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11.
Treatment of aliphatic aldehyde with lithium pentamethylcyclopentadienide in the presence of chlorodimethylaluminum provided the corresponding carbinol in excellent yield. The carbinol returns to the parent aldehyde and pentamethylcyclopentadiene by the action of a catalytic amount of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ). 相似文献
12.
Treatment of aromatic aldehyde with lithium pentamethylcyclopentadienide provided the corresponding carbinol in excellent yield. The carbinol returns to the parent aldehyde and pentamethylcyclopentadiene upon exposure to an acid or due to heating. The combination of the two reactions can represent a protection of aromatic aldehyde. 相似文献
13.
A selective cleavage of acetals of 1,2- and 1,3-diols has been achieved under mild conditions using ZnBr2 in dichloromethane at room temperature. Acetal types cleavable by this procedure include benzylidene, isopropylidene and cyclohexylidene acetals. This method is compatible with several other types of hydroxyl protecting groups such as Bn, Bz, TBDPS, TIPS and TBDMS. 相似文献
14.
Fluoroalkylated 1,2,3-triketone 2-arylhydrazones and 2-arylhydrazono-3-oxo esters react variously with methylamine depending on the structure of the fluorinated substituent. 2-Arylhydrazono-1,3-dicarbonyl compounds having “short” fluoroalkyl substituents condense with methylamine at the carbonyl group attached to the non-fluorinated substituent whereas ones containing a lengthy polyfluoroalkyl substituent undergo haloformic cleavage as a result of the amine addition at the carbonyl group bearing such a substituent. The resulting 2-arylazo-3-(N-methyl)amino-1-polyfluoroket-2-en-1-ones and 1-(N-methyl)amino-2-arylhydrazono-3-fluoroalkyl-3-oxopropanamides have complexing properties, and they can bind to nickel(II) and copper(II) ions. Nickel chelates can be obtained by a three-component condensation of 2-arylhydrazono-1,3-dicarbonyl compounds and methylamine in the presence of nickel(II) cations. 相似文献
15.
Kosuke Katagiri Yukina Yamamoto Yuui Takahata Ryoga Kishibe Naoki Fujimoto 《Tetrahedron letters》2019,60(30):2026-2029
Anthracenyl(diphenyl)phosphine oxide and dianthracenylphenylphosphine oxide as photoactive compounds have been synthesized. Anthracenyl group of these compounds indicate the multi-functional roles such as an emission component, a photodimerization component, and a leaving group. When the light irradiation was performed under an oxygen atmosphere, photo-oxidative PC bond cleavage to leave the antharacenyl group was observed. Moreover, phosphonyl radical was produced and then PP bond formation to form diphosphane was observed. 相似文献
16.
A bicyclic diphenyldisilane bearing two tetramethylene tethers reacts with lithium to form predominantly the disilanyllithium as a result of Si-CPh bond fission, while the pentamethylene homolog undergoes ordinary Si-Si bond cleavage to afford the expected phenylsilyllithium. The compressed Si-Si bond incorporated in the bicyclic ring system may be kinetically stabilized (compression effect), resulting in the unusual Si-C bond fission. When the reaction is carried out in the presence of chlorotrimethylsilane, a Calas-type reaction takes place on the phenyl rings. This result suggests that electron transfer to the phenyl group is the primary process in these bicyclic disilanes, followed by Si-Si or Si-C bond cleavage to afford the corresponding silyllithium species. 相似文献
17.
N-Acyl-β-hydroxy-4-phenyl-oxazolidinethiones could be rapidly converted into their ethyl thiol esters in high yields by treatment with EtSH at 0 ℃ in CH3CN or 9 : 1 (V : V) THF-H2O in the presence of a catalytic amount of K2CO3. 相似文献
18.
