Process for preparing organic compounds by a transition metal-catalysed cross-coupling reaction of an aryl-x, heteroaryl-x, cycloalkenyl-x or alkenyl-x compound with an alkyl, alkenyl, cycloalkyl or cycloalkenyl halide

This invention relates to a process for preparing functionalized aryl, heteroaryl, cycloalkenyl, or alkenyl compounds, by a transition-metal-catalyzed cross-coupling reaction of a substituted or unsubstituted aryl-X, heteroaryl-X, cycloalkenyl-X or alkenyl-X compound with an alkyl, alkenyl, cycloalkyl or cycloalkenyl halide, where X is a halide, diazonium, tosylate (p-toluenesulphonate), mesylate (methanesulphonate) or triflate (trifluoromethanesulphonate) leaving group.

Method for synthesis of secondary alcohols

A method for synthesis of secondary alcohols is provided for pharmaceutical secondary alcohol by addition of organoboronic acids with aldehydes in presence of the cobalt ion and bidentate ligands as the catalyst. In addition, an enantioselective synthesis method for secondary alcohols is also herein provided in the present invention. The present invention has advantages in using less expensive cobalt ion and commercially available chiral ligands as the catalyst, wide scope of organoboronic acids and aldehydes compatible with this catalytic reaction and achieving excellent yields and/or enantiomeric excess.

METHOD OF PREPARING 3,3,5,5-TETRAMETHYLCYCLOHEXANONE

Method of preparing 3,3,5,5-tetramethylcyclohexanone comprising step (i): (i) converting isophorone to 3,3,5,5-tetramethylcyclohexanone in the presence of methylmagnesium chloride. The thus prepared 3,3,5,5-tetramethylcyclohexanone may be employed in a method of preparing 1-amino-1,3,3,5,5-pentamethylcyclohexane (Neramexane) or a pharmaceutically acceptable salt thereof. 116.-. (canceled)17. A method of preparing 3 ,3 ,5 ,5-tetramethylcyclohexanone comprising step (i):(i) converting isophorone to 3,3,5,5-tetramethylcyclohexanone in the presence of methylmagnesium chloride.18. The method according to claim 17 , wherein step (i) is performed in the presence of a copper compound.19. The method according to claim 18 , wherein the copper compound is a copper(I) halide.20. The method according to claim 19 , wherein the copper(I) halide is copper(I) iodide.21. The method according to claim 17 , wherein step (i) performed in the presence of a lithium compound.22. The method according to claim 21 , wherein the lithium compound is a lithium halide claim 21 ,23. The method according to claim 22 , wherein the lithium halide is lithium chloride.24. The method according to claim 22 , wherein the molar ratio of copper(I) halide to lithium halide is in the range of from 1:1.5 to 1:2.5.25. The method according to claim 17 , wherein step (i) is performed in a solvent comprising an ether.26. The method according to claim 25 , wherein the ether is tetrahydrofuran.27. The method according to claim 17 , wherein in step (i) isophorone is converted to 3 claim 17 ,3 claim 17 ,5 claim 17 ,5-tetramethylcyclohexanone in the presence of methylmagnesium chloride claim 17 , copper(I) iodide and lithium chloride in tetrahydrofuran.28. The method according to claim 27 , wherein a solution comprising methylmagnesium chloride in tetrahydrofuran is added to a solution comprising isophorone claim 27 , copper(I) iodide and lithium chloride.29. A method of preparing 1-amino-1 claim 27 ,3 claim 27 ,3 ...

PROCESS FOR THE PRODUCTION OF SUBSTITUTED ELECTRON RICH DIPHENYLACETYLENES

The present invention relates to an improved process of production of substituted diphenylacetylenes (tolanes) of formula (I) which are starting materials for production of stilbenes products. 2. A process according to claim 1 , wherein a compound of formula (IIa) is reacted with a compound of formula (IIIa).3. A process according to claim 1 , wherein a compound of formula (IIb) is reacted with a compound of formula (IIIb).4. A process according to claim 1 , wherein{'sub': 1', '3', '2', '3', '2, 'Ris H; —CH; —CHCH, or —CH-phenyl;'}{'sub': 2', '2', '2', '3', '2', '3, 'Ris H or OR′, wherein R′is —CHor —CHCH;'}{'sub': 3', '3', '2', '3', '2, 'Ris H; —CH; —CHCH, or —CH-phenyl;'}{'sub': 4', '4', '4', '3', '2', '3, 'Ris H or OR′, wherein R′is —CHor —CHCH; and'}{'sub': 5', '3', '2', '3', '2, 'Ris H; —CH; —CHCH, or —CH-phenyl.'}5. A process according to claim 1 , wherein{'sub': 1', '3', '2', '3, 'Ris H; —CH; or —CHCH;'}{'sub': 2', '2', '2', '3', '2', '3, 'Ris H or OR′, wherein R′is —CHor —CHCH;'}{'sub': 3', '3', '2', '3, 'Ris H; —CH; or —CHCH;'}{'sub': 4', '4', '4', '3', '2', '3, 'Ris H or OR′, wherein R′is —CHor —CHCH; and'}{'sub': 5', '3', '2', '3, 'Ris H; —CH; or —CHCH;'}8. A process according to claim 1 , wherein the catalytic system is a heterogeneous system with catalysts on a carrier.9. A process according to claim 8 , wherein the catalytic system is chosen from the group consisting of Pd/BaSO claim 8 , Pd/CaCO claim 8 , Pd/AlO claim 8 , Pd/TiO claim 8 , Pd/SiO claim 8 , Pd/ZnO and Pd/C.11. A process according to claim 10 , which is carried out solvent free. The present invention relates to an improved process for the production of substituted electron rich diphenylacetylenes (tolanes), which are starting materials for the production of stilbenes.The present invention relates to the process for production of a compound of formula (I)These tolanes are characterized in that at least one of the phenyl rings is substituted by at least two substituents. The compounds ...

METHOD FOR THE PREPARATION OF PHOSPHINE BUTADIENE LIGANDS, COMPLEXES THEREOF WITH COPPER AND USE THEREOF IN CATALYSIS

A method for the creation of a carbon-carbon (C—C) bond or of a carbon-heteroatom (C-HE) bond includes reacting a compound carrying a leaving group with a nucleophilic compound carrying a carbon atom or a heteroatom (HE) capable of replacing the leaving group, thus creating a C—C or C-HE bond, in which process the reaction is carried out in the presence of an effective amount of a catalytic system comprising at least one copper/butadienylphosphine complex. 1. A method for the creation of a carbon-carbon (C—C) bond or of a carbon-heteroatom (C-HE) bond by reacting a compound carrying a leaving group with a nucleophilic compound carrying a carbon atom or a heteroatom (HE) capable of replacing the leaving group , thus creating a C—C or C-HE bond , in which process the reaction is carried out in the presence of an effective amount of a catalytic system comprising at least one copper/butadienylphosphine complex.3. The method as claimed in claim 1 , in which the Rand Rsubstituents of the butadienylphosphine of formula (1) are identical and each represent a radical chosen independently from alkyl claim 1 , aryl claim 1 , heteroaryl claim 1 , monoalkylamino claim 1 , dialkylamino claim 1 , alkoxy claim 1 , aryloxy and heteroaryloxy.4. The method as claimed in claim 1 , in which the Rand/or Rsubstituents can be connected so as to form claim 1 , with the carbon atom which carries them claim 1 , a carbocyclic or heterocyclic group having from 3 to 20 carbon atoms which is saturated claim 1 , unsaturated claim 1 , monocyclic or polycyclic claim 1 , in the latter case comprising two or three rings claim 1 , it being possible for the adjacent rings to be aromatic in nature.5. The method as claimed in claim 1 , in which the butadienylphosphine of formula (1) is of Z configuration or of E configuration or is in the form of a mixture in all proportions of the Z and E configurations.6. The method as claimed in claim 1 , in which the butadienylphosphine of formula (1) exhibits the ...

CARBON NANOHOOPS AND METHODS OF MAKING

The present invention provides cycloparaphenylene compounds, their macrocyclic precursors, and methods for making the compounds. The cycloparaphenylene compounds can be used to prepare armchair carbon nanotubes. 15.-. (canceled)7. The compound of claim 6 , wherein each Ris Calkyl.8. The compound of claim 6 , wherein each Ris methyl.9. The compound of claim 6 , wherein subscript m is an integer selected from the group consisting of 3 claim 6 , 4 and 6.10. The compound of claim 6 , wherein{'sup': '1', 'each Ris methyl; and'}subscript m is an integer selected from the group consisting of 3, 4 and 6.1118.-. (canceled)20. The method of claim 19 , wherein the contacting step comprises at least one compound of formula IIIa where each Ris a halogen and at least one compound of formula IIIa where each Ris a boronate.21. The method of claim 19 , wherein the contacting step comprises a plurality of compounds where one Ris a halogen and one Ris a boronate.22. The method of claim 19 , wherein each dashed line is a bond.23. The compound of claim 6 , wherein subscript m is an integer from 3 to 10.24. The method of claim 19 , wherein subscript m is an integer from 3 to 10. This application claims priority to U.S. Provisional Application No. 61/266,667, filed Dec. 4, 2009, which is incorporated in its entirety herein for all purposes.This invention was made with Government support under Grant No. DE-AC02-05CH11231, awarded by the U.S. Department of Energy. The Government has certain rights in this invention.Carbon nanotubes (also herein referred to as CNTs) are very small tube-shaped structures essentially having a composition of a graphite sheet in a tubular form. Carbon nanotubes have interesting and potentially useful electrical and mechanical properties and offer potential for various uses in electronic devices. Carbon nanotubes also feature extremely high electrical conductivity, very small diameters (much less than 100 nanometers), large aspect ratios (i.e. length/diameter ...

Method of carrying out cc-coupling reactions

The present invention is directed to a method of carrying out Suzuki-Miyaura CC-coupling reactions, including reacting an aryl halide with an aryl boronic acid in an organic solvent in the presence of a carbon supported palladium catalyst and a base, wherein the reactions are carried out at constant pH. The invention is also directed to a palladium on carbon catalyst suitable for catalyzing Suzuki-Miyaura CC-coupling reactions.

(PER)FLUOROPOLYETHERS WITH bi- OR ter-PHENYL END GROUPS

The present invention relates (per)fluoropolyether compounds comprising a (per)fluoropolyether chain (R) having at least two chain ends, wherein at least one of said chain ends have a bi- or ter-phenyl group bearing at least one nitro group and, optionally one or more further substituents. The invention also relates to processes for the preparation of such compounds and to their use for the preparation of lubricant compositions in the form of oils or greases. 1. A (per)fluoropolyether compound comprising a (per)fluoropolyether chain (R) having at least two chain ends , wherein at least one of said chain ends have a bi- or ter-phenyl group bearing at least one nitro group and , optionally , one or more further substituents.2. A (per)fluoropolyether compound according to claim 1 , wherein the (per)fluoropolyether chain (R) has two chain ends claim 1 , and wherein one or both chain ends have a bi- or ter-phenyl group bearing at least one nitro group and claim 1 , optionally claim 1 , one or more further substituents.3. The (per)fluoropolyether according to claim 1 , wherein the (per)fluoropolyether chain (R) is a fully or partially fluorinated polyoxyalkylene chain comprising repeating units R° claim 1 , statistically distributed along the chain claim 1 , said repeating units being selected from the group consisting of: —CFXO— claim 1 , —CFCFO— claim 1 , —CFCFCFO— claim 1 , —CFCF(CF)O— claim 1 , —CF(CF)CFO— claim 1 , —CFCFCFCFO— claim 1 , and —CRRCFCFO— wherein Rand R claim 1 , equal to or different from one another claim 1 , represent hydrogen claim 1 , chlorine claim 1 , a (per)fluoroalkoxy group or a (per)fluoroalkyl group.4. The (per)fluoropolyether compound according to claim 3 , wherein Ris a straight (per)fluoropolyoxyalkylene chain complying with formula (A):{'br': None, 'sub': 2', '2', 'm', '2', 'n', '2', '2', 'z', 'h, '—(CFCFO)(CFO)(CF(CF)O)—\u2003\u2003(A)'}wherein m and n are integers and h is 0 or an integer, selected in such a way that the number average ...

METHODS FOR PHOSPHINE OXIDE REDUCTION IN CATALYTIC WITTIG REACTIONS

A method for increasing the rate of phosphine oxide reduction, preferably during a Wittig reaction comprising use of an acid additive is provided. A room temperature catalytic Wittig reaction (CWR) the rate of reduction of the phosphine oxide is increased due to the addition of the acid additive is described. Furthermore, the extension of the CWR to semi-stabilized and non-stabilized ylides has been accomplished by utilization of a masked base and/or ylide-tuning.

Transfer Hydroformylation for the Production of Oxygenates

The present disclosure provides a method for forming oxygenates from olefins which includes hydroformylation of aldehydes as a formyl source alternative to syngas. In at least one embodiment, a hydroformylation process is performed at low-temperature and at or near ambient pressure for the conversion of olefins into aldehydes, thus reducing the formation of by-products such as via double bond or skeletal isomerization of the feedstock; or via further conversion of the formed aldehydes and alcohols. In at least one embodiment, the use of gaseous olefinic products (e.g., ethylene) instead of strained olefins (e.g., norbornene) improves the control equilibria in transfer hydroformylation reactions. 1. A method for preparing aldehydes , comprising:{'sub': x', 'y, 'contacting a Caldehyde, a Colefin, and a metal catalyst in a reaction vessel, wherein x is an integer of from 3 to 41 and y is an integer of from 2 to 40; and'}{'sub': y+1', 'x−1, 'obtaining a Caldehyde product and a Calkene product.'}2. The method of claim 1 , wherein the olefin is an alpha olefin.3. The method of claim 1 , further comprising maintaining a reaction temperature of from 80° C. to 100° C.4. The method of claim 1 , further comprising maintaining a reaction pressure of 150 psig or less.5. The method of claim 1 , wherein the method is free of introducing syngas into the reaction vessel.6. The method of claim 1 , wherein the method is free of introducing carbon monoxide into the reaction vessel.7. The method of claim 1 , wherein the alkene product is ethylene.9. The method of claim 8 , wherein Rand Rare hydrogen.10. The method of claim 8 , wherein Rand Ris independently hydrogen or Cto Calkyl.11. The method of claim 8 , wherein each of Rand Ris hydrogen.14. The method of claim 13 , wherein M is Rh or Co.15. The method of claim 14 , wherein the metal catalyst is selected from Rh(CO) claim 14 , Rh(CO) claim 14 , (acetylacetonato)dicarbonylrhodium(I) claim 14 , chlorodicarbonylrhodium dimer claim 14 , ...

