13360-63-9Relevant articles and documents
Alkyl coupling in tertiary amines as analog of Guerbet condensation reaction
Zhou, Yage,Wu, Dan,Hernández, Willinton Yesid,Ma, Changru,Su, Huangyang,Ordomsky, Vitaly
, p. 9845 - 9849 (2019/04/01)
We report here that C-C coupling in tertiary amines for the synthesis of long chain and hindered amines might be efficiently performed over Pt and Pd catalysts. The mechanism study confirms similarity with the Guerbet reaction through dehydrogenation of the alkyl group and subsequent attack of the α-carbon atom by an alkyl group of another molecule. Finally, secondary amines and tertiary amines with longer alkyl chains are formed.
Selective one-pot synthesis of asymmetric secondary amines via N-alkylation of nitriles with alcohols
Segobia,Trasarti,Apesteguía
, p. 178 - 185 (2019/11/13)
The synthesis of asymmetric secondary amines (ASA) is commonly achieved by N-alkylation of primary amines with alcohols. Here, we investigated the ASA synthesis via the direct amination of alcohols with nitriles, which avoids the synthesis, separation and purification of the primary amines in a first step. Specifically, the ASA synthesis via N-alkylation of butyronitrile (BN) with primary (n-propanol, iso-butanol and n-octanol) and secondary (2‐propanol, 2‐butanol and 2‐octanol) alcohols was studied on SiO2-supported Co, Ni and Ru catalysts. Competitive BN hydrogenation‐condensation reactions formed dibutylamine (the symmetric secondary amine) and tertiary amines as main secondary products. On Co/SiO2, the ASA selectivities for BN/primary alcohol reactions were between 49 and 58% at complete BN conversion, forming dibutylamine and tertiary amines as byproducts. For BN/secondary alcohol reactions, Co/SiO2 formed selectively (ASA + dibutylamine) mixtures containing 78–85% of ASA, thereby showing that the alcohol amination with nitriles is an attractive alternative route for the synthesis of valuable asymmetric secondary amines.
N-ethyl-n-butylamine production method
-
Paragraph 0047; 0050; 0053, (2017/01/05)
The invention relates to a production method of N-ethyl-n-butylamine. According to the production method, n-butanol and monoethylamine are taken as raw materials; a supported non-noble metal catalyst is used under hydrogen conditions; and amination synthe
Catalytic hydrogenation of amides to amines under mild conditions
Stein, Mario,Breit, Bernhard
supporting information, p. 2231 - 2234 (2013/03/28)
Under (not so much) pressure: A general method for the hydrogenation of tertiary and secondary amides to amines with excellent selectivity using a bimetallic Pd-Re catalyst has been developed. The reaction proceeds under low pressure and comparatively low temperature. This method provides organic chemists with a simple and reliable tool for the synthesis of amines. Copyright
The synthesis of N-ethyl-n-butylamine by amines disproportionation
Xu, Lu-Feng,Huang, Jia-Min,Qian, Chao,Chen, Xin-Zhi,Feng, Lie,Chen, Yun-Bin,He, Chao-Hong
, p. 2697 - 2704 (2013/07/26)
A synthesis of N-ethyl-n-butylamine with simple separation method in a fixed-bed reactor using CuO-NiO-PtO/γ-Al2O3 as the catalyst was proposed and investigated. The present catalytic system gave high activity and good selectivity, and the reaction conditions such as temperature and liquid hourly space velocity were optimized. Since no water was generated, the protocol proved to be easy to separate, and N-ethyl-n-butylamine was collected at 110 °C by distillation. The yield and the purity were 60.7 and 99.5 %, respectively.
