107-15-3

This work is dealing with basic hydrolysis in water of allophanic esters as possible models of carboxybiotin. A complex mechanism is involved likely due to competition of nucleophilic attack on the two carbonyl groups of the substrate. The rate of hydrolysis is significantly increased by metallic cation (Mg++), a specific effect which allows to consider characterization of selectivity of bond breaking between nitrogen and carboxylate group with other nucleophiles.

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.

The photolysis of mixtures of CH4, NH3, and H2O with a low-pressure mercury lamp led to the formation of considerable amounts of methylamine and ethylenediamine with oxygen-containing compounds, ethane, and hydrogen.CH2NH2 radicals formed during photolysis were detected by ESR applying a spin trap technique, and it was suggested that the coupling of the radicals leads to the formation of ethylenediamine.

The natural aminocarboxylic acid product ethylenediamine-N,N′-disuccinic acid [(S,S)-EDDS] is able to form a stable complex with metal ions, making it an attractive biodegradable alternative for the synthetic metal chelator ethylenediaminetetraacetic acid (EDTA), which is currently used on a large scale in numerous applications. Previous studies have demonstrated that biodegradation of (S,S)-EDDS may be initiated by an EDDS lyase, converting (S,S)-EDDS via the intermediate N-(2-aminoethyl)aspartic acid (AEAA) into ethylenediamine and two molecules of fumarate. However, current knowledge of this enzyme is limited because of the absence of structural data. Here, we describe the identification and characterization of an EDDS lyase from Chelativorans sp. BNC1, which has a broad substrate scope, accepting various mono- and diamines for addition to fumarate. We report crystal structures of the enzyme in an unliganded state and in complex with formate, succinate, fumarate, AEAA, and (S,S)-EDDS. The structures reveal a tertiary and quaternary fold that is characteristic of the aspartase/fumarase superfamily and support a mechanism that involves general base-catalyzed, sequential two-step deamination of (S,S)-EDDS. This work broadens our understanding of mechanistic diversity within the aspartase/fumarase superfamily and will aid in the optimization of EDDS lyase for asymmetric synthesis of valuable (metal-chelating) aminocarboxylic acids.

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Two new niobium and zinconiobium fluorophosphates, NbOF(PO 4)2(C2H10N2)2 (1) and Zn3(NbOF)(PO4)4-(C2H 10N2)2 (2), have been prepared under hydrothermal conditions using ethylenediamine as a template. The structures were determined by single crystal diffraction to be triclinic, space group P1 (No. 2), a = 8.1075 (6) A, b = 9.8961 (7) A, c = 10.1420(8) A, α = 111.655(1)°, β = 111.51(1)°, γ = 93.206(1)°, V = 686.19(9) A3, and Z = 2 for 1 and orthorhombic, space group Fddd (No. 70), a = 9.1928(2) A, b = 14.2090(10) A, c = 32.2971 (6) A, V = 4218.66(12) A3, and Z = 8 for 2, respectively. Compound 1 is an infinite linear chain consisting of corner-sharing [Nb 2P2] 4-MRs bridged at the Nb centers with organic amines situated between chains, and compound 2, containing the chains similar to that in 1, forms a zeotype framework with organic amines situated in the gismondine-type [4684] cavities. The topology of 2 was previously unknown with vertex symbol 4·4·4·4· 8·8 (vertex 1), 4·4·4·82·8· 8 (vertex 2), 4·4·8·8·82·8 2 (vertex 3), and 4·4·4·8 2·8·8 (vertex 4). The topological relationships between the 4-connected network of 2 and several reported (3,4)-connected networks were discussed.

A novel liquid organic hydrogen carrier (LOHC) system, with a high theoretical hydrogen capacity, based on the unpresented hydrogenation of ethylene urea to ethylenediamine and methanol, and its reverse dehydrogenative coupling, was established. For the dehydrogenation only a small amount of solvent is required. This system is rechargeable, as the H2-rich compounds could be regenerated by hydrogenation of the resulting dehydrogenation mixture. Both directions for hydrogen loading and unloading were achieved using the same catalyst, under relatively mild conditions. Mechanistic studies reveal the likely pathway for H2-lean compounds formation.

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Carbene complexes of chromium and tungsten with a bridging furan substituent were synthesized from lithiated furan precursors and metal hexacarbonyls. The binuclear biscarbene complexes [(CO)5M{C(OEt)- C4H2O-C(OEt)}-M′(CO)5] (M = M′ = Cr (3), W (4)) were obtained as well as the corresponding monocarbene complexes [M{C(OEt)-C4H3O}(CO)5] (M = Cr (1), W (2)). A method of protecting the carbene moiety during the metal acylate stage was used to increase not only the yields of the binuclear Fischer biscarbene complexes 3 and 4 but to establish a method to synthesize analogous mixed heterobinuclear carbene complexes (M = W, M′ = Cr (5)) in high yields. The binuclear biscarbene complexes 3 and 5 were reacted with 3-hexyne and yielded the corresponding benzannulated monocarbene complexes [M{C(OEt)-C14H 17O3}(CO)5] (M = Cr (6), W(7)). Complex 5 reacted regioselectively with the benzannulation reaction occurring at the chromium-carbene centre. The major products from refluxing 3 in the presence of [Pd(PPh3)4] were a monocarbene-ester complex [Cr{C(OEt)-C4H2O-C(O)OEt}(CO)5] (8), the 2,5-diester of furan (9) and a carbene-carbene coupled olefin EtOC(O)-C 4H2O-C(OEt)=C(OEt)-C4H2O-C(O)OEt (10). X-Ray structure analysis of 4 and 6 confirmed the molecular structures of the compounds in the solid state and aspects of electron conjugation between the transition metals and the furan substituents in the carbene ligands were investigated. The Royal Society of Chemistry 2005.

