6674-22-2Relevant articles and documents
Photoinduced redox initiation for fast polymerization of acrylaytes based on latent superbase and peroxides
He, Minghui,Huang, Xun,Huang, Yugang,Zeng, Zhaohua,Yang, Jianwen
, p. 3172 - 3177 (2012)
The article presents a highly effective strategy for photopolymerization of acrylates via photolatent redox-accelerated reaction based on the synergistic photoinitiating systems containing photolatent superbase and readily available peroxides. Polymerization of acrylates could be instantly initiated with the effective interaction between the photogenerated amine and peroxides. Due to the persistent interaction of produced longeval amine with peroxides, remarkable post conversion after irradiation, which is significant for radiation crosslinking of photo-screened materials, was thus initially achieved in photoinitiated free radical polymerization. To explore the synergistic interactions of the photoinitiating systems, the effect of peroxide structures and QA-DBU:BPO ratios had been examined by RTIR, showing that all peroxides are applicable as the final conversion rate of acrylates is concerned. Further, BPO and CHP significantly accelerated the photopolymerization rate in air atmosphere. The synergistic efficiency of QA-DBU and BPO as a photopolymerization initiatiation system was close to that of the conventional D-1173 photoinitiator.
Basicities and Nucleophilicities of Pyrrolidines and Imidazolidinones Used as Organocatalysts
An, Feng,Maji, Biplab,Min, Elizabeth,Ofial, Armin R.,Mayr, Herbert
supporting information, p. 1526 - 1547 (2020/02/04)
The Br?nsted basicities pKaH (i.e., pKa of the conjugate acids) of 32 pyrrolidines and imidazolidinones, commonly used in organocatalytic reactions, have been determined photometrically in acetonitrile solution using CH acids as indicators. Most investigated pyrrolidines have basicities in the range 16 aH aH aH 12.6) and the 2-imidazoliummethyl-substituted pyrrolidine A21 (pKaH 11.1) are outside the typical range for pyrrolidines with basicities comparable to those of imidazolidinones. Kinetics of the reactions of these 32 organocatalysts with benzhydrylium ions (Ar2CH+) and structurally related quinone methides, common reference electrophiles for quantifying nucleophilic reactivities, have been measured photometrically. Most reactions followed second-order kinetics, first order in amine and first order in electrophile. More complex kinetics were observed for the reactions of imidazolidinones and several pyrrolidines carrying bulky 2-substituents, due to reversibility of the initial attack of the amines at the electrophiles followed by rate-determining deprotonation of the intermediate ammonium ions. In the presence of 2,4,6-collidine or 2,6-di-tert-butyl-4-methyl-pyridine, the deprotonation of the initial adducts became faster, which allowed the rate of the attack of the amines at the electrophiles to be determined. The resulting second-order rate constants k2 followed the correlation log?k2(20 °C) = sN(N + E), where electrophiles are characterized by one parameter (E) and nucleophiles are characterized by the two solvent-dependent parameters N and sN. In this way, the organocatalysts A1-A32 were integrated in our comprehensive nucleophilicity scale, which compares n-, -, and σ-nucleophiles. The nucleophilic reactivities of the title compounds correlate only poorly with their Br?nsted basicities.
A 1, 8 - diazabicyclo synthetic method (by machine translation)
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Paragraph 0014-0017, (2019/06/27)
The present invention provides a 1, 8 - diazabicyclo synthetic method, the technical scheme of the DBU synthetic route to an innovative design. Specific perspective, the invention first of all the use of ε-caprolactam, acrylonitrile and hydroquinone reaction generating N - (β - cyanoethyl) - ε-caprolactam, on this basis, will it and to toluene sulfonic acid in catalytic reaction under the condition, and then carry on ice bath, and then under the protection of nitrogen with benzyl chloride reaction, the resulting product to EDTA as the catalyst with high sodium borate reaction, the product of the reaction 3 - phenylpropanoic acid mixed with 4 - nitro benzyl chloride reaction to obtain the product. For the reaction product, filtered and the filtrate is extracted with ethyl acetate, the combined solid-liquid separation after solid phase, then the solid phase for reducing the drying to obtain the final product. The invention adopts the brand new synthetic route, its mild reaction conditions, material cost is relatively low, promotion prospect. (by machine translation)
MANUFACTURING METHOD OF DIAZABICYCLO COMPOUND
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Paragraph 0018; 0042; 0044; 0048, (2018/06/08)
PROBLEM TO BE SOLVED: To provide a manufacturing method for providing a diazabicyclo compound from hydrochloric acid having a diazabicyclo group, which is suitable for industrial production. SOLUTION: There is provided a method for manufacturing a diazabicyclo compound by neutralization with using 20 wt.% to 50 wt.% of an alkali metal hydroxide solution or 10 wt.% to 50 wt.% of an alcohol solution of alkali metal alkoxide of 2.0 times molar equivalent to 3.5 times molar equivalent to hydrochloric acid having a diazabicyclo group. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPO&INPIT