Gold-Catalyzed C-C Cross-Coupling of Boron- and Silicon-Containing Aryl Compounds and Aryldiazonium Compounds by Visible-Light

The present invention relates to a method for producing (functionalized) biaryls by employing a visible-light-driven, gold-catalyzed C—C cross-coupling reaction system involving boron- and silicon-containing aryl compounds and aryldiazonium compounds. Moreover, the present invention relates to the use of such boron- and silicon-containing aryl compounds and aryldiazonium compounds, as well as related gold catalysts, in the manufacture of (functionalized) biaryls. 6. The method according to claim 1 , wherein Ris selected from BF claim 1 , PF claim 1 , SbF claim 1 , OTf claim 1 , NTf claim 1 , OSOCF claim 1 , F claim 1 , OSOF claim 1 , BArF claim 1 , BArF claim 1 , brosylate claim 1 , carborane claim 1 , C(TF) claim 1 , B(Ph) claim 1 , Altebat claim 1 , Bortebat claim 1 , PFTB claim 1 , and C(CF).7. The method according to claim 1 , wherein the aryl groups Arand Arare independently selected from furanyl claim 1 , pyrrolyl claim 1 , thiophenyl claim 1 , imidazolyl claim 1 , pyrazolyl claim 1 , oxazolyl claim 1 , isoxazolyl claim 1 , thiazolyl claim 1 , phenyl claim 1 , pyridinyl claim 1 , pyrazinyl claim 1 , pyrimidinyl claim 1 , pyradizinyl claim 1 , benzofuranyl claim 1 , indolyl claim 1 , benzothiophenyl claim 1 , benzimidazolyl claim 1 , indazolyl claim 1 , benzoxazolyl claim 1 , benzisoxazolyl claim 1 , benzothiazolyl claim 1 , isobenzofuranyl claim 1 , isoindolyl claim 1 , purinyl claim 1 , naphthyl claim 1 , chinolinyl claim 1 , chinoxalinyl and chinazolinyl.8. The method according to claim 1 , wherein each of the aryl groups Arand Arof the boron- or silicon-containing aryl compounds and the aryldiazonium compound claim 1 , respectively claim 1 , comprises one or more substituents which are independently selected from the group consisting of hydrogen claim 1 , halogen claim 1 , nitro claim 1 , hydroxy claim 1 , cyano claim 1 , carboxyl claim 1 , C-Ccarboxylic acid ester claim 1 , C-Cether claim 1 , C-Caldehyde claim 1 , C-Cketone claim 1 , sulfonyl claim 1 , C- ...

HARDMASK COMPOSITION, METHOD OF FORMING PATTERN BY USING THE HARDMASK COMPOSITION, AND HARDMASK FORMED USING THE HARDMASK COMPOSITION

Provided are a hardmask composition, a method of forming a pattern using the hardmask composition, and a hardmask formed using the hardmask composition. The hardmask composition includes a polar nonaqueous organic solvent and one of: i) a mixture of graphene quantum dots and at least one selected from a diene and a dienophile, ii) a Diels-Alder reaction product of the graphene quantum dots and the at least one selected from a diene and a dienophile, iii) a thermal treatment product of the Diels-Alder reaction product of graphene quantum dots and the at least one selected from a diene and a dienophile, or iv) a combination thereof. 1. A hardmask composition comprising: a mixture of graphene quantum dots and at least one selected from a diene and a dienophile,', 'a Diels-Alder reaction product of the graphene quantum dots and the at least one selected from a diene and a dienophile,', 'a thermal treatment product of the Diels-Alder reaction product of the graphene quantum dots and the at least one selected from a diene and a dienophile, or', 'a combination thereof; and, 'one of,'}a polar nonaqueous organic solvent.2. The hardmask composition of claim 1 , whereinthe graphene quantum dots include at an end thereof at least one first functional group, andthe at least one first functional group is selected from the group consisting of a hydroxyl group, a carbonyl group, a carboxyl group, an epoxy group, and an amine group.3. The hardmask composition of claim 1 , wherein the diene and the dienophile include a second functional group that is the same as or similar to that of the polar nonaqueous organic solvent.4. The hardmask composition of claim 3 , wherein the second functional group is at least one selected from the group consisting of a C1-C20 alkenylene group including a carboxyl group claim 3 , an organic group including a carbonyl group claim 3 , an organic group including —COOR (wherein R is a C1-C20 alkyl group or a C2-C20 alkenyl group) claim 3 , a hydrogenated C1 ...

METHOD OF PRODUCING FARNESYL ACETONE

The present invention relates to a process for preparing farnesyl acetone. 19.-. (canceled)13. The process according to claim 10 , wherein the solvent of the solvent/water mixture in step a) is selected from among C-C-alkanols claim 10 , C-C-dialkanols claim 10 , saturated cyclic ethers claim 10 , saturated acyclic ethers claim 10 , nitriles claim 10 , saturated ketones claim 10 , lactams claim 10 , esters of saturated C-C-monocarboxylic acids with C-C-alkanols claim 10 , C-C-alkylamides and di-C-C-alkylamides of saturated C-C-monocarboxylic acids and mixtures thereof.14. The process according to claim 10 , wherein the solvent/water mixture in step a) is present in a volume ratio of from 1:5 to 5:1 calculated as pure material.15. The process according to claim 10 , wherein the solvent/water mixture in step a) is present in a volume ratio of from 2:1 to 1:2 calculated as pure material.16. The process according to claim 10 , wherein the solvent/water mixture in step a) is present in a volume ratio of 1:1 calculated as pure material.17. The process according to claim 10 , wherein dispersing in step a) is carried out at a power input in the range from 0.1 to 5000 W/l.18. The process according to claim 10 , wherein dispersing in step a) is carried out at a power input in the range from 10 to 600 W/l.19. The process according to claim 10 , wherein dispersing in step a) is carried out at a power input in the range from 20 to 100 W/l.20. The process according to claim 10 , wherein dispersing in step a) is carried out using a stirrer at a circumferential velocity in the range from 1 to 80 m/s.21. The process according to claim 10 , wherein dispersing in step a) is carried out using a stirrer at a circumferential velocity in the range from 1.8 to 30 m/s.22. The process according to claim 10 , wherein dispersing in step a) is carried out at a temperature in the range from 50 to 200° C.23. The process according to claim 10 , wherein dispersing in step a) is carried out at a ...

EFFICIENT CATALYST FOR THE FORMATION OF POLYARYL HYDROCARBONS SUITABLE AS PRECURSORS FOR POLYDENTATE ORGANOPHOSPHORUS CATALYST LIGANDS

The disclosure relates to the efficient preparation of aromatic hydrocarbons useful as intermediates for di-, tri-, tetra- and poly-dentate organophosphorus ligands having value in particular as hydroformylation catalysts. The use of triarylphosphine halide catalysts have been found to be more efficient in forming these intermediates by the use of excess triarylphosphine in an amount beyond what is required to form a coordination complex. 2. The method of claim 1 , wherein the nickel based catalyst solution is prepared by the reaction of a nickel source with a triarylphosphine.3. The method of wherein the triarylphosphine is triphenylphosphine.4. The method of claim 1 , wherein the mole ratio of triarylphosphine/Ni is comprised of a range from about 2.2/1 up to about 100/1.5. The method of claim 1 , wherein the mole ratio of triarylphosphine/Ni is comprised of a range from about 10/1 up to about 100/16. The method of claim 1 , wherein the mole ratio of triarylphosphine/Ni is about 5/1 up to about 10/1.7. The method of claim 1 , wherein the triarylphosphine is tri(orthotolyl)phosphine claim 1 , tri(p-methylphenyl)phosphine claim 1 , diphenyl(o-tolyl)phosphine claim 1 , diphenyl(p-methylphenyl)phosphine claim 1 , or di-o-tolylyl(phenyl)phosphine.8. The method of wherein the nickel source comprises anhydrous Ni (II) chloride or bromide.9. The method of claim 2 , wherein the nickel source comprises (TPP)2Ni(II)X2.10. The method of claim 1 , further comprising adding coupling co-solvent to the mixture of the nickel based catalyst solution and polyhalogentated aromatic hydrocarbon to facilitate coupling of the mixture with the Grignard reactant.11. The method of claim 10 , wherein the coupling co-solvent is diethyl ether.12. The method of claim 10 , wherein the coupling co-solvent is tetrahydrofurane.13. (canceled)14. The method of claim 1 , wherein the Grignard reactant is prepared by reacting a bromo or chloro aromatic hydrocarbon with magnesium metal in a solvent.15. ...

NOVEL NICKEL CATALYST, PROCESS FOR PREPARATION AND USE THEREOF

The present invention disclosed to a novel nickel catalyst of formula (I) process for preparation of the same and use of nickel catalyst of formula (I) for C—H bond alkylation, and benzylation of heteroarenes. 2. The compound as claimed in claim 1 , wherein said nickel catalyst of formula (I) is selected from (NNN)-H [2-(diethylamino)-N-(quinolin-8-yl)acetamide] claim 1 , (NNN)NiCl [2-(diethylamino)-N-(quinolin-8-yl)acetamide](NiCl) claim 1 , (NNN)Ni(OAc) [2-(diethylamino)-N-(quinolin-8-yl)acetamide]Ni(OAc).3. A process for the preparation of nickel catalyst of formula (I) as claimed in claim 1 , wherein said process comprising the steps of:{'sup': R2', '8-Quin, 'a) Refluxing the reaction mixture of 2-bromo-N-(quinolin-8-yl) acetamide and amino compound in solvent for the period ranging from 20 to 24 hrs at temperature ranging from 60 to 80° C. afford (NNN)-H [2-(dialkylamino)-N-(quinolin-8-yl)acetamide] Ligand;'}b) Adding triethylamine to the mixture of compound of step (a), nickel compound and solvent followed by refluxing the reaction mixture for the period in the range of 3 to 12 hrs at a temperature ranging from 60 to 70° C. to afford nickel catalyst of formula (I).4. The process as claimed in claim 3 , wherein said amino compound is selected from diisopropyl amine claim 3 , diethylamine claim 3 , dimethyl amine claim 3 , morpholine claim 3 , N-methyl piperazine claim 3 , cyclopentyl amine claim 3 , cyclohexyl amine and said nickel compound is selected from (DME)NiCl claim 3 , (THF)NiBr claim 3 , Ni(OAc).5. The process as claimed in claim 3 , wherein said solvent in step (a) and (b) is selected from acetone or tetrahydrofuran (THF).6. A process for the alkylation or benzylation of heteroarene using nickel catalyst of formula (I) as claimed in claim 1 , comprising stirring the reaction mixture of heteroarene claim 1 , organic halide compound or benzyl compound claim 1 , catalyst of formula (I) claim 1 , base and solvent at temperature ranging from 120 to 160° C. ...

METHOD FOR PRODUCING 1-(4-HYDROXYPHENYL)-4-(4-TRIFLUOROMETHOXYPHENOXY)PIPERIDINE OR SALT THEREOF

The present invention provides a method for producing 1-(4-hydroxyphenyl)-4-(4-trifluoromethoxyphenoxy)piperidine or a salt thereof, the method including the step of heating hydroquinone and 4-(4-trifluoromethoxyphenoxy)piperidine. This method can produce 1-(4-hydroxyphenyl)-4-(4-trifluoromethoxyphenoxy)piperidine or a salt thereof in an industrially advantageous manner. 2. The production method according to claim 1 , wherein the hydroquinone represented by Formula (2) or a salt thereof is used in an amount of 2 to 10 moles per mole of the 4-(4-trifluoromethoxyphenoxy)piperidine represented by Formula (3) or a salt thereof.3. The production method according to claim 1 , wherein the heating step comprises heating at 150° C. or more.4. The production method according to claim 1 , wherein the heating step is performed under solvent-free conditions.9. A method for producing the compound represented by Formula (9) or a salt thereof by using 1-(4-hydroxyphenyl)-4-(4-trifluoromethoxyphenoxy)piperidine or a salt thereof claim 1 ,the method comprising:{'claim-ref': {'@idref': 'CLM-00006', 'claim 6'}, 'steps (c2) and (c3) according to .'}10. A method for producing the compound represented by Formula (9) or a salt thereof by using 1-(4-hydroxyphenyl)-4-(4-trifluoromethoxyphenoxy)piperidine or a salt thereof claim 1 ,the method comprising:{'claim-ref': {'@idref': 'CLM-00007', 'claim 7'}, 'steps (c1), (c2), and (c3) according to .'}11. A method for producing the compound represented by Formula (9) or a salt thereof by using 1-(4-hydroxyphenyl)-4-(4-trifluoromethoxyphenoxy)piperidine or a salt thereof claim 1 ,the method comprising:{'claim-ref': {'@idref': 'CLM-00008', 'claim 8'}, 'step (b1) according to .'} The present invention relates to a method for producing 1-(4-hydroxyphenyl)-4-(4-trifluoromethoxyphenoxy)piperidine or a salt thereof, and use thereof.1-(4-Hydroxyphenyl)-4-(4-trifluoromethoxyphenoxy)piperidine and salts thereof are compounds that are useful as an ...

CATALYSTS, LIGANDS AND USE THEREOF

According to the present invention, there is provided a catalytic complex comprising a metal, one or more ligands and one or more counterions, wherein said one or more ligands include a non-racemic chiral ligand and wherein said one or more counterions include a triflimide counterion. Also provided are methods of making said catalytic complex and processes for producing chiral compounds which involve the use of said catalytic complex. In addition, the present invention provides compounds of the formula (2) as defined herein. The compounds of formula (2) may be useful as ligands in catalytic complexes. 125-. (canceled)27. A compound according to claim 26 , wherein the moiety —O—C—O— is a moiety derived from a binaphthol compound claim 26 , e.g. (R)-1 claim 26 ,1′-bi-2-naphthol or (S)-1 claim 26 ,1′-bi-2-naphthol.28. (canceled)29. A compound according to claim 26 , wherein each Ris optionally substituted aryl claim 26 , e.g. phenyl or naphthyl claim 26 , either of which is optionally substituted.30. (canceled)31. A compound according to claim 29 , wherein each Ris phenyl or phenyl substituted with 1 claim 29 , 2 claim 29 , 3 claim 29 , 4 or 5 substituents independently selected from Calkyl (e.g. methyl) claim 29 , halogen (e.g. fluoro) claim 29 , trifluoromethyl and Calkoxy (e.g. methoxy).32. A compound according to claim 31 , wherein each Ris phenyl.33. A compound according to claim 26 , wherein each Ris optionally substituted alkyl claim 26 , e.g. optionally substituted Calkyl claim 26 , e.g. methyl claim 26 , ethyl or propyl.34. (canceled)35. A compound according to claim 33 , wherein each Ris methyl.36. A compound according to claim 26 , wherein Rand R claim 26 , together with the carbon atom to which they are attached claim 26 , form an achiral cyclic organic group claim 26 , e.g. an optionally substituted cycloalkyl group claim 26 , e.g. selected from cyclopentyl claim 26 , cyclohexyl claim 26 , cycloheptyl and cyclooctyl claim 26 , any of which is optionally ...