The reaction of chromium(III) chloride, 3-hydroxy-2-naphthoic acid (3-HNA) and ethylenediamine (en) led to the formation of complex [Cr(3-HNA)(en)2]Cl · H2O · CH3OH, Bis(ethylenediamine-κ2N,N′)(3-hydroxy-2-napht

Ni-Re/SiO2 catalysts with controllable Ni particle sizes (4.5–18.0 nm) were synthesized to investigate the effects of the particle size on the amination of monoethanolamine (MEA). The catalysts were characterized by various techniques and evaluated for the amination reaction in a trickle bed reactor at 170°C, 8.0 MPa, and 0.5 h?1 liquid hourly space velocity of MEA (LHSVMEA) in NH3/H2 atmosphere. The Ni-Re/SiO2 catalyst with the lowest Ni particle size (4.5 nm) exhibited the highest yield (66.4%) of the desired amines (ethylenediamine (EDA) and piperazine (PIP)). The results of the analysis show that the turnover frequency of MEA increased slightly (from 193 to 253 h?1) as the Ni particle sizes of the Ni-Re/SiO2 catalysts increased from 4.5 to 18.0 nm. Moreover, the product distribution could be adjusted by varying the Ni particle size. The ratio of primary to secondary amines increased from 1.0 to 2.0 upon increasing the Ni particle size from 4.5 to 18.0 nm. Further analyses reveal that the Ni particle size influenced the electronic properties of surface Ni, which in turn affected the adsorption of MEA and the reaction pathway of MEA amination. Compared to those of small Ni particles, large particles possessed a higher proportion of high-coordinated terrace Ni sites and a higher surface electron density, which favored the amination of MEA and NH3 to form EDA.

The acid decomposition of some substituted methyldithiocarbamates was studied in water at 25°C in the range of rio -5 and pH 5. The pH-rate profiles showed a bell-shaped curve from which were calculated the acid dissociation constants of the free and conjugate acid species and the specific acid catalysis rate constants k(H). The Bronsted plot of k(H) vs pK(N), the dissociation constant of the conjugate acid of the parent amine, suggests that the acid cleavage occurs through two mechanisms that depend on the pK(N). The plot presents a convex upward curve with a maximum at pK(N) 9.2, which is consistent with the cleavage of the dithiocarbamate anion through a zwitterion intermediate and two transition states. For pK(N) 9.2, the C-N bond breakdown is the slowest step, and according to the inverse SIE, the transition state changes rapidly with the increase of pK(N) to a late transition state. The plot shows a minimum at pK(N) ?10, indicating that a new mechanism emerges at higher values, and it is postulated that it represents a path of intramolecular S to N proton-transfer concerted with the C-N bond breakdown. The thiocarbonyl group acts as a powerful electron- withdrawing group, decreasing the basicity of the nitrogen of the parent amine by 14.1 pK units.

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Dihydropyrazines reacted with 1,2-diamines to form tetraazadecalins as intermediates, and then the reaction proceeded forward to dissociate into alternate dihydropyrazine and diamine, or backward to dissociate into the starting materials in certain equilibrium. The product distribution is controlled by diamine-exchange equilibrium reaction. The various equilibrium reactions were analyzed by NMR spectroscopy.

The lactonisation of N-(2-aminoethyl)-6-endo-hydroxybicycloheptane-2-endo-carboxamide shows a sigmoid pH-rate profile which is interpreted, kinetically, in terms of the hydroxide-ion-catalysed hydrolysis of the amide with the terminal amino-group unprotonated and protonated.Reaction of the latter species occurs with a rate enhancement of ca. 109 compared with an amide lacking the hydroxy- and protonated amino-groups.This is attributed to intramolecular nucleophilic and general acid-catalysis.The relative effectiveness of these two processes are compared and it is concluded that intramolecular general acid-catalysis makes a relatively minor contribution to the rate enhancement even though the breakdown of the tetrahedral intermediate is thought to be a concerted process.Some comments are made about the mechanisms proposed for the chymotrypsin-catalysed hydrolysis of amides and concerted breakdown of the tetrahedral intermediate is suggested as a possible mechanism.

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Monoprotonated ethylenediamine (ENH+) and aminoacetonitrile (AAN) are highly effective catalysts for the decarboxylation of oxalacetate (OA2-) with the latter amine showing 50percent faster rates.The mechanisms of the reactions are the same as that earlier proposed by Guthrie and Jordan from studies on the carboxylation of acetoacetate (AA-): amine and keto acid react to form ketimine which either decarboxylates or is competitively converted to enamine.We find that a prton is required to effect decarboxylation, but it also promotes enamine formation, the more so the greater basicity of the parent amine.Owing to this side reaction, the more basic amines tend to show lower catalytic activity with respect to decarboxylation. a second effect also contributes to the high activity of AAN: even though the rate constants for imine formation appear to be roughly similar with AAN and ENH+, proton catalysis has a much larger net influence on the AAN rate because changes in +> are not canceled by inverse changes in . 4-Ethyloxalacetate forms an adduct with ENH+ that has a considerably greater enamine content and a higher stability than its OA2- analogue.These differences in substrate behavior must be taken into account when esters are used as models for the parent keto acids in these reactions.Comparison of our results with those previously published for OA2- decarboxylation catalyzed by a partially quaternized poly(ethylenimine) suggests that OA2- is predominantly bound to the quaternary amine sites but decarboxylation likely proceeds via a Schiff-base mechanism.