Hydrogenation of nitriles to primary amines on metal-supported catalysts: Highly selective conversion of butyronitrile to n-butylamine
Segobia,Trasarti,Apesteguía
, p. 69 - 75 (2013/02/23)
The selective liquid-phase hydrogenation of butyronitrile to n-butylamine was studied in a batch reactor on Co(9.8%)/SiO2, Ni(10.5%)/SiO 2, Cu(9.2%)/SiO2, Pt(0.27%)/SiO2, Pd(0.33%)/SiO2, and Ru(1.8%)/SiO2 catalysts. At 373 K and 13 bar (H2), the initial butyronitrile conversion rate (rBN0, mmol/h g) followed the order Ni > Co > Pt > Ru > Cu > Pd. Cu/SiO 2 and Pd/SiO2 did not form n-butylamine and rapidly deactivated during the progress of the reaction. Pt/SiO2 produced mainly dibutylamine and only minor amounts of n-butylamine and tributylamine. In contrast, Ru/SiO2 formed preponderantly n-butylamine but also produced significant amounts of dibutylamine and butylidene-butylamine, an intermediate in the formation pathway of the secondary amine. The highest yield to n-butylamine was obtained on Ni/SiO2 (84%). Co/SiO2 was initially highly selective to n-butylamine but with the progress of the reaction the butylamine concentration in the reaction mixture diminished because it partially reacted with the solvent (ethanol) to form N-ethylbutylamine. In an attempt to reduce the formation of byproducts, Ni/SiO2 and Co/SiO2 catalysts were tested at lower temperatures and higher H 2 pressures. Butyronitrile was selectively converted to n-butylamine on Co/SiO2 at 343 K and 25 bar, yielding 97% of n-butylamine, similarly to the highest yields reported on Raney Co catalysts.
A novel method for N-alkylation of aliphatic amines with ethers over ?3-Al2O3
Chen, Hangeng,Zhang, Tao,Qian, Chao,Chen, Xinzhi
, p. 537 - 540 (2015/03/05)
A novel and simple method for the N-alkylation of amines with different ethers as alkylating reagents has been developed, using cheap ?3-Al2O3 as the catalyst at atmospheric pressure in the temperature range of 260-320?°C. For example, the reaction of equ
Discovery and mechanistic study of AlIII-catalyzed transamidation of tertiary amides
Hoerter, Justin M.,Otte, Karin M.,Gellman, Samuel H.,Cui, Qiang,Stahl, Shannon S.
, p. 647 - 654 (2008/10/09)
Cleavage of the C-N bond of carboxamides generally requires harsh conditions. This study reveals that tris(amido)AlIII catalysts, such as Al2(NMe2)6, promote facile equilibrium-controlled transamidation of tertiary carboxamides with secondary amines. The mechanism of these reactions was investigated by kinetic, spectroscopic, and density functional theory (DFT) computational methods. The catalyst resting state consists of an equilibrium mixture of a tris(amido)AlIII dimer and a monomeric tris(amido)Al III-carboxamide adduct, and the turnover-limiting step involves intramolecular nucleophilic attack of an amido ligand on the coordinated carboxamide or subsequent rearrangement (intramolecular ligand substitution) of the tetrahedral intermediate. Fundamental mechanistic differences between these tertiary transamidation reactions and previously characterized transamidations involving secondary amides and primary amines suggest that tertiary amide/secondary amine systems are particularly promising for future development of metal-catalyzed amide metathesis reactions that proceed via transamidation.
2,3,4,5-TETRAHYDRO-1H-1,5-BENZODIAZEPINE DERIVATIVE AND MEDICINAL COMPOSITION
-
, (2008/06/13)
The present invention has its object to provide a 2,3,4,5-tetrahydro-1H-1,5-benzodiazepine derivative represented with the Formula (1) , or the pharmaceutically acceptable salt, which is effective as a therapeutic and prophylactic agent for diabetes, diabetic nephropathy, or glomerulosclerosis.
Perfluoro-tagged benzyloxycarbonyl protecting group and its application in fluorous biphasic systems
Schwinn, Dominik,Bannwarth, Willi
, p. 255 - 264 (2007/10/03)
The synthesis of a new perfluoro-tagged benzyloxycarbonyl protecting group is reported, as well as its application in the parallel protection of amines. Isolation of the protected amines was performed by simple liquid-liquid extraction between perfluorinated and organic solvents. Deprotection was achieved by standard hydrogenolysis. The novel protecting group was also applied to cyclization protocols leading to quinazoline-2,4-diones. These products were isolated by simple extraction procedures.