LIGAND, NICKEL COMPLEX COMPRISING THE LIGAND, AND REACTION USING THE NICKEL COMPLEX

An object of the present invention is to provide a method for directly performing arylation (particularly α-arylation) of carbonyl or thiocarbonyl compounds using a more inexpensive phenol derivative and nickel catalyst. Another object of the present invention is to provide a novel nickel catalyst that can be used in this method, and a novel ligand of the nickel catalyst. The novel compounds of the present invention are a compound having a diphosphine skeleton in which a five- or six-membered heterocyclic ring is substituted with two dialkylphosphines and/or dicycloalkylphosphines, or a salt thereof, and a compound having the diphosphine skeleton that is bound to nickel. Moreover, coupling reaction of a carbonyl compound and a phenol derivative can be advanced in the presence of a nickel compound having a monodentate or bidentate dialkylphosphine and/or dicycloalkylphosphine skeleton. 1. A compound having a diphosphine skeleton in which a five- or six-membered heterocyclic ring is substituted with two dialkylphosphines and/or dicycloalkylphosphines , or a salt thereof.3. The compound or a salt thereof according to claim 2 , wherein Rto Rin Formula (1) are the same or different claim 2 , and each is optionally substituted cycloalkyl.4. The compound or a salt thereof according to claim 1 , which is used to produce a catalyst for coupling reaction of a carbonyl compound and a phenol derivative.5. A compound having a diphosphine skeleton in which a five- or six-membered heterocyclic ring is substituted with two dialkylphosphines and/or dicycloalkylphosphines claim 1 , the diphosphine skeleton being bound to nickel.7. The compound according to claim 6 , wherein Rto Rin Formula (2) are the same or different claim 6 , and each is optionally substituted cycloalkyl.8. The compound according to claim 5 , which is a catalyst for coupling reaction of a carbonyl compound and a phenol derivative.9. A method for producing an arylcarbonyl compound claim 5 ,{'claim-ref': {'@idref': ...

SYNTHETIC METHOD OF 9,9-BIS[4-(2-HYDROXYETHOXY)PHENYL]FLUORENE

A synthetic method of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, belonging to the technical field of chemical synthesis. 9-fluorenone, phenoxyethanol, a catalyst and a cocatalyst are stiffed in an alkane solvent and heated until refluxing, the generated water is removed from the reaction solution via an azeotropic method while reacting, the reaction solution is diluted with water after the reaction is ended, uniformly stirred and cooled to separate out crystals and then filtered, a filter cake is rinsed and dried to obtain a 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene finished product; the filtered crystallization mother liquor is subjected to standing and layering, a water phase is removed, then an organic phase is distilled to recycle the alkane solvent, and the concentrate is rectified to recycle phenoxyethanol.

DIRECT ANTI-MARKOVNIKOV ADDITION OF ACIDS TO ALKENES

A method of making an anti-Markovnikov addition product, comprises reacting an acid with an alkene or alkyne in a dual catalyst reaction system to the exclusion of oxygen to produce said anti-Markovnikov addition product; the dual catalyst reaction system comprising a single electron oxidation catalyst in combination with a hydrogen atom donor catalyst. Dual catalyst composition useful for carrying out such methods are also described. 1. A method of making an anti-Markovnikov addition product , comprising:reacting an acid with an alkene or alkyne in a dual catalyst reaction system to the exclusion of oxygen to produce said anti-Markovnikov addition product;said dual catalyst reaction system comprising a single electron oxidation catalyst in combination with a hydrogen atom donor catalyst;wherein said hydrogen atom donor catalyst is a compound of the Formula A-SH, where A is alkyl, aryl, or an electron withdrawing group.2. The method of claim 1 , wherein said anti-Markovnikov addition product is produced regio selectively in a ratio of at least 5:1 of anti-Markovnikov addition product as compared to the corresponding Markovnikov addition product.3. The method of claim 1 , wherein A is selected from the group consisting of alkyl claim 1 , aryl claim 1 , carboxyl claim 1 , and carbonyl groups.4. The method of claim 1 , wherein said single electron oxidation catalyst is a photocatalyst.5. The method of claim 4 , wherein said photocatalyst comprises a carbocyclic or heterocyclic aromatic compound containing ring nitrogen heteroatoms.6. The method of claim 5 , wherein said photocatalyst comprises an anthracene claim 5 , aza-anthracene or polyaza-anthracene nucleus which is unsubstituted claim 5 , substituted or polysubstituted at any position with halogen claim 5 , and/or with one or more lower alkyl or cycloalkyl radicals claim 5 , and/or with other phenyl substituents.7. The method of claim 4 , wherein said photocatalyst has a reduction potential of about −1.0 V to +0.1 ...

PROCESS FOR PREPARING CHLORINATED BIPHENYLANILIDES AND BIPHENYLANILINES

The present invention relates to a process for preparing substituted biphenylanilides of the formula (I) 2. Process according to claim 1 , wherein the compound (II) is selected from the group consisting of N-(2-bromo-4-fluorophenyl)acetamide claim 1 , N-(2-bromophenyl)acetamide claim 1 , N-(2-bromophenyl)-3-oxobutanamide claim 1 , N-(2-bromo-4-fluorophenyl)-3-oxobutanamide claim 1 , 2-bromo-N-(propan-2-ylidene)aniline claim 1 , 2-bromo-4-fluoro-N-(propan-2-ylidene)aniline claim 1 , 2-bromo-4-fluoroaniline claim 1 , 2-bromoaniline.3. Process according to claim 1 , wherein the compound of the formula (III) is selected from the group consisting of bis(3 claim 1 ,4-dichlorophenyl)borinic acid claim 1 , bis(2 claim 1 ,3-dichlorophenyl)borinic acid claim 1 , bis(3-dichlorophenyl)borinic acid claim 1 , bis(4-dichlorophenyl)borinic acid claim 1 , 4-chlorophenylboronic acid claim 1 , 3-chlorophenylboronic acid claim 1 , 2-chlorophenylboronic acid claim 1 , 3 claim 1 ,4-dichlorophenylboronic acid and 2 claim 1 ,3-dichlorophenylboronic acid.4. Process according to claim 1 , wherein the base is selected from alkali metal hydroxides claim 1 , alkali metal carbonates and alkali metal hydrogencarbonates.5. Process according to claim 1 , wherein the palladium catalyst a) is a complex of palladium in the 0 oxidation state and a phosphine ligand of the formula (V) or a salt thereof.6. Process according to claim 1 , wherein a palladium catalyst b) is used.7. Process according to claim 1 , wherein a palladium catalyst c) is used claim 1 , and this palladium catalyst c) comprises or consists of metallic palladium on activated carbon in the presence of a phosphine ligand of formula (V) or a salt thereof.8. Process according to claim 6 , wherein the salt of the palladium catalyst b) is selected from the group consisting of palladium chloride claim 6 , palladium acetate claim 6 , palladium acetylacetonate and bis(acetonitrile)palladium chloride.9. Process according to claim 1 , wherein the ...

High Throughput Process for Manufacturing Molecular Sieves of MFI Framework Type

A process for converting hydrocarbons comprising the step of contacting said hydrocarbons under conversion conditions with a crystalline molecular sieve having a pore size in the range of from about 2 to about 19 Å, said molecular sieve made by a method comprising the steps of (a) providing a mixture comprising at least one source of ions of tetravalent element (Y), at least one trivalent element hydroxide source (OH), and water, said mixture having a solid-content in the range of from about 15 wt. % to about 50 wt. % .%, preferably of from about 20% to about 30%; and (b) treating said mixture to form the desired crystalline molecular sieve with stirring at crystallization conditions sufficient to obtain a weight hourly throughput from about 0.005 to about 1 hr, wherein said crystallization conditions comprise a temperature in the range of from about 200° C. to about 500° C. and a crystallization time less than 100 hr, wherein said crystalline molecular sieve has a zeolite framework type of MFI. 2. The process recited in claim 1 , wherein said crystalline molecular sieve formed in step (b) is substantially free of non-crystalline material.3. The process recited in claim 1 , wherein said weight hourly throughput is in the range of from about 0.008 to about 1 hr.4. The process recited in wherein the mixture comprises a structure-directing agent for the molecular sieve.5. The process recited in claim 1 , wherein said temperature range is from about 225° C. to about 250° C.6. The process recited in claim 1 , wherein said mixture further comprises from about 0.01 to 20 wt. % based on the total weight of said mixture of at least one seed source.7. The process recited in claim 1 , wherein said trivalent element is aluminum.8. The process recited in claim 1 , wherein said crystallization temperature is in the range of from about 200° C. to about 300° C. claim 1 , and crystallization time is less than 72 hr.9. The process recited in claim 1 , wherein said crystallization ...

PROCESS FOR SYNTHESIS OF INDENES

The present invention relates to a new process for the synthesis of 2,3,4,5,6,7-substituted indenes, which are useful precursors for the formation of certain ansa-metallocene catalysts. 2. The process according to claim 1 , wherein Rand Rare each independently selected from (1-3C)alkyl.3. The process according to claim 2 , wherein Rand Rare both methyl.4. The process according to claim 1 , wherein in step (i) the chlorinating agent is selected from oxalyl chloride claim 1 , PCl claim 1 , PCland SOCland the brominating agent is selected from PBrand PBr.5. The process according to claim 1 , wherein in step (i) a chlorinating agent is used and the chlorinating agent is selected from oxalyl chloride claim 1 , PCland PCl.6. The process according to claim 5 , wherein the chlorinating agent is oxalyl chloride.7. The process according to claim 1 , wherein the Lewis acid catalyst is selected from AlCl claim 1 , AlBrand BCl.8. The process according to claim 7 , wherein the Lewis acid catalyst is AlCl.9. The process according to claim 1 , wherein the reaction between the compound of formula B and 1 claim 1 ,2 claim 1 ,3 claim 1 ,4-tetramethylbenzene is quenched by the addition of an acid.10. The process according to claim 1 , wherein in step (ii) the solution of a hydride transfer reagent is selected from a solution of LiAlHand NaBH.11. The process according to claim 10 , wherein the hydride transfer reagent is LiAlH.12. The process according to claim 1 , wherein in step (ii) the dehydrating agent is an acid selected from sulphuric claim 1 , hydrochloric or phosphoric acid.14. The process according to claim 13 , wherein L is —CH—CH— claim 13 , —CH—CH—CH— or a group —SiRRwherein Rand Rare each independently selected from methyl claim 13 , propyl and allyl.15. The process according to claim 13 , wherein in step (ii) the compound of formula I is reacted with an organolithium compound.16. The process according to claim 15 , wherein the organolithium compound is n-butyllithium.17. ...

PREPARATION OF 4-BROMO-2-(4'-ETHOXYPHENYL)-1-CHLOROBENZENE

A more environmentally friendly synthesis method of 4-bromo-2-(4′-ethoxyphenyl)-1-chlorobenzene with simplified steps provides a more effective synthetic strategy for producing key intermediates of SGLT-2 inhibitors such as dapagliflozin, sotagliflozin, and ertugliflozin. In the presence of trifluoroacetic anhydride, 5-bromo-2-chlorobenzoic acid and phenetole are selected to complete a direct acylation reaction under the catalysis of boron trifluoride diethyl etherate, and triethylsilane is added thereinto without treatment for one-pot reaction to obtain a target compound 4-bromo-2-(4′-ethoxyphenyl)-1-chlorobenzene. 1. A one-pot synthesis method of 4-bromo-2-(4′-ethoxyphenyl)-1-chlorobenzene, comprising: preparing the 4-bromo-2-(4′-ethoxyphenyl)-1-chlorobenzene by the following reaction formula:{'sub': '3', 'wherein after 5-bromo-2-chlorobenzoic acid reacts with phenetole in the presence of trifluoroacetic anhydride (TFAA) and a catalytic amount of boron trifluoride diethyl etherate (BF.EtOEt) to obtain a reaction product, triethylsilane is directly added into the reaction product without treatment for one-pot reaction to obtain the 4-bromo-2-(4′-ethoxyphenyl)-1-chlorobenzene.'} The present disclosure belongs to the field of synthesis methods of compounds, and particularly relates to a synthesis method of compound 4-bromo-2-(4′-ethoxyphenyl)-1-chlorobenzene.SGLT-2 protein is present in the lumen of the human glomerular epithelial cell. In the presence of the SGLT-2 protein, 90% of glucose filtrated by renal tubules is reabsorbed. Hence, the blood glucose can go down provided that the biological action of the SGLT-2 protein is inhibited. The unique hypoglycemic mechanism of SGLT-2 inhibitors, as novel hypoglycemic agents, is not related to insulin, and the SGLT-2 inhibitors are new targets of insulin-independent anti-hyperglycemic agents, which pose a very low risk of hypoglycemia. Compared with other anti-hyperglycemic agents, the SGLT-2 inhibitors have a novel ...

Complexes for Nucleophilic, Radical, and Electrophilic Polyfluoroalkylation

Disclosed herein are borazine complexes and use of the same in perfluoroalkylation reactions. 2. The complex of claim 1 , wherein Ris NRR.3. The complex of claim 2 , wherein Rand Rare each Calkyl.4. The complex of claim 1 , wherein Ris Calkoxy.5. The complex of claim 4 , wherein Ris methoxy.6. The complex of claim 1 , wherein Ris Calkyl.7. The complex of claim 6 , wherein Ris methyl.8. The complex of any one of - claim 6 , wherein Ris Calkyl.9. The complex of claim 1 , wherein Rand Rtaken together with the atoms to which they are attached form a 5-6-membered ring.10. The complex of claim 9 , wherein Rand Rtaken together with the atoms to which they are attached form a 5-membered ring.11. The complex of or claim 9 , wherein the ring is substituted.12. The complex of any one of to which is chiral.13. The complex of claim 10 , wherein Rand Rtaken together are —CHCHO—.14. The complex of claim 1 , wherein Ris CH claim 1 , OCH claim 1 , N(CH) claim 1 , or Rand Rtaken together are —CHCHO—.15. The complex of any one of - claim 1 , wherein Y comprises one or more F.16. The complex of any one of - claim 1 , wherein Y is Cperfluoroalkyl.17. The complex of claim 16 , wherein Y is CF claim 16 , CHF claim 16 , or CF.18. The complex of claim 16 , wherein Y is CF.19. The complex of any of - claim 16 , wherein M comprises Na claim 16 , K claim 16 , Rb claim 16 , Cs claim 16 , or NH.20. The complex of any one of - claim 16 , further comprising a crown ether.21. The complex of claim 20 , wherein the crown ether is 18-crown-6 or 15-crown-5.24. The method of claim 23 , wherein the base is KDMSO claim 23 , NaDMSO claim 23 , KOC(CH) claim 23 , KCHPh claim 23 , KH claim 23 , NaH claim 23 , or a mixture thereof.25. The method of or claim 23 , wherein the base comprises KDMSO.26. The method of or claim 23 , wherein the base comprises NaDMSO.27. The method of any one of - claim 23 , wherein Ris NRR.28. The method of claim 27 , wherein Rand Rare each Calkyl.29. The method of any one of - claim ...

