# US 8,785,693 B2 · Process for the preparation of primary amines by homogeneously catalyzed alcohol amination > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,785,693 B2 - Document ID: US8785693B2 - Status: Granted - Kind: B2 - Application number: 13/415,412 - Filed: 2012-03-08 - Published: 2012-09-13 - Granted: 2014-07-22 - Earliest claimed: 2011-03-08 - Assignees: BASF SE - Applicants: Thomas Schaub; Boris Buschhaus; Marion Kristina Brinks; Mathias Schelwies; Rocco Paciello; Johann-Peter Melder; Martin Merger - Inventors: Thomas Schaub; Boris Buschhaus; Marion Kristina Brinks; Mathias Schelwies; Rocco Paciello; Johann-Peter Melder; Martin Merger - Web page: https://patentgrep.com/patent/US8785693B2 ## CPC - C07C 209/16: with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings - C07C 213/02: by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups - C07D 207/04: having no double bonds between ring members or between ring members and non-ring members - C07D 207/20: with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms - C07D 295/023: Preparation; Separation; Stabilisation; Use of additives - C07D 307/52: Radicals substituted by nitrogen atoms not forming part of a nitro radical - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08) ## Abstract Process for the preparation of primary amines which have at least one functional group of the formula (—CH2—NH2) by alcohol amination of starting materials which have at least one functional group of the formula (—CH2—OH), with ammonia, with the elimination of water, where the alcohol amination is carried out under homogeneous catalysis in the presence of at least one complex catalyst which comprises at least one element selected from groups 8 and 9 of the Periodic Table of the Elements, and also at least one phosphorus donor ligand of the general formula (I). ## Claims ### Claim 1 A process for producing a primary amine comprising a functional group having a formula of —CH2—NH2, the process comprising: aminating a starting material comprising a functional group having a formula of —CH2—OH with ammonia, thereby eliminating water, to obtain the primary amine, wherein the aminating is homogeneously catalyzed in the presence of a complex catalyst comprising at least one element selected from groups 8 and 9 of the Periodic Table of the Elements, and a phosphorus donor ligand of formula (I); wherein: n is 0 or 1; R1, R2, R3, R4, R5, R6 are each independently an unsubstituted or at least monosubstituted C1-C10-alkyl, C1-C4-alkyldiphenylphosphine (—C1-C4-alkyl-P(phenyl)2), C3-C10-cycloalkyl, C3-C10-heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S, C5-C14-aryl, or C5-C10-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and a C1-C10-alkyl; A is i) a bridging group selected from the group consisting of an unsubstituted or at least monosubstituted N, O, P, C1-C6-alkane, C3-C10-cycloalkane, C3-C10-heterocycloalkane comprising at least one heteroatom selected from the group consisting of N, O, and S, C5-C14-aromatic, and C5-C6-heteroaromatic comprising at least one heteroatom selected from the group consisting of N, O and S, wherein the substituents are selected from the group consisting of a C1-C4-alkyl, phenyl, F, Cl, Br, OH, OR7, NH2, NHR7, and N(R7)2, wherein R7 is a C1-C10-alkyl or a C5-C10-aryl, or ii) a bridging group of formula (II) or (III): wherein m, q are each independently 0, 1, 2, 3, or 4, R8, R9 are each independently selected from the group consisting of a C1-C10-alkyl, F, Cl, Br, OH, OR7, NH2, NHR7, and N(R7)2, wherein R7 is a C1-C10-alkyl or a C5-C10-aryl, X1, X2 are each independently NH, O, or S, X3 is a bond, NH, NR10, O, S, or CR11R12, R10 is a an unsubstituted or at least monosubstituted C1-C10-alkyl, C3-C10-cycloalkyl, C3-C10-heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S, C5-C14-aryl, or C5-C10-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and a C1-C10-alkyl, R11, R12 are each independently an unsubstituted or at least monosubstituted C1-C10-alkyl, C3-C10-cycloalkyl, C3-C10-cycloalkoxy, C3-C10-heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S, C5-C14-aryl, C5-C14-aryloxy, or C5-C10-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and C1-C10-alkyl; and Y1, Y2, Y3 are each independently a bond, or an unsubstituted or at least monosubstituted methylene, ethylene, trimethylene, tetramethylene, pentamethylene, or hexamethylene, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, OR7, CN, NH2, NHR7, N(R7)2, and a C1-C10-alkyl, and wherein R7 is a C1-C10-alkyl or a C5-C10-aryl. ### Claim 2 (depends on 1) The process of claim 1, wherein R1, R2, R3, R4, R5, R6 are each independently an unsubstituted C1-C10-alkyl, C1-C4-alkyldiphenylphosphine, C3-C10-cycloalkyl, C3-C10-heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S, C5-C14-aryl, or C5-C10-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S; A is i) a bridging group selected from the group consisting of an unsubstituted N, O, P, C1-C6-alkane, C3-C10-cycloalkane, C3-C10-heterocycloalkane comprising at least one heteroatom selected from the group consisting of N, O, and S, C5-C14-aromatic, and C5-C6-heteroaromatic comprising at least one heteroatom selected from the group consisting of N, O, and S; or ii) a bridging group of the formula II or III: wherein m, q are each independently 0, 1, 2, 3, or 4, R8, R9 are each independently selected from the group consisting of a C1-C10-alkyl, F, Cl, Br, OH, OR7, NH2, NHR7, and N(R7)2, wherein R7 is selected from C1-C10-alkyl