The hydrolysis of some tailor-made Schiff bases having flexible spacers between aldimine groups and alkoxy groups at ortho (o) or para (p) position in the benzene ring has been investigated in microemulsion media. The kinetic data of acid-catalyzed hydrolysis in anionic (sodium lauryl sulphate: NaLS) and cationic (cetyltrimethyl ammoniumbromide: CTAB) microemulsion media have been explained considering the localization of the Schiff bases at various probable pockets of the microemulsion droplet. The results are in conformity to the solubilization studies of the reported Schiff bases in microemulsions (Dash et al., Spectrochim Acta 1996, 52A, 349). The change in reactivity due to change in the spacer length and position of the alkoxy group in the Schiff bases has been rationalized on the basis of localization sites of the reaction center at different polarity pockets of the reaction media.

(Matrix presented) (Trifluoroacetyl)azobenzene dyes were previously employed as amine reporter groups (chemosensors) in a dendrimer-based monomolecular imprinting system. Kinetic and binding studies with a range of amines and diamines show that the highly selective signaling observed for alkane diamines by these imprinted dendrimers arises from a kinetic effect due to intramolecular general base-catalyzed carbinolamine formation with the dye itself. The relationship between diamine structure and carbinolamine stability and rate of formation is described.

The oxidation of ethanolamine (EtA), ethylene glycol, and several other diols by Ag(II) has been studied at pH ca. 8.5.In the basic pH range, complexation of the substrate by Ag(II) has been found to take place in two steps by successive ligand uptake.Complexation rates are higher 1 order of magnitude in the basic pH range as compared to the acidic pH range.Oxidation then takes place through intramolecular electron transfer from substrate to Ag(II) within the complex.Oxidation rates for cis- and trans-1,2-cyclohexanediols are quite similar.

7-(Imidazolidin-1-ylmethyl)quinoline-8-ol, an N-substituted imidazolidine, was synthesized in a one-step reaction between 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane (TATD) and 8-hydroxyquinoline. Obtaining this substance enhanced the scope of possibilities in the synthesis of unsymmetrically N,N-disubstituted imidazolidines. 1H-NMR spectral studies revealed that this type of substance does not undergo ring-chain tautomerism.

The equilibrium kinetics in aqueous solutions of the chromium(II)-ethylenediamine (en) and -iminodiacetate (ida) complexes has been studied using a n.m.r. relaxation method.The paramagnetic relaxation rate and shift of the CH2 protons of the ligands were

In this paper, Ni/Al2O3 catalysts (15 wt% Ni) with different Re loadings were prepared to investigate the effect of Re on the structure and catalytic performance of Ni-Re/Al2O3 catalysts for the reductive amination of monoethanolamine. Reaction results reveal that the conversion and ethylenediamine selectivity increase significantly with increasing Re loading up to 2 wt%. Ni-Re/Al2O3 catalysts show excellent stability during the reductive amination reaction. The characterization of XRD, DR UV-Vis spectroscopy, H2-TPR, and acidity-basicity measurements indicates that addition of Re improves the Ni dispersion, proportion of octahedral Ni2+ species, reducibility, and acid strength for Ni-Re/Al2O3 catalysts. The Ni15 and Ni15-Re2 catalysts were chosen for in-depth study. The results from SEM-BSE, TEM, and CO-TPD indicate that smaller Ni0 particle size and higher Ni0 surface area are obtained in the reduced Ni-Re/Al2O3 catalysts. Results from in situ XPS and STEM-EDX line scan suggest that Re species show a mixture of various valances and have a tendency to aggregate on the surface of Ni0 particles. During reaction, the Ni0 particles on the Al2O3 support are stabilized and the sintering process is effectively suppressed by the incorporation of Re. It could be concluded that sufficient Ni0 sites, the collaborative effect of Ni-Re, and brilliant stability contribute to the excellent catalytic performance of Ni-Re/Al2O3 catalysts for the reductive amination of monoethanolamine.

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A new strategy for determining thermodynamic effective molarities (EM) for macrocylisation reactions using dynamic combinatorial chemistry under dilute conditions is presented. At low concentrations, below the critical value, Dynamic Libraries (DLs) of bifunctional building blocks contain only cyclic species, so it is not possible to quantify the equilibria between linear and cyclic species. However, addition of a monofunctional chain stopper can be used to promote the formation of linear oligomers allowing measurement of EM for all cyclic species present in the DL. The effectiveness of this approach was demonstrated for DLs generated from mixtures of 1,3-diimine calix[4]arenes, linear diaminoalkanes and monoaminoalkanes. For macrocycles deriving from one bifunctional calixarene and one diamine, there is an alternating pattern of EM values with the number of methylene units in the diamine: odd numbers give significantly higher EMs than even numbers. For odd numbers of methylene units, the alkyl chain can adopt an extended all anti conformation, whereas for even numbers of methylene units, gauche conformations are required for cyclisation, and the associated strain reduces EM. The value of EM for the five-carbon linker indicates that this macrocycle is a strainless ring. This journal is

A dehydrogenation reaction step in which (A) monoethanolamine is dehydrogenated to form aminoacetaldehyde in the presence of a reductive amination catalyst containing cobalt, yttrium and palladium as an active ingredient. A dehydration reaction step of contacting (B) said aminoacetaldehyde with an amine compound to form iminoethanamine. A hydrogenation process wherein (C) is contacted with iminoethaneamine and hydrogen to form ethylenetriamine. Method for manufacturing a semiconductor device A process for the preparation of ethyleneamine.