TRI-(ADAMANTYL)PHOSPHINES AND APPLICATIONS THEREOF

In one aspect, phosphine compounds comprising three adamantyl moieties (PAd) and associated synthetic routes are described herein. Each adamantyl moiety may be the same or different. For example, each adamantyl moiety (Ad) attached to the phosphorus atom can be independently selected from the group consisting of adamantane, diamantane, triamantane and derivatives thereof. Transition metal complexes comprising PAdligands are also provided for catalytic synthesis including catalytic cross-coupling reactions. 1. A method of synthesizing a tri-(adamantyl)phosphine compound , PAd , comprising:{'sub': 2', '2', 'N', '3, 'providing a reaction mixture including di-(adamantyl)phosphine (PAd) and a substituted adamantyl moiety and reacting the PAdand substituted adamantyl moiety via an S1 pathway to provide the PAd.'}2. The method of claim 1 , wherein adamantyl moieties (Ad) of the PAdare independently selected from the group consisting of adamantane claim 1 , diamantane claim 1 , triamantane and derivatives thereof.3. The method of claim 1 , wherein the substituted adamantyl moiety comprises a leaving group.4. The method of claim 3 , wherein the leaving group is selected from the group consisting of acetate claim 3 , triflate claim 3 , tosylate and hydroxyl.5. The method of claim 1 , wherein yield of the PAdis greater than 50 percent.6. The method of claim 1 , wherein yield of the PAdis greater than 60 percent.7. The method of claim 1 , wherein synthesizing the tri-(adamantyl)phosphine is performed at room temperature.8. A method of synthesizing a tri-(adamantyl)phosphine compound claim 1 , PAd claim 1 , comprising:{'sub': 2', 'N', '3, 'providing a reaction mixture including di-(adamantyl)phosphide and a substituted adamantyl moiety and reacting the PAdand substituted adamantyl moiety via an S1 pathway to provide the PAd.'}9. The method of claim 8 , wherein adamantyl moieties (Ad) of the di-(adamantyl)phosphide are independently selected from the group consisting of ...

SPIRO-1,1'-BINDANE-7,7-BISPHOSPHINE OXIDES AS HIGHLY ACTIVE SUPPORTING LIGANDS FOR PALADIUM-CATALYZED ASYMMETRIC HECK REACTION

The present invention relates to catalyst complexes comprising palladium (Pd) and at least one spiro-1,1′-biindane-7,7′-bisphosphine oxide ligand as disclosed herein, and their use. The present invention is further directed to the asymmetric catalyzed covalent carbon-carbon single bond formation from aryl, heteroaryl and alkenyl triflates and halides and olefins utilising the said catalyst complexes.

METHODS FOR ENANTIOSELECTIVE ALLYLIC ALKYLATION OF ESTERS, LACTONES, AND LACTAMS WITH UNACTIVATED ALLYLIC ALCOHOLS

The present disclosure provides methods for enantioselective synthesis of cyclic and acyclic α-quaternary carboxylic acid derivatives via nickel-catalyzed allylic alkylation. 2. The method of claim 1 , wherein:X is O;{'sub': '1', 'Ris ethyl;'}{'sub': '2', 'Ris H;'}the organic solvent is toluene, diethyl ether, MTBE, THF, or dioxane; andthe reaction temperature is 0° C., −10° C., or 23° C.3. The method of claim 2 , wherein Rand Rare each H and the organic solvent is diethyl ether.4. The method of claim 3 , wherein 10 mol % Ni(COD)and 12 mol % of ligand are used.5. The method of claim 3 , wherein the reaction temperature is 0° C. claim 3 , the ligand is (R)-P-phos claim 3 , and 5 mol % Ni(COD)and 6 mol % of ligand are used.6. The method of claim 2 , wherein:{'sub': 8', '9, 'Rand Rare each H;'}{'sub': '2', '10 mol % Ni(COD)and 12 mol % of ligand are used;'}the reaction temperature is 23° C.; andthe organic solvent is toluene, MTBE, THF, or dioxane.7. The method of claim 1 , wherein:X is O;the compound of Formula (II) is a compound of Formula (IIb);{'sub': '2', '10 mol % of Ni(COD)and 12 mol % of L are used;'}L is (R)-P-phos; andthe organic solvent is diethyl ether.8. The method of claim 7 , wherein{'sub': '2', 'Ris H;'}{'sub': 8', '9, 'Rand Rare each H; and'}the reaction temperature is −10° C.9. The method of claim 7 , wherein{'sub': '1', 'Ris ethyl;'}{'sub': '2', 'Ris H;'}{'sub': 8', '9', '8', '9, 'Rand Rcombine to form a phenyl ring including the carbon atoms to which Rand Rare attached; and'}the reaction temperature is −10° C.10. The method of claim 7 , wherein{'sub': '1', 'Ris ethyl;'}{'sub': '2', 'Ris Ph, 4-methylphenyl, 4-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-trifluoromethylphenyl, 3,5-dimethylphenyl, 2-naphthyl, 2-methoxyphenyl, 2-furyl, 2-thienyl, methyl, or styryl;'}{'sub': 8', '9, 'Rand Rare each H; and'}the reaction temperature is 10° C.11. The method of claim 1 , wherein X is N-PG claim 1 , PG is benzoyl claim 1 , Ris ethyl claim 1 , Ris H claim ...

METHOD FOR PRODUCING RUTHENIUM CATALYST AND METHOD FOR PRODUCING ALKYL GROUP- OR ALKENYL GROUP-SUBSTITUTED COMPOUND USING RUTHENIUM CATALYST

This invention relates to a method for producing a ruthenium catalyst in which ruthenium supported on at least one metal oxide is pretreated with an aldehyde compound, a phosphorus compound, and a lower alcohol compound, and a method for producing alkyl- or alkenyl-substituted compound using the ruthenium catalyst. 2. The method for producing a ruthenium catalyst according to claim 1 , wherein the aldehyde compound is at least one member selected from the group consisting of formaldehyde claim 1 , 1 claim 1 ,3 claim 1 ,5-trioxane claim 1 , paraformaldehyde claim 1 , glyoxal claim 1 , methylglyoxal claim 1 , malonaldehyde claim 1 , acetaldehyde claim 1 , and propionaldehyde.3. The method for producing a ruthenium catalyst according to claim 1 , wherein the aldehyde compound is formaldehyde.4. The method for producing a ruthenium catalyst according to claim 1 , wherein the phosphorus compound is at least one member selected from the group consisting of phosphines claim 1 , phosphites claim 1 , and phosphine oxides.5. The method for producing a ruthenium catalyst according to claim 1 , wherein the phosphorus compound is triphenylphosphine.6. The method for producing a ruthenium catalyst according to claim 1 , wherein the lower alcohol compound is at least one member selected from the group consisting of lower alcohols claim 1 , lower alkylene glycols claim 1 , and lower alkoxy-lower alcohols.7. The method for producing a ruthenium catalyst according to claim 1 , wherein the lower alcohol compound is 2-methoxyethanol.8. The method for producing a ruthenium catalyst according to claim 1 , wherein the heating temperature is 40 to 200° C. The present invention relates to a method for producing a ruthenium catalyst supported on at least one metal oxide, and a method for producing an alkyl- or alkenyl-substituted compound using a heterogeneous catalyst that is a ruthenium catalyst supported on at least one metal oxide.A method for producing an alkyl- or alkenyl-substituted ...

METHODS OF PREPARING OXA-BICYCLOALKENE

Disclosed is a method of preparing an oxa-bicycloalkene via the reaction of a cycloalkanone and an allyl alcohol compound in the presence of an organic acid, a manganese catalyst, and oxygen at a predetermined temperature. 1. A method of preparing an oxa-bicycloalkene comprising reacting (i) a cycloalkanone and (ii) an allyl alcohol compound in the presence of an organic acid , a manganese catalyst , and oxygen at a temperature of 60 to 200° C. for 1 to 24 hours.2. The method of claim 1 , wherein the cycloalkanone has 4 to 16 ring atoms selected from carbon claim 1 , oxygen claim 1 , sulfur claim 1 , and nitrogen; the allyl alcohol compound is allyl alcohol or an ester claim 1 , ether claim 1 , oxime claim 1 , or silyl of allyl alcohol; the organic acid is acetic acid claim 1 , and the manganese catalyst is a manganese (II) compound selected from the group consisting of manganese (II) acetate claim 1 , manganese (II) sulfate claim 1 , manganese (II) chloride claim 1 , manganese (II) bromide claim 1 , manganese (II) iodide claim 1 , manganese (II) oxide claim 1 , manganese (II) triflate claim 1 , and manganese (II) perchlorate.3. The method of claim 2 , wherein the allyl alcohol compound is allyl alcohol or allyl acetate claim 2 , and the manganese catalyst is supported on a zeolite claim 2 , aluminophosphate claim 2 , polyoxometallate claim 2 , or combination thereof.4. The method of claim 1 , wherein the molar ratio between the cycloalkanone and the allyl alcohol compound is 20:1 to 1:6 claim 1 , the molar ratio between the organic acid and the allyl alcohol is 100:1 to 1:1 claim 1 , and the molar ratio between the manganese catalyst and the allyl alcohol is 1:1000 to 1:1.5. The method of claim 1 , wherein the reaction is performed in the presence of peracetic acid claim 1 , the molar ratio between the peracetic acid and the allyl alcohol compound is 1:1 to 100:1 claim 1 , and the peracetic acid is added to the reaction or generated in-situ from the reaction of ...

METHOD FOR COUPLING A FIRST AROMATIC COMPOUND TO A SECOND AROMATIC COMPOUND

In one aspect, there is provided a method of coupling a first aromatic compound having a fluorosulfonate substituent to a second aromatic compound having a boron-containing substituent. In another aspect, there is provided a method of coupling a first aromatic compound having a hydroxyl substituent to a second aromatic compound having a boron-containing substituent in a one-pot reaction. 1. A method of coupling a first aromatic compound to a second aromatic compound , the method comprising:providing the first aromatic compound having a fluorosulfonate substituent; 'reacting the first aromatic compound and the second aromatic compound in a reaction mixture, the reaction mixture including a catalyst having at least one group 10 atom, the reaction mixture under conditions effective to couple the first aromatic compound to the second aromatic compound.', 'providing the second aromatic compound having a boron-containing substituent; and'}2. The method of claim 1 , wherein the reaction mixture further includes a ligand claim 1 , and a base.3. The method of claim 1 , wherein at least one of the first aromatic compound or the second aromatic compound is heteroaryl.4. The method of wherein the catalyst is a palladium catalyst or a nickel catalyst.5. The method of claim 4 , wherein the catalyst is generated in-situ from a palladium precatalyst claim 4 , the palladium precatalyst is selected from the group consisting of: Palladium(II) acetate claim 4 , Palladium(II) chloride claim 4 , Dichlorobis(acetonitrile)palladium(II) claim 4 , Dichlorobis(benzonitrile)palladium(II) claim 4 , Allylpalladium chloride dimer claim 4 , Palladium(II) acetylacetonate claim 4 , Palladium(II) bromide claim 4 , Bis(dibenzylideneacetone)palladium(0) claim 4 , Bis(2-methylallyl)palladium chloride dimer claim 4 , Crotylpalladium chloride dimer claim 4 , Dichloro(1 claim 4 ,5-cyclooctadiene)palladium(II) claim 4 , Dichloro(norbornadiene)palladium(II) claim 4 , Palladium(II) trifluoroacetate claim 4 , ...

Ylide-functionalised phosphanes for use in metal complexes and homogeneous catalysis

The invention relates to ylide-functionalized phosphane ligands, the production of same and use in transition metal compounds, as well as the use of same as catalysts in organic reactions.

IONIC METAL ALKYLIDENE COMPOUNDS AND USE THEREOF IN OLEFINIC METATHESIS REACTIONS

A compound of formula (I) wherein: M is selected from Mo or W; X is selected from O or NR; Rand Rare independently selected from H, Calkyl, and aryl; Calkyl and aryl optionally being substituted with one or more of Calkyl, Calkoxy, and O—CH; Ris selected from a nitrogen-containing aromatic heterocycle being bound to M via said nitrogen; and from halogen; Ris an aryl oxy group being bound to M via said oxygen of said aryl oxy group; wherein said aryl group Ar of said aryl oxy group is bound to a group Cat such to form a cationic ligand Cat-Z—ArO—, wherein Z is either a covalent bond or a linker; Ris alkyl or aryl, optionally substituted. 2. The compound of claim 1 , wherein Rand Rare independently selected from H claim 1 , C(CH) claim 1 , C(CH)CH claim 1 , and phenyl substituted in o-position with Calkoxy.3. The compound of claim 1 , wherein Ris selected from pyrrol-1-yl claim 1 , pyrazol-1-yl claim 1 , imidazol-1-yl claim 1 , 1H-1 claim 1 ,2 claim 1 ,3-triazol-1-yl claim 1 , 2H-1 claim 1 ,2 claim 1 ,3-triazol-2-yl claim 1 , 1H-1 claim 1 ,2 claim 1 ,4-triazol-1-yl claim 1 , 4H-1 claim 1 ,2 claim 1 ,4-triazo-4-yl claim 1 , indol-1-yl claim 1 , indazol-1-yl claim 1 , and azaindol-1-yl claim 1 , optionally substituted with one or more substituents selected independently from Calkyl claim 1 , Calkoxy claim 1 , phenyl claim 1 , halogen claim 1 , or cyano claim 1 , preferably pyrrol-1-yl claim 1 , 2 claim 1 ,5-dimethylpyrrol-1-yl claim 1 , and 2 claim 1 ,5-diphenylpyrrol-1-yl or indol-1-yl or a substituted indol-1-yl.4. The compound of claim 1 , wherein Ris selected from halogen.5. The compound of claim 1 , wherein said Ar in said Cat-Z—ArO— is phenyl substituted in 2 claim 1 ,6-position with phenyl claim 1 , optionally substituted claim 1 , or with isopropyl or t-butyl claim 1 , respectively; or{'sup': +', '+, 'said Ar in Cat-Z—ArO— is phenyl substituted in 4-position with Cat-Z—; or'}{'sup': '+', 'said Ar in Cat-Z—ArO— is phenyl substituted in 2,6 position with phenyl, ...

Alkylated Anisole-Containing Lubricating Oil Base Stocks and Processes for Preparing the Same

Compounds having the formula (F-I) below are provided herein: 2. The compound of claim 1 , wherein n is 1.3. The compound of claim 1 , wherein a Ris hydrogen.4. The compound of claim 1 , wherein a Ris a C-Calkyl group.5. The compound of claim 1 , wherein Rand Rat each occurrence are each independently a C-Calkyl group.6. The compound of claim 1 , wherein:{'sup': '1', 'sub': 1', '30, 'an Ris a C-Clinear alkyl group; and'}{'sup': '2', 'sub': 1', '5000, 'an Ris a linear or a branched C-Calkyl group.'}8. The compound of claim 7 , wherein Ris a branched alkyl group represented by formula (F-II) claim 7 , and one of the following conditions is met:{'sup': 6', '7, 'sub': 1', '30, '(i) at least 50% of Rare hydrogen, and at least 50% of Rare independently a C-Clinear alkyl groups; and'}{'sup': 6', '7, 'sub': 1', '30, '(ii) at least 50% of Rare independently C-Clinear alkyl groups, and at least 50% of Rare hydrogen.'}9. The compound of claim 7 , wherein k is from 50 to 500.10. The compound of claim 7 , wherein k is from 2 to 50.11. The compound of claim 1 , wherein Rand Rat each occurrence are the same or different and are independently a C-Clinear alkyl group.12. The compound of claim 1 , wherein Ris a C-Clinear alkyl group.13. The compound of claim 1 , wherein Ris hydrogen.14. The compound of claim 7 , having an isotacticity of at least about 60 mol %.16. The process of claim 15 , wherein the olefin-containing material comprises at least about 75 wt % of the compound of formula (F-Ib) where Ris hydrogen.17. The process of claim 15 , wherein the olefin-containing material comprises at least about 50 wt % of the compound of formula (F-Ib) where Ris a C-Calkyl group.18. The process of claim 15 , wherein the olefin-containing material comprises a mixture of: (i) about 1.0 to about 99 wt % of the compound of formula (F-Ib) where Ris hydrogen; and (ii) about 1.0 to about 99 wt % of the compound of formula (F-Ib) where Ris a C-Calkyl group.19. The process of claim 15 , wherein the ...

