公开(公告)号：US20220073344A1

公开(公告)日：2022-03-10

申请号：US17416772

申请日：2019-12-30

Applicant: YEDA RESEARCH AND DEVELOPMENT CO., LTD.

Inventor： David MILSTEIN ,  You-Quan ZHOU ,  Aviel ANABY

IPC: C01B3/00 ,  B01J31/20 ,  B01J31/18 ,  B01J31/24

Abstract: This invention provides a reversible hydrogen loading and discharging system and a reversible method for loading and discharging hydrogen. The system and the methods of this invention comprise ethylene glycol as a liquid organic hydrogen carrier and at least one transition metal. By reacting ethylene glycol with at least one transition metal; at least one hydrogen molecule and at least one oligoester of ethylene glycol are formed (hydrogen releasing)⋅, and by reacting at least one oligoester of ethylene glycol with at least one transition metal and at least one hydrogen molecule, at least one ethylene glycol is formed (hydrogen loading).

公开(公告)号：US20160152663A1

公开(公告)日：2016-06-02

申请号：US15017049

申请日：2016-02-05

Applicant: YEDA RESEARCH AND DEVELOPMENT CO. LTD.

Inventor： David MILSTEIN ,  Chidambaram GUNANATHAN ,  Yehoshua BEN-DAVID ,  Ekambaram BALARAMAN ,  Boopathy GNANAPRAKASAM ,  Jing ZHANG

IPC: C07K5/12 ,  C07C231/02 ,  C07C45/00 ,  C07D241/12 ,  C07C51/235 ,  C07C67/28 ,  C07D487/14 ,  C07D295/185

CPC classification number: C07K5/12 ,  C07C29/136 ,  C07C45/002 ,  C07C51/235 ,  C07C67/03 ,  C07C67/28 ,  C07C67/39 ,  C07C209/50 ,  C07C213/00 ,  C07C231/00 ,  C07C231/02 ,  C07C2601/08 ,  C07C2601/14 ,  C07D241/12 ,  C07D295/185 ,  C07D307/52 ,  C07D487/14 ,  C07K1/02 ,  C07K1/10 ,  C08L79/02 ,  Y02P20/52 ,  C07C233/05 ,  C07C235/06 ,  C07C235/10 ,  C07C233/36 ,  C07C211/27 ,  C07C215/28 ,  C08L1/00 ,  C07C69/14 ,  C07C69/24 ,  C07C31/04 ,  C07C31/08 ,  C07C31/10 ,  C07C31/12

Abstract: 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.

Abstract translation: 在钌络合物的存在下通过伯胺和伯醇反应制备酰胺以产生酰胺和分子氢的方法。 伯胺通过等摩尔量的醇直接酰化，以高产率和高周转数产生酰胺和分子氢（仅副产物）。 还公开了将酰胺氢化成醇和胺的方法; 将有机碳酸酯氢化成醇; 将氨基甲酸酯或脲衍生物氢化成醇和胺; 酯化酰胺化; 使用酯酰化醇; 醇与水和碱偶联形成羧酸; β-氨基醇的脱氢形成吡嗪和环状二肽; 并将仲醇脱氢成酮。 这些反应由基于式A1的脱芳香族PNN型配体或式A2或A3的前体的钌络合物催化。

公开(公告)号：US20150284417A1

公开(公告)日：2015-10-08

申请号：US14702641

申请日：2015-05-01

Applicant: YEDA RESEARCH AND DEVELOPMENT CO., LTD.

Inventor： David MILSTEIN ,  Ekambaram BALARAMAN ,  Chidambaram GUNANATHAN ,  Boopathy GNANAPRAKASAM ,  Jing ZHANG

IPC: C07F15/00 ,  C07D305/06 ,  C07D307/44 ,  C07D295/023 ,  C07K5/12 ,  C07C29/149 ,  C07C213/02 ,  C07C67/00 ,  C07C231/10 ,  C07D307/52 ,  C07D295/185 ,  C07C51/00 ,  C07D309/30 ,  C07D307/33 ,  C07D307/83 ,  C07D241/12 ,  C07K1/00 ,  C07B41/08 ,  C07B41/02 ,  C07B41/12 ,  C07B43/06 ,  C07B43/04 ,  B01J31/24 ,  C07C209/62

