201157-19-9Relevant academic research and scientific papers
Lewis acid-catalyzed direct amination of benzhydryl alcohols
Terrasson, Vincent,Marque, Sylvain,Georgy, Marie,Campagne, Jean-Marc,Prim, Damien
, p. 2063 - 2067 (2006)
The Lewis acid-mediated direct amination of benzylic alcohols is described, providing various benzylic amine derivatives in good yields under mild and environmentally benign conditions. Among the different Lewis acids tested, gold(III) proved to be the catalyst of choice for both chemical (yield, conversion) and practical reasons (a filtration over a silica pad is generally sufficient to obtain the corresponding benzylic amine in analytically pure form).
Gold(III)/Sodium Diphenylphosphinobenzene-3-sulfonate (TPPMS) Catalyzed Dehydrative N-Benzylation of Electron-Deficient Anilines in Water
Azumaya, Isao,Hikawa, Hidemasa,Kikkawa, Shoko,Matsumoto, Mika,Tawara, Sayoko
supporting information, p. 2729 - 2736 (2019/06/19)
A strategy for the dehydrative N-benzylation of electron-deficient anilines in water has been developed. The gold(III)/sodium diphenylphosphinobenzene-3-sulfonate (TPPMS) catalyst is highly effective as a Lewis acid for the activation of alcohols and tolerates aerobic conditions. A Hammett study in the reaction of para -substituted benzhydryl alcohols shows negative σ values, indicating a build-up of cationic charge during the rate-determining sp 3 C-O bond-cleavage step. The inverse kinetic solvent isotope effect (KSIE = 0.6) is consistent with a specific acid catalysis mechanism. This simple protocol can be performed under mild conditions in an atom-economic process without the need for base or other additives, furnishing the electron-deficient N -benzylic anilines in moderate to excellent yields along with water as a sole coproduct.
Hofmann N-alkylation of aniline derivatives with alcohols using ferric perchlorate immobilized on SiO2 as a catalyst through Box–Behnken experimental design
Ghanimati, Mahdi,Abdoli Senejani, Masumeh,Isfahani, Tahereh Momeni,Bodaghifard, Mohammad Ali
, (2018/11/06)
An efficient method for the N-alkylation of poorly nucleophilic amines using ferric perchlorate immobilized on SiO2 as a catalyst is described. Fe(ClO4)3 was prepared from mixing iron(III) hydroxide and perchloric acid and adsorbed on silica gel. The catalyst was characterized using various techniques. The supported ferric perchlorate (Fe(ClO4)3/SiO2) revealed high efficiency and selectivity for N-alkylation of aromatic amines with alcohols to provide alkylated amines. Various secondary amines were synthesized from primary amines and alcohols in good to excellent yields, with water as the only by-product. The optimization of the reaction conditions was investigated using the response surface method, and involving the Box–Behnken design matrix. The conditions for optimal reaction yield and time were: amount of catalyst?=?0.34?mmol, temperature?=?60°C and molar ratio of amine to alcohol?=?1.2. The catalyst was recovered and reused for five cycles without a considerable decrease in catalytic activity. The stability of the recycled catalyst was investigated. The proposed method has numerous advantages including procedure simplicity, short reaction times, low cost, good to excellent yields, reusability of the catalyst and mild and environmentally benign conditions.
A by a process for preparing amine derivatives of green method (by machine translation)
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Paragraph 0116 - 0119, (2017/08/14)
The invention discloses a by a process for preparing amine derivatives of green method, dumping with amine compound in a non-transition metal catalyst under solvent-free conditions and through the controllable high selection dehydration alkylation reaction different amine derivatives, a non-transition metal catalyst is a halogenated hydrocarbon, halogenated hydrocarbon in an amount of 1 - 50 μM %, under the catalysis of the mellow and amine in halogenated hydrocarbon can be directly performed by the amine derivative dehydration reaction, the reaction temperature is 100 - 180 °C, the reaction time is 12 - 48 hours, the by-product is water, the reaction needs to be carried out under the protection of inert gas, simple conditions, easy to operate, the by-product is water, the reaction selectivity is controllable, the target high selectivity. Requirements for reaction condition of relatively low, primary and secondary alcohol can be used for the alkylation reagent, is suitable for the dehydration of the primary and secondary amines single alkylation reaction, is also suitable for the dehydration of the double alkylation reaction of a primary amine, with wider scope, should also has certain research and industrial application prospect. (by machine translation)
Highly Stable Mesoporous Zirconium Porphyrinic Frameworks with Distinct Flexibility
Xu, Lei,Luo, Yan-Ping,Sun, Lin,Xu, Yan,Cai, Zhong-Sheng,Fang, Min,Yuan, Rong-Xin,Du, Hong-Bin
supporting information, p. 6268 - 6276 (2016/05/02)
The construction of highly stable metal-porphyrinic frameworks (MPFs) is appealing as these materials offer great opportunities for applications in artificial light-harvesting systems, gas storage, heterogeneous catalysis, etc. Herein, we report the synthesis of a novel mesoporous metal-porphyrinic framework (denoted as NUPF-1) and its catalytic properties. NUPF-1 is constructed from a new porphyrin linker and a Zr6O8 structural building unit, possessing an unprecedented doubly interpenetrating scu net. The structure exhibits not only remarkable chemical and thermal stabilities, but also a distinct structural flexibility, which is seldom seen in metal-organic framework (MOF) materials. By the merit of high chemical stability, NUPF-1 could be easily post-metallized with [Ru3(CO)12], and the resulting {NUPF-1-RuCO} is catalytically active as a heterogeneous catalyst for intermolecular C(sp3)-H amination. Excellent yields and good recyclability for amination of small substrates with various organic azides have been achieved.
