110-70-3Relevant articles and documents
Identifying the roles of amino acids, alcohols and 1,2-diamines as mediators in coupling of haloarenes to arenes
Zhou, Shengze,Doni, Eswararao,Anderson, Greg M.,Kane, Ryan G.,Macdougall, Scott W.,Ironmonger, Victoria M.,Tuttle, Tell,Murphy, John A.
, p. 17818 - 17826 (2014)
Coupling of haloarenes to arenes has been facilitated by a diverse range of organic additives in the presence of KOtBu or NaOtBu since the first report in 2008. Very recently, we showed that the reactivity of some of these additives (e.g., compounds 6 and 7) could be explained by the formation of organic electron donors in situ, but the role of other additives was not addressed. The simplest of these, alcohols, including 1,2-diols, 1,2-diamines, and amino acids are the most intriguing, and we now report experiments that support their roles as precursors of organic electron donors, underlining the importance of this mode of initiation in these coupling reactions.
Ureas and amides as dipolar aprotic solvents in highly basic media. The dependence of kinetic basicity on solvent composition
Kankaanperae, Alpo,Scharlin, Pirketta,Kuusisto, Ilona,Kallio, Riitta,Bernoulli, Emma
, p. 169 - 174 (1999)
The basicity of dipolar aprotic solvent water HO systems with amides and ureas as the organic component has been studied kinetically because previous information is not available. excluding some H values measured for aqueous dimethylformamide (DMF) and tetramethylurea (TMU). It was found that the increase in basicity with the mole fraction of organic component is at least of the same magnitude as in aqueous dimethyl sulfoxide (DMSO). For instance, in the detritiation of chloroform-t the slopes of the plots log(k2/mol 1 dm3 s 1) vs. x(urea) varied between 11.4 14.6 (as compared to 11.0 in aqueous DMSO) when TMU and cyclic ureas. 1.3-dimethylimidazolidin-2-one (DMI) and 1.3-dimethyl-3.4.5.6-tetrahydropyrimidin-2(1H)-one (DMPU). were used as the organic component in solvent mixture. In aqueous TMU acidity functions H were extrapolated from kinetic results using linear free energy correlations. Agreement with literature values was evident. This method was also used to extrapolate the H values in aqueous DMPU. On the basis of present work aqueous ureas can be recommended as solvents in highly basic media. The utility of amides. dimethylformamide and dimethylacetamide. is limited by their instability in basic water solutions.
New method for preparing N,N'-dimethylethylenediamine and N,N'-dimethyl-1,3-propanediamine
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Paragraph 0009-0014, (2019/10/01)
The present invention relates to a new method for preparing N,N'-dimethylethylenediamine and N,N'-dimethyl-1,3-propanediamine, wherein 1,3-dimethyl-2-imidazolidinone or 1,3-dimethyl-tetrahydro-2-pyrimidone is used as a raw material, a suitable alkali is added, and a heating ring-opening reaction is perform to prepare N,N'-dimethylethylenediamine and N,N'-dimethyl-1,3-propanediamine. In the prior art, the conventional method performs alkylation by using the amine as the raw material to generate more by-products. According to the present invention, the method completely avoids the problem in theprior art, has characteristics of simple operation, high yield, less three-waste and high product purity, and is suitable for industrial production.
Low-Temperature Reductive Aminolysis of Carbohydrates to Diamines and Aminoalcohols by Heterogeneous Catalysis
Pelckmans, Michiel,Vermandel, Walter,Van Waes, Frederik,Moonen, Kristof,Sels, Bert F.
, p. 14540 - 14544 (2017/10/23)
Short amines, such as ethanolamines and ethylenediamines, are important compounds in today's bulk and fine chemicals industry. Unfortunately, current industrial manufacture of these chemicals relies on fossil resources and requires rigorous safety measures when handling explosive or toxic intermediates. Inspired by the elegant working mechanism of aldolase enzymes, a novel heterogeneously catalyzed process—reductive aminolysis—was developed for the efficient production of short amines from carbohydrates at low temperature. High-value bio-based amines containing a bio-derived C2 carbon backbone were synthesized in one step with yields up to 87 C%, in the absence of a solvent and at a temperature below 405 K. A wide variety of available primary and secondary alkyl- and alkanolamines can be reacted with the carbohydrate to form the corresponding C2-diamine. The presented reductive aminolysis is therefore a promising strategy for sustainable synthesis of short, acyclic, bio-based amines.