Rapid Thermal Isomerization of Lycopene

The use of lycopene has been demonstrated to be effective in decreasing risk factors associated with cardiovascular disease, skin cancer and prostate cancer in mammals. Lycopene is difficult to solubilize in its native trans-lycopene form. Cis-lycopene, formed by applying thermal energy generated by excitation of polar molecules through microwave-assisted processing, appears in several isomeric forms. The cis isomers are effective in improving lycopene micellularization, bioaccessibility and mammalian absorption. The cis isomers are effective in improving vascular circulation of lycopene by way transport vesicle low density lipo-protein (LDL). Lycopene-based ingredients, end products, functional foods, medical foods and nutraceuticals, containing isomerized cis-lycopene can be used in place of ingredients with more naturally abundant trans-lycopene as phytonutrient, micronutrient and antioxidant delivery vehicles through dietary consumption to improve the outcomes of a variety of conditions, including hypertension, cardiovascular disease, skin cancer, prostate cancer, macular degeneration and related proinflammatory conditions. 1. A process for the rapid thermal isomerization of a mixture of all-trans-lycopene and its cis-isomers of any composition to increase the proportion of cis-isomers , wherein the isomerization takes place in a polar solvent.2. A functional ingredient , nutraceutical , functional food , medical food composition suitable for administration to mammal , comprising greater than 4% of isomerized cis-lycopene compared to total lycopene content.3. A process claimed in claim 1 , wherein the isomerization takes place by way of energizing polar water molecules and ionic salt compounds through friction within the food mixture matrix using microwave-assisted heating4. A process claimed in claim 1 , wherein the isomerization takes place by way of energizing food mixture matrix using volumetric heating.5. A process as claimed in claim 1 , wherein the ...

Carbon Dioxide as a Directing Group for C-H Functionalization Reactions Involving Lewis Basic Amines, Alcohols, Thiols, and Phosphines for the Synthesis of Compounds

Methods of synthesizing compounds using COas a directing group for C—H functionalization, and compounds made thereby, are described. 1. A method of functionalizing a C—H bond , the method comprising using COas a directing group to convert a C—H bond in a substrate compound into a C—C , C—B , C—N , C—O , C—F , C—Cl , C—Br , C—I , C—P , or C—S bond , wherein the substrate compound comprises an amine , alcohol , thiol , or phosphine functional group.2. The method of claim 1 , wherein the C—H bond is in a γ-position relative to the amine claim 1 , alcohol claim 1 , thiol claim 1 , or phosphine functional group.3. The method of claim 1 , wherein the substrate compound is reacted with a reactant in the presence of COand a transition metal catalyst.4. The method of claim 3 , wherein the transition metal catalyst comprises palladium.5. The method of claim 1 , wherein the amine is a primary amine.6. The method of claim 5 , wherein the primary amine is selected from the group consisting of: 1-ethylcyclopentan-1-amine (S-1) claim 5 , 1-ethylcyclohexan-1-amine (S-2) claim 5 , 1-ethylcycloheptan-1-amine (S-3) claim 5 , 4-(tert-butyl)-1-ethylcyclohexan-1-amine (S-4) claim 5 , 9-ethyl-9H-fluoren-9-amine (S-5) claim 5 , 3-methylheptan-3-amine (S-6) claim 5 , 3-methylnon-3-amine (S-7) claim 5 , 3-methylpentan-3-amine (S-8) claim 5 , 3-ethylpentan-3-amine (S-9) claim 5 , and heptan-3-amine (S-10).7. The method of claim 1 , wherein the amine is a secondary amine.8. The method of claim 7 , wherein the secondary amine is selected from the group consisting of: N-(tert-pentyl)propan-1-amine (S-12) claim 7 , N-(tert-pentyl)butan-1-amine (S-13) claim 7 , N-(tert-pentyl)pentan-1-amine (S-14) claim 7 , 2-methyl-N-phenethylbutan-2-amine (S-15) claim 7 , N-benzyl-2-methylbutan-2-amine (S-16) claim 7 , N-(4-methoxybenzyl)-2-methylbutan-2-amine (S-17) claim 7 , N-(3-methoxybenzyl)-2-methylbutan-2-amine (S-18) claim 7 , N-(4-tolyl)-2-methylbutan-2-amine (S-19) claim 7 , N-(3-tolyl)-2-methylbutan-2 ...

METHOD FOR PRODUCING ASYMMETRICAL BIPHENOLS USING SELENIUM DIOXIDE

The present invention concerns a method for producing asymmetrical biphenols using selenium dioxide. 1. A process for preparing unsymmetric biphenols , comprising the process steps of:a) adding a first substituted phenol to the reaction mixture,b) adding a second substituted phenol having different substitution than the first phenol to the reaction mixture,c) adding selenium dioxide to the reaction mixture,d) adding a solvent,e) heating the reaction mixture such that the first substituted phenol and the second phenol having different substitution are converted to an unsymmetric biphenol.3. The process as claimed in claim 2 , wherein the R claim 2 , R claim 2 , R claim 2 , R claim 2 , RR claim 2 , R claim 2 , R claim 2 , R claim 2 , R° radicals are each independently selected from:{'sub': 1', '12', '1', '12', '6', '20', '6', '20, '—H, —(C-C)-alkyl, —O—(C-C)-alkyl, —(C-C)-aryl, —O—(C-C)-aryl, —Cl,'}{'sup': 1', '5', '2', '3, 'and at least one of the R, R, Rand Rradicals is —H,'}{'sup': 6', '10', '7', '9, 'and at least one of the R, R, Rand Rradicals is —H,'}where the alkyl and aryl groups mentioned may be substituted,and formula (I) is not the same as formula (II).4. The process as claimed in or claim 2 , wherein the R claim 2 , R claim 2 , R claim 2 , R claim 2 , RR claim 2 , R claim 2 , R claim 2 , R claim 2 , Rradicals are each independently selected from:{'sub': 1', '12', '1', '12, '—H, —(C-C)-alkyl, —O—(C-C)-alkyl'}{'sup': 1', '5', '2', '3, 'and at least one of the R, R, Rand Rradicals is —H,'}{'sup': 6', '10', '7', '9, 'and at least one of the R, R, Rand Rradicals is —H,'}where the alkyl and aryl groups mentioned may be substituted,and formula (I) is not the same as formula (II).5. The process as claimed in claim 1 , wherein a halogenated solvent is added in process step d).6. The process as claimed in claim 1 , wherein the solvent added is a fluorinated or chlorinated solvent.7. The process as claimed in claim 1 , wherein the solvent added is a fluorinated ...

Process for preparing branched allyl compounds

Disclosed are a process for preparing branched allyl compounds with an unsymmetrical 1,1-disubstituted alkene, and compounds prepared therewith.

NOVEL SUGAR DERIVATIVE GELATORS

A novel gelator including a sugar derivative; a gelator including a compound of Formula (1) or Formula (2): 4. A gel comprising:{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'the gelator as claimed in ; and'}a hydrophobic organic solvent, a hydrophilic organic solution, a hydrophobic organic solution, or an aqueous solution.5. A gel comprising:{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'the gelator as claimed in ;'}a surfactant; anda hydrophobic organic solvent, a hydrophilic organic solvent, water, a hydrophilic organic solution, a hydrophobic organic solution, or an aqueous solution.6. The gel according to claim 4 , wherein the hydrophobic organic solvent is at least one solvent selected from the group consisting of vegetable oils claim 4 , esters claim 4 , silicone oils claim 4 , and hydrocarbons.7. The gel according to claim 4 , wherein the hydrophobic organic solution is a mixed solvent of water and the hydrophobic organic solvent wherein the hydrophobic organic solvent is at least one solvent selected from the group consisting of vegetable oils claim 4 , esters claim 4 , silicone oils claim 4 , and hydrocarbons.8. The gel according to claim 5 , wherein the hydrophilic organic solvent is at least one solvent selected from the group consisting of methanol claim 5 , ethanol claim 5 , 2-propanol claim 5 , i-butanol claim 5 , pentanol claim 5 , hexanol claim 5 , 1-octanol claim 5 , iso-octanol claim 5 , acetone claim 5 , cyclohexanone claim 5 , acetonitrile claim 5 , dioxane claim 5 , glycerol claim 5 , propylene glycol claim 5 , ethylene glycol claim 5 , and dimethyl sulfoxide.9. The gel according to claim 4 , wherein the hydrophilic organic solution is a mixed solvent of water and the hydrophilic organic solvent wherein the hydrophilic organic solvent is at least one solvent selected from the group consisting of methanol claim 4 , ethanol claim 4 , 2-propanol claim 4 , i-butanol claim 4 , pentanol claim 4 , hexanol claim 4 , 1-octanol claim 4 , iso- ...

Iron bisphenolate complexes and methods of use and synthesis thereof

The present application, relates to iron bisphenolate complexes and methods of use and synthesis thereof. The iron complexes are prepared from tridentate or tetradentate ligands of Formula I: wherein R 1 and R 2 are as defined herein. Also provided are methods and processes of using the iron bisphenolate complexes as catalysts in cross-coupling reactions and in controlled radical polymerizations.

Conversion of glucose to sorbose

The present invention is directed to methods for preparing sorbose from glucose, said method comprising: (a) contacting the glucose with a silica-containing structure comprising a zeolite having a topology of a 12 membered-ring or larger, an ordered mesoporous silica material, or an amorphous silica, said structure containing Lewis acidic Ti 4+ or Zr 4+ or both Ti 4+ and Zr 4+ framework centers, said contacting conducted under reaction conditions sufficient to isomerize the glucose to sorbose. The sorbose may be (b) separated or isolated; or (c) converted to ascorbic acid.

Process for Preparing Substituted Biphenyls

The present invention relates to a process for preparing substituted biphenyls via Suzuki coupling using specific phosphorus ligands and a solvent mixture containing water, a non-polar organic solvent and a polar aprotic co-solvent. 120-. (canceled)22. The process of claim 21 , wherein Ris nitro.23. The process of claim 21 , wherein Ris fluorine or chlorine claim 21 , and n is 1 claim 21 , 2 or 3.24. The process of claim 21 , wherein Ris hydrogen or fluorine.25. The process of claim 21 , wherein Rand Rare in para positions to one another.26. The process of claim 21 , wherein the biphenyl I is 4-chloro-2′-nitro-biphenyl claim 21 , 3 claim 21 ,4-dichloro-2′-nitro-biphenyl claim 21 , 3 claim 21 ,4-difluoro-2′-nitro-biphenyl claim 21 , 3 claim 21 ,4 claim 21 ,5-trifluoro-2′-nitro-biphenyl claim 21 , 3-chloro-4 claim 21 ,5-difluoro-2′-nitro-biphenyl claim 21 , 3 claim 21 ,4-dichloro-5′-fluoro-2′-nitro-biphenyl claim 21 , 3 claim 21 ,5-dichloro-4-fluoro-2′-nitro-biphenyl claim 21 , 4′-chloro-biphenyl-2-ylamine claim 21 , 3′ claim 21 ,4′-dichloro-biphenyl-2-ylamine claim 21 , 3′ claim 21 ,4′-difluoro-biphenyl-2-ylamine claim 21 , 3′ claim 21 ,4′ claim 21 ,5′-trifluoro-biphenyl-2-ylamine claim 21 , 3′-chloro-4′ claim 21 ,5′-difluoro-biphenyl-2-ylamine claim 21 , 3′ claim 21 ,4′-dichloro-5-fluoro-biphenyl-2-ylamine or 3′ claim 21 ,5′-dichloro-4′-fluoro-biphenyl-2-ylamine.28. The process of claim 21 , wherein the palladium source is a palladium(II) salt or a palladium(0) complex.29. The process of claim 21 , wherein the palladium source claim 21 , calculated on the basis of the Pd content claim 21 , is used in an amount of from 0.0001 mol % to 0.5 mol % claim 21 , relative to 1 mol of compound II or compound IV claim 21 , if these are used in equimolar amounts claim 21 , or claim 21 , if compounds II and IV are not used in equimolar amounts claim 21 , relative to 1 mol of that compound II or IV which is not used in excess.30. The process of claim 29 , wherein the palladium ...

DIBENZOTHIOPHENE SALT AS ALKYNYLATING AND CYANATING AGENT

The present invention describes a new alkynylation and cyanation agent, as well as its preparation and use to introduce nitrile (cyano) or alkyne groups into chemical target molecules by means of an electrophilic reaction. To enable an electrophilic reaction, the chemical backbone of dibenzothiophene was used. 114-. (canceled)16. The salt according to claim 15 , wherein R is an R′silyl group claim 15 , wherein the three R′ substituents are independently selected from the group consisting of: optionally substituted linear claim 15 , branched or cyclic Chydrocarbon groups optionally having one or more unsaturated bonds and optionally one or more heteroatoms.17. The salt according to claim 15 , wherein R and the three R′ substituents of the R′silyl group are independently selected from the group consisting of: optionally substituted Ccycloalkenyl groups having one or more unsaturated C—C double bonds claim 15 , optionally substituted Caryl groups claim 15 , optionally substituted Ccycloalkyl groups claim 15 , optionally substituted Calkyl groups claim 15 , optionally substituted Calkenyl groups having one or more unsaturated C—C double bonds claim 15 , optionally substituted Calkynyl groups claim 15 , optionally substituted Cheteroalkyl groups claim 15 , optionally substituted Cheteroalkenyl groups having one or more unsaturated double bonds claim 15 , optionally substituted Cheteroalkynyl groups optionally having one or more unsaturated bonds claim 15 , optionally substituted Cheteroaryl groups claim 15 , optionally substituted Cheterocycloalkyl groups claim 15 , optionally substituted Cheterocycloalkenyl groups having one or more unsaturated double bonds.18. The salt according to claim 15 , wherein the compound of formula I or formula II represents the cation and the anion is selected from the group consisting of: triflate (TfO); perchlorates; nitrate; TfN; [{3 claim 15 ,5-(CF)CH}B]; PF6; BF4; B(CF); BF; BR* claim 15 , wherein R* is optionally substituted Calkyl ...

