Patent classifications
C07C209/50
LIQUID-ORGANIC HYDROGEN CARRIER SYSTEMS BASED ON CATALYTIC PEPTIDE FORMATION AND HYDROGENATION
The present invention provides a system and method of storing hydrogen (H.sub.2) and releasing it on demand, comprising and making use of diaminoalkanes and alcohols, or aminoalcohols as liquid-organic hydrogen carrier systems (LOHC). 2-amino-ethanol (AE) or its N-methyl derivative 2-(methylamino)ethanol undergo catalytic dehydrogenation to form a cyclic dipeptide (glycine anhydride—GA) or its N,N-dimethyl derivative (N,N-dimethyl GA) with release of hydrogen. Similarly, ethylenediamine (ED) and ethanol undergo catalytic dehydrogenation to form N,N′-diacetylethylenediamine (DAE) with release of hydrogen. Glycine anhydride (GA) or N,N-dimethyl-GA may be hydrogenated back to 2-aminoethanol (AE) or 2-(methylamino)ethanol, respectively, each of which functions as a hydrogen storage system. N,N′-diacetylethylenediamine (DAE) may be hydrogenated back to ED and ethanol, which functions as a hydrogen storage system. These reactions may be catalyzed by a variety of compounds or complexes, including Ruthenium complexes as described herein.
LIQUID-ORGANIC HYDROGEN CARRIER SYSTEMS BASED ON CATALYTIC PEPTIDE FORMATION AND HYDROGENATION
The present invention provides a system and method of storing hydrogen (H.sub.2) and releasing it on demand, comprising and making use of diaminoalkanes and alcohols, or aminoalcohols as liquid-organic hydrogen carrier systems (LOHC). 2-amino-ethanol (AE) or its N-methyl derivative 2-(methylamino)ethanol undergo catalytic dehydrogenation to form a cyclic dipeptide (glycine anhydride—GA) or its N,N-dimethyl derivative (N,N-dimethyl GA) with release of hydrogen. Similarly, ethylenediamine (ED) and ethanol undergo catalytic dehydrogenation to form N,N′-diacetylethylenediamine (DAE) with release of hydrogen. Glycine anhydride (GA) or N,N-dimethyl-GA may be hydrogenated back to 2-aminoethanol (AE) or 2-(methylamino)ethanol, respectively, each of which functions as a hydrogen storage system. N,N′-diacetylethylenediamine (DAE) may be hydrogenated back to ED and ethanol, which functions as a hydrogen storage system. These reactions may be catalyzed by a variety of compounds or complexes, including Ruthenium complexes as described herein.
Catalysts and processes for the hydrogenation of amides
There is provided a process for the reduction of one or more amide moieties in a compound comprising contacting the compound with hydrogen gas and a transition metal catalyst in the presence or absence of a base under conditions for the reduction an amide bond. The presently described processes can be performed at low catalyst loading using relatively mild temperature and pressures, and optionally, in the presence or absence of a base or high catalyst loadings using low temperatures and pressures and high loadings of base to effect dynamic kinetic resolution of achiral amides.
Catalysts and processes for the hydrogenation of amides
There is provided a process for the reduction of one or more amide moieties in a compound comprising contacting the compound with hydrogen gas and a transition metal catalyst in the presence or absence of a base under conditions for the reduction an amide bond. The presently described processes can be performed at low catalyst loading using relatively mild temperature and pressures, and optionally, in the presence or absence of a base or high catalyst loadings using low temperatures and pressures and high loadings of base to effect dynamic kinetic resolution of achiral amides.
Catalysts and processes for the hydrogenation of amides
There is provided a process for the reduction of one or more amide moieties in a compound comprising contacting the compound with hydrogen gas and a transition metal catalyst in the presence or absence of a base under conditions for the reduction an amide bond. The presently described processes can be performed at low catalyst loading using relatively mild temperature and pressures, and optionally, in the presence or absence of a base or high catalyst loadings using low temperatures and pressures and high loadings of base to effect dynamic kinetic resolution of achiral amides.
Use of ruthenium complexes for preparing amides, polypeptides and cyclic dipeptides
A process for preparing amides by reacting a primary amine and a primary alcohol in the presence of a Ruthenium complex to generate the amide and molecular hydrogen. Primary amines are directly acylated by equimolar amounts of alcohols to produce amides and molecular hydrogen (the only byproduct) in high yields and high turnover numbers. Also disclosed are processes for hydrogenation of amides to alcohols and amines; hydrogenation of organic carbonates to alcohols; hydrogenation of carbamates or urea derivatives to alcohols and amines; amidation of esters; acylation of alcohols using esters; coupling of alcohols with water and a base to form carboxylic acids; dehydrogenation of beta-amino alcohols to form pyrazines and cyclic dipeptides; and dehydrogenation of secondary alcohols to ketones. These reactions are catalyzed by a Ruthenium complex which is based on a dearomatized PNN-type ligand of formula A1 or precursors thereof of formulae A2 or A3.