Merging constitutional and motional covalent dynamics in reversible imine formation and exchange processes
Kovaricek, Petr,Lehn, Jean-Marie
supporting information; experimental part, p. 9446 - 9455 (2012/07/14)
The formation and exchange processes of imines of salicylaldehyde, pyridine-2-carboxaldehyde, and benzaldehyde have been studied, showing that the former has features of particular interest for dynamic covalent chemistry, displaying high efficiency and fast rates. The monoimines formed with aliphatic α,ω-diamines display an internal exchange process of self-transimination type, inducing a local motion of either "stepping-in- place" or "single-step" type by bond interchange, whose rate decreases rapidly with the distance of the terminal amino groups. Control of the speed of the process over a wide range may be achieved by substituents, solvent composition, and temperature. These monoimines also undergo intermolecular exchange, thus merging motional and constitutional covalent behavior within the same molecule. With polyamines, the monoimines formed execute internal motions that have been characterized by extensive one-dimensional, two-dimensional, and EXSY proton NMR studies. In particular, with linear polyamines, nondirectional displacement occurs by shifting of the aldehyde residue along the polyamine chain serving as molecular track. Imines thus behave as simple prototypes of systems displaying relative motions of molecular moieties, a subject of high current interest in the investigation of synthetic and biological molecular motors. The motional processes described are of dynamic covalent nature and take place without change in molecular constitution. They thus represent a category of dynamic covalent motions, resulting from reversible covalent bond formation and dissociation. They extend dynamic covalent chemistry into the area of molecular motions. A major further step will be to achieve control of directionality. The results reported here for imines open wide perspectives, together with other chemical groups, for the implementation of such features in multifunctional molecules toward the design of molecular devices presenting a complex combination of motional and constitutional dynamic behaviors.
Nitric oxide reactivity of copper(ii) complexes of bidentate amine ligands: Effect of substitution on ligand nitrosation
Sarma, Moushumi,Mondal, Biplab
experimental part, p. 2927 - 2934 (2012/04/10)
Three copper(ii) complexes with bidentate ligands L1, L 2 and L3 [L1, N,N/- dimethylethylenediamine; L2, N,N/-diethylethylenediamine and L3, N,N/-diisobutylethylenediamine], respectively, were synthesized as their perchlorate salts. The single crystal structures for all the complexes were determined. The nitric oxide reactivity of the complexes was studied in acetonitrile solvent. The formation of thermally unstable [CuII-NO] intermediate on reaction of the complexes with nitric oxide in acetonitrile solution was observed prior to the reduction of copper(ii) centres to copper(i). The reduction was found to result with a simultaneous mono- and di-nitrosation at the secondary amine sites of the ligand. All the nitrosation products were isolated and characterized. The ratio of the yield of mono- and di-nitrosation product was found to be dependent on the N-substitution present in the ligand framework.