A dehydrogenation reaction step in which (A) monoethanolamine is dehydrogenated to form aminoacetaldehyde in the presence of a reductive amination catalyst containing cobalt, scandium, and palladium as an active ingredient. A dehydration reaction step of contacting (B) said aminoacetaldehyde with an amine compound to form iminoethanamine. A hydrogenation process wherein (C) is contacted with iminoethaneamine and hydrogen to form ethylenetriamine. Method for manufacturing a semiconductor device A process for the preparation of ethyleneamine.

The present invention relates to a process for preparing alkanolamines and/or ethyleneamines in the liquid phase, by reacting ethylene glycol and/or monoethanolamine with ammonia in the presence of an amination catalyst comprising Co, Ru and Sn.

The present invention relates to a process for preparing ethanolamines and/or ethyleneamines in the gas phase by reacting ethylene glycol with ammonia in the presence of an amination catalyst. It is a characteristic feature of the process that the amination catalyst is prepared by reducing a calcined catalyst precursor comprising an active composition, where the active composition comprises one or more active metals selected from the group consisting of the elements of groups 8, 9, 10 and 11 of the Periodic Table of the Elements and optionally one or more added catalyst elements selected group consisting of the metals and semimetals of groups 3 to 7 and 12 to 17, the element P and the rare earth elements. It is a further characteristic feature of the process that a catalyst precursor having low basicity is used, the low basicity being achieved in that a) the catalyst precursor is prepared by coprecipitation and the active composition additionally comprises one or more basic elements selected from the group consisting of the alkali metals and alkaline earth metals; orb) the catalyst precursor, as well as the active composition, additionally comprises a support material and is prepared by impregnating the support material or precipitative application onto the support material and the support material comprises one or more basic elements selected from the group consisting of the alkali metals, Be, Ca, Ba and Sr or one or more minerals selected from the group consisting of hydrotalcite, chrysotile and sepiolite; orc) the catalyst precursor, as well as the active composition, additionally comprises a support material and is prepared by impregnating the support material or precipitative application onto the support material and the active composition of the catalyst support comprises one or more basic elements selected from the group consisting of the alkali metals and the alkaline earth metals; ord) the catalyst precursor is calcined at temperatures of 600° C. or more; ore) the catalyst precursor is prepared by a combination of variants a) and d) or by a combination of variants b) and d) or by a combination of variants c) and d).

The invention pertains to a process for converting cyclic alkyleneureas into their corresponding alkyleneamines, comprising - in a first step converting cyclic alkyleneureas into their corresponding alkyleneamines by reacting cyclic alkyleneureas in the liquid phase with water with removal of CO2, so as to convert between 5 mole% and 95 mole% of alkyleneurea moieties in the feedstock to the corresponding amines, and - in a second step adding an inorganic base and reacting cyclic alkylene ureas remaining from the first step with the inorganic base to convert them partially or completely into their corresponding alkyleneamines. It has been found that the two-step process of the present invention makes it possible to still obtain a high conversion of cyclic alkyleneureas, while using substantially less strong inorganic base. The process according to the invention also shows a higher selectivity to amines than the prior art process.

The present invention relates to a process for the conversion of 2-aminoethanol to ethane-1,2-diamine and/or linear polyethylenimines of the formula H2N—[CH2CH2NH]n—CH2CH2NH2 wherein n≥1 comprising: (i) providing a catalyst comprising a zeolitic material having the MOR framework structure comprising YO2 and X2O3, wherein Y is a tetravalent element and X is a trivalent element, said zeolitic material containing copper as extra-framework ions; (ii) providing a gas stream comprising 2-aminoethanol and ammonia; (iii) contacting the catalyst provided in (i) with the gas stream provided in (ii) for converting 2-aminoethanol to ethane-1,2-diamine and/or linear polyethylenimines.

Sophisticated chemical processes widely observed in biological cells require precise apportionment regulation of building units, which inspires researchers to develop tailorable architectures with controllable heterogeneity for replication, recognition and information storage. However, it remains a substantial challenge to endow multivariate materials with internal sequences and controllable apportionments. Herein, we introduce a novel strategy to manipulate the apportionment of functional groups in multivariate metal-organic frameworks (MTV-MOFs) by preincorporating interlocked linkers into framework materials. As a proof of concept, the imprinted apportionment of functional groups within ZIF-8 was achieved by exchanging imine-based linker templates with original linkers initially. The removal of linker fragments by hydrolysis can be achieved via postsynthetic labilization, leading to the formation of architectures with controlled heterogeneity. The distributions of functional groups in the resulting imprinted MOFs can be tuned by judicious control of the interlocked chain length, which was further analyzed by computational methods. This work provides synthetic tools for precise control of pore environment and functionality sequences inside multicomponent materials.

