64352-98-3Relevant academic research and scientific papers
Triazine-Based Cationic Leaving Group: Synergistic Driving Forces for Rapid Formation of Carbocation Species
Fujita, Hikaru,Kakuyama, Satoshi,Fukuyoshi, Shuichi,Hayakawa, Naoko,Oda, Akifumi,Kunishima, Munetaka
, p. 4568 - 4580 (2018/04/26)
A new triazine-based cationic leaving group has been developed for the acid-catalyzed alkylation of O- and C-nucleophiles. There are two synergistic driving forces, namely, stable C=O bond formation and charge-charge repulsive effects, involved in the rapid generation of the carbocation species in the presence of trifluoromethanesulfonic acid (～200 mol %). Considerable rate acceleration of benzylation, allylation, and p-nitrobenzylation was observed as compared to the reactions with less than 100 mol % of the acid catalyst. The triazine-based leaving group showed superior p-nitrobenzylation yield and stability in comparison to common leaving groups, trichloroacetimidate and bromide. A plausible reaction mechanism (the cationic leaving group pathway) was proposed on the basis of mechanistic and kinetic studies, NMR experiments, and calculations.
Development of triazine-based benzylating reagents possessing T-butyl group on the triazine core: Thermally controllable reagents for the initiation of reaction
Karuo, Yukiko,Yamada, Kohei,Kunishima, Munetaka
, p. 303 - 308 (2018/03/09)
Benzylating reagents, 4-(4,6-di-t-butyl-1,3,5-triazin-2-yl)-4-benzylmorpholinium triflate, and related derivatives have been developed. The reagents release benzyl triflate as a benzyl cation equivalent upon heating the solution to 40°C under neutral conditions. The O-benzylation of alcohols using a stoichiometric amount of these reagents afforded corresponding benzyl ethers in good to high yields. This was due to the presence of a bulky t-butyl group on the triazine ring of these reagents that prevents the consumption of benzyl triflate via a side reaction with a morpholinotriazine derivative.
Specific reactivity of 2,4,6-tri-tert-butylanilide anions and its application to benzylation reagent
Yamada, Tomoyuki,Tsukagoshi, Shiori,Kitagawa, Osamu
, p. 317 - 320 (2017/01/03)
The reaction of methyl iodide with an anilide anion prepared from 2,4,6-tri-tert-butylanilide and NaH in CH3CN gave N-methyl anilide (N-alkylation product) as a major product, while in the reaction of benzyl bromide with the anilide anion in DMF, O-benzyl imidate (O-alkylation product) was obtained with almost complete selectivity. The treatment of O-benzyl imidate with alcohols and carboxylic acids in the presence of trifluoromethane sulfonic acid gave benzyl ethers and benzyl esters, respectively.
N,N′-Dimethylated Benzyloxytriazinedione: A Stable Solid Reagent for Acid-Catalyzed O-Benzylation
Fujita, Hikaru,Kakuyama, Satoshi,Kunishima, Munetaka
, p. 833 - 839 (2017/02/15)
N,N′-Dimethylated 6-(benzyloxy)-1,3,5-triazine-2,4(1H,3H)-dione (DMBOT) has been developed as a triazinedione-based, stable solid reagent for acid-catalyzed O-benzylation. The conceptual basis of the design was to fix the core triazinedione skeleton, and
TRIAZINE DIONE COMPOUND
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Paragraph 0125-0127, (2017/07/11)
PROBLEM TO BE SOLVED: To provide a novel triazine dione compound useful as an alkylating agent for a nucleophilic compound. SOLUTION: This invention relates to a compound represented by formula (I) [where each symbol is as defined in the specification] and an alkylating agent comprising the compound, and a method for alkylating a nucleophilic compound using the alkylating agent. SELECTED DRAWING: None COPYRIGHT: (C)2017,JPOandINPIT
Gold(I)-catalyzed synthesis of unsymmetrical ethers using alcohols as alkylating reagents
Liu, Yongxiang,Wang, Xiaoyu,Wang, Yanshi,Du, Chuan,Shi, Hui,Jin, Shengfei,Jiang, Chongguo,Xiao, Jianyong,Cheng, Maosheng
, p. 1029 - 1036 (2015/03/30)
A microwave-irradiated alcohol-protecting strategy based on gold catalysis utilizing benzyl alcohol, tert-butyl alcohol and triphenylmethanol as alkylating reagents has been developed. This protecting strategy has wide functional group tolerance with satisfactory yields for the majority of the selected alcohols. The mechanism of this transformation was probed with oxygen-18 isotope labelled alcohols assisted by GC-MS techniques and chemical kinetic experiments. This strategy provides an efficient, straightforward and alternative approach to the preparation of benzyl, tert-butyl and trityl ethers in organic synthesis.