Petr Zuman 《Microchemical Journal》2002,72(3):241-250
Applications of chromatographic and atomic absorption methods are compared with those of electroanalytical techniques. The limitations of electroanalytical procedures and their advantages, such as speed, sensitivity and speciation are discussed. Among applications of polarography and voltammetry to a solution of basic problems, attention has been paid to the possibility to distinguish the degree of conjugation (e.g. of compounds containing the grouping CNNC), to a contribution to understanding of solution chemistry of mitomycin C and to processes involved in the reduction of cephalosporins. Among practical applications, the possibility to analyze suspensions, which can be carried out without separation offers advantages. Examples are interactions in suspensions of bile salts in the presence of metal (II) ions, adsorptions of various pesticides and other toxic materials on lignin and the possibility to follow alkaline cleavage of lignin in buffers pH 8-12 at 25 °C. Most of these studies would not be possible to carry out using other techniques. 相似文献
19.
Walter E. Kowtoniuk 《Tetrahedron letters》2005,46(3):451-453
Herein we report the cleaving of aryl alkyl ethers on BINOL derivatives, using the common reducing agent LAH. The cleavage of the alkyl oxygen bond is observed when the BINOL derivative is treated with LAH, in refluxing dioxane, for 60 h. The resulting BINOL derivative can then be re-alkylated using a standard Williamson ether synthesis. The same procedure was tested on 6-hydroxy-2-naphthoic acid derivatives and cleavage was not observed, thus suggesting a chelating mechanism for the BINOL ether cleavage. 相似文献
20.
Klaus Rakus Sergej P. Verevkin Hans-Dieter Beckhaus Christoph Rüchardt 《欧洲无机化学杂志》1994,127(11):2225-2234
The thermolysis reactions of the tricyanomethyl compounds 10a-c were studied in solution. 2,2-Dicyano-3-methyl-3-phenylbutyronitrile ( 10a ) and 2,2-dicyano-3-methyl-3-(4-nitrophenyl)butyronitrile ( 10b ) decomposed heterolytically into carbenium ions and (CN)3C− anions, while 9-methyl-9-(tricyanomethyl)fluorene ( 10c ) underwent about 11% homolytic C-C bond cleavage into 9-methyl-9-fluorenyl- and tricyanomethyl radicals. The rates of the homolysis were determined by a radical scavenger procedure under conditions of pseudozero order kinetics. From the temperature effect on the rate constants the activation parameters were determined [ΔH ( 10c ) = 155· 2 kJ mol−1, ΔS ( 10c ) = 58· 5 J mol−1 K−1]. Standard enthalpies of formation ΔH (g) were determined for 2,2-dicyanopropionitrile ( 2 ) (422.45 kJ mol−1), 2,2-dicyanohexanenitrile ( 3 ) (349.74 kJ mol−1), 2,2-dicyano-3-phenylpropionitrile ( 4 ) (540.75 kJ mol−1), 2-butyl-2-methylhexanentrile ( 5 ) (-133.20 kJ mol−1), 2,2-dimethylpentanenitrile ( 6 ) (-45.78 kJ mol−1), and 2-methylbutyronitrile ( 7 ) (2.44 kJ mol−1) from the enthalpies of combustion and enthalpies of sublimation/vaporization. From these data and known Δ (g) values for alkanenitriles and -dinitriles, thermochemical increments for ΔH (g) were derived for alkyl groups with one, two, or three cyano groups attached. The comparison of these increments with those of alkanes reveals a strong geminal destabilization, which is interpreted by dipolar repulsions between the cyano groups. - From ΔH (g) of 10c and ΔH of its homolytic decomposition the radical stabilization enthalpy for the tricyanomethyl radical 1 RSE ( 1 ) = -18 kJ mol−1 was determined. Thus, 1 is destabilized, in comparison with the RSEs of tertiary α-cyanalkyl (23 kJ mol−1) and α,α-dicyanoalkyl (27 kJ mol−1) radicals, which were recalculated from bond homolysis measurements[4] and the new thermochemical data. This change of RSE on increasing the number of α-cyano groups is discussed as the result of the additive contributions by resonance stabilization and increasing destabilization by dipolar repulsion. The amount of the dipolar energies was estimated by molecular mechanics (MM2). 相似文献