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91.
An efficient method for the synthesis of 2-alkyl- and 2-aryl pyrrolidines, piperidines, and azepanes from lactams, in either racemic or enantiopure form, is presented. The lactam nitrogens are acylated with either Boc anhydride or trans-cumylcyclohexyl (TCC) chloroformate. Selective reduction of the lactam carbonyl to the carbinolamide is followed by treatment with benzotriazole. Substitution of the benzotriazole is accomplished by treatment with organometallics, yielding the 2-substituted heterocycles. With TCC, up to 90% diastereoselectivity is achieved. After diastereomer purification, reductive removal of the auxiliary affords enantiopure 2-substituted heterocycles. A mechanistic hypothesis is presented that details the conformational equilibria of the key step. 相似文献
92.
Chemoselective reductions of alkenes, α,β-unsaturated carbonyl compounds, nitro and nitroso compounds, N,N-hydrogenolysis of azo and hydrazo functions as well as simultaneous reduction and hydrodehalogenation of substituted aryl halides, including bulkier substrates, were achieved by catalytic transfer hydrogenation (CTH) using mesoporous PdMCM-41 catalyst. The yields were practically unaffected upon recycling of the catalyst. Further, the CTH process is accomplished without affecting the reduction of any other reducible functional group. 相似文献
93.
Alkylation of O-silylated N-alkylmalonylhydroxamic acids provides a method for the synthesis of 2-substituted N-alkylmalonyl hydroxamic acids. The substituent at C-2 does not materially change the chemistry of the alpha-lactam intermediates produced from them. They can be converted to unsymmetric ureas and hydantoins in high yields. The addition of unsaturated substituents at C-2 is used to produce cyclic ureas containing medium rings via RCM reactions. 相似文献
94.
A simple, rapid, and precise method is developed for the quantitative simultaneous determination of metformin and pioglitazone in a combined pharmaceutical-dosage form. Separation is achieved with a Zorbax XDB C(18), 15-cm analytical column using buffer-acetonitrile (66:34, v/v) of pH 7.1, adjusted with orthophosphoric acid as the mobile phase. The buffer used in the mobile phase contains 10mM disodium hydrogen phosphate and 5mM sodium dodecyl sulphate in double-distilled water. The instrumental settings are flow rate of 1 mL/min, column temperature at 40 degrees C, and detector wavelength of 226 nm. The internal standard method is used for the quantitation of the ingredients of this combination. Methylparaben is used as an internal standard. The method is validated and shown to be linear for metformin and pioglitazone. The correlation coefficients for metformin and pioglitazone are 0.9991 and 0.9999, respectively. The relative standard deviations for six replicate measurements in two sets of each drug in the tablets are always less than 2%. 相似文献
95.
Sachin Handa James C. Fennewald Bruce H. Lipshutz 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(13):3500-3503
On the basis of the far higher solubility of oxygen gas inside the hydrocarbon core of nanomicelles, metal and peroxide free aerobic oxidation of aryl alkynes to β‐ketosulfones has been achieved in water at room temperature. Many examples are offered that illustrate broad functional group tolerance. The overall process is environmentally friendly, documented by the associated low E Factors. 相似文献
96.
97.
Gadekar Sachin P. Dipake Sudarshan S. Gaikwad Suresh T. Lande Machhindra K. 《Research on Chemical Intermediates》2018,44(12):7509-7518
Research on Chemical Intermediates - TS-1 zeolite was prepared for the synthesis of 5-arylidene-2,4-thiazolidinediones/Rhodanines in aqueous medium by incorporating titanium(IV) cations in a... 相似文献
98.
Partially bio‐based poly(amide imide)s by polycondensation of aromatic diacylhydrazides based on lignin‐derived phenolic acids and aromatic dianhydrides: Synthesis,characterization, and computational studies 下载免费PDF全文
Sachin S. Kuhire Pragati Sharma Suman Chakrabarty Prakash P. Wadgaonkar 《Journal of polymer science. Part A, Polymer chemistry》2017,55(21):3636-3645
Two new bio‐based diacylhydrazide monomers, namely, 4,4′‐(propane‐1,3‐diylbis(oxy))bis(3‐methoxybenzohydrazide) and 4,4′‐(propane‐1,3‐diylbis(oxy))bis(3,5‐dimethoxybenzohydrazide) were synthesized starting from lignin‐derived phenolic acids, namely, vanillic acid and syringic acid. A series of poly(amide imide)s was synthesized by polycondensation of these diacylhydrazide monomers with commercially available aromatic dianhydrides. Poly(amide imide)s showed inherent viscosity in the range 0.44–0.56 dL g?1 and exhibited good solubility in organic solvents. Poly(amide imide)s could be cast into transparent, flexible, and tough films from their N ,N‐dimethylacetamide solutions. Poly(amide imide)s showed 10% weight loss in the temperature range 340–364 °C indicating their good thermal stability. Glass transition temperature (T g) of poly(amide imides)s were measured by DSC and DMA which were in the range 201–223 °C and 214–248 °C, respectively. The T g values of poly(amide imide)s were dependent on the number methoxy substituents on aromatic rings of diacylhydrazide monomers. Molecular dynamics simulation studies revealed that chain rigidity is the dominant factor for observed trends in T g. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 3636–3645 相似文献
99.