Synthesis of some acyclic quaternary ammonium compounds. Alkylation of secondary and tertiary amines in a two-phase system
Kharlamov,Artyushin,Bondarenko
, p. 2445 - 2454 (2015/08/03)
A series of acyclic symmetrical and asymmetrical quaternary ammonium chlorides of the general formula R1R2R3N+AR4Cl- (R1 = Me, Bu; R2 = n-C12H25, PhCH2, C n H2n+1(OCH2CH2) m, n = 9 and 12, m = 1 and 2; R3 = n-C12H25, PhCH2, HOCH2CH2,-OOCCH2; R4 = n-C12H25, PhCH2; A = (CH2CH2O)1,2, CH2C(O)O) was synthesized by the alkylation of tertiary amines in a two-phase system containing water. A convenient method for the synthesis of the initial symmetrical and asymmetrical tertiary amines of the general formula MeNR1R2 (R1 = Me, Bu; R2 = n-C12H25, PhCH2, CnH2n+1(OCH2CH2) m, n = 9 and 12, m = 1 and 2) in an organic phase-aqueous phase heterogeneous system, which allows the use of aqueous solutions of alkali and amines, was developed. The improved method for the preparation of intermediate ethylene glycol and diethylene glycol monoethers is monoalkylation of glycols in dioxane using solid KOH in a two-phase system.
Development of a new benzylating reagent spontaneously releasing benzyl cation equivalents at room temperature
Yamada, Kohei,Tsukada, Yuichi,Karuo, Yukiko,Kitamura, Masanori,Kunishima, Munetaka
supporting information, p. 12274 - 12278 (2015/03/31)
A new O-benzylating reagent, that is, 4-(4,6-diphenoxy-1,3,5-triazin-2-yl)-4-benzylmorpholinium trifluoromethanesulfonate (DPT-BM), has been developed. Benzyl cation equivalents are generated from DPT-BM by dissolving the compound in a solvent at room tem
A novel acid-catalyzed O-benzylating reagent with the smallest unit of imidate structure
Yamada, Kohei,Fujita, Hikaru,Kunishima, Munetaka
, p. 5026 - 5029,4 (2012/12/12)
Formal trimerization of the smallest unit of benzyl imidate leads to 2,4,6-tris(benzyloxy)-1,3,5-triazine (TriBOT), which can be used as an acid-catalyzed O-benzylating reagent. The reaction of various functionalized alcohols with 0.4 equiv of TriBOT in the presence of trifluoromethanesulfonic acid afforded the benzyl ethers in good yields. TriBOT is an inexpensive stable crystalline solid with high atom economy.
A novel acid-catalyzed O-benzylating reagent with the smallest unit of imidate structure
Yamada, Kohei,Fujita, Hikaru,Kunishima, Munetaka
, p. 5026 - 5029 (2013/01/15)
Formal trimerization of the smallest unit of benzyl imidate leads to 2,4,6-tris(benzyloxy)-1,3,5-triazine (TriBOT), which can be used as an acid-catalyzed O-benzylating reagent. The reaction of various functionalized alcohols with 0.4 equiv of TriBOT in the presence of trifluoromethanesulfonic acid afforded the benzyl ethers in good yields. TriBOT is an inexpensive stable crystalline solid with high atom economy.
