Home About us Contact
|
Home About us Contact | ||
|
|
||
Methyl Substituent (methyl + substituent)
Selected AbstractsNovel Triaromatic Ester Mesogenic Liquid Crystalline Epoxy Resin Containing Both Methyl Substituent and Ethoxy Flexible Spacer: Synthesis and CuringMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 11 2008Guo-dong Liu Abstract A novel triaromatic ester liquid crystalline epoxy resin (LCER) that contains both a methyl substituent and an ethoxy flexible spacer, p -methylphenylene di{4-[(2,3-epoxypropoxy)ethoxy]benzoate} (MPEPEB), has been synthesized. The mesotropic property has been investigated by differential scanning calorimetry (DSC) and polarized light optical microscopy (POM). MPEPEB shows a lower melting temperature at 78.7,°C and a broad nematic mesophase temperature range of about 55,°C. Meanwhile MPEPEB shows a mesophase to ,50,°C upon cooling. The curing behavior of MPEPEB with 2,6-diamino-3,5-diethyltoluene (DAE) has been investigated by means of DSC and POM during isothermal and dynamic processes. Although there is little difference between the activation energies obtained from the kinetic data, a marked difference is found between the isothermal and dynamic investigation. The curing reaction in the isothermal investigation roughly obeys n- th order kinetics, while two exothermal peaks appear in the dynamic DSC curves of MPEPEB/DAE. A comparison of the isothermal and dynamic data shows that the curing rate is not a unique function of temperature and curing degree. The cured networks have lower glass temperatures and show a mesophase at room temperature which disappears at about 86,88,°C. [source] Effects of Methyl Substituents on the Activity and Enantioselectivity of Homobenzotetramisole-Based Catalysts in the Kinetic Resolution of AlcoholsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 14-15 2009Yuhua Zhang Abstract Substitution of the tetrahydropyrimidine ring in the enantioselective acyl transfer catalyst homobenzotetramisole (HBTM) 6 with methyl groups exerts a dramatic influence on its performance in the kinetic resolution of secondary alcohols. The syn- 3-methyl analogue of HBTM (9a) has proved to be superior to the parent compound in terms of catalytic activity, enantioselectivity, and synthetic accessibility. [source] The Role of the 11-cis-Retinal Ring Methyl Substituents in Visual Pigment Formation.CHEMINFORM, Issue 2 2007Marta Dominguez Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Synthesis and calcium channel modulating effects of modified Hantzsch nitrooxyalkyl 1,4-dihydro-2,6-dimethyl-3-nitro-4-(pyridinyl or 2-trifluoromethylphenyl)-5-pyridinecarboxylatesDRUG DEVELOPMENT RESEARCH, Issue 4 2000Ramin Miri Abstract A group of racemic nitrooxyalkyl 1,4-dihydro-2,6-dimethyl-3-nitro-4-(pyridinyl or 2-trifluoromethylphenyl)-5-pyridinecarboxylates 8a,o were synthesized using modified Hantzsch reactions. In vitro calcium channel antagonist activities, determined using a guinea pig ileum longitudinal smooth muscle (GPILSM) assay, showed that compounds 8a,o exhibited weaker calcium antagonist activity (10,5 to 10,7 M range) than the reference drug nifedipine (IC50 = 1.43 × 10,8 M). Compounds 8 possessing a C-4 R1 = 2-pyridyl substituent were always more potent than the approximately equiactive analogs having an R1 = 3-pyridyl, 4-pyridyl or 2-CF3 -C6H4 -substituent, within each subgroup of nitrooxyalkyl compounds [R2 = , (CH2)nONO2 (n = 2, 3, 4) or ,CH(CH2ONO2)2]. Although the length of the R2 = ,(CH2)nONO2 substituent (n = 2,4) was not a determinant of smooth muscle calcium antagonist activity when the C-4 R1 -substituent was 2-pyridyl, when R1 was a 3-pyridyl, 4-pyridyl, or 2-CF3 -C6H4 -substituent, the relative potency order with respect to the R2 = ,(CH2)nONO2 substituent was n = 3 and 4 > n = 2. Replacement of the isopropyl substituent of the ester moiety of the calcium antagonist (±)-2-pyridyl 3a by a ,(CH2)nONO2 (n = 2,4) moiety increased calcium antagonist activity on GPILSM by 8-fold. In contrast, replacement of the isopropyl substituent of the ester moiety of the calcium agonists (±)-3-pyridyl 3b, (±)-4-pyridyl 3c or the methyl substituent of the ester moiety of Bay K8644 by a R2 nitrooxyalkyl substituent resulted in abolition of their calcium agonist effects on GPILSM that is replaced by a smooth muscle calcium antagonist effect. These calcium antagonist data support the concept that incorporation of a nitrooxyalkyl ester substituent constitutes a valuable drug design strategy to enhance Hantzsch 1,4-dihydropyridine calcium antagonist and/or abolish calcium agonist effects on smooth muscle. Replacement of the isopropyl (8b,c), or the methyl (8d) group by a ,CH2CH2ONO2 moiety resulted in retention of the cardiac positive inotropic effect where the relative potency order