Temperature and pH dual stimuli responsive PCL‐b‐PNIPAAm block copolymer assemblies and the cargo release studies 下载免费PDF全文
Sachin S. Patil Prakash P. Wadgaonkar 《Journal of polymer science. Part A, Polymer chemistry》2017,55(8):1383-1396
A new atom transfer radical polymerization (ATRP) initiator, namely, 2‐(1‐(2‐azidoethoxy)ethoxy)ethyl 2‐bromo‐2‐methylpropanoate containing both “cleavable” acetal linkage and “clickable” azido group was synthesized. Well‐defined azido‐terminated poly(N‐isopropylacrylamide)s (PNIPAAm‐N3)s with molecular weights and dispersity in the range 11,000–19,000 g mol?1 and 1.20–1.28, respectively, were synthesized employing the initiator by ATRP. Acetal containing PCL‐b‐PNIPAAm block copolymer was obtained by alkyne–azide click reaction of azido‐terminated PNIPAAm‐N3 with propargyl‐terminated PCL. Critical aggregation concentration (CAC) of PCL‐b‐PNIPAAm copolymer in aqueous solution was found to be 8.99 × 10?6 M. Lower critical solution temperature (LCST) of PCL‐b‐PNIPAAm copolymer was found to be 32 °C which was lower than that of the precursor PNIPAAm‐N3 (36.4 °C). The effect of dual stimuli viz . temperature and pH on size and morphology of the assemblies of PCL‐b‐PNIPAAm block copolymer revealed that the copolymer below LCST assembled in spherical micelles which subsequently transformed to unstable vesicles above the LCST. Heating these assemblies above 40 °C led to the precipitation of PCL‐b‐PNIPAAm block copolymer. Whereas, at decreased pH, micelles of PCL‐b‐PNIPAAm copolymer disintegrate due to the cleavage of acetal linkage and precipitation of hydrophobic hydroxyl‐terminated PCL. The encapsulated pyrene release kinetics from the micelles of synthesized PCL‐b‐PNIPAAm copolymer was found to be faster at higher temperature and at lower pH. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1383–1396 相似文献
100.
Enantiomeric separation of a melatonin agonist Ramelteon using amylose-based chiral stationary phase
Sachin D. Patil Nandkumar Khandekar Gajanan B. Kasawar K.A. Shaikh 《Arabian Journal of Chemistry》2013,6(1):103-109
A new simple isocratic chiral liquid chromatographic method was developed for the enantiomeric purity of Ramelteon[(S)-N-[2-(1,6,7,8-tetrahydro-2H-indeno[5,4-b]furan-8-yl) ethyl]-propionamide], a melatonin agonist in bulk drugs. The chromatographic separation was achieved on Chiralpak AD-H, 250 mm × 4.6 mm, 5 μm column using a mobile phase system consisting of n-hexane, ethanol and methanesulfonic acid in the ratio of 900:100:0.1 (v/v/v). The mobile phase was pumped on the column at the flow rate of 1 mL min?1. Addition of methane sulfonic acid in the mobile phase enhanced chromatographic efficiency and resolution between the enantiomers. The resolution between the enantiomers was found to be more than four. The developed method was subsequently validated and proved to be accurate and precise. The experimentally established limit of detection and quantification of (R)-enantiomer were found to be 25.5 and 77.2 ng ml?1, respectively, for 20 μl injection volumes. The percentage recovery of (R)-enantiomer was ranged from 98.5 to 101.9 in bulk drug samples of Ramelteon. The stability of Ramelteon sample in analytical solution was checked for about 48 h at room temperature and was found to be stable for about 48 h. The proposed method was found to be suitable and accurate for the quantitative determination of (R)-enantiomer in drug substance. 相似文献