37975-18-1Relevant academic research and scientific papers
1,2-Diazacyclopentane-3,5-diyl Diradicals: Electronic Structure and Reactivity
Yoshidomi, Shohei,Abe, Manabu
supporting information, p. 3920 - 3933 (2019/03/07)
Localized singlet diradicals are key intermediates in bond homolysis. A thorough study of the reactive species is needed to clarify the mechanisms of the homolytic bond cleavage and formation processes. In general, the singlet diradicals are quite short-lived because of the fast radical-radical coupling reactions. The short-lived characteristic has retarded the thorough study on bond homolysis. In this study, a new series of long-lived singlet diradicals, viz., 1,2-diazacyclopentane-3,5-diyl, were identified, and their electronic structures and novel reactivities were thoroughly studied using laser-flash photolysis (LFP), product analysis, and computational studies. A direct observation of the thermal equilibration (fast process) between the singlet diradicals and the corresponding ring-closing compounds was undertaken on the submicrosecond time scale. The solvent and substituent effects on the equilibration constant and rate constants for the ring-closing reaction and ring-opening reaction clarify the novel nitrogen-atom effect on the localized singlet 1,3-diyl diradicals. Two types of alkoxy-migrated compounds, 9 and 10, were isolated with high yields as the final products. Crossover, spin-trapping, and LFP experiments for the formation of alkoxy-group migration products (i.e., 9 versus 10) revealed the unique temperature effect on the product ratio of the two types of alkoxy-migration products. The temperature-insensitive intersystem crossing process (slow process, millisecond time scale) was found to be a key step in the formation of 9, which is an entropy-controlled pathway. An intramolecular migration process was identified for the formation of 10 that was accelerated by a polar solvent in an enthalpy-controlled process. This unique heteroatom effect has opened up a new series of localized singlet diradicals that are crucial intermediates in bond homolysis.
Transition-metal-free formal decarboxylative coupling of ?±-oxocarboxylates with ?±-bromoketones under neutral conditions: A simple access to 1,3-diketones
He, Zhen,Qi, Xiaotian,Li, Shiqing,Zhao, Yinsong,Gao, Ge,Lan, Yu,Wu, Yiwei,Lan, Jingbo,You, Jingsong
supporting information, p. 855 - 859 (2015/02/05)
A transition-metal-free formal decarboxylative coupling reaction between ?±-oxocarboxylates and ?±-bromoketones to synthesize 1,3-diketone derivatives is presented. In this reaction, a broad scope of substrates can be employed, and neither a metal-based reagent nor an additional base is required. DFT calculations reveal that this reaction proceeds through a coupling followed by decarboxylation mechanism and the ?±-bromoketone unprecedentedly serves as a nucleophile under neutral conditions. The rate-determining step is an unusual hydrogen-bond-assisted enolate formation by thermolysis.
Te-1-acylmethyl and Te-1-iminoalkyl telluroesters: Synthesis and thermolysis leading to 1,3-diketones and O-alkenyl and O-imino esters
Nakaiida, Shoho,Kato, Shinzi,Niyomura, Osamu,Ishida, Masaru,Ando, Fumio,Koketsu, Jugo
experimental part, p. 930 - 946 (2010/08/04)
A series of Te-1-acylmethyl carbotelluroates was prepared in good isolated yields from the reaction of potassium carbotelluroates with -haloketones in acetonitrile. Thermolysis of the telluroesters afforded vinyl esters in 20-50% yields, while treatment of the carbotellurorates with potassium t-butanolate led to 1,3-diketones in 30-75% yields with the liberation of black tellurium. The reaction of potassium carbotelluroates with -haloaceto oximes gave O-acyl oximes in 50-70% yields via Te-1-iminomethylcarbotelluroates. Copyright Taylor & Francis Group.
Synthesis and structure of new 1,3,5-triazine-pyrazole derivatives
Mikhaylichenko, Svetlana N.,Patel, Saurabh M.,Dalili, Shadi,Chesnyuk, Aleksey A.,Zaplishny, Vladimir N.
supporting information; experimental part, p. 2505 - 2508 (2009/09/05)
We have studied the reaction of methylenedicarbonyl compounds with 4,6-disubstituted 2-hydrazinyl-1,3,5-triazine in order to obtain novel coupled biheterocyclic aromatic systems with potential bioactivity. Reaction conditions were studied and optimized, a
1,3-Diketones from acid chlorides and ketones: A rapid and general one-pot synthesis of pyrazoles
Heller, Stephen T.,Natarajan, Swaminathan R.
, p. 2675 - 2678 (2007/10/03)
1,3-Diketones were synthesized directly from ketones and acid chlorides and were then converted in situ into pyrazoles by the addition of hydrazine. This method is extremely fast, general, and chemoselective, allowing for the synthesis of previously inaccessible pyrazoles and synthetically demanding pyrazole-containing fused rings.
Boron difluoride β-diketonates: II. Synthesis of boron difluoride naphthoyl- and anisoylbenzoylmethanates substituted in the benzene ring
Gukhman,Reutov
, p. 1608 - 1611 (2007/10/03)
Destructive acylation of copper(II) naphthoyl- and anisoylacetonates with substituted benzoyl chlorides yielded β-diketones containing two aromatic substituents. Their reaction with boron trifluoride etherate in the presence of tributyl borate gave the co
Synthesis and antimicrobial activity of 1-(4-chlorophenyl)-3-(4-methoxy/3,4-dimethoxyphenyl)propan-1,3-diones and their 2-analogs
Singh, Rajvir,Malik, Om Parkash
, p. 455 - 459 (2007/10/02)
The condensation of substituted acetophenones 1-5 with 4-methoxy- or 3,4-dimethoxy-benzaldehyde (6,7) in ethanolic NaOH gives the corresponding substituted 2-propen-1-ones (8-17) which on bromination yields substituted propan-1-ones (18-27).Refluxing of 1