with respect to the C-4 substituent was 2-CF3 -C6H6 - (8d) > 3-pyridyl (8b) , 4-pyridyl (8c). Model hybrid (calcium channel modulation, ·NO release) compounds, that exhibit dual cardioselective agonist / smooth muscle selective antagonist activities, represent a novel type of 1,4-dihydropyridine CC modulator that offers a potential approach to drug discovery targeted toward the treatment of congestive heart failure and for use as probes to study the structure,function relationship of calcium channels. Drug Dev. Res. 51:225,232, 2000. © 2001 Wiley-Liss, Inc. [source] Stable Ion and Electrophilic Substitution (Nitration and Bromination) Study of A-Ring Substituted Phenanthrenes: Novel Carbocations and Substituted Derivatives; NMR, X-ray Analysis, and Comparative DNA BindingEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 3 2007Cédric Brulé Abstract Persistent carbocations were generated from five A-ring mono- and di-substituted phenanthrenes [3-OMe; 4-OMe, 1,3-bis(OMe), 2,4-bis(OMe), and 1,3-bis(Me)]. In all cases protonation occurs in the A-ring, ortho/para relative to methoxy or methyl substituent(s). Complete NMR assignments of the resulting carbocations are reported and their charge delocalization modes are discussed. Mild nitration (with 20,50,% aqueous HNO3 at ,10 °C or at room temp.) and bromination (NBS/MeCN/room temp.) of these substrates resulted in the synthesis of several novel mononitro-/dinitro- as well as monobromo/dibromo derivatives, including those with nitro or bromo substituent in the bay-region. Correspondence between the site of attack in low-temperature protonation study and nitro substitution in ambient mild nitrations are examined. Complete NMR assignments for the new derivatives are reported as well as X-ray structures for 2,4-dimethoxy-1-nitro- and 1,3-dimethyl-4-nitrophenanthrenes. A comparative DNA binding study with MCF cells on three of the synthesized mononitro and one dinitro derivative showed that 1,3-dimethyl-9-nitro- (nitro at the meso position), 3-methoxy-4-nitro- (nitro in bay-region), and 1,3-dimethoxy-4,9-dinitrophenanthrenes (nitro in both meso and bay-regions) formed DNA adducts. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Gold(III) Chloride-Catalyzed Diastereoselective Alkylation Reactions with Chiral Benzylic AcetatesADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 7-8 2008Philipp Rubenbauer Abstract Gold(III) chloride was shown to be an efficient catalyst for the diastereoselective CC bond formation of various chiral para -methoxybenzylic acetates and different nucleophiles. All electrophilic acetates carried next to the reacting center a stereogenic carbon center bound to a functional group (FG), a methyl substituent and a proton. Selectivities were good (dr>80/20) in favor of the anti -product for FG=COOMe, NO2, CN and in favor of the syn -product for FG=SO2Et, PO(OEt)2. The reactions proceed most likely via a free carbocation, in which a face differentation is facilitated by a preferred conformation. Several arene nucleophiles were shown to be compatible with the catalysis conditions providing the corresponding substitution products in high yields (13 examples, 62,98%). Moreover, other nucleophiles (allyltrimethylsilane, trimethylsilyl cyanide, 2,2-dimethyl-3-(trimethylsilyloxy)butane, p -toluenesulfonamide, and acetylacetone) reacted with a representative chiral electrophile in a high yielding and diastereoselective fashion. [source] Stability studies of oxazolidine-based compounds using 1H NMR spectroscopyJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 8 2010Gerard P. Moloney Abstract A series of oxazolidine-based compounds with a variety of substituents in positions 2 and 3 was synthesized and their stability studied. Ring opened intermediates formed on addition of limiting amounts of D2O to oxazolidine solutions, as observed by NMR. As the hydrolysis reactions proceeded, a series of novel dimeric ,-amino alcohol compounds formed via an internal reaction between ephedrine and the ring opened intermediates. 2-Phenyl substituted oxazolidine compounds containing electron withdrawing nitro substituents were more rapidly hydrolyzed than the unsubstituted derivative and methoxy substituted compounds, with the nitro substituents appearing to stabilize the ring opened intermediates. Two oxazolidine derivatives, with a methyl and proton at position 2, were found to be more stable to oxazolidine hydrolysis than the 2-phenyl substituted compounds. Oxazolidines incorporating phenyl substituents at position 3 were synthesized and found to be less stable than those incorporating a methyl substituent at position 3. These fundamental structure,activity relationships may be useful when choosing oxazolidine derivatives as synthetic intermediates and as prodrugs for the