The invention pertains to a process to prepare ethylene amines with n ethyleneunits and n+1 amine groups wherein n is at least 4, or urea derivatives of said ethylene amines, by reacting an ethanolamine-functional compound, an amine-functional compound, and a carbon oxide delivering agent, wherein the ethanolamine-functional compound is of the formula HO-(C2H4-NH-)qH, q is at least 1, the amine-functional compound is of the formula H2N-(C2H4-NH-)rH, r is at least 1, the sum q+r is at least 4 and wherein optionally one or more of the ethanol-amine functional compound or amine-functional compound are at least partly used as their cyclic carbamate derivative, or linear or cyclic urea derivative. The process provides TEPA and higher ethylene amines in high yield and high selectivity, without having to use expensive or hazardous startingmaterials. Various urea derivatives of TEPA and PEHA are also claimed.

Direct hydrogenation of a broad variety of cyclic imides to diols and amines using a ruthenium catalyst is reported here. We have applied this strategy toward the development of a new liquid organic hydrogen carrier system based on the hydrogenation of bis-cyclic imide that is formed by the dehydrogenative coupling of 1,4-butanediol and ethylenediamine using a new ruthenium catalyst. The rechargeable system has a maximum gravimetric hydrogen storage capacity of 6.66 wt%.

The present invention relates to a process for the conversion of ethylene oxide to 2-aminoethanol and/or ethane-1,2-diamine and/or linear polyethylenimines of the formula H2N- (CH2CH2NH)n-CH2CH2-NH2 wherein n≥ 1 comprising (i) providing a catalyst comprising a zeolitic material comprising YO2 and X2O3, wherein Y is a tetravalent element and X is a trivalent element; (ii) providing a gas stream comprising ethylene oxide and ammonia; (iii) contacting the catalyst provided in (i) with the gas stream provided in (ii) for converting ethylene oxide to 2-aminoethanol and/or ethane-1,2-diamine and/or linear polyethylenimines.

The invention discloses a preparation method of ethylene carbonate (propylene carbonate), and belongs to a novel method for synthesizing cyclic allyl carbonate. According to the method, alkyl polyamine-carbamate prepared in a lab and ethylene oxide (propylene oxide) carry out reactions in the presence of a catalyst to prepare an organic chemical product namely ethylene carbonate (propylene carbonate) with a high additional valve. Moreover, an absorption solvent (alkyl polyamine) can be obtained. The catalyst has a high activity and selectivity, so the yield of ethylene oxide (propylene oxide) is high and can reach more than 90%. The yield of byproduct (alkyl polyamine) can reach more than 95%. The byproduct (alkyl polyamine) can be recovered to cyclically absorb CO2. The fixed C1 resources are converted into an importation chemical product by the preparation method, the greenhouse effect is effectively relieved; at the same time, the problem of large energy consumption for desorption of CO2 in an organic amine solution is solved, and the recovered byproduct can be used to absorb CO2 circularly.

The present invention relates to novel Ruthenium complexes of formulae A1-A4 and their use, inter alia, for (1) dehydrogenative coupling of alcohols to esters; (2) hydrogenation of esters to alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di-lactones), or polyesters); (3) preparing amides from alcohols and amines—(including the preparation of polyamides (e.g., polypeptides) by reacting dialcohols and diamines and/or polymerization of amino alcohols and/or forming cyclic dipeptides from p-aminoalcohols; (4) hydrogenation of amides (including cyclic dipeptides, polypeptides and polyamides) to alcohols and amines; (5) hydrogenation of organic carbonates (including polycarbonates) to alcohols or hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (6) dehydrogenation of secondary alcohols to ketones; (7) amidation of esters (i.e., synthesis of amides from esters and amines); (8) acylation of alcohols using esters; (9) coupling of alcohols with water and a base to form carboxylic acids; and (10) preparation of amino acids or their salts by coupling of amino alcohols with water and a base. The present, invention further relates to the use of certain known Ruthenium complexes for the preparation of amino acids or their salts from amino alcohols.

The present invention relates to a method for preparing ethylene amine-based compounds which allows selective preparation of ethylene amine compounds having a higher molecular weight at a high ratio while improving the overall energy efficiency. The method for preparing ethylene amine-based compounds according to the present invention comprises a first reaction step and a second reaction step in which ethylene dichloride reacts with aqueous ammonia so that the molar ratio of ethylene dichloride (EDC) to ammonia may be 1:4-1:10. In the method, ethylene dichloride is introduced in an amount corresponding to 30-70 mol% of the total feed, and the balance amount is introduced in the second reaction step.COPYRIGHT KIPO 2017

A novel and simple hydrogen storage system was developed, based on the dehydrogenative coupling of inexpensive ethylenediamine with ethanol to form diacetylethylenediamine. The system is rechargeable and utilizes the same ruthenium pincer catalyst for both hydrogen loading and unloading procedures. It is efficient and uses a low catalyst loading. Repetitive reversal reactions without addition of new catalyst result in excellent conversions in both the dehydrogenation and hydrogenation procedures in three cycles. In support of the hydrogen economy: An efficient and simple homogeneous hydrogen carrier system was developed based on the dehydrogenative coupling of ethylenediamine with ethanol to form diacetylethylenediamine. The same ruthenium pincer catalyst is used for both hydrogen loading and unloading reactions.