COMPOSITIONS AND METHODS OF PROMOTING ORGANIC PHOTOCATALYSIS

The invention provides novel compounds and methods that are useful in promoting reactions that proceed through an oxidative quenching pathway. In certain embodiments, the reactions comprise atom transfer radical polymerization. 1. A method of promoting reaction of at least one reagent , wherein the reaction comprises a quenching step , wherein the method comprises irradiating the at least one reagent in the presence of an organic compound with an excited-state reduction potential that is equal to or more negative than about −1.0 V vs. SCE.2. The method of claim 1 , wherein the excited state comprises a singlet or triplet excited state.3. The method of claim 1 , wherein the excited-state reduction potential is equal to or more negative than one selected from the group consisting of about −2.4 V vs. SCE claim 1 , −2.3 V vs. SCE claim 1 , about −2.2 V vs. SCE claim 1 , about −2.1 V vs. SCE claim 1 , about −2.0 V vs. SCE and about −1.5 V vs. SCE.4. The method of claim 1 , wherein the reaction comprises at least one selected from the group consisting of atom transfer radical addition/polymerization claim 1 , dehalogenation claim 1 , cycloaddition claim 1 , cyclization claim 1 , dimerization claim 1 , coupling claim 1 , reduction claim 1 , ring-opening claim 1 , alkylation claim 1 , arylation claim 1 , oxygenation claim 1 , energy transfer claim 1 , and radical addition.5. The method of claim 1 , wherein the reaction comprises atom transfer radical addition/polymerization.6. The method of claim 1 , wherein the at least one reagent comprises a (meth)acrylate and an organic halide.7. The method of claim 6 , wherein the organic halide comprises an α-halo ester.8. The method of claim 1 , wherein the reaction is essentially free of a metal or metalloid.9. The method of claim 1 , wherein the radiation comprises visible light.10. The method of claim 9 , wherein the radiation comprises sunlight or a natural light source.11. The method of claim 9 , wherein the radiation comprises ...

RUTHENIUM-CATALYZED SYNTHESIS OF BIARYL COMPOUNDS IN WATER

Using a [RuCl(arene)]complex and a formate source, a directed ortho C—H insertion and aryl-aryl coupling sequence in water provides biaryl compounds useful in the preparation of biologically active molecules and intermediates. Reactions may be conducted in the ambient atmosphere. Ruthenium catalysts prepared from [RuCl(arene)]and a formate source may be prepared in situ or isolated for later use. 1. A method of preparing a biaryl compound in water comprising:{'sub': 2', '2, 'reacting a first aryl compound with a second aryl compound in water in the presence of a catalytically effective amount of a [RuCl(arene)]complex and an effective amount of a source of formate;'}the first aryl compound comprising first and second ring atoms, the second ring atom having a directing group appended thereto and being located ortho to the first ring atom;the second aryl compound comprising a first ring atom, the first ring atom being substituted with a leaving group;wherein the reacting of the first aryl compound with the second aryl compound forms a bond between the first ring atom of the first aryl compound and the first ring atom of the second aryl compound.37-. (canceled)8. The method of claim 1 , wherein the formate source is an alkali metal formate claim 1 , alkaline earth metal formate claim 1 , N(R)HC(O)O claim 1 , HC(O)—OCalkyl claim 1 , sodium thioformate claim 1 , sodium formamide claim 1 , glyoxal claim 1 , sodium glyoxalate or potassium glyoxalates claim 1 , or a combination thereof; and Ris hydrogen or Calkyl.9. (canceled)10. The method of claim 1 , wherein the first aryl compound comprises a first 6-membered carbocyclic ring claim 1 , the first 6-membered carbocyclic ring comprising the first and second ring atoms of the first aryl compound.1112-. (canceled)13. The method of claim 1 , wherein the second aryl compound comprises a 5-6-membered heteroaryl ring claim 1 , the 5-6-membered heteroaryl ring comprising the first ring atom of the second aryl compound and the ...

Metathesis Catalyst

The current invention describes new metathesis catalysts, a method for their preparation and their use in metathesis reactions. 1. Compounds of formula (I)Ru stands for ruthenium,R1 stands for alkyl,R2 stands for alkyl,R3 stands for an electron-withdrawing substituent,Hal stands for chlorine or bromine, independently of each other,Lig stands for the ligand Lig1 or Lig2.in which The current invention describes new metathesis catalysts, a method for their preparation and their use.Numerous metathesis catalysts are already known; refer to for example: Tetrahedron Lett. 1999, 40, 1091-1094, J. Am. Chem. Soc. 2000, 122, 58-71, Angew. Chem. 2003, 115, 1944-1968. It is known from these publications that substrates comprising acetal-groups considerably inhibit metathesis reactions.New metathesis catalysts comprising acetal-groups with the formula (I) have been found in whichIt was further found that the catalysts of formula (I) can be produced from compounds of formula (II)In which R1, R2 and R3 have the above given meanings, by reaction with 2generation Grubbs catalyst (see Aldrich Chemistry Handbook Fine Chemicals 2009-2010, page 1453) in the presence of CuCl (J. Org. Chem. 2004, 69, 6894-6896).It was finally found out that the catalysts of formula (I) are suitable for the modification of butadiene acrylonitrile copolymers.whereinEspecially preferred are catalysts of formula (I), in whichwhereinPreparation of the catalyst of formula (I), wherein R1=Me, R2=C12H25, R3=NO2, Hal=C1, Lig=Lig1.In a Schlenk apparatus, the 2-generation Grubbs catalyst (0.108 g, 0.13 mmol) is mixed with a solution of compound (I-1):(0.059 g, 0.14 mmol) in 5 ml dichloromethane and 25 mg of copper-(I)-chloride and was stirred for about 50 minutes to about 60 minutes at ambient temperature under an argon atmosphere. The solvent was then removed under vacuum and the residue was purified by column chromatography. The catalyst (I) was obtained as a green solid.Preparation of the catalyst of formula (I), ...

IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOUNDS

A process of converting a carbon-carbon multiple bond to a cyclopropane ring, comprising the addition of a N-alkyl-N-nitroso compound to a mixture of alkene precursor, aqueous base and Pd(II)-catalyst, with the N-alkyl-N-nitroso compound obtained directly from an alkyl amine derivative, NaNOand an acid via phase separation of the N-alkyl-N-nitroso compound from the aqueous phase. 1. A process of ring formation across a carbon-carbon multiple bond , the process comprising the steps of reacting a N-alkyl-N-nitroso compound with a substrate bearing a carbon-carbon multiple bond , wherein the N-alkyl-N-nitroso compound is generated in-situ , and the N-alkyl-N-nitroso compound is added to the substrate without being first isolated.2. The process according to wherein the N-alkyl-N-nitroso compound is an organic solution of N-alkyl-N-nitroso urea claim 1 , and wherein the N-alkyl-N-nitroso urea is added to the substrate without being first isolated in solid form.3. The process according to wherein the N-alkyl-N-nitroso compound is a N-methyl-N-nitroso compound (MNC).4. The process according to wherein the N-alkyl-N-nitroso compound is selected from the group consisting of N-methyl-N-nitroso-urea (MNU) claim 1 , N-methyl-N-nitroso-p-toluenesulfonamide claim 1 , N-nitroso-dimethylurethane claim 1 , nitroso-EMU and N-nitroso-β-methylaminoisobutyl methyl ketone (NMK).5. The process according to wherein the N-alkyl-N-nitroso compound is generated in-situ from a mixture of a HNRR′ compound claim 1 , water claim 1 , NaNOand an acid claim 1 , before partitioning into an organic solvent to form an organic solution of N-alkyl-N-nitroso compound.6. The process according to wherein the N-alkyl-N-nitroso compound is formed in-situ from a N-alkylamine.7. The process according to claim 1 , wherein a biphasic mixture is formed with the N-alkyl-N-nitroso compound in an organic layer.8. The process according to claim 1 , wherein the N-alkyl-N-nitroso compound in liquid phase is separated ...

PROCESS FOR THE PREPARATION OF 4-BROMO-1-CHLORO-2-(4-ETHOXYBENZYL)BENZENE

The present invention provides a process for the preparation of 4-bromo-1-chloro-2-(4-ethoxybenzyl)benzene of Formula III, which can be used as an intermediate for the preparation of dapagliflozin, or solvates thereof. 2. The process according to claim 1 , wherein the process is carried out in the presence of a Lewis acid selected from the group consisting of AlCl claim 1 , FeCl claim 1 , GaCl claim 1 , BF claim 1 , SbCl claim 1 , BiCl claim 1 , and Bi(OTf).3. The process according to claim 1 , wherein the reduction is carried out in the presence of a reducing agent selected from the group consisting of metal hydrides and organosilanes.4. The process according to claim 1 , wherein the process is carried out in the absence of acetonitrile. The present invention provides a process for the preparation of 4-bromo-1-chloro-2-(4-ethoxybenzyl)benzene of Formula III, which can be used as an intermediate for the preparation of dapagliflozin, or solvates thereof.Dapagliflozin propanediol monohydrate is chemically designated as (1S)-1,5-anhydro -1 -C-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-D-glucitol, (S)-propylene glycol, monohydrate and is marketed in Europe for the treatment of type 2 Diabetes mellitus. Its chemical structure is represented by Formula I:U.S. Pat. No. 6,515,117 (“the '117 patent”) discloses a process for the preparation of 4-bromo-1-chloro-2-(4-ethoxybenzyl)benzene of Formula III, comprising the reaction of 5-bromo-2-chlorobenzoyl chloride with phenetole thereby isolating 5-bromo-2-chloro-4′-ethoxybenzophenone, which upon reduction in acetonitrile at 50° C. gives 4-bromo-1-chloro-2-(4-ethoxybenzyl)benzene of Formula III. The '117 patent discloses that further increasing the temperature during the reduction step results in the formation of N-acetyl-5-bromo-2-chloro-4′-ethoxydiphenylmethylamine—an impurity of Formula VI. This impurity may be formed by the nucleophilic addition of acetonitrile to 5-bromo-2-chloro-4′-ethoxybenzophenone, followed by ...

BISMUTH PERFLUOROALKYLPHOSPHINATES AS LEWIS ACID CATALYSTS

The invention relates to bismuth perfluoroalkylphosphinates as Lewis acid catalysts, the compounds, and processes for the preparation thereof. 1. Compounds the formula (Ia) or (Ib){'br': None, 'sub': x', 'f', '2', '3-x, 'ArBi[OP(O)(R)]\u2003\u2003(Ia),'}{'br': None, 'sub': 3', 'f', '2', '2, 'ArBi[OP(O)(R)]\u2003\u2003(Ib)'}whereAr in each case, independently of one another, denotes an aryl group having 6 to 12 C atoms, which may be unsubstituted or substituted;{'sub': 'f', 'Rin each case, independently of one another, denotes a straight-chain or branched perfluoroalkyl group having 1 to 8 C atoms and'}x denotes 0, 1 or 2.2. Compounds according to claim 1 , where Ar is identical on each occurrence.3. Compounds according to claim 1 , where the perfluoroalkyl group Ris identical on each occurrence.4. Compounds according to claim 1 , where Ris selected from pentafluoroethyl or n-nonafluorobutyl.5. Process for the preparation of compounds of the formula (Ia) according to claim 1 , where x denotes 0 claim 1 , characterised in that bismuth is reacted with a compound of the formula (II){'br': None, 'sub': f', '2, 'HOP(O)(R)\u2003\u2003(II),'}where{'sub': 'f', 'Rin each case, independently of one another, denotes a straight-chain or branched perfluoroalkyl group having 1 to 8 C atoms.'}6. Process for the preparation of compounds of the formula (Ia) according to claim 1 , where x denotes 1 or 2 claim 1 , characterised in that a compound of the formula (II){'br': None, 'sub': f', '2, 'HOP(O)(R)\u2003\u2003(II),'}where{'sub': 'f', 'Rin each case, independently of one another, denotes a straight-chain or branched perfluoroalkyl group having 1 to 8 C atoms,'}is reacted with triarylbismuthane, where the aryl in each case, independently of one another, denotes an aryl group having 6 to 12 C atoms.7. Process for the preparation of compounds of the formula (Ib) according to claim 1 , characterised in that triarylbismuthane is converted to triaryldichlorobismuthane claim 1 , where ...

METAL PARTICLE-CHITIN COMPOSITE MATERIALS AND METHODS OF MAKING THEREOF

Methods for making metal particle-chitin composite materials are described. The methods can comprise contacting an ionic liquid with chitin, thereby forming a mixture; contacting the mixture with a non-solvent, thereby forming a chitin substrate in the non-solvent; collecting the chitin substrate from the non-solvent; deacetylating the collected chitin substrate, thereby forming a deacetylated chitin substrate; contacting the deacetylated chitin substrate with a metal salt, thereby forming an impregnated precursor composite material; and contacting the impregnated precursor composite material with a reducing agent, thereby reducing the metal salt to form a plurality of metal particles dispersed on the chitin substrate and forming the metal particle-chitin composite material. 1. A method of making a metal particle-chitin composite material comprising:contacting an ionic liquid with chitin, thereby forming a mixture;contacting the mixture with a non-solvent, thereby forming a chitin substrate in the non-solvent;collecting the chitin substrate from the non-solvent;deacetylating the collected chitin substrate, thereby forming a deacetylated chitin substrate;contacting the deacetylated chitin substrate with a metal salt, thereby forming an impregnated precursor composite material; andcontacting the impregnated precursor composite material with a reducing agent, thereby reducing the metal salt to form a plurality of metal particles dispersed on the chitin substrate and forming the metal particle-chitin composite material.3. The method of claim 1 , wherein the ionic liquid contains an imidazolium cation.4. The method of claim 1 , wherein the ionic liquid is a 1-alkyl-3-alkyl imidazolium C-Ccarboxylate.5. The method of claim 1 , wherein the concentration of chitin in the mixture is from 0.1 wt % to 25 wt %.6. The method of claim 1 , wherein the non-solvent is water claim 1 , a C-Calcohol claim 1 , ketone claim 1 , or a mixture thereof.7. The method of claim 1 , further ...

Organic compounds

A process of converting a carbon-carbon multiple bond to a cyclopropane ring, comprising the addition of a N-alkyl-N-nitroso compound to a mixture of alkene precursor, aqueous base and Pd(II)-catalyst, with the N-alkyl-N-nitroso compound obtained directly from an alkyl amine derivative, NaNO 2 and an acid via phase separation of the N-alkyl-N-nitroso compound from the aqueous phase.

METHOD OF PREPARING TRISUBSTITUTED ETHYLENE COMPOUNDS

Method of forming a trisubstituted ethylene compound, the method comprising: (A) providing a trisubstituted ethylene compound bearing a first, a second and a third substituent, in which the first and the second substituent are bound to the one olefinic carbon atom and are different from one another; (B) providing a monosubstituted ethylene compound or a disubstituted ethylene compound in which the substituents are vicinally bound to the olefinic carbon atoms, bearing at least a fourth substituent, respectively; (C) subjecting the trisubstituted ethylene compound provided in step (A) to a cross-metathesis reaction with olefin provided in step (B) to form said trisubstituted ethylene, wherein the cross-metathesis reaction is catalysed by a transition metal complex bearing ligands from which one ligand is a carbene ligand, wherein the carbene complex is characterized by a M═C moiety, wherein M is the transition metal; and wherein the reaction proceeds stereoselectively. 2. Method of claim 1 , wherein said third substituent is a C-alkyl residue.3. Method of or claim 1 , wherein said third substituent is a methyl group.4. Method of any one of the preceding claims claim 1 , wherein at least one of the first substituent claim 1 , the second substituent and the fourth substituent is a functional group or comprises a functional group.5. Method of any one of the preceding claims claim 1 , wherein the transition metal is selected from Mo claim 1 , W or Ru.6. Method of any one of the preceding claims claim 1 , wherein the carbon atom of the carbene complex is substituted with hydrogen or hydrogen and a residue selected from alkyl claim 1 , preferably Calkyl claim 1 , optionally substituted claim 1 , or aryl claim 1 , preferably phenyl claim 1 , optionally substituted with one or more of Calkyl claim 1 , Calkoxy claim 1 , halogen claim 1 , nitro claim 1 , —C(O)—N(Calkyl) claim 1 , —S(O)—N(Calkyl) claim 1 , —NH—C(O)(Calkyl) or CF.7. Method of any one of the preceding claims claim ...