delivery of compounds containing either ,-amino alcohol or aldehyde components. © 2010 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 99:3362,3371, 2010 [source] Novel Triaromatic Ester Mesogenic Liquid Crystalline Epoxy Resin Containing Both Methyl Substituent and Ethoxy Flexible Spacer: Synthesis and CuringMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 11 2008Guo-dong Liu Abstract A novel triaromatic ester liquid crystalline epoxy resin (LCER) that contains both a methyl substituent and an ethoxy flexible spacer, p -methylphenylene di{4-[(2,3-epoxypropoxy)ethoxy]benzoate} (MPEPEB), has been synthesized. The mesotropic property has been investigated by differential scanning calorimetry (DSC) and polarized light optical microscopy (POM). MPEPEB shows a lower melting temperature at 78.7,°C and a broad nematic mesophase temperature range of about 55,°C. Meanwhile MPEPEB shows a mesophase to ,50,°C upon cooling. The curing behavior of MPEPEB with 2,6-diamino-3,5-diethyltoluene (DAE) has been investigated by means of DSC and POM during isothermal and dynamic processes. Although there is little difference between the activation energies obtained from the kinetic data, a marked difference is found between the isothermal and dynamic investigation. The curing reaction in the isothermal investigation roughly obeys n- th order kinetics, while two exothermal peaks appear in the dynamic DSC curves of MPEPEB/DAE. A comparison of the isothermal and dynamic data shows that the curing rate is not a unique function of temperature and curing degree. The cured networks have lower glass temperatures and show a mesophase at room temperature which disappears at about 86,88,°C. [source] Synthesis, Characterization, and Protonation Reactions of Ar-BIAN and Ar-BICAT Diimine Platinum Diphenyl ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2010Jerome Parmene Abstract PtII diphenyl complexes (N,N)PtPh2 [N,N = diimines Ar,N=C(An)C=N,Ar with Ar = substituted aryl groups] have been prepared and characterized by 1H, 13C, and 195Pt NMR spectroscopy. The 195Pt NMR spectroscopic data establish the electronic influence exerted by substituents at the backbone of the diimine ligand system to the metal center. When compared to diimines Ar,N=CMe,CMe=N,Ar, the electron-withdrawing ability of the Ar-BIAN ligand and the electron-donating ability of the O,O-heterocyclic Ar-BICAT systems are demonstrated. Trends in 195Pt NMR chemical shifts suggest that electronic tuning of the metal center is better achieved through variations of the diimine backbone substituents rather than variation of the substituents at the N-Aryl groups. Protonation of (N,N)PtPh2 in dichloromethane/acetonitrile at ,78 °C furnishes the corresponding PtIV hydrides (N,N)PtPh2H(NCMe)+. The PtIV hydrides liberate benzene with the formation of (N,N)PtPh(NCMe)+ when the temperature is raised. A second protonation and rapid benzene elimination produces the dicationic PtII species (N,N)Pt(NCMe)22+ at approximately 50 °C. Protonation of (N,N)PtPh2 in the absence of acetonitrile results in the clean formation of (N,N)PtPh(,2 -C6H6)+ at temperatures that depend on the steric hindrance provided by the alkyl substituents at the diimine N-aryl groups. These findings support the notion that the metal is the kinetically preferred site of protonation. The results qualitatively agree with a recent mechanistic study of protonation-induced reactions of (diimine)PtPh2 complexes that bear simple methyl substituents at the diimine backbone. Several compounds have been crystallographically characterized. All complexes have the expected square planar environment at the metal. Modest variations in the metric parameters suggest that the Ar-BICAT system has a weaker trans influence than the Ar-BIAN and Ar-DAB systems. [source] Monophosphanylcalix[6]arene Ligands: Synthesis Characterization, Complexation, and Their Use in CatalysisEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2006Yasushi Obora Abstract Novel phosphanylcalix[6]arenes having mono- O -diphenylphosphanylmethyl (3) and mono- O -(4-diphenylphosphanylphenyl)methyl substituents (5) have been synthesized. The structures of these monophosphanylcalix[6]arenes were determined by NMR spectroscopy, mass spectrometry, and X-ray crystal structure analysis. The X-ray structure reveals that 3 adopts a flattened 1,2,3-alternate conformation in the crystalline state, while the NMR spectra show that 3 and 5 have a cone conformation in solution. Structure optimization and energy calculations for 3 and 5 at the B3LYP/LANL2DZ-CONFLEX5/MMFF94s level of theory show that the cone conformation is slightly more stable than the 1,2,3-alternate conformation by 0.36 kcal,mol,1 for 3 and 0.96 kcal,mol,1 for 5. Complexation of 3 with [PtCl2(COD)] and [Rh(COD)2]BF4 gives cis -coordinated [PtCl2(3)2] and [Rh(COD)(3)2]BF4, respectively. The X-ray analysis of [PtCl2(3)2] shows that 3 adopts a cone conformation upon complexation. Combination of 3 and 5 with [Rh(COD)2]BF4 provides an active catalyst for the hydroformylation of a variety of terminal alkenes.