41 |
Preparation and use of (2-butene-1,4-diyl)magnesium complexes in organic
synthesis |
US100058 |
1993-07-30 |
US5498734A |
1996-03-12 |
Reuben D. Rieke |
The magnesium complexes of cyclic hydrocarbons containing conjugated dienes, such as 1,2-dimethylenecycloalkanes, and 1,3-butadienes, are readily prepared in high yields using highly reactive magnesium. Reactions of these (2-butene-1,4 diyl)magnesium reagents with electrophiles such as dibromoalkanes, alkylditosylates, alkylditriflates, bromoalkylnitriles, esters, or amides serve as a convenient method for synthesizing carbocyclic systems. Significantly, carbocycles prepared by this method contain functional groups such as the exocyclic double bond or a keto group in one of the rings which could be used for further elaboration of these molecules. Furthermore, fused bicyclic systems containing a substituted five-membered ring can be conveniently prepared at high temperatures by the reactions of (2-butene-1,4-diyl)magnesium complexes with carboxylic esters or acid halides whereas low temperatures lead to regioselective synthesis of .beta.,.gamma.-unsaturated ketones. Additionally, .gamma.-lactones, including spiro .gamma.-lactones, can be easily prepared in a one pot synthesis from the reaction of (2-butene-1,4-diyl)magnesium complexes with a ketone or aldehyde and carbon dioxide. Also, .delta.-lactones can be easily prepared in a one pot synthesis from the reaction of (2-butene-1,4-diyl)magnesium complexes with epoxides followed by reaction with CO.sub.2. Use of .alpha.-hydroxy epoxides without the addition of CO.sub.2 leads to the synthesis of vicinal diols. Chiral epoxides lead to chiral alcohols. |
42 |
Preparation and use of (2-butene-1,4-diyl)magnesium complexes in organic
synthesis |
US763629 |
1991-09-23 |
US5231205A |
1993-07-27 |
Reuben D. Rieke |
The magnesium complexes of cyclic hydrocarbons, such as 1,2-dimethylenecycloalkanes, are readily prepared in high yields using highly reactive magnesium. Reactions of these (2-butene-1,4-diyl)magnesium reagents with electrophiles such as dibromoalkanes, alkylditosylates, or bromoalkylnitriles serve as a convenient method for synthesizing spirocyclic systems. Significantly, spirocarbocycles prepared by thisThe present invention was made with Government support under Contract No. GM35153 awarded by the National Institute of Health. The Government has certain rights in the invention. |
43 |
Carboxylation of grignard reagents in the presence of liquid co2 |
US30627963 |
1963-09-03 |
US3360551A |
1967-12-26 |
DAVID REGENBOGEN |
|
44 |
PROCESS FOR THE PREPARATION OF TRIAZINES |
US15571113 |
2016-05-12 |
US20180170886A1 |
2018-06-21 |
Nadine GREINER; Sandro SCHMID; René Tobias STEMMLER |
The invention relates to an improved process for the manufacture of bis-resorcinyl triazines of formula (I) wherein R1 is a C1C18alkyl group or C2-C18alkenyl group as well as the respective alkyl substituted bis-resorcinyl derivatives of formula (II) wherein R1 is a C1-C18alkyl group or C2-C18alkenyl group and R2 and R3 are independently of each other a C1-C18alkyl group or a C2-C18alkenyl group. |
45 |
TRICYCLIC ANALOGUES, PREPARATION METHOD AND USES THEREOF |
US15556932 |
2016-03-03 |
US20180064696A1 |
2018-03-08 |
Fajun NAN; Boliang LI; Yang ZHAN; Xiaowei ZHANG; Ying XIONG; Xichan HU; Yangming ZHANG |
The present invention relates to a series of analogues of natural product Pyripyropene A represented by general formula I and a preparation method and use thereof. More particularly, the present invention relates to analogues of the natural product Pyripyropene A, a preparation method and use thereof as the acyl-CoA:cholesterol acyltransferase 2 (ACAT2) inhibitors for the treatment of cardiovascular diseases such as atherosclerosis and the like. |
46 |
Method for allylating and vinylating aryl, heteroaryl, alkyl, and alkene halogenides using transition metal catalysis |
US13577278 |
2011-02-01 |
US09309188B2 |
2016-04-12 |
Matthias Gotta; Bernd Wilhelm Lehnemann; Waldemar Maximilian Czaplik; Matthias Mayer; Axel Jacobi Von Wangelin |