CPC classification number: C07K5/12 ,  B01J31/18 ,  B01J31/189 ,  B01J31/2404 ,  B01J31/2409 ,  B01J31/248 ,  B01J31/2485 ,  B01J2231/40 ,  B01J2231/49 ,  B01J2231/643 ,  B01J2231/763 ,  B01J2531/0244 ,  B01J2531/821 ,  C07B41/02 ,  C07B41/08 ,  C07B41/12 ,  C07B43/04 ,  C07B43/06 ,  C07C29/136 ,  C07C29/149 ,  C07C29/177 ,  C07C41/16 ,  C07C41/26 ,  C07C45/002 ,  C07C45/006 ,  C07C51/00 ,  C07C51/02 ,  C07C51/23 ,  C07C51/295 ,  C07C67/00 ,  C07C67/03 ,  C07C67/297 ,  C07C209/00 ,  C07C209/62 ,  C07C213/00 ,  C07C213/02 ,  C07C231/02 ,  C07C231/10 ,  C07C2601/08 ,  C07C2601/10 ,  C07C2601/14 ,  C07D207/06 ,  C07D207/08 ,  C07D211/12 ,  C07D213/38 ,  C07D241/08 ,  C07D241/12 ,  C07D295/023 ,  C07D295/027 ,  C07D295/185 ,  C07D305/06 ,  C07D307/14 ,  C07D307/33 ,  C07D307/44 ,  C07D307/52 ,  C07D307/83 ,  C07D309/30 ,  C07D487/14 ,  C07F9/58 ,  C07F9/65583 ,  C07F15/0046 ,  C07F15/0053 ,  C07K1/00 ,  C08G69/00 ,  Y02P20/52 ,  C07C233/05 ,  C07C235/06 ,  C07C233/07 ,  C07C235/16 ,  C07C235/14 ,  C07C235/10 ,  C07C211/27 ,  C07C211/07 ,  C07C211/35 ,  C07C211/46 ,  C07C211/10 ,  C07C215/28 ,  C07C217/58 ,  C07C69/14 ,  C07C69/24 ,  C07C31/125 ,  C07C31/12 ,  C07C49/78 ,  C07C49/04 ,  C07C49/10 ,  C07C49/08 ,  C07C49/403 ,  C07C31/205 ,  C07C31/202 ,  C07C31/04 ,  C07C31/08 ,  C07C33/20 ,  C07C33/22 ,  C07C31/1355 ,  C07C31/10 ,  C07C43/13 ,  C07C69/78 ,  C07C69/75 ,  C07C53/124 ,  C07C53/126 ,  C07C59/125 ,  C07C57/32 ,  C07C61/08 ,  C07C57/30 ,  C07C65/21 ,  C07C63/08 ,  C07C63/06

Abstract: The present invention relates to novel Ruthenium complexes and related borohydride complexes, and their use for (1) hydrogenation of amides (including polyamides) to alcohols and amines; (2) preparing amides from alcohols with amines (including preparing polyamides (e.g., polypeptides) by reacting dialcohols and diamines or by polymerization of amino alcohols); (3) hydrogenation of esters to alcohols (including hydrogenation of cyclic esters (lactones), cyclic di-esters (di-lactones) or polyesters); (4) hydrogenation of organic carbonates (including polycarbonates) to alcohols and of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (5) dehydrogenative coupling of alcohols to esters; (6) hydrogenation of secondary alcohols to ketones; (7) amidation of esters (synthesis of amides from esters and amines); (8) acylation of alcohols using esters; (9) coupling of alcohols with water to form carboxylic acids; and (10) dehydrogenation of beta-amino alcohols to form pyrazines. The present invention further relates to novel uses of certain pyridine Ruthenium complexes.

Abstract translation: 本发明涉及新型钌络合物和相关硼氢化物配合物及其用于（1）将酰胺（包括聚酰胺）氢化成醇和胺的用途; （2）由醇与胺（包括通过使二元醇和二胺反应制备聚酰胺（如多肽）或通过氨基醇的聚合）制备酰胺; （3）将酯氢化成醇（包括环酯（内酯）的加氢，环状二酯（二内酯）或聚酯））; （4）有机碳酸酯（包括聚碳酸酯）对醇和氨基甲酸酯（包括聚氨基甲酸酯）或脲衍生物氢化成醇和胺; （5）醇与酯的脱氢偶联; （6）将仲醇醇化成酮类; （7）酯的酰胺化（由酯和胺合成酰胺）; （8）使用酯酰化醇; （9）将醇与水偶联以形成羧酸; 和（10）β-氨基醇脱氢形成吡嗪。 本发明还涉及某些吡啶钌络合物的新用途。

公开(公告)号：US20170107251A1

公开(公告)日：2017-04-20

申请号：US15355082

申请日：2016-11-18

Applicant: YEDA RESEARCH AND DEVELOPMENT CO. LTD.