The invention relates to a preparation method of ethylene diamine. The preparation method comprises the following steps: in the presence of a catalyst, carrying out reactions between ethanolamine and ammonia for 10 to 30 seconds at a temperature of 300 to 380 DEG C; and then making the reaction system go on carrying out reactions for 10 to 30 seconds at a temperature of 200 to 280 DEG C in the present of the catalyst so as to obtain ethylene diamine. The preparation method takes ethanolamine and ammonia as the raw materials, then carries out a gas-phase condensation amination reaction in the presence of a catalyst so as to synthesize ethylene diamine, adopts two serially-connected reactors with different reaction temporaries in the synthesis process; solves the contradiction between the ethanolamine conversion rate and the ethylene diamine selectivity, and raises the reaction conversion rate of ethanolamine from 50% to 80%.

The novel cationic [RuH{PPh2(2-OMeC6H4)}2]BPh4and neutral trans-[Ru(NH3)2{PPh2(2-OC6H4)}2] complexes were isolated from phosphine substitution reactions with [RuH(1,5-cod)(NH2NMe2)3]BPh4and [RuCl(1,5-cod)(NH3)2(NH2NMe2)]BPh4respectively. Ligand induced bisdemethylation of the pendent ether moieties of the phosphines occurred to give rise to the bis-phosphanylphenoxy moieties. Both complexes catalyzed the one-pot reductive amination of carbonyl compounds where excellent selectivity of aryl aldehydes over aryl ketones as precursors to the alcoholic species existed. Through substrate screening and1H NMR studies, both steric and electronic effects of the substrates were found to influence the hydrogenation/amination mechanistic pathway, as well as direct the alcohol:amine selectivity.

PROBLEM TO BE SOLVED: To provide a method for producing alkanol amines by alcohol amination of diols using ammonia under elimination of water. SOLUTION: The invention relates to a method for producing alkanol amines which comprise a primary amino group (-NH2) and a hydroxyl group (-OH), by alcohol amination of diols comprising two hydroxyl groups (-OH) using ammonia under elimination of water. The reaction is homogeneously catalyzed in the presence of at least one complex catalyst which contains at least one element selected from groups 8, 9 and 10 of the periodic table and at least one donor ligand. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPO&INPIT

The invention relates to a method for producing primary amines by means of the alcohol amination of alcohols with ammonia, with water being eliminated. The method comprises the steps of: (a) a homogenously-catalysed reaction of a reaction mixture which contains at least one alcohol, ammonia, at least one non-polar solvent, and at least one catalyst containing at least one element selected from groups 8, 9 and 10 of the periodic table in the liquid phase, a product mixture (P) thus being obtained; (b) separating the phases of product mixture (P) which was obtained in step (a), if necessary after a reduction in temperature, a reduction in pressure and/or the addition of at least one polar solvent with a miscibility gap in relation to the non-polar solvent, and thus obtaining at least one polar product phase (A) and at least one non-polar phase (B) containing at least one portion of the catalyst that was introduced, with said non-polar phase (B) being separated off, (c) returning at least one portion of the non-polar phase (B) into the reaction in step (a), and (d) separating the amination product from the polar product phase (A). The non-polar solvent introduced in (a) and the catalyst introduced in step (a) are selected such that the catalyst in the non-polar phase (B) becomes enriched.

Method for preparing piperazine of formula I by reacting diethanolamine (DEOA) of formula II with ammonia in the presence of hydrogen and a metal-containing supported catalyst. Before the catalyst is reduced with hydrogen, the catalytically active mass of the catalyst contains oxygen-containing aluminum, copper, nickel and cobalt compounds and 0.2 to 5.0 wt.% oxygen-containing tin compounds calculated as SnO, and the reaction is carried out in the liquid phase at an absolute pressure ranging from 160 to 220 bar, at a temperature ranging from 180 to 220°C, ammonia is used at a molar ratio ranging from 5 to 25 in relation to the DEOA used in the process, the method being carried out in the presence of 0.2 to 9.0 wt.% hydrogen relative to the total amount of DEOA and ammonia used in the process.

The invention relates to a method for producing primary amines, which contain at least one functional group of the formula (-CH2-NH2) and at least one further primary amino group, by the alcohol amination of reactants, which contain at least one functional group of the formula (-CH2-OH) and at least one further functional group (-X), wherein (-X) is selected from hydroxyl groups and primary amino groups, using ammonia with removal of water, wherein the reaction is carried out in a homogeneously catalyzed manner in the presence of at least one complex catalyst containing at least one element selected from groups 8, 9 and 10 of the periodic table and at least one donor ligand.

This communication describes a disassembly based approach for the detection of biologically relevant di- and triphosphates in water using locked fluorescent salicylaldehyde probes.

Hydrogenation of 3-formyl-4-hydroxycoumarin aliphatic imines leads to 3-aminomethyl-4-hydroxycoumarins, which undergo a retro-Mannich reaction in dimethyl sulfoxide containing even traces of water.

Disclosed is a process for the preparation of an amine (particularly diamines and polyamines) by reacting an alkanolamine or a polyol with ammonia in the presence of a catalyst composed of two active metals from the group of transition metals, namely nickel and chromium supported on a microporous refractory substrate, in a hydrogenated, trickle bed reactor.

The deprotection of wide varieties of oximes, imines, and azines to their corresponding carbonyls has been achieved using Cu-nanoparticles on a cellulose template as a reusable catalyst. The reactions were carried out at 80-100 °C using microwave irradiation in water under neutral condition. The catalyst can be reused for several cycles with good to excellent yield.