What is described is a process for preparing organic compounds of the general formula (I) R—R′ (I) by converting a corresponding compound of the general formula (II) R—X (II) in which X is fluorine, chlorine, bromine or iodine to an organomagnesium compound of the general formula (III) [M+]n[RmMgXkY1] (III) wherein compounds of the formula (III) are reacted with a compound of the general formula (IV) characterized in that the reaction of (III) with (IV) is performed in the presence of a) catalytic amounts of an iron compound, based on the compound of the general formula (II), and optionally in the presence of b) a nitrogen-, oxygen- and/or phosphorus-containing additive in a catalytic or stoichiometric amount, based on the compound of the general formula (II). |
47 |
Process of preparing Grignard reagent |
US14083842 |
2013-11-19 |
US09145341B2 |
2015-09-29 |
Yair Ein-Eli; Daniel Luder; Alexander Kraytsberg |
A novel process of preparing a Grignard reagent is disclosed. The process is effected by electrochemically reacting a Grignard precursor with an electrode which comprises a metal for forming the Grignard reagent, in the presence an electrolyte solution that comprises a room temperature ionic liquid (RTIL). Electrochemical cells and systems for performing the process, and uses thereof in various applications are also disclosed. |
48 |
PROCESS OF PREPARING GRIGNARD REAGENT |
US14083842 |
2013-11-19 |
US20140142332A1 |
2014-05-22 |
Yair Ein-Eli; Daniel Luder; Alexander Kraytsberg |
A novel process of preparing a Grignard reagent is disclosed. The process is effected by electrochemically reacting a Grignard precursor with an electrode which comprises a metal for forming the Grignard reagent, in the presence an electrolyte solution that comprises a room temperature ionic liquid (RTIL). Electrochemical cells and systems for performing the process, and uses thereof in various applications are also disclosed. |
49 |
Solutions of anhydrous lanthanide salts and its preparation |
US11991131 |
2006-09-01 |
US08470982B2 |
2013-06-25 |
Paul Knochel; Arkady Krasovskiy; Felix Kopp |
The present invention relates to anhydrous solutions of MX3-Z LiA in a solvent, wherein M is a lanthanide including lanthanum, or yttrium or indium; z>0; and X and A are independently or both monovalent anions, preferably Cl, Br or I. The solution is readily prepared by dissolving or suspending MX3 or its hydrate and z equiv LiA in water or hydrophilic solvents, or mixtures thereof, removing the solvent under vacuum and dissolving the resulting powder in another solvent. The solution of MX3-Z LiA can advantageously be used e.g. in addition reactions of Grignard reagents to ketones and imines. Even the catalytic use of MX3-Z LiA is possible. |
50 |
Universal grignard metathesis polymerization |
US11849229 |
2007-08-31 |
US08288508B2 |
2012-10-16 |
Richard D. McCullough; Mihaela C. Iovu; Itaru Osaka |
Universal Grignard Metathesis (GRIM) reactions which provide access to conjugated polymers by GRIM methods. A method comprising: providing an unsaturated ring compound comprising at least two halogen ring substituents, providing an organomagnesium reagent comprising an organomagnesium component and a metal activation agent, combining the unsaturated ring compound with the reagent to form a second compound by metal-halogen exchange, wherein the metal activation agent activates the metal-halogen exchange, coupling the second compound to itself in an oligomerization or polymerization reaction. Metal activation agent can be lithium chloride. The process is commercially attractive and can be executed in good yields. Polyfluorenes, polypyrroles, and polythiophenes can be prepared for use in OLED, PLED, photovoltaic, transistor, antistatic coatings, and sensor applications. |
51 |
Preparation and use of magnesium amides |
US12087351 |
2007-01-18 |
US08134005B2 |
2012-03-13 |
Paul Knochel; Arkady Krasovskiy; Valeria Krasovskaya; Christoph Josef Rohbogner; Giuliano Cesar Clososki |
