3399-73-3Relevant articles and documents
Pd-Catalyzed Remote Site-Selective and Stereoselective C(Alkenyl)-H Alkenylation of Unactivated Cycloalkenes
Mao, Chun-Li,Zhao, Sheng,Zang, Zhong-Lin,Xiao, Lin,Zhou, Cheng-He,He, Yun,Cai, Gui-Xin
, p. 774 - 787 (2020/01/09)
A palladium-catalyzed alkenylation involving remote δ-position C(alkenyl)-H activation of cycloalkenes reacting with electron-deficient alkenes is described. This method features excellent site selectivity and stereoselectivity to efficiently afford only E-selective highly substituted 1,3-diene derivatives with extra-ligand-free and good functional group tolerance including estrone and free N-H tryptamine under weakly alkaline conditions. Mechanistic studies suggest that picolinamide as a bidentate directing group enables the formation of unique alkenyl palladacycle intermediates.
Synthesis method of 2-(1-cyclohexenyl) ethylamine
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Paragraph 0050-0057, (2020/11/02)
The invention belongs to the technical field of organic chemistry, and particularly relates to a synthesis method of a compound 2-(1-cyclohexenyl) ethylamine (I). Cyclohexanone (II) and a Grignard reagent are subjected to a Grignard reaction in an organic solvent to be converted into 1-vinyl cyclohexanol (III), the 1-vinyl cyclohexanol (III) and a chlorination reagent are subjected to a chlorination/rearrangement one-pot reaction in an organic solvent in the presence of organic alkali to prepare (2-chloroethylene methylene) cyclohexane (IV), the (2-chloroethylene methylene) cyclohexane (IV) and urotropine are subjected to quaternization in an organic solvent to form N-cyclohexylidene ethyl urotropine hydrochloride (V), and finally, hydrolysis rearrangement is carried out in a solvent in the presence of inorganic mineral acid to obtain the 2-(1-cyclohexenyl) ethylamine (I). The compound (I) has important industrial application value as an intermediate for synthesizing the antitussive drug dextromethorphan hydrobromide. The method has the advantages of cheap and accessible raw materials, mild reaction conditions, high yield and high product purity, is simple to operate, and is convenient for industrial production.
Palladium-Catalyzed Regioselective C-H Iodination of Unactivated Alkenes
Schreib, Benedikt S.,Carreira, Erick M.
supporting information, p. 8758 - 8763 (2019/06/13)
A palladium-catalyzed C-H iodination of unactivated alkenes is reported. A picolinamide directing group enables the regioselective functionalization of a wide array of olefins to furnish iodination products as single stereoisomers. Mechanistic investigations suggest the reversible formation of a six-membered alkenyl palladacycle intermediate through a turnover-limiting C-H activation.
Regioselective intramolecular Markovnikov and anti-Markovnikov hydrofunctionalization of alkenes: Via photoredox catalysis
Li, Na,Man, Yunquan,Tang, Bo,Wang, Hongyu,Wang, Kaiye,Xiang, Yanan
supporting information, p. 11426 - 11429 (2019/09/30)
Highly regioselective Markovnikov hydrofunctionalization of alkenes was successfully realized via photoredox catalysis by introducing a urea group and fine tuning the hydrogen atom transfer catalysts. The anti-Markovnikov hydroamination of alkenes was also achieved with high yields and stereoselectivities in this work.
Method for preparing 1-cyclohexene ethylamine by selective reduction
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Paragraph 0037-0042, (2018/11/27)
The invention discloses a method for preparing 1-cyclohexene ethylamine by selective reduction. The method comprises the following steps: (1) dissolving a raw material 1-cyclohexene acetonitrile in asolvent under the protection of inert gas, then slowly dropwise adding a reducing agent vitride solution at a certain temperature, and reacting at a certain temperature after dropwise adding; quenching by dropwise adding a reaction liquid into an alkali aqueous solution, extracting with an organic solvent, drying with a drying agent, carrying out desolvation with an organic phase to obtain a 1-cyclohexene ethylamine crude product; and (2) heating the 1-cyclohexene ethylamine crude product under a certain vacuum condition for distillation purification so as to obtain a 1-cyclohexene ethylaminepure product. the invention has the following advantages: 1, the vitride solution used in the method has lower toxicity and is cheaper and more easily available, thus greatly reducing raw material andoperational costs; 2, reaction steps of the method are few, the intermediate reaction is easy to control, operation is simple, and the method is easy for large-scale production; and 3, purity and yield of the product prepared by the method are high and both can reach 90% and above.
