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91.
Ludwig Maier Walter Kunz Guenther Rist 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):41-52
Abstract Attempts to prepare 1H-1,2,4-triazol-1-ylmethylphosphonates (4 and 5) by a Mannichtype reaction or by transesterification of 1-hydroxymethyl-1H-1,2,4-triazol 1 with tertiary phosphites failed. On the other hand 4 and 5 are obtained by a Michaelis-Becker reaction from 1-chloromethyl-1H-1,2,4-triazol 3 and sodium phosphites in high yield. The Michaelis-Arbuzov reaction is less suited for the preparation of 4 and 5. 3 is obtained in good yield as a water clear liquid, b.p. 52–54°C/0.2 torr, from the interaction of 1 with thionyl chloride followed by treatment with a base. On standing at 0° or 20°C it decomposes within hours and yields the unsymmetrical methylen-bis(triazol) 3a in addition to other products. However an acetonitrile solution of 3 is stable for months. Heating this solution with tertiary phosphines gives triazolylsubstituted phosphoniumsalts 6 to 8. The Wittig-Horner reaction with 4 to 6 gives the olefinically substituted triazols 9–12 as a Z/E mixture in high yield. Alkylation of 4 with methyl-and ethyl iodide gives the corresponding alkylated diethyl-1H-1,2,4-triazol-1-yl-ethyl-1-and-propyl-1-phosphonates 14 and 15 which on hydrolysis with HCI yield 1H-1,2,4-triazol-1-yl-ethyl-1-and propyl-1-phosphonic acids 17 and 18, respectively. Hydrolysis of 4 gives the unsubstituted 1H-1,2,4-triazol-1-ylmethyl-phosphonic acid, 16. 相似文献
92.
Olaf Böge Eckhart Nietzschmann Joachim Heinicke 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):25-29
Abstract 2-Bromoaryloxy-chloromethyldiorganosilanes react with sodium in a one-pot-reaction via metallation, [1,3]-carbanionic rearrangement and cyclization to give diorgano-1,3-benzoxasilolenes. The title compounds have been characterized by n.m.r. spectroscopic data and an alternative independent synthesis. 相似文献
93.
《Green Chemistry Letters and Reviews》2013,6(3):213-216
Abstract A simple, efficient, and practical procedure for the synthesis of various substituted 2,3-dihydro-2-phenyl-1H-naphtho[1,2-e][1,3]oxazines and 3,4-dihydro-3-phenyl-2H-naphtho[2,1-e][1,3]oxazines using KAl(SO4)2 12H2O (alum) as a non-toxic, reusable, inexpensive, and easily available catalyst is described using water as a solvent. These improved reaction conditions allow the preparation of a wide variety of substituted [1,3]oxazines in high yields and purity under mild reaction conditions. 相似文献
94.
95.
A novel synthetic method is introduced to prepare the biologically important montagnetol and erythrin compounds starting from a 1,3-benzodioxin-4-one, synthesized from commercially available orsellinic acid and erythritol. 相似文献
96.
A novel and metal free catalysis of synthesizing 5-substituted 1H-tetrazoles through 1,3-dipolar cycloaddition of boron-azides and nitriles is reported with broad substrate scope and excellent yields. 相似文献
97.
A novel Wang resin–bound 1-phenylselenoacrylate reagent has been developed and used as dipolarophile for the 1,3-dipolar cycloaddition with nitrile oxides to the regioselective synthesis of methyl 3-substituted isoxazole-5-carboxylates in good yields and purities. 相似文献
98.
Hiroyuki Okamura Hiroki SakaeKeiji Kidani Naoki HirayamaNoboru Aoyagi Takumi SaitoKojiro Shimojo Hirochika NaganawaHisanori Imura 《Polyhedron》2012,31(1):748-753
The extraction constant and the two-phase stability constant (KD,Mβ3) of tris(2-thenoyltrifluoroacetonato)europium(III) between 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][Tf2N]) as an ionic liquid and an aqueous phase were determined by considering the extraction equilibria including anionic tetrakis(2-thenoyltrifluoroacetonato)europate(III). Specific solute-solvent interactions between the neutral Eu(III) chelate and [C4mim][Tf2N] molecules were revealed from the relationships between the distribution constant of the enol form of 2-thenoyltrifluoroacetone (Htta) as a proton chelate and the distribution constant (KD,M) of the neutral Eu(III) chelate because the [C4mim][Tf2N] system gave the high KD,Mβ3 value compared with those in conventional molecular solvents such as benzene and 1,2-dichloroethane. The coordination environment of Eu3+ in the neutral Eu(III) chelate in [C4mim][Tf2N] was investigated by time-resolved laser-induced fluorescence spectroscopy and infrared absorption spectroscopy. Both methods consistently indicated that not only the Eu(III) chelate extracted but also Eu(tta)3(H2O)3 synthesized as a solid crystal were almost completely dehydrated in [C4mim][Tf2N] saturated with water. Consequently, the higher KD,M or extractability of the neutral Eu(III) chelate in the [C4mim][Tf2N] system can be ascribed to the dehydration of the Eu(III) chelate, which is caused by the specific solvation with [C4mim][Tf2N] molecules. 相似文献
99.
100.
Mark Farrell Bruno Melillo Amos B. Smith 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2016,128(1):240-243
The design, synthesis, and validation of new highly effective bifunctional linchpins for type II anion relay chemistry (ARC) has been achieved. The mechanistically novel negative‐charge migration that comprises the Brook rearrangement is now initiated by a stabilized tetrahedral intermediate, which is generated by nucleophilic addition to a Weinreb amide, rather than by a simple oxyanion that is generated from an epoxide. As a result, the linchpin preserves the carbonyl functionality in the ARC adducts, thus permitting access to functionally complex systems in a single flask without the need for further chemical manipulations. This tactic was validated with the one‐pot preparation of monoprotected 1,3‐diketones as well as pyran and spiroketal scaffolds, depending on the choice of nucleophile, electrophile, and work‐up conditions. 相似文献