The present application relates to mixed Mg/Li amides of the general formula R1R2N—Mg(NR3R4)mX,.m zLiY (II) wherein R1, R2, R3, and R4 are, independently, selected from H, substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or silyl derivatives thereof; and R1 and R2 together, or R3 and R4 together can be part of a cyclic or polymeric structure; and wherein at least one of R1 and R2 and at least one of R3 and R is other than H; X and Y are, independently, selected from the group consisting of F; Cl; Br; I; CN; SCN; NCO; HaIOn, wherein n=3 or 4 and Hal is selected from Cl, Br and I; NO3; BF4; PF6; H; a carboxylate of the general formula RXCO2; an alcoholate of the general formula ORX; a thiolate of the general formula SRX; RXP(O)O2; or SCORX; or SCSRX; OnSRx, wherein n=2 or 3; or NOn, wherein n=2 or 3; and a derivative thereof; wherein Rx is a substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or derivatives thereof, or H; m is O or 1; and z>O; as well as a process for the preparation of the mixed Mg/Li amides and the use of these amides, e.g. as bases. |
52 |
Method for grignard type reactions in microreactors |
US12373636 |
2007-07-11 |
US07939698B2 |
2011-05-10 |
Dominique Roberge; Nikolaus Bieler; Laurent Ducry |
The present invention relates to a process for Grignard type reactions comprising mixing at least two fluids in a microreactor having at least two injection points. |
53 |
Process for production of biphenyl derivatives |
US12092466 |
2006-10-25 |
US07893306B2 |
2011-02-22 |
Tamio Hayashi; Jiro Nakatani |
A process for producing biphenyl derivatives represented by formula (1), including reacting a chlorine atom of a benzene derivative represented by formula (2) with metallic magnesium to form a Grignard reagent, and coupling two molecules of the Grignard reagent with each other in the presence of a catalyst. (wherein A represents at least one member selected from the group consisting of trifluoromethyl and fluoro, and n is an integer of 1 to 4.) (wherein A represents at least one member selected from the group consisting of trifluoromethyl and fluoro, and n is an integer of 1 to 4.) |
54 |
METHOD FOR PRODUCING BIPHENYL DERIVATIVE |
US12377892 |
2007-10-12 |
US20100230634A1 |
2010-09-16 |
Tamio Hayashi; Jiro Nakatani |
A method produces a biphenyl derivative, with an industrially high yield and excellent productivity, by use of a raw material which is low in cost and toxicity. The method for producing the biphenyl derivative represented by Formula (1) is characterized in that a chlorine atom in a benzene derivative represented by Formula (2) reacts with magnesium metal to convert the benzene derivative into a Grignard reagent, and then the Grignard reagent is subjected to a coupling reaction in the presence of a catalyst and a dichloropropane: (wherein A represents at least one selected from alkyl groups, alkoxy groups, alkoxymethyl groups, a vinyl group, phenyl groups and chlorine, and n represents an integer of 1 to 4). |
55 |
Preparation and Use of Magnesium Amides |
US12087351 |
2007-01-18 |
US20090176988A1 |
2009-07-09 |
Paul Knochel; Arkady Krasovskiy; Valeria Krasovskaya; Christoph Josef Rohbogner; Giuliano Cesar Clososki |
The present application relates to mixed Mg/Li amides of the general formula R1R2N—Mg(NR3R4)mX,m zLiY (II) wherein R1, R2, R3, and R4 are, independently, selected from H, substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or silyl derivatives thereof; and R1 and R2 together, or R3 and R4 together can be part of a cyclic or polymeric structure; and wherein at least one of R1 and R2 and at least one of R3 and R is other than H; X and Y are, independently, selected from the group consisting of F; Cl; Br; I; CN; SCN; NCO; HalOn, wherein n=3 or 4 and Hal is selected from Cl, Br and I; NO3; BF4; PF6; H; a carboxylate of the general formula RXCO2; an alcoholate of the general formula ORX; a thiolate of the general formula SRX; RXP(O)O2; or SCORX; or SCSRX; OnSRx, wherein n=2 or 3; or NOn, wherein n=2 or 3; and a derivative thereof; wherein Rx is a substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or derivatives thereof, or H; m is O or 1; and z>O; as well as a process for the preparation of the mixed Mg/Li amides and the use of these amides, e.g. as bases. |
56 |
Solvents containing cycloakyl alkyl ethers and process for production of the ethers |
US10481340 |
2002-06-27 |