Reversible aminal formation: Controlling the evaporation of bioactive volatiles by dynamic combinatorial/covalent chemistry
Buchsnee Levrand, Barbara,Godin, Guillaume,Trachsel, Alain,De Saint Laumer, Jean-Yves,Lehn, Jean-Marie,Herrmann, Andreas
experimental part, p. 681 - 695 (2011/03/22)
Dynamic mixtures generated by reversible aminal formation efficiently prolong the duration of evaporation of bioactive volatile aldehydes. Secondary diamines used for the generation of dynamic mixtures are obtained by treatment of primary diamines with carbonyl compounds and reduction of the diimines with NaBH4. The reversibilities of the reactions were demonstrated by NMR measurements in buffered aqueous solutions. Kinetic rate constants and equilibrium constants for the formation and hydrolysis of aminals were determined. The performance of dynamic mixtures as delivery systems for perfumery ingredients was tested after deposition onto cotton, and the long-lastingness of fragrance evaporation was investigated by dynamic headspace analysis against a reference sample. The simplicity of the concept together with its excellent performance makes this delivery system highly interesting for applied perfumery. Reversible aminal formation might also be successfully applicable to dynamic combinatorial/covalent chemistry for screening of pharmaceutically or catalytically active ligands and receptors. The evaporation of bioactive volatiles that are emitted from flowers to attract insects and that are used as fragrances in our everyday life is limited in time. Dynamic mixtures obtained by reversible aminal formation of suitably designed diamines with volatile aldehydes prolong the perception of these compounds in functional perfumery.
CONTROLLED RELEASE OF ACTIVE ALDEHYDES AND KETONES FROM EQUILIBRATED DYNAMIC MIXTURES
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Page/Page column 31-33, (2008/12/07)
The present invention concerns a dynamic mixture obtained by combining, in the presence of water, at least one diamine derivative, comprising at least one benzylamine moiety, with at least one active aldehyde or ketone. The invention's mixture is capable of releasing in a controlled and prolonged manner said active compound, in particular perfuming ingredients, in the surrounding environment.
METHOD FOR PRODUCING N-MONOALKYL-SUBSTITUTED ALKYLENE AMINE
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Page/Page column 8, (2010/02/11)
PROBLEM TO BE SOLVED: To provide a method for producing an N-monoalkyl-substituted alkylene amine especially useful for uses such as medicine intermediates, agrochemical intermediates, urethane resin-foaming catalysts, surfactants and the like among alkyl-substituted alkylene amine compounds from an alcohol and an alkylene amine as raw materials. SOLUTION: This method for producing the N-monoalkyl-substituted alkylene amine is characterized by reacting the alkylene amine with a ≥2C alkyl alcohol in the presence of a copper-containing oxide catalyst system. The N-monoalkyl-substituted alkylenamine is produced in high conversion and in N-monoalkylation selectivity.
Continuous chemoselective methylation of functionalized amines and diols with supercritical methanol over solid acid and acid-base bifunctional catalysts
Oku, Tomoharu,Arita, Yoshitaka,Tsuneki, Hideaki,Ikariya, Takao
, p. 7368 - 7377 (2007/10/03)
The selective N-methylation of bifunctionalized amines with supercritical methanol (scCH3OH) promoted by the conventional solid acids (H-mordenite, β-zeolite, amorphous silica-alumina) and acid-base bifunctional catalysts (Cs-P-Si mixed oxide and γ-alumina) was investigated in a continuous-flow, fixed-bed reactor. The use of scCH 3OH in the reaction of 2-aminoethanol with methanol (amine/CH 3OH = 1/10.8) over the solid catalysts led to a significant improvement in the chemoselectivity of the N-methylation. Among the catalysts examined, the Cs-P-Si mixed oxide provided the most efficient catalyst performance in terms of selectivity and reactivity at 300 °C and 8.2 MPa; the N-methylation selectivity in the products reaching up to 94% at 86% conversion. The present selective methylation was successfully applied to the synthesis of N-methylated amino alcohols and diamines as well as O-methylated ethylene glycol. Noticeably, ethoxyethylamine was less reactive, suggesting that the hydroxy group of the amino alcohols is a crucial structural factor in determining high reactivity and selectivity, possibly because of the tethering effect of another terminus, a hydroxo group, to the catalyst surface. The magic-angle-spinning NMR spectroscopy and X-ray diffraction analysis of the Cs-P-Si mixed oxide catalyst revealed that the acidic and basic sites originate from P2O5/SiO2 and Cs/SiO2, respectively, and the weak acid-base paired sites are attributed to three kinds of cesium phosphates on SiO2. The weak acid-base sites on the catalyst surface might be responsible for the selective dehydrative methylation.