and C5-C10-aryl, X1, X2 are each independently NH, O, or S, X3 is a bond, NH, NR10, O, S, or CR11R12, R10 is an unsubstituted C1-C10-alkyl, C3-C10-cycloalkyl, C3-C10-heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S, C5-C14-aryl, or C5-C10-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S, R11, R12 are each independently an unsubstituted C1-C10-alkyl, C1-C10-alkoxy, C3-C10-cycloalkyl, C3-C10-cycloalkoxy, C3-C10-heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S, C5-C14-aryl, C5-C14-aryloxy, or C5-C10-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S; and Y1, Y2, Y3 are each independently a bond, an unsubstituted methylene, ethylene, trimethylene, tetramethylene, pentamethylene, or hexamethylene. ### Claim 3 (depends on 1) The process of claim 1, wherein the phosphorus donor ligand has a formula (V): wherein: Y1, Y2 are each independently a bond, or an unsubstituted or at least monosubstituted methylene, ethylene, trimethylene, tetramethylene, pentamethylene, or hexamethylene, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, OR7, CN, NH2, NHR7, N(R7)2, and C1-C10-alkyl, and wherein R7 is a C1-C10-alkyl or a C5-C10-aryl. ### Claim 4 (depends on 1) The process of claim 1, wherein the phosphorus donor ligand has a formula (VI): wherein R1, R2, R3, R4, R5, R6 are each independently an unsubstituted or at least monosubstituted C1-C10-alkyl, C3-C10-cycloalkyl, C3-C10-heterocyclyl comprising at least one heteroatom selected from the group consisting of N, O, and S, C5-C14-aryl, or C5-C10-heteroaryl comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of F, Cl, Br, OH, CN, NH2, and a C1-C10-alkyl; and A is a bridging group selected from the group consisting of an unsubstituted or at least monosubstituted N, P, C1-C6-alkane, C3-C10-cycloalkane, C3-C10-heterocycloalkane comprising at least one heteroatom selected from the group consisting of N, O, and S, C5-C14-aromatic, and C5-C6-heteroaromatic comprising at least one heteroatom selected from the group consisting of N, O, and S, wherein the substituents are selected from the group consisting of a C1-C4-alkyl, F, Cl, Br, OH, OR7, NH2, NHR7, and N(R7)2, wherein R7 is a C1-C10-alkyl or a C5-C10-aryl. ### Claim 5 (depends on 1) The process of claim 1, wherein the phosphorus donor ligand has a formula (IX) or (X), ### Claim 6 (depends on 1) The process of claim 1, wherein the complex catalyst comprises at least one element selected from the group consisting of ruthenium and iridium, and at least one phosphorus donor ligand selected from the group consisting of 1,2-bis(diphenylphosphino)ethane (dppe), 1,2-bis(dicyclohexylphosphino)ethane, 1,2-bis(diphenylphosphino)propane (dppp), 1,2-bis(diphenylphosphino)butane (dppb), 2,3-bis(dicyclohexylphosphino)ethane (dcpe), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos), bis(2-diphenylphosphinoethyl)phenylphosphine, and 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos). ### Claim 7 (depends on 1) The process of claim 1, wherein the complex catalyst comprises ruthenium and at least one phosphorus donor ligand selected from the group consisting of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos), bis(2-diphenylphosphinoethyl)phenylphosphine, and 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos). ### Claim 8 (depends on 7) The process of claim 7, wherein the phosphorus donor ligand is selected from the group consisting of bis(2-diphenylphosphinoethyl)phenylphosphine and triphos. ### Claim 9 (depends on 1) The process of claim 1, wherein the complex catalyst comprises iridium and at least one phosphorus donor ligand selected from the group consisting of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos), bis(2-diphenylphosphinoethyl)phenylphosphine, and 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos). ### Claim 10 (depends on 1) The process of claim 1, wherein the starting material comprises at least two functional groups having a formula —CH2—OH. ### Claim 11 (depends on 1) The process of claim 1, wherein the aminating is carried out in the presence of a nonpolar solvent. ### Claim 12 (depends on 11) The process of claim 11, wherein the aminating is carried out in the presence of a solvent selected from the group consisting of saturated hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, mesitylene, THF, diethyl ether, 1,4-dioxane, MTBE, diglyme, and 1,2-dimethoxyethane. ### Claim 13 (depends on 1) The process of claim 1, wherein the aminating is carried out at a temperature in a range from 20 to 250° C. and a pressure from 0.1 to 20 MPas absolute. ### Claim 14 (depends on 1) The process of claim 1, wherein the aminating is carried out in the presence of a base. ### Claim 15 (depends on 7) The process of claim 7, wherein the phosphorus donor ligand is bis(2-diphenylphosphinoethyl)phenylphosphine. ### Claim 16 (depends on 7) The process of claim 7, wherein the phosphorus donor ligand is triphos. ### Claim 17 (depends on 9) The process of claim 9, wherein the phosphorus donor ligand is 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos). ### Claim 18 (depends on 9) The process of claim 9, wherein the phosphorus donor ligand is bis(2-diphenylphosphinoethyl)phenylphosphine. ### Claim 19 (depends on 9) The process of claim 9, wherein the phosphorus donor ligand is 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos). ### Claim 20 (depends on 11) The process of claim 11, wherein the nonpolar solvent is selected from the group consisting of toluene, xylene, and mesitylene.