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Bis[4-(dimethylamino)pyridine-,N1]silver(I) nitrate dihydrateACTA CRYSTALLOGRAPHICA SECTION C, Issue 9 2009Al-shima'a A. Massoud The title compound, [Ag(C7H10N2)2]NO3·2H2O or [Ag(dmap)2]NO3·2H2O, where dmap is 4-(dimethylamino)pyridine, has a distorted linear coordination geometry around the AgI ion. A novel pattern of water,nitrate hydrogen-bonded anionic strands is formed in the c direction, with the cationic [Ag(dmap)2]+ monomers trapped between them. The AgI ion and the nitrate group atoms, as well as the water molecules (including the H atoms), are on a crystallographic mirror plane (Wyckoff position 4a). The influence of bulky methyl substituents in position 4 of the 4-(dimethylamino)pyridine ligand on packing is discussed. The absolute structure was determined unequivocally. [source] Ring-Closing Olefin Metathesis on Ruthenium Carbene Complexes: Model DFT Study of StereochemistryCHEMISTRY - A EUROPEAN JOURNAL, Issue 13 2005Sergei F. Vyboishchikov Dr. Abstract Ring-closing metathesis (RCM) is the key step in a recently reported synthesis of salicylihalamide and related model compounds. Experimentally, the stereochemistry of the resulting cycloolefin (cis/trans) depends strongly on the substituents that are present in the diene substrate. To gain insight into the factors that govern the observed stereochemistry, density functional theory (DFT) calculations have been carried out for a simplified dichloro(2-propylidene)(imidazole-2-ylidene)ruthenium catalyst I, as well as for the real catalyst II with two mesityl substituents on the imidazole ring. Four model substrates are considered, which are closely related to the systems studied experimentally, and in each case, two pathways A and B are possible since the RCM reaction can be initiated by coordination of either of the two diene double bonds to the metal center. The first metathesis yields a carbene intermediate, which can then undergo a second metathesis by ring closure, metallacycle formation, and metallacycle cleavage to give the final cycloolefin complex. According to the DFT calculations, the stereochemistry is always determined in the second metathesis reaction, but the rate-determining step may be different for different catalysts, substrates, and pathways. The ancillary N-heterocyclic carbene ligand lies in the Ru-Cl-Cl plane in the simplified catalyst I, but is perpendicular to it in the real catalyst II, and this affects the relative energies of the relevant intermediates and transition states. Likewise, the introduction of methyl substituents in the diene substrates influences these relative energies appreciably. Good agreement with the experimentally observed stereochemistry is only found when using the real catalyst II and the largest model substrates in the DFT calculations. [source] Mechanistic Study of the Reaction of Thiol-Containing Enzymes with ,,,-Unsaturated Carbonyl Substrates by Computation and ChemoassaysCHEMMEDCHEM, Issue 6 2010Alexander Paasche Abstract We investigated the reactions between substituted ,,,-unsaturated carbonyl compounds (Michael systems) and thiols by computations as well as chemoassays. The results give insight into variations in the underlying mechanisms as a function of the substitution pattern. This is of interest for the mechanisms of inhibition of the SARS coronavirus main protease (SARS-CoV Mpro) by etacrynic acid derivatives as well as for the excess toxicity of substituted ,,,-unsaturated carbonyl compounds. This study compares possible reaction courses including 1,4-addition followed by a ketonization step, and underscores the importance of a base-catalyzed step for the reactivity of thiol groups in enzymes. Phenyl and methyl substituents at the Michael system decrease the reactivity of the electrophilic compound, but chlorophenyl substituents partly recover the reactivity. Computations also indicate that electron-pushing substituents lead to a change in the reaction mechanism. The conformation of the Michael system is also found to significantly influence reactivity: the s - cis conformation leads to higher reactivity than the s - trans conformation. The computed data explain the trends in measured inhibition potencies of substituted ,,,-unsaturated carbonyl compounds and of reaction rates in chemical assays. They also indicate that the reversibility of inhibition does not stand in contrast to the formation of a new covalent bond between inhibitor and protease. [source] | ||||||||||