Process for preparing piperazine of the formula I by reacting diethanolamine (DEOA) of the formula II with ammonia (NH3) in the presence of hydrogen and a supported, metal-containing catalyst, wherein the catalytically active mass of the catalyst, prior to its reduction with hydrogen, comprises 20 to 85% by weight of oxygen-containing compounds of zirconium, calculated as ZrO2, 1 to 30% by weight of oxygen-containing compounds of copper, calculated as CuO, 14 to 70% by weight of oxygen-containing compounds of nickel, calculated as NiO, and 0 to 5% by weight of oxygen-containing compounds of molybdenum, calculated as MoO3, and the reaction is carried out in the liquid phase at an absolute pressure in the range from 160 to 220 bar, a temperature in the range from 180 to 220° C., using ammonia in a molar ratio to DEOA used of from 5 to 20 and in the presence of 0.2 to 9.0% by weight of hydrogen, based on the total amount of DEOA used and ammonia.

Process for preparing piperazine of the formula I by reacting diethanolamine (DEOA) of the formula II with ammonia in the presence of hydrogen and a supported, metal-containing catalyst has been found, wherein the catalytically active mass of the catalyst, prior to its reduction with hydrogen, comprises oxygen-containing compounds of aluminum, copper, nickel and cobalt and in the range from 0.2 to 5.0% by weight of oxygen-containing compounds of tin, calculated as SnO, and the reaction is carried out in the liquid phase at an absolute pressure in the range from 160 to 220 bar, a temperature in the range from 180 to 220° C., using ammonia in a molar ratio to DEOA used of from 5 to 25 and in the presence of 0.2 to 9.0% by weight of hydrogen, based on the total amount of DEOA used and ammonia.

The present invention relates to method for producing ethyleneamines that includes: reacting ethylenedichloride with ammonia water under conditions optimizing the molar ratio of ethylenedichloride to ammonia in a defined range to produce amine compounds, ammonium chloride, and water; and isolating the amine compounds, ammonium chloride, and water, respectively. The present invention provides a continuous process for producing ethyleneamines using ethylenedichloride and ammonia by efficiently controlling the composition of the ethyleneamine product in accordance with the supply and demand of ethyleneamines to optimize the distribution of ethyleneamines.

The present invention relates to a process for reacting glycolaldehyde with an aminating agent in the presence of hydrogen and of a catalyst, the catalyst being activated by reducing a catalyst precursor or by reducing a passivated catalyst, which comprises effecting the reaction in the presence of a solvent and contacting the glycolaldehyde with the activated catalyst.

Branched end reactants having two or three functional groups at the ends are disclosed. The branched end reactants are used to prepare crosslinked hydrogel tissue adhesives, which have a good balance of mechanical properties in an aqueous environment. Kits comprising the branched end reactants and methods for applying a coating to an anatomical site on tissue of a living organism are also disclosed.

Process for preparing primary amines which have at least one functional group of the formula (—CH2—NH2) and at least one further primary amino group by alcohol amination of starting materials having at least one functional group of the formula (—CH2—OH) and at least one further functional group (—X), where (—X) is selected from among hydroxyl groups and primary amino groups, by means of ammonia with elimination of water, wherein the reaction is carried out homogeneously catalyzed in the presence of at least one complex catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table and also at least one donor ligand.

Process for preparing alkanolamines which have a primary amino group (—NH2) and a hydroxyl group (—OH) by alcohol amination of diols having two hydroxyl groups (—OH) by means of ammonia with elimination of water, wherein the reaction is carried out homogeneously catalyzed in the presence of at least one complex catalyst comprising at least one element selected from groups 8, 9 and 10 of the Periodic Table and also at least one donor ligand.

Preparing a primary amine by alcohol amination of alcohol with ammonia and elimination of water includes reacting, in a homogeneously catalyzed reaction, a mixture of alcohol, ammonia, nonpolar solvent, and catalyst, in a liquid phase, to obtain a product mixture. The process then includes phase separating the product mixture into a polar product phase and a nonpolar product phase, and separating off the nonpolar product phase. At least some of the nonpolar phase returns to the homogenously catalyzed reaction. The process further includes separating off amination product from the polar product phase. At least some of the catalyst is in the nonpolar phase, and the catalyst accumulates in the nonpolar phase.

An N-salicylidenaniline (SA), compound 1 with 15-crown-5 moiety, was synthesized. The time-dependent NMR was used to track its photochromic process. The experimental results showed that ultraviolet irradiation would lead compound 1 to decompose into the corresponding salicylaldehyde and amine in chloroform solution, instead of experiencing a photochromic process. By the same method, the reported photochromic results of other SAs were also corrected.

Poly(ester-acrylate) and poly(ester/epoxide) dendrimers. These materials can be synthesized by utilizing the so-called “sterically induced stoichiometric” principles. The preparation of the dendrimers is carried out by reacting precursor amino/polyamino-functional core materials with various branch cell reagents. The branch cell reagents are dimensionally large, relative to the amino/polyamino-initiator core and when reacted, produce generation=1 dendrimers directly in one step. There is also a method by which the dendrimers can be stabilized and that method is the reaction of the dendrimers with surface reactive molecules to pacify the reactive groups on the dendrimers.