Inventor： David MILSTEIN ,  Ekambaram Balaraman ,  Chidambaram Gunanathan ,  Boopathy Gnanaprakasam ,  Jing Zhang

IPC: C07K5/12 ,  C07C209/62 ,  C07D305/06 ,  C07D307/44 ,  C07C29/149 ,  C07D295/027 ,  C07D207/06 ,  C07D207/08 ,  C07D211/12 ,  C07C231/10 ,  C07D307/52 ,  C07D295/185 ,  C07C67/00 ,  C07C213/02 ,  C07C51/00 ,  C07D309/30 ,  C07D307/33 ,  C07D307/83 ,  C07C67/297 ,  C07D241/12 ,  C07B41/02 ,  C07B43/04 ,  C07B41/08 ,  C07B41/12 ,  C07B43/06 ,  B01J31/24 ,  C07C41/26

CPC classification number: C07K5/12 ,  B01J31/18 ,  B01J31/189 ,  B01J31/2404 ,  B01J31/2409 ,  B01J31/248 ,  B01J31/2485 ,  B01J2231/40 ,  B01J2231/49 ,  B01J2231/643 ,  B01J2231/763 ,  B01J2531/0244 ,  B01J2531/821 ,  C07B41/02 ,  C07B41/08 ,  C07B41/12 ,  C07B43/04 ,  C07B43/06 ,  C07C29/136 ,  C07C29/149 ,  C07C29/177 ,  C07C41/16 ,  C07C41/26 ,  C07C45/002 ,  C07C45/006 ,  C07C51/00 ,  C07C51/02 ,  C07C51/23 ,  C07C51/295 ,  C07C67/00 ,  C07C67/03 ,  C07C67/297 ,  C07C209/00 ,  C07C209/62 ,  C07C213/00 ,  C07C213/02 ,  C07C231/02 ,  C07C231/10 ,  C07C2601/08 ,  C07C2601/10 ,  C07C2601/14 ,  C07D207/06 ,  C07D207/08 ,  C07D211/12 ,  C07D213/38 ,  C07D241/08 ,  C07D241/12 ,  C07D295/023 ,  C07D295/027 ,  C07D295/185 ,  C07D305/06 ,  C07D307/14 ,  C07D307/33 ,  C07D307/44 ,  C07D307/52 ,  C07D307/83 ,  C07D309/30 ,  C07D487/14 ,  C07F9/58 ,  C07F9/65583 ,  C07F15/0046 ,  C07F15/0053 ,  C07K1/00 ,  C08G69/00 ,  Y02P20/52 ,  C07C233/05 ,  C07C235/06 ,  C07C233/07 ,  C07C235/16 ,  C07C235/14 ,  C07C235/10 ,  C07C211/27 ,  C07C211/07 ,  C07C211/35 ,  C07C211/46 ,  C07C211/10 ,  C07C215/28 ,  C07C217/58 ,  C07C69/14 ,  C07C69/24 ,  C07C31/125 ,  C07C31/12 ,  C07C49/78 ,  C07C49/04 ,  C07C49/10 ,  C07C49/08 ,  C07C49/403 ,  C07C31/205 ,  C07C31/202 ,  C07C31/04 ,  C07C31/08 ,  C07C33/20 ,  C07C33/22 ,  C07C31/1355 ,  C07C31/10 ,  C07C43/13 ,  C07C69/78 ,  C07C69/75 ,  C07C53/124 ,  C07C53/126 ,  C07C59/125 ,  C07C57/32 ,  C07C61/08 ,  C07C57/30 ,  C07C65/21 ,  C07C63/08 ,  C07C63/06

Abstract: The present invention relates to novel Ruthenium complexes and related borohydride complexes, and their use for (1) hydrogenation of amides (including polyamides) to alcohols and amines; (2) preparing amides from alcohols with amines (including preparing polyamides (e.g., polypeptides) by reacting dialcohols and diamines or by polymerization of amino alcohols); (3) hydrogenation of esters to alcohols (including hydrogenation of cyclic esters (lactones), cyclic di-esters (di-lactones) or polyesters); (4) hydrogenation of organic carbonates (including polycarbonates) to alcohols and of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (5) dehydrogenative coupling of alcohols to esters; (6) hydrogenation of secondary alcohols to ketones; (7) amidation of esters (synthesis of amides from esters and amines); (8) acylation of alcohols using esters; (9) coupling of alcohols with water to form carboxylic acids; and (10) dehydrogenation of beta-amino alcohols to form pyrazines. The present invention further relates to novel uses of certain pyridine Ruthenium complexes.

公开(公告)号：US20240391866A1

公开(公告)日：2024-11-28

申请号：US18692847

申请日：2022-10-12

Applicant: YEDA RESEARCH AND DEVELOPMENT CO. LTD.