METHOD FOR PRODUCING P-XYLENE AND/OR P-TOLUALDEHYDE

Disclosed is a method for producing p-xylene and/or p-tolualdehyde with high yield through a short process using biomass resource-derived substances as raw materials. The method for producing p-xylene and/or p-tolualdehyde of the present invention comprises: a cyclization step of producing 4-methyl-3-cyclohexenecarboxaldehyde from isoprene and acrolein; and an aromatization step of producing p-xylene and/or p-tolualdehyde from 4-methyl-3-cyclohexenecarboxaldehyde by gas-phase flow reaction using a catalyst(s). 1. A method for producing p-xylene and/or p-tolualdehyde , said method comprising:a cyclization step of producing 4-methyl-3-cyclohexenecarboxaldehyde from isoprene and acrolein; andan aromatization step of producing p-xylene and/or p-tolualdehyde from 4-methyl-3-cyclohexenecarboxaldehyde by gas-phase flow reaction using a catalyst(s).2. The production method according to claim 1 , wherein the catalyst used in the aromatization step comprises a carrier which carries a metal(s) and/or metal oxide(s).3. The production method according to claim 1 , wherein the catalyst used in the aromatization step comprises a carrier which carries at least one metal or metal oxide claim 1 , said metal or metal oxide being selected from the group consisting of platinum claim 1 , nickel claim 1 , palladium claim 1 , ruthenium claim 1 , platinum oxide claim 1 , copper oxide claim 1 , iron oxide and chromium oxide.4. The production method according to claim 1 , wherein the catalyst used in the aromatization step comprises a carrier selected from the group consisting of alumina claim 1 , silica-alumina claim 1 , silica claim 1 , zeolite claim 1 , titania claim 1 , magnesia and carbon.5. The production method according to claim 1 , wherein the catalyst used in the aromatization step is chromium oxide on alumina claim 1 , chromium oxide on silica-alumina or chromium oxide on silica.6. The production method according to claim 1 , wherein the reaction temperature in the gas-phase flow ...

METHOD FOR PREPARING 1-(4-CHLOROPHENYL)-2-CYCLOPROPYL-1-PROPANONE AND INTERMEDIATE THEREOF

A method is for preparing 1-(4-chlorophenyl)-2-cyclopropyl-1-propanone and an intermediate thereof, where in the method for preparing a compound of formula (I), α-alkoxy p-chlorobenzyl phosphonate (II) and cyclopropyl methyl ketone are used as raw materials, and subjected to a Homer-Wadsworth-Emmons reaction in an organic solvent in the presence of a base, so as to prepare a derivative of alkoxy propylene with the structure of formula (III); and the resulting derivative of alkoxy propylene (III) is hydrolyzed under acidic conditions to obtain 1-(4-chlorophenyl)-2-cyclopropyl-1-propanone (I). 2. The method according to claim 1 , wherein Ris methyl or ethyl.3. The method according to claim 1 , wherein the base is selected from sodium amide claim 1 , sodium hydride claim 1 , lithium diisopropylamide claim 1 , sodium methoxide claim 1 , sodium ethoxide claim 1 , sodium iso-propoxide claim 1 , sodium iso-butoxide claim 1 , potassium iso-butoxide claim 1 , sodium tert-butoxide claim 1 , or potassium tert-butoxide; and is preferably sodium amide claim 1 , sodium tert-butoxide or potassium tert-butoxide.4. The method according to claim 1 , wherein a reaction solvent for preparing the derivative of alkoxy propylene shown as formula (III) is selected from one or more of polar solvents such as methanol claim 1 , ethanol claim 1 , 1-propanol claim 1 , isopropanol claim 1 , 1-butanol claim 1 , isobutanol claim 1 , tert-butanol claim 1 , dimethyl formamide claim 1 , dimethyl acetamide claim 1 , N-methyl-pyrrolidone claim 1 , dimethyl sulfoxide claim 1 , dioxane and tetrahydrofuran claim 1 , or a mixture of one or more of the aforementioned polar solvents and a non-polar solvent such as benzene claim 1 , toluene claim 1 , dichloromethane or dichloroethane.5. The method according to claim 1 , wherein claim 1 , in the reaction for preparing the derivative of alkoxy propylene shown as formula (III) claim 1 , the molar ratio of α-alkoxy p-chlorobenzyl phosphonate (II) claim 1 , ...

TRI-(ADAMANTYL)PHOSPHINES AND APPLICATIONS THEREOF

In one aspect, phosphine compounds comprising three adamantyl moieties (PAd) and associated synthetic routes are described herein. Each adamantyl moiety may be the same or different. For example, each adamantyl moiety (Ad) attached to the phosphorus atom can be independently selected from the group consisting of adamantane, diamantane, triamantane and derivatives thereof. Transition metal complexes comprising PAdligands are also provided for catalytic synthesis including catalytic cross-coupling reactions. 1. A method of synthesizing a tri-(adamantyl)phosphine compound , PAd , comprising:{'sub': 2', '2', 'N', '3, 'providing a reaction mixture including di-(adamantyl)phosphine (PAd) and a substituted adamantyl moiety and reacting the PAdand substituted adamantyl moiety via an S1 pathway to provide the PAd.'}2. The method of claim 1 , wherein adamantyl moieties (Ad) of the PAdare independently selected from the group consisting of adamantane claim 1 , diamantane claim 1 , triamantane and derivatives thereof.3. The method of claim 1 , wherein the substituted adamantyl moiety comprises a leaving group.4. The method of claim 3 , wherein the leaving group is selected from the group consisting of acetate claim 3 , triflate claim 3 , tosylate and hydroxyl.5. The method of claim 1 , wherein yield of the PAdis greater than 50 percent.6. The method of claim 1 , wherein yield of the PAdis greater than 60 percent.7. A method of cross-coupling comprising:{'sub': '3', 'providing a reaction mixture including a substrate, a coupling partner and a transition metal complex comprising PAdligand; and'}reacting the substrate and coupling partner in the presence of the transition metal complex or derivative thereof to provide cross-coupled reaction product.8. The method of claim 7 , wherein the transition metal complex comprises one or more metals selected from Group VIIIA claim 7 , IB or IIB of the Periodic Table.9. The method of claim 7 , wherein the transition metal complex comprises ...

PROCESS FOR PREPARING 2,2'-DIHYDROXY-3,3'-DI-TERT-BUTYL-5,5'-DIMETHOXY-1,1'-BIPHENOL

Process for preparing 2,2′-dihydroxy-3,3′-di-tert-butyl-5,5′-dimethoxy-1,1′-biphenol. 1. Process for preparing 2 ,2′-dihydroxy-3 ,3′-di-tert-butyl-5 ,5′-dimethoxy-1 ,1′-biphenol by oxidative coupling of 3-tert-butyl-4-hydroxyanisole , comprising the process steps of:a) heating a mixture comprising at least one solvent, an inorganic base and 3-tert-butyl-4-hydroxyanisole to a temperature above room temperature,b) adding a hydrogen peroxide solution to the mixture,c) removing the 2,2′-dihydroxy-3,3′-di-tert-butyl-5,5′-dimethoxy-1,1′-biphenol product. The present invention relates to a novel process for preparing 2,2′-dihydroxy-3,3′-di-tert-butyl-5,5′-dimethoxy-1,1′-biphenol by oxidative coupling of 3-tert-butyl-4-hydroxyanisole (3-BHA).Symmetric biphenols are great interest for industrial applications (cf. WO 2005/042547). These are employed particularly as ligand components for catalysts. In this case, the biphenol can be used, for example, as ligand unit in enantioselective catalysis (cf. Y. Chen, S. Yekta, A. K. Yudin, Chem. Rev. 2003, 103, 3155-3211; J. M. Brunel Chem. Rev. 2005, 105, 857-898; S. Kobayashi, Y. Mori, J. S. Fossey, Chem. Rev. 2011, 11, 2626-2704).However, the direct coupling of phenols to give the corresponding biphenol derivatives continues to be a challenge since these reactions are often neither regio- nor chemoselective.The literature describes a multitude of potential oxidizing agents capable of coupling phenols, especially o,p-disubstituted phenols, to give 2,2′-dihydroxybiphenols. In this context, particularly potassium hexacyanoferrate(III), K[Fe(CN)(see: a) Adv. Synth. Catal. 2004, 346, 993-1003; b) J. Org. Chem. 2011, 76, 8376-8385) and sodium peroxodisulphate play a crucial role.However, the two aforementioned oxidizing agents are relatively costly, which has an immediate effect on the overall cost of the product in an industrial scale synthesis. Moreover, in the case of use of potassium hexacyanoferrate(III) and in the case of use of ...

Build Sequences for Mechanosynthesis

Processes for creating build sequences are described which use computational chemistry algorithms to simulate mechanosynthetic reactions, and which may use the mechanosynthesis process conditions or equipment limitations in these simulations, and which facilitate determining a set of mechanosynthetic reactions that will build an atomically-precise workpiece with a desired degree of reliability. Included are methods for error correction of pathological reactions or avoidance of pathological reactions. Libraries of reactions may be used to reduce simulation requirements. 1. A method of creating a build sequence for a workpiece , comprising:a. storing the atomic coordinates of the workpiece in a data storage means;b. using computation chemistry algorithms in conjunction with computing means, coupled to the data storage means, to determine a set of mechanosynthetic reactions sufficient to build the workpiece; andc. determining an order in which said mechanosynthetic reactions may be performed to result in the workpiece.2. The method of further comprising:a. assessing the reliability of one or more of the mechanosynthetic reactions; andb. revising the build sequence if the reliability is insufficient.3. The method of wherein the order in which said mechanosynthetic reactions are performed is determined at least in part by steric considerations.4. The method of wherein the order in which mechanosynthetic reactions are performed is determined at least in part to avoid undesired rearrangements in intermediate workpiece structures.5. The method of wherein determining a set of mechanosynthetic reactions is done by choosing from a set of known mechanosynthetic reactions.6. The method of wherein one or more of the mechanosynthetic reactions use a plurality of tips simultaneously.7. The method of wherein the computational chemistry algorithms simulate the use of atomically-precise tips.8. The method of wherein the atomically-precise tips are comprised of adamantane-like ...

CARBON MONOXIDE-RELEASING MOLECULES FOR THERAPEUTIC APPLICATIONS AND METHODS FOR THE PREPARATION AND USE THEREOF

Carbon monoxide-releasing organic molecules are described herein. The molecules can be synthesized prior to administration (e.g., ex vivo) or formed in vivo. In those embodiments where the molecules are formed in vivo, reactants are administered under physiological conditions and undergo a cycloaddition reaction to form a product which releases carbon monoxide. In applying such reactions for therapeutic applications in vivo, the cycloaddition and CO release typically occur only under near-physiological or physiological conditions. For example, in some embodiments, the cycloaddition reaction and/or release of carbon monoxide occur at a temperature of about 37° C. and pH of about 7.4. Pharmaceutical compositions and methods for release carbon monoxide are also described. 2. The compound of claim 1 , wherein Rand Rare hydrogen.3. The compound of claim 2 , wherein subscript n is 1 or 2.4. The compound of claim 1 , wherein X is NRand Ris selected from the group consisting of hydrogen claim 1 , alkyl claim 1 , and heteroalkyl.5. The compound of claim 4 , wherein Rand Rare hydrogen.6. The compound of claim 5 , wherein subscript n is 1 or 2.7. A method for generating carbon monoxide in vivo or ex vivo claim 5 , the method comprising:{'claim-ref': {'@idref': 'CLM-00001', 'claim 1'}, 'allowing a precursor molecule according to to react to form an organic molecule that releases carbon monoxide under physiological conditions.'}8. The method of claim 7 , wherein the carbon monoxide is released in an amount effective for the treatment of inflammation claim 7 , cardiovascular disease claim 7 , cancer claim 7 , sepsis claim 7 , or a combination thereof.9. The method of claim 8 , wherein Rand Rare hydrogen.10. The method of claim 9 , wherein subscript n is 1 or 2.11. The method of claim 8 , wherein X is NRand Ris selected from the group consisting of hydrogen claim 8 , alkyl claim 8 , and heteroalkyl.12. The method of claim 11 , wherein Rand Rare hydrogen.13. The method of claim 12 ...

Process for producing aromatic compound, and palladium complex

A process for producing an aromatic compound in high yield and a palladium complex are provided. The palladium complex is represented by formula (D) or formula (D′): In formula (D), X represents a chlorine atom, A represents an alkyl group having 1 to 3 carbon atoms, B represents an alkyl group having 4 to 20 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms, R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, or an alkoxy group having 1 to 20 carbon atoms, and R 6 , R 7 and R 8 represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 4 to 20 carbon atoms. In formula (D′), X, A, B and R 4 to R 8 are the same as defined above.

Alkylated Anisole-Containing Lubricating Oil Base Stocks and Processes for Preparing the Same

Compounds having the formula (F-I) below are provided herein: 114-. (canceled)16. The process of claim 15 , wherein the olefin-containing material comprises at least about 75 wt % of the compound of formula (F-Ib) where Ris hydrogen.17. The process of claim 15 , wherein the olefin-containing material comprises at least about 50 wt % of the compound of formula (F-Ib) where Ris a C-Calkyl group.18. The process of claim 15 , wherein the olefin-containing material comprises a mixture of: (i) about 1.0 to about 99 wt % of the compound of formula (F-Ib) where Ris hydrogen; and (ii) about 1.0 to about 99 wt % of the compound of formula (F-Ib) where Ris a C-Calkyl group.19. The process of claim 15 , wherein the olefin-containing material has an isotacticity of at least about 60 mol %.20. The process of claim 15 , wherein the acid catalyst is a solid acid catalyst selected from the group consisting of a solid Lewis acid claim 15 , an acid clay claim 15 , a polymeric acidic resin claim 15 , silica-alumina claim 15 , a mineral acid and a combination thereof.21. The process of claim 15 , wherein the acid catalyst comprises one or more molecular sieve having a framework structure selected from the group consisting of BEA claim 15 , EUO claim 15 , FAU claim 15 , FER claim 15 , HEU claim 15 , MEL claim 15 , MFI claim 15 , MOR claim 15 , MRE claim 15 , MTW claim 15 , MTT claim 15 , MWW claim 15 , OFF claim 15 , and combinations thereof.22. The process of claim 21 , wherein the molecular sieve is selected from the group consisting of ZSM-5 claim 21 , ZSM-11 claim 21 , ZSM-12 claim 21 , ZSM-23 claim 21 , ZSM-35 claim 21 , ZSM-48 claim 21 , ZSM-50 claim 21 , Zeolite Beta claim 21 , MCM-56 claim 21 , MCM-22 claim 21 , MCM-36 claim 21 , MCM-49 claim 21 , zeolite Y claim 21 , zeolite X claim 21 , and combinations thereof.23. The process of claim 15 , wherein at least about 50 mol % of the compounds produced have the moiety comprising R claim 15 , R claim 15 , and Rbonded to the phenyl ...

