B01J27/13

COATED OPTICAL FIBRES HAVING IMPROVED FEATURES
20180045884 · 2018-02-15 ·

A waveguide for high efficiency transmission of high energy light useful in ablation procedures at predetermined bandwidths over predetermined distances comprising: an optical fiber core; a silanization agent; layered cladding surrounding the optical fiber core comprising: a first thin metal layer comprising at least two types of metals the first thin metal layer covalently bonded to the core and a second thin metal layer bonded to the second metal layer, and a catalyst component; wherein the silanization agent comprising organofunctional alkoxysilane molecule, such as 3-aminopropyltriethoxysilane (APTS), is a self supporting bridge between the surface of the optical fiber and the first metal layer; the first metal layer is uniformly chemisorbed onto the surface of the optical fiber by means of covalent SiOSi bonds with the optical fiber; further wherein the catalyst component derived from an activation solution for enhancing the layered cladding upon the optical fiber.

COATED OPTICAL FIBRES HAVING IMPROVED FEATURES
20180045884 · 2018-02-15 ·

A waveguide for high efficiency transmission of high energy light useful in ablation procedures at predetermined bandwidths over predetermined distances comprising: an optical fiber core; a silanization agent; layered cladding surrounding the optical fiber core comprising: a first thin metal layer comprising at least two types of metals the first thin metal layer covalently bonded to the core and a second thin metal layer bonded to the second metal layer, and a catalyst component; wherein the silanization agent comprising organofunctional alkoxysilane molecule, such as 3-aminopropyltriethoxysilane (APTS), is a self supporting bridge between the surface of the optical fiber and the first metal layer; the first metal layer is uniformly chemisorbed onto the surface of the optical fiber by means of covalent SiOSi bonds with the optical fiber; further wherein the catalyst component derived from an activation solution for enhancing the layered cladding upon the optical fiber.

METHOD FOR PREPARING DI- OR TRICARBOXYLIC ESTERS BY ALKOXYCARBONYLATION OF DIENES HAVING CONJUGATED DOUBLE BONDS

The invention relates to a method comprising the method steps of: a) initially charging a diene having two conjugated double bonds; b) adding a phosphine ligand and a catalyst precursor selected from palladium dichloride, palladium dibromide, palladium diiodide, palladium(II) acetylacetonate, palladium(II) acetate, bis(dibenzylideneacetone)palladium, bis(acetonitrile)dichloropalladium(II), palladium (cinnamyl) dichloride; c) adding an alcohol; d) feeding in CO; d) heating the reaction mixture, with conversion of the diene to a di- or tricarboxylic ester;
wherein the phosphine ligand is a compound according to formula (I)

##STR00001##

where R.sup.1, R.sup.2, R.sup.3, R.sup.4 are selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.3-C.sub.20)-heteroaryl; R.sup.5, R.sup.6 are selected from H, (C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.3-C.sub.20)-heteroaryl; and R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, in the case that these are (C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl or (C.sub.3-C.sub.20)-heteroaryl, may be each substituted independently of one another by one or more substituents selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, O(C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl, O(C.sub.3-C.sub.12)-cycloalkyl, S(C.sub.1-C.sub.12)-alkyl, S(C.sub.3-C.sub.12)-cycloalkyl, COO(C.sub.1-C.sub.12)-alkyl, COO(C.sub.3-C.sub.12)-cycloalkyl, CONH(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.3-C.sub.12)-cycloalkyl, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.3-C.sub.12)-cycloalkyl, N[(C.sub.1-C.sub.12)-alkyl].sub.2, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl, (C.sub.3-C.sub.20)-heteroaryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl-O(C.sub.1-C.sub.12)-alkyl, COOH, OH, SO.sub.3H, NH.sub.2, halogen.

METHOD FOR PREPARING DI- OR TRICARBOXYLIC ESTERS BY ALKOXYCARBONYLATION OF DIENES HAVING CONJUGATED DOUBLE BONDS

The invention relates to a method comprising the method steps of: a) initially charging a diene having two conjugated double bonds; b) adding a phosphine ligand and a catalyst precursor selected from palladium dichloride, palladium dibromide, palladium diiodide, palladium(II) acetylacetonate, palladium(II) acetate, bis(dibenzylideneacetone)palladium, bis(acetonitrile)dichloropalladium(II), palladium (cinnamyl) dichloride; c) adding an alcohol; d) feeding in CO; d) heating the reaction mixture, with conversion of the diene to a di- or tricarboxylic ester;
wherein the phosphine ligand is a compound according to formula (I)

##STR00001##

where R.sup.1, R.sup.2, R.sup.3, R.sup.4 are selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.3-C.sub.20)-heteroaryl; R.sup.5, R.sup.6 are selected from H, (C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.3-C.sub.20)-heteroaryl; and R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, in the case that these are (C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl or (C.sub.3-C.sub.20)-heteroaryl, may be each substituted independently of one