US07494962B2 |
2009-02-24 |
Idan Kin; Genichi Ohta; Kazuo Teraishi; Kiyoshi Watanabe |
The present inventions are (A) a solvent comprising at least one cycloalkyl alkyl ether (1) represented by the general formula: R1-O—R2 (wherein R1 is cyclopentyl or the like; and R2 is C1-10 alkyl or the like); (B) a method of preparations the ethers (1) characterized by reacting an alicyclic olefin with an alcohol in the presence of an acid ion-exchange resin having a water content of 5 wt % or less. The solvent is useful as cleaning solvent for electronic components, precision machinery components or the like, reaction solvent using various chemical reactions, extraction solvent for extracting objective organic substances, solvent or remover for electronic and electrical materials, and so on. The process enables industrially advantageous production of the objective cycloalkyl alkyl ethers (1). |
57 |
Grignard processes with improved yields of diphenylchlorosilanes as products |
US10585154 |
2004-12-17 |
US20070066826A1 |
2007-03-22 |
Binh Nguyen; Curtis Bedbury; Roger Humburg; Susan Jacob; Sarah Ratcliff; John Waterman |
A Grignard process for preparing phenyl-containing chlorosilane products, in particular diphenylchlorosilanes, is carried out in three embodiments. In the first embodiment, the reactants of the Grignard process are a phenyl Grignard reagent, an ether solvent, a trichlorosilane, and an aromatic hydrocarbon coupling solvent. In the second embodiment, the reactants of the Grignard process are a phenyl Grignard reagent, an ether solvent, a phenylchlorosilane, and an aromatic hydrocarbon coupling solvent. In the third embodiment, the reactants of the Grignard process are a phenyl Grignard reagent, an ether solvent, a trichlorosilane, a phenylchlorosilane, and an aromatic hydrocarbon coupling solvent. In each embodiment, the reactants are present in a particular mole ratio. |
58 |
Process for preparing unsymmetrical biaryls and alkylated aromatic compounds from arylnitriles |
US10202483 |
2002-07-23 |
US06962999B2 |
2005-11-08 |
Joseph A. Miller |
Methods are provided for the construction of unsymmetrical biaryl compounds and alkylated aromatic compounds from arylnitriles using a nickel or palladium catalyzed coupling in which the catalyst has at least one phosphine or phosphite ligand. |
59 |
Method of preparing organomagnesium compounds |
US11097707 |
2005-04-01 |
US20050218532A1 |
2005-10-06 |
Paul Knochel; Arkady Krasovskiy |
The present invention is directed to a reagent for use in the preparation of organomagnesium compounds as well as to a method of preparing such organomagnesium compounds. The present invention furthermore provides a method of preparing functionalized or unfunctionalized organic compounds as well as the use of the reagents of the present invention in the preparation of organometallic compounds and their reaction with electrophiles. Finally, the present invention is directed to the use of lithium salts—LiY in the preparation of organometallic compounds and their reactions with electrophiles and to an organometallic compound which is obtainable by the disclosed method. |
60 |
Solvents containing cycloakyl alkyl ethers and process for production of the ethers |
US10481340 |
2002-06-27 |
US20050065060A1 |
2005-03-24 |
Idan Kin; Genichi Ohta; Kazuo Teraishi; Kiyoshi Watanabe |
The present inventions are (A) a solvent comprising at least one cycloalkyl alkyl ether (1) represented by the general formula: R1-O-R2 (wherein R1 is cyclopentyl or the like; and R2 is C1-10 alkyl or the like); (B) a method of preparations the ethers (1) characterized by reacting an alicyclic olefin with an alcohol in the presence of an acid ion-exchange resin having a water content of 5 wt % or less. The solvent is useful as cleaning solvent for electronic components, precision machinery components or the like, reaction solvent using various chemical reactions, extraction solvent for extracting objective organic substances, solvent or remover for electronic and electrical materials, and so on. The process enables industrially advantageous production of the objective cycloalkyl alkyl ethers (1). |