Processo para preparação de olefinas aromáticas

Lewis acid catalyst-containing composition

α-二亚胺镍金属有机配体、多孔有机聚合物及其应用

本公开提供了α‑二亚胺镍金属有机配体、多孔有机聚合物及其应用，多孔有机聚合物包括如下化学结构式： 本公开提供的多孔有机聚合物能够获得用于催化Suzuki偶联反应的催化剂，且该催化剂的催化活性高、成本低，使用量少，而且能够重复利用。

Use of a catalyst system comprising nickel, palladium, or platinum and imidazoline-2-ylidene of imidazolidine-2-ylidene in suzuki coupling reactions

This invention provides a process for conducting Suzuki coupling reactions. The processes of the present invention make use of N-heterocyclic carbenes as ancillary ligands in Suzuki couplings of aryl halides and aryl pseudohalides. A Suzuki coupling can be carried out by mixing, in a liquid medium, at least one strong base; at least one aryl halide or aryl pseudohalide in which all substituents are other than boronic acid groups, wherein the aryl halide has, directly bonded to the aromatic ring(s), at least one halogen atom selected from the group consisting of a chlorine atom, a bromine atom, and an iodine atom; at least one arylboronic acid in which all substituents are other than chlorine atoms, bromine atoms, iodine atoms, or pseudohalide groups; at least one metal compound comprising at least one metal atom selected from nickel, palladium, and platinum, wherein the formal oxidation state of the metal is zero or two; and at least one N-heterocyclic carbene. One preferred type of N-heterocyclic carbene is an imidazoline-2-ylidene of the formula wherein R 1 and R 2 are each, independently, alkyl or aryl groups having at least 3 carbon atoms, R 3 and R 4 are each, independently, a hydrogen atom, a halogen atom, or a hydrocarbyl group.

Transition metal complexes with diaminocarbene ligands and their use in reactions catalyzed by transition metals

The invention relates to novel transition metal complexes containing at least one diaminocarbene ligand, to processes for preparing these transition metal complexes and to their use as catalysts in organic reactions.

Processo para a preparação de nitrobifenilas

Processo para a preparacao de nitrobifenileno

Process for the production of aromatic olefins

Process for preparing aromatic olefins

The preparation of aromatic olefins from haloaromatics and olefins (Heck reaction) is carried out in the presence of palladium complexes as catalysts, which complexes contain heterocyclic carbenes as ligands.

Process for the production of aromatic olefines

Method for producing aromatic olefin

방향족 올레핀의 제조방법

할로방향족 및 올레핀으로부터 방향족 올레핀의 제조(헥크(Heck) 반응)은 촉매로서 팔라듐 착물(여기서, 착물이 리간드로서 헤테로사이클릭 카벤을 함유한다)의 존재하에 수행한다.

制备芳族烯烃的方法

在作为催化剂的钯配合物存在下，从卤代芳族化合物和烯烃类制备芳族烯烃(Heck反应)，该配合物含有作为配位体的杂环碳烯。

Process for preparing aromatic olefins

Prodn. of mono-, di- or poly-functional aromatic olefins is effected by reacting haloaromatic cpds. with olefins at 20-220 degrees C in the presence of a Pd complex catalyst of formula: (LaPdbXc)<n>An (I) X = a charged or uncharged mono- or poly-dentate ligand co-ordinated to Pd; L = a carbene ligand of formulae (II)-(V) co-ordinated to Pd: R1-R6 = opt. sulphonated 1-7C alkyl, 5-18C alicyclic, 2-5C alkenyl, 6-14C aryl or 7-19C aralkyl gps.; or R3-R6 may also be H; or R3+R4 and R5+R6 = opt. sulphonated 3-7C divalent gps.; or R1, R2, R4 or R6 may form a ring with X; Y = a satd. or unsatd. 1-4C alkylidene gp. or a dialkylsilylene or tetraalkyldisilylene gp.; A = an anion; b = 1-3; a = 1 to 4b; c = 0 to 4b; n = 0-6.

Process for preparing aromatic olefins

The preparation of aromatic olefins from haloaromatics and olefins (Heck reaction) is carried out in the presence of palladium complexes as catalysts, which complexes contain heterocyclic carbenes as ligands. The palladium complexes are compounds of the formula [L a Pd b X c]n A n which includes compounds such as bis (1,3-dimethylimidazolin-2-ylidene) palladium(II) dichloride, dibromide and diiodide.

Menetelmä aromaattisten olefiinien valmistamiseksi

Process for preparing aromatic olefins

THE PREPARATION OF AROMATIC OLEFINS FROM HALOAROMATICS AND OLEFINS (HECK REACTION) IS CARRIED OUT IN THE PRESENCE OF PALLADIUM COMPLEXES AS CATALYSTS, WHICH COMPLEXES CONTAIN HETEROCYCLIC CARBENES AS LIGANDS.

Method of obtaining aromatic olefins

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Process for preparing aromatic olefins

Process for the production of aromatic olefins under the catalysis of palladacycles

Process for the synthesis of aromatically substituted olefins

The invention relates to a new method for synthesising aromatically substituted olefins, whereby olefins are reacted with aryl halides in the presence of catalysts consisting of palladium compounds and tetraarylphosphonium salts.

(Hetero)aryl-substituted olefin preparation for use e.g. as polymer or drug intermediate, by Heck reaction using inexpensive catalyst system of divalent palladium compound and nitrogen-containing additive

In the preparation of (hetero)aryl-substituted olefins (I) by palladium-catalyzed reaction of a (hetero)aromatic halide, sulfonate or diazonium halide (II) with an olefin (III), the catalyst is a specific divalent palladium compound (IV) used in presence of a nitrogen-containing additive (V), and reaction is in the absence of phosphonium salts and phosphanes. Preparation of (hetero)aryl-substituted olefins of formula Ar-C(R1)=CR2R3 (I) involves palladium-catalyzed reaction of a (hetero)aromatic compound of formula ArZ (II) with an olefin of formula HC(R1)=CR2R3 (III). The catalyst is a divalent palladium compound of formula PdXY (IV) (or its acetonitrile of benzonitrile complex) used in presence of a nitrogen-containing additive (V). Reaction is carried out at 60-180 deg C, in the presence of a solvent and a base, but in the absence of phosphonium salts and phosphanes. Ar = aryl or heteroaryl (both optionally substituted); R1-R3 = H, 1-8C alkyl, Ph, 1- or 2-naphthyl, 1-8C alkoxy, OPh, CN, COOH,(1-8C) alkoxycarbonyl, COOPh, CONH2, N-(1-5C alkyl)-amido, N,N-di-(1-5C alkyl)-amido, F, Cl, PO(Ph)2, PO(1-5C alkyl)2, Ph-CO, 1-5C alkyl-CO, 1-4C alkylamino, PO3H (sic), 1-4C alkylsulfonate or 1-4C alkylsulfonyl; or R1 + R2 or R2 + R3 = (CH2)n; n = 2-12; Z = Cl, Br, OSO2Me, OS2-tolyl, OSO2CF3, OS2C4F9 or N2<+>.Cl<->; X, Y = Cl, Br, I, NO3, RCOO or R'SO3; R = 1-22C group, CF3, CCl3, CH2OMe or Ph; R' = 1-22C group, CF3, C4F9, CCl3, Ph or p-tolyl.

Process for the preparation of olefin-substituted aromatics or heteroaromatics

Both low-molecular and high-molecular aromatic or heteroaromatic compounds, which are substituted with olefins, play an important role in industry, for example as auxiliary agents or additives in cosmetic preparations such as sunscreen agents, in diverse fine chemicals and chemicals for the electronics industry and in intermediate products for the pharmaceutical and agrochemical industries. Such compounds are of outstanding importance particularly in the rapid-growth field of organic semiconductors, (e.g. for use in organic or polymer LEDs, organic solar cells and organic integrated circuits). The invention relates to a method for producing olefin-substituted aromatic or heteroaromatic compounds of this type, by reacting a functional aryl or heteroaryl compound with an olefin derivative, which has at least one H-atom on its double bond, in the presence of a simple palladium compound, optionally in the presence of an additive containing nitrogen and of a base in a solvent, to form a C-C-linkage and a formal splitting-off of the aryl, or heteroaryl derivative functional group and of one H-atom of the olefin compound. The invention is characterised by the presence of at least one additive containing metal, which is different from palladium.

Nucleophilic heterocyclic carbene derivatives of Pd(acac)2 for cross-coupling reactions

Embodiments in accordance with the present invention provide for a palladium complex characterized by the general formula: where A is a bidentate monoanionic ligand, NHC is a nucleophilic heterocyclic carbene, and Z is an anionic ligand. Such palladium complexes are useful in initiating cross-coupling reactions.

Process for the production of aromatic olefins

制备芳族烯烃的方法

在作为催化剂的钯配合物存在下，从卤代芳族化合物和烯烃类制备芳族烯烃(Heck反应)，该配合物含有作为配位体的杂环碳烯。

Process for the preparation of aromatic olefins

Process for the production of aromatic olefines

Prodn. of mono-, di- or poly-functional aromatic olefins is effected by reacting haloaromatic cpds. with olefins at 20-220 degrees C in the presence of a Pd complex catalyst of formula: (LaPdbXc)<n>An (I) X = a charged or uncharged mono- or poly-dentate ligand co-ordinated to Pd; L = a carbene ligand of formulae (II)-(V) co-ordinated to Pd: R1-R6 = opt. sulphonated 1-7C alkyl, 5-18C alicyclic, 2-5C alkenyl, 6-14C aryl or 7-19C aralkyl gps.; or R3-R6 may also be H; or R3+R4 and R5+R6 = opt. sulphonated 3-7C divalent gps.; or R1, R2, R4 or R6 may form a ring with X; Y = a satd. or unsatd. 1-4C alkylidene gp. or a dialkylsilylene or tetraalkyldisilylene gp.; A = an anion; b = 1-3; a = 1 to 4b; c = 0 to 4b; n = 0-6.

Process for Preparing Aromatic Olefins

The preparation of aromatic olefins from haloaromatics and olefins (Heck reaction) is carried out in the presence of palladium complexes as catalysts, which complexes contain heterocyclic carbenes as ligands. The palladium complexes are compounds of the formula [L a Pd b X c]n A n which includes compounds such as bis (1,3-dimethylimidazolin-2-ylidene) palladium(II) dichloride, dibromide and diiodide.

CATALYSTS FOR THE CONDUCT OF CROSSED COUPLING REACTIONS.

SE PROPONE UN SISTEMA DE CATALIZADOR, EN ESPECIAL PARA LAS REACCIONES DE ACOPLAMIENTO CRUZADAS, QUE SE PUEDE OBTENER MEDIANTE REACCION A) DE UNA COMPOSICION DE PALADIO (II) CON B) UN LIGANDO DE FOSFANO SOLUBLE EN AGUA Y C) UN SULFOXIDO O UN ALCOHOL POLIVALENTE. A CATALYSTING SYSTEM IS PROPOSED, ESPECIALLY FOR CROSSED COUPLING REACTIONS, WHICH CAN BE OBTAINED BY REACTION A) OF A PALADIO COMPOSITION (II) WITH B) A WATER SOLUBLE PHOSPHANE BINDING AND C) A SULFOXIDE OR A POLYAL ALCOHOL .

IMIDAZOLIDINONIC ACID SUITES AS REACTION CATALYSTS

Synthesis and application of vapor grafted porous materials

This invention provides an article, compositions, methods of making and uses of vapor-deposited metal compounds immobilized on porous substrates. The substrate is a porous substrate having an average pore size of at least about 8 Å and a surface area of at least about 10 m2/g. The methods describe the vapor-deposition of an inorganic compound onto the substrate where the deposition is accomplished with a relatively small amount of ligand loss. The substrate can be pre-treated to achieve a uniformly dispersed metal compound deposited on the substrate. The inorganic compound can decompose into a metal compound. The article can also function as a catalyst for carbon-heteroatom coupling reactions such as carbon-carbon coupling reactions, most notably, the Heck reaction.

Hydroboronation process

New catalyst

Lewis acid catalyst composition

A Lewis acid catalyst composition comprising a specific mixed medium and a Lewis acid catalyst, wherein the Lewis acid catalyst is at least one compound selected from the group consisting of compounds respectively represented by the following formulae (1) and (2): [(R f 1 SO 2 )(R f 2 SO 2 )N] n M  (1), and [(R f 1 SO 2 )(R f 2 SO 2 )(R f 3 SO 2 )C] n M  (2). A method for continuously performing a reaction which proceeds in the presence of the above-mentioned Lewis acid catalyst by using a specific mixed medium and the above-mentioned Lewis acid catalyst. A novel Lewis acid catalyst.

Lewis acid catalyst composition

A Lewis acid catalyst composition comprising a specific mixed medium and a Lewis acid catalyst, wherein the Lewis acid catalyst is at least one compound selected from the group consisting of compounds respectively represented by the following formulae (1) and (2): [(R f 1 SO 2 )(R f 2 SO 2 )N] n M,  (1) and [(R f 1 SO 2 )(R f 2 SO 2 )(R f 3 SO 2 )C] n M.   (2) A method for continuously performing a reaction which proceeds in the presence of the above-mentioned Lewis acid catalyst by using a specific mixed medium and the above-mentioned Lewis acid catalyst. A novel Lewis acid catalyst.

Asymmetric cycloaddition reactions

The present invention relates to a process for stereoselective cycloaddition reactions which generally comprises a cycloaddition reaction between a pair of substrates, each either chiral or prochiral, that contain reactive π-systems, in the presence of a non-racemic chiral catalyst, to produce a stereoisomerically enriched product. The present invention also relates to novel asymmetric catalyst complexes comprising a metal and an asymmetric tridentate ligand.

Asymmetric cycloaddition reactions

The present invention relates to a process for stereoselective cycloaddition reactions which generally comprises a cycloaddition reaction between a pair of chiral or prochiral substrates that contain reactive pi -systems, in the present of a non-racemic chiral catalyst, to produce a stereoisomerically enriched product.

New transition metal complexes with diamino carbene ligands and their use in transition metal catalyzed reactions

Die Erfindung betrifft neue Übergangsmetallkomplexe, die mindestens einen Diamino-Carbenliganden besitzen, Verfahren zur Herstellung dieser Übergangsmetallkomplexe sowie ihre Verwendung als Katalysatoren in organischen Reaktionen. The invention relates to new transition metal complexes which have at least one diamino-carbene ligand, processes for the preparation of these transition metal complexes and their use as catalysts in organic reactions.