Functional ion liquid method for catalytic synthesis of amine compounds
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Paragraph 0156; 0157; 0158, (2016/10/07)
The invention discloses a method for synthesizing an amine compound catalyzed by functionalized ionic liquid. According to the method, functionalized ionic liquid is used as a catalyst to catalyze N-alkylation of amine and alcohol to synthesize corresponding compound derivatives. Acid functionalized ionic liquid is used as the catalyst to synthesize a series of compounds of amine. The method has the following advantages: a catalytic system is a metal-free system; the usage amount of the catalyst is small, and the catalyst has high catalytic activity, good stability and low corrosivity; operation is simple, and reaction is mild; post-treatment is easy, and the catalyst can be cyclically used.
A Radical Pathway for Direct Substitution of Benzyl Alcohols with Water-Soluble Copper Catalyst in Water
Hikawa, Hidemasa,Mori, Yuki,Kikkawa, Shoko,Azumaya, Isao
, p. 765 - 773 (2016/03/09)
We have developed a novel strategy for the direct substitution of benzyl alcohols with anthranilic acids using water-soluble copper catalysts through a radical pathway in water, which offers efficient and environmentally friendly N-, S-, and C-benzylations under neutral conditions. Radical scavengers strongly inhibited the benzylation. Radical clock experiments using α-cyclopropylbenzyl alcohol were conducted to observe the rapid isomerization of the cyclopropylmethyl radical to the allylmethyl radical. Hammett plots could be fitted to a two-parameter Hammett relationship containing both radical and polar contributions [log (kX/kH)=-1.24 σ.-0.38 σ, R2=0.99]. The relative parameter ρ./ρ of 3.3 suggested that these reactions involved a strong radical character with minor polar influence at the transition state.
Selective catalytic Hofmann: N -alkylation of poor nucleophilic amines and amides with catalytic amounts of alkyl halides
Xu, Qing,Xie, Huamei,Zhang, Er-Lei,Ma, Xiantao,Chen, Jianhui,Yu, Xiao-Chun,Li, Huan
supporting information, p. 3940 - 3944 (2016/07/21)
Using only catalytic amounts of alkyl halides in the reactions of poor nucleophilic amines/amides and alcohols led to a selective Hofmann N-alkylation reaction catalytic in alkyl halides, providing a practical and efficient method for the practical synthesis of mono- or di-alkylated amines/amides in high selectivities. This new method avoids the use of large amounts of bases, alkyl halides, and solvents, and generates water as the only byproduct. Preliminary mechanistic studies showed that alkyl halides are key intermediates/catalysts regeneratable in the reaction cycle.
Fe2(SO4)3·xH2O on silica: An efficient and low-cost catalyst for the direct nucleophilic substitution of alcohols in solvent-free conditions
Li, Lingjun,Zhu, Anlian,Zhang, Yuqin,Fan, Xincui,Zhang, Guisheng
, p. 4286 - 4291 (2014/01/17)
Fe2(SO4)3·xH2O on silica has been found to be a novel efficient catalyst for the direct nucleophilic substitution of alcohols in solvent-free conditions. In this reaction system, the alcohols can react with various nucleophilic reagents for the convenient construction of C-C bonds and C-N bonds with the benefits of high conversion, no requirement to use excessive amounts of the nucleophile, only a catalytic amount of iron catalyst required, solvent-free and benign reaction conditions, and the feasible reusability of the catalyst.
Acidic-functionalized ionic liquid as an efficient, green, and metal-free catalyst for benzylation of sulfur, nitrogen, and carbon nucleophiles to benzylic alcohols
Chu, Xue-Qiang,Jiang, Ran,Fang, Yi,Gu, Zheng-Yang,Meng, Hua,Wang, Shun-Yi,Ji, Shun-Jun
supporting information, p. 1166 - 1174 (2013/02/25)
A series of HSO4- functionalized ILs was synthesized and used as efficient, green, and metal-free catalysts for benzylation. Notably, the catalytic system has wide substrate scopes and the ionic liquid catalysts were applied to investigate three different types of nucleophiles to give the desired benzylation products with moderate to excellent yields.