To provide a process for producing a hydroxyalkyltriethylenediamine or hydroxytriethylenediamine simply and in a small number of steps without requiring multistage reaction steps; a novel catalyst composition whereby a polyurethane product can be obtained with good productivity and good moldability without bringing about odor problems or environmental problems; and a process for producing a polyurethane resin using the catalyst composition. For example, a hydroxyalkyltriethylenediamine or hydroxytriethylenediamine is produced by subjecting a mono-substituted dihydroxyalkylpiperazine and/or a di-substituted hydroxyalkylpiperazine to an intramolecular dehydration condensation reaction in the presence of an acid catalyst. Further, for example, a polyurethane resin is produced by using a catalyst composition which comprises a hydroxyalkyltriethylenediamine or hydroxytriethylenediamine (A), and an amine compound (B) having, in its molecule, one or more substituents selected from the group consisting of a hydroxy group, a primary amino group and a secondary amino group, or a tertiary amine compound (C) having a value of [blowing reaction rate constant/gelling reaction rate constant] of at least 0.5.

The selective, direct hydrogenation of amides to the corresponding alcohols and amines with cleavage of the C-N bond was discovered. The expected products of C-O cleavage are not formed (except as traces in the case of anilides). The reaction proceeds under mild pressure and neutral, homogeneous conditions using a dearomatized, bipyridyl-based PNN Ru(II) pincer complex as a catalyst. The postulated mechanism involves metal-ligand cooperation by aromatization- dearomatization of the heteroaromatic pincer core and does not involve hydrolytic cleavage of the amide. The simplicity, generality, and efficiency of this environmentally benign process make it attractive for the direct transformations of amides to alcohols and amines in good to excellent yields.

The present invention provide a process for the production of compounds of general formula (I), Y-CH2CH2-Z (I) wherein Y and Z are functional groups independently selected from the group consisting of a hydroxyl group and R1R2N and wherein R1 and R2 may be the same or different and are functional groups selected from the group consisting of hydrogen and substituted or non- substituited alkyl groups comprising 1 to 8 carbon atoms, or R1R2N is a cyclic compound selected from the group of aromatic and non-aromatic cyclic compounds optionally comprising one or more heteroatoms in addition to the nitrogen atom, said process comprising the steps of: (i) reacting carbon monoxide and an amine in the presence of oxygen to provide a compound of general formula (II) wherein R1 and R2 or R1R2N are as defined above and X is selected from the group consisting of R1R2N and R3O, wherein R3 is selected from alkyl groups comprising 1 to 8 carbon atoms; and (ii) converting the compound of general formula (II) into a compound of general formula (I) by a process that comprises a hydrogenation reaction.

The present invention relates to a process for preparing amines by reacting glycerol with hydrogen and an aminating agent from the group of ammonia and primary and secondary amines in the presence of a catalyst at a temperature of from 100° C. to 400° C. and a pressure of from 0.01 to 40 MPa (from 0.1 to 400 bar). Preference is given to using glycerol based on renewable raw materials. The catalyst preferably comprises one metal or a plurality of metals or one or more oxygen compounds of the metals of groups 8 and/or 9 and/or 10 and/or 11 of the Periodic Table of the Elements. The invention further relates to the use of the reaction products as an additive in cement or concrete production and in other fields of use. This invention further provides the compounds 1,2,3-triaminopropane, 2-aminomethyl-6-methylpiperazine, 2,5-bis(aminomethyl)piperazine and 2,6-bis(aminomethyl)piperazine.

The present invention provides methods of manufacturing ethyleneamines that makes use of an ethyleneamine-generating process that is coupled to a transamination process. The combination of an ethyleneamine-generating process with a transamination process improves the mix flexibility that can be obtained from the single process allowing the production of ethyleneamine compositions having an improved and more desirable product mix.

The present invention relates to processes for the manufacture of one or more ethanolamines and one or more ethyleneamines starting from the reaction of ethylene oxide with ammonia to produce one or more ethanolamines and the conversion of the ethanolamine(s) to ethyleneamine(s). The present invention also relates to separating alkylethyleneamines from ethyleneamines.

The invention relates to a process for preparing ethylenediamine by hydrogenation of aminoacetonitrile over a catalyst, wherein the hydrogenation is carried out in a solution comprising aminoacetonitrile, water in a proportion of from 0 to 60% by weight and a solvent and the aminoacetonitrile comprised in the solution is fed into the reaction vessel at a rate which is not greater than the rate at which the aminoacetonitrile reacts with hydrogen in the hydrogenation.

The invention relates to a process for preparing an ethylene amine mixture, which comprises hydrogenating an amino nitrile mixture comprising at least 30% by weight of aminoacetonitrile (AAN) and at least 5% by weight of iminodiacetonitrile (IDAN) in the presence of a catalyst. Ethylenediamine (EDA) and/or diethylenetriamine (DETA) and, if appropriate, further ethylene amines can be isolated from the ethylene amine mixtures obtained.

The invention relates to a process for preparing an ethylene amine mixture, which comprises hydrogenating an amino nitrile mixture comprising at least two α-amino nitriles in an amount of at least 5% by weight in each case in the presence of a catalyst and, if appropriate, a solvent.

The present invention relates to a process for preparing amines by reacting sugar alcohols with hydrogen and an aminating agent selected from the group of ammonia and primary and secondary amines in the presence of a catalyst at a temperature of from 100° C. to 400° C. and a pressure of from 1 to 40 MPa (from 10 to 400 bar). The catalyst preferably comprises one metal or a plurality of metals or one or more oxygen compounds of the metals of groups 8 and/or 9 and/or 10 and/or 11 of the Periodic Table of the Elements. The sugar alcohol is preferably obtained by hydrogenating the corresponding sugars. The invention further relates to the use of the reaction products as an additive in cement or concrete production and in other fields of use.