introduction of the second ortho-methyl group.Enthalpy of activation measurements indicated that there was no increase in the proton tunnelling contribution to the isotope effect when the amount of steric hindrance is increased with ortho-methyl groups.
- Leffek, Kenneth T.,Pruszynski, Przemyslaw
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p. 1454 - 1458
(2007/10/02)
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- 2-[(Aminophenyl and amidophenyl)amino]-1-azacycloalkanes having antidiarrheal activity
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This invention relates to the novel use of certain aromatic substituted amidines as antidiarrheals.
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- A CHEMOSELECTIVE CONVERSION OF ALKYL AND ARYL AZIDES TO AMINES WITH SODIUM HYDROGENTELLURIDE
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By treatment with sodium hydrogentelluride in ethanol/ether at room temperature, alkyl and aryl azides are easily converted to the corresponding primary amines in good yields.
- Suzuki, Hitomi,Takaoka, Koji
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p. 1733 - 1736
(2007/10/02)
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- Potential antitumor agents. 39. Anilino ring geometry of amsacrine and derivatives: Relationship to DNA binding and antitumor activity
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The clinical antileukemic drug amsacrine and analogues are thought to exert their biological activity by binding tightly but reversibly to DNA, with the acridine chromophore intercalated and the anilino group making additional binding contact in the minor
- Denny,Atwell,Baguley
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p. 1625 - 1630
(2007/10/02)
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- Lidocaine antigens and antibodies
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Derivatives of anesthetics involving anilides, lidocaine being illustrative, are provided, having an annular amino group. A difunctional linking group is provided, which provides a link to the annular amino group and an antigen, with the resulting conjugate being employed for the preparation of antibodies. The antibodies find particular use in competitive protein binding assays. Conjugates to enzymes are prepared which find particular use in homogeneous enzyme immunoassays.
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