Use of ruthenium complexes for preparing amides, polypeptides and cyclic dipeptides
A process for preparing amides by reacting a primary amine and a primary alcohol in the presence of a Ruthenium complex to generate the amide and molecular hydrogen. Primary amines are directly acylated by equimolar amounts of alcohols to produce amides and molecular hydrogen (the only byproduct) in high yields and high turnover numbers. Also disclosed are processes for hydrogenation of amides to alcohols and amines; hydrogenation of organic carbonates to alcohols; hydrogenation of carbamates or urea derivatives to alcohols and amines; amidation of esters; acylation of alcohols using esters; coupling of alcohols with water and a base to form carboxylic acids; dehydrogenation of beta-amino alcohols to form pyrazines and cyclic dipeptides; and dehydrogenation of secondary alcohols to ketones. These reactions are catalyzed by a Ruthenium complex which is based on a dearomatized PNN-type ligand of formula A1 or precursors thereof of formulae A2 or A3.
Use of ruthenium complexes for preparing amides, polypeptides and cyclic dipeptides
A process for preparing amides by reacting a primary amine and a primary alcohol in the presence of a Ruthenium complex to generate the amide and molecular hydrogen. Primary amines are directly acylated by equimolar amounts of alcohols to produce amides and molecular hydrogen (the only byproduct) in high yields and high turnover numbers. Also disclosed are processes for hydrogenation of amides to alcohols and amines; hydrogenation of organic carbonates to alcohols; hydrogenation of carbamates or urea derivatives to alcohols and amines; amidation of esters; acylation of alcohols using esters; coupling of alcohols with water and a base to form carboxylic acids; dehydrogenation of beta-amino alcohols to form pyrazines and cyclic dipeptides; and dehydrogenation of secondary alcohols to ketones. These reactions are catalyzed by a Ruthenium complex which is based on a dearomatized PNN-type ligand of formula A1 or precursors thereof of formulae A2 or A3.
Viscoelastic surfactants for self-diverting acid under high temperature and preparation method
A viscoelastic surfactant (VES) for a self-diverting acid under high temperature has a structural formula shown as formula (I), wherein, n is saturated hydrocarbon with 2 to 8 carbon atoms; R.sub.1 is saturated or unsaturated hydrocarbon with 18 to 28 carbon atoms; R.sub.2 and R.sub.3 are independently methyl, ethyl or hydrogen, and R.sub.2 and R.sub.3 can be the same or different; and X.sup.− is any one of Cl.sup.−, Br.sup.−, CO.sub.3.sup.2−, SO.sub.4.sup.2−, HCOO.sup.− and CH.sub.3COO.sup.−. The method for preparing the surfactant includes subjecting a fatty acid and an organic amine to acid-amine condensation to obtain an intermediate. The intermediate reacts with a metal hydride to obtain a fatty amine. Then, an acid solution is used to protonate the fatty amine to obtain an ultra-long-chain viscoelastic cationic surfactant. The present invention also provides use of the surfactant as a thickener for a self-diverting acid.
Viscoelastic surfactants for self-diverting acid under high temperature and preparation method
A viscoelastic surfactant (VES) for a self-diverting acid under high temperature has a structural formula shown as formula (I), wherein, n is saturated hydrocarbon with 2 to 8 carbon atoms; R.sub.1 is saturated or unsaturated hydrocarbon with 18 to 28 carbon atoms; R.sub.2 and R.sub.3 are independently methyl, ethyl or hydrogen, and R.sub.2 and R.sub.3 can be the same or different; and X.sup.− is any one of Cl.sup.−, Br.sup.−, CO.sub.3.sup.2−, SO.sub.4.sup.2−, HCOO.sup.− and CH.sub.3COO.sup.−. The method for preparing the surfactant includes subjecting a fatty acid and an organic amine to acid-amine condensation to obtain an intermediate. The intermediate reacts with a metal hydride to obtain a fatty amine. Then, an acid solution is used to protonate the fatty amine to obtain an ultra-long-chain viscoelastic cationic surfactant. The present invention also provides use of the surfactant as a thickener for a self-diverting acid.