Inventor： David MILSTEIN ,  Kumar Das UTTAM ,  Kar SAYAN

IPC: C07C217/70 ,  B01J31/18

Abstract: This invention is directed to a catalytic hydrogenation process for the preparation of 1-(4-(benzyloxy)-3-(hydroxymethyl)phenyl)-2-(tert-butylamino)ethanol, which is an intermediate for the preparation of Salbutamol.

公开(公告)号：US20230372915A1

公开(公告)日：2023-11-23

申请号：US18351557

申请日：2023-07-13

Applicant: YEDA RESEARCH AND DEVELOPMENT CO. LTD.

Inventor： David MILSTEIN ,  Alex NERUSH ,  Matthias VOGT ,  Arup MUKHERJEE ,  Noel Angel ESPINOSA-JALAPA ,  Subrata CHAKRABORTY

IPC: B01J31/18 ,  B01J31/24 ,  C07C249/02

CPC classification number: B01J31/181 ,  B01J31/2428 ,  C07C249/02 ,  B01J2231/348 ,  B01J2531/72 ,  C07B43/06

Abstract: The present invention relates to novel manganese complexes and their use, inter alia, for homogeneous catalysis in (1) the preparation of imine by dehydrogenative coupling of an alcohol and amine; (2)C—C coupling in Michael addition reaction using nitriles as Michael donors; (3) dehydrogenative coupling of alcohols to give esters and hydrogen gas (4) hydrogenation of esters to form alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di-lactones), or polyesters); (5) hydrogenation of amides (including cyclic dipeptides, lactams, diamide, polypeptides and polyamides) to alcohols and amines (or diamine); (6) hydrogenation of organic carbonates (including polycarbonates) to alcohols or hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (7) dehydrogenation of secondary alcohols to ketones; (8) amidation of esters (i.e., synthesis of amides from esters and amines); (9) acylation of alcohols using esters; (10) coupling of alcohols with water and a base to form carboxylic acids; and (11) preparation of amino acids or their salts by coupling of amino alcohols with water and a base. (12) preparation of amides (including formamides, cyclic dipeptides, diamide, lactams, polypeptides and polyamides) by dehydrogenative coupling of alcohols and amines; (13) preparation of imides from diols.

公开(公告)号：US20220024758A1

公开(公告)日：2022-01-27

申请号：US17427929

申请日：2020-02-06

Applicant: YEDA RESEARCH AND DEVELOPMENT CO., LTD.

Inventor： David MILSTEIN ,  Yinjun XIE

IPC: C01B3/00

Abstract: The present invention provides a system, a process and a method of storing hydrogen (H2) and releasing it on demand, comprising and making use of N-heterocycles as liquid organic hydrogen carriers (LOHCs).

公开(公告)号：US20170283447A1

公开(公告)日：2017-10-05

申请号：US15508114

申请日：2015-09-03

Applicant: YEDA RESEARCH AND DEVELOPMENT CO. LTD.

Inventor： David MILSTEIN ,  Peng HU ,  Eran FOGLER ,  Jai Anand Garg Narayana RAO

IPC: C07F15/00 ,  C07C67/40 ,  C07C29/149 ,  C07D241/08 ,  C07D207/16 ,  C07C231/08 ,  C07C213/00 ,  C07C249/02 ,  C07C227/02 ,  B01J31/24 ,  C07C231/10

CPC classification number: C07F15/0046 ,  B01J31/24 ,  B01J31/2404 ,  B01J31/28 ,  B01J2231/641 ,  B01J2231/763 ,  B01J2531/0244 ,  B01J2531/821 ,  C07C29/149 ,  C07C67/00 ,  C07C67/40 ,  C07C209/00 ,  C07C209/50 ,  C07C213/00 ,  C07C227/02 ,  C07C231/02 ,  C07C231/08 ,  C07C231/10 ,  C07C249/02 ,  C07C2601/14 ,  C07D207/16 ,  C07D241/08 ,  C07C69/24 ,  C07C69/78 ,  C07C69/92 ,  C07C69/708 ,  C07C69/63 ,  C07C31/125 ,  C07C31/08 ,  C07C35/08 ,  C07C31/12 ,  C07C31/20 ,  C07C31/38 ,  C07C33/22 ,  C07C33/20 ,  C07C233/36 ,  C07C237/08 ,  C07C211/10 ,  C07C215/08 ,  C07C229/08 ,  C07C229/12 ,  C07C229/56 ,  C07C233/11 ,  C07C229/14 ,  C07C233/05 ,  C07C211/03 ,  C07C229/36

Abstract: 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.