Method for preparing 1-cyclohexenylethylamine through catalytic selective hydrogenation of modified Pd/C catalyst
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Paragraph 0022; 0025; 0028; 0029-0031; 0034; 0037; 0039, (2017/09/01)
The invention discloses a method for preparing 1-cyclohexenylethylamine through catalytic selective hydrogenation of a modified Pd/C catalyst. The method comprises the steps of (1) modifying a Pd/C catalyst, namely modifying the Pd/C catalyst through one or more of dimethyl disulfide, ethanethiol, dimethyl sulfide, thiophene, hydrogen sulfide and sulfur dioxide, adjusting the pH to be 7-11 by using an alkaline substance, filtering and washing to obtain a modified Pd/C catalyst; and (2) putting the modified Pd/C catalyst and 1-cyclohexenylacetonitrile into a reaction kettle of an ethanol solvent and reacting under the conditions that hydrogen pressure is 1-10MPa, the rate is 200-800r/min and the temperature is 50-140 DEG C to obtain the 1-cyclohexenylethylamine. According to the method for preparing the 1-cyclohexenylethylamine through catalytic selective hydrogenation of the modified Pd/C catalyst, the raw material conversion rate is greater than 80%, the selectivity is greater than 85% and the method can be used for industrial production.
Copper-Catalyzed Divergent Trifluoromethylation/Cyclization of Unactivated Alkenes
Zheng, Jing,Deng, Ziyang,Zhang, Yan,Cui, Sunliang
supporting information, p. 746 - 751 (2016/03/09)
Most of the precedent copper-catalyzed trifluoromethylation reactions of unactivated alkenes concern terminal alkenes, and these processes are terminated in elimination, or nucleophilic addition, or semipinacol rearrangement, or C-H bond functionalization steps. In this study, we develop a trifluoromethylation method for both unactivated terminal and internal alkenes to enable divergent late-stage radical cyclization and achieve high molecular complexity. These cyclizations are well consistent with Baldwin's rule. Furthermore, a kinetic isotope effect (KIE) study and control reactions were conducted, and a plausible mechanism is proposed.
2-(1-cyclohexenyl)ethylamine and preparation method thereof
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, (2016/12/22)
The invention discloses 2-(1-cyclohexenyl)ethylamine and a preparation method thereof. The method comprises the following steps that 1, 1-cyclohexene-1-acetonitrile and hydrogen bromide react to generate 1-bromocyclohexane acetonitrile; 2, under the action of a catalyst, 1-bromocyclohexane acetonitrile prepared in the first step and hydrogen are subjected to addition, and 1-bromocyclohexane ethylamine is generated; 3, 1-bromocyclohexane ethylamine prepared in the second step reacts with NaOH, and a finial needed product 2-(1-cyclohexenyl)ethylamine is obtained. According to the 2-(1-cyclohexenyl)ethylamine and the preparation method thereof, the synthetic process can be achieved only through three-step reactions; compared with the prior art, the synthetic process has the advantages of being simple in synthetic route and low in cost. In addition, the conversion ratio of the final product is increased, and the 2-(1-cyclohexenyl)ethylamine and the preparation method thereof are particularly suitable for industrial production.
Structure-selectivity relationship in the chemoselective hydrogenation of unsaturated nitriles
Kukula, Pavel,Koprivova, Klara
, p. 161 - 171 (2007/10/03)
Several unsaturated nitriles of various structures (cinnamonitrile, cyclohex-1-enyl-acetonitrile, acrylonitrile, 3,3-dimethyl-acrylonitrile, geranylnitrile, and 2- and 3-pentenenitrile) with different substituents at the double bond were hydrogenated over
Chemoselective hydrogenation of α,β-unsaturated nitriles
Kukula, Pavel,Studer, Martin,Blaser, Hans-Ulrich
, p. 1487 - 1493 (2007/10/03)
The chemoselective hydrogenation of cinnamonitrile to 3-phenylallylamine proceeds with up to 80% selectivity at conversions of > 90% with Raney cobalt and up to 60% selectivity with Raney nickel catalysts. Best results were obtained with a doped Raney cobalt catalyst (RaCo/Cr/Ni/Fe 2724) in ammonia saturated methanol at 100°C and 80 bar. Major problems are the formation of hydrocinnamonitrile and of secondary amines, and overreduction to 3-phenylpropylamine. Important parameters are the catalyst type and composition, the solvent type and the presence and concentration of ammonia. The catalytic system tolerates functional groups like OH, OMe, Cl, C=O, but not aromatic nitro groups. Preliminary experiments indicate that other unsaturated nitriles with di- or trisubstituted C=C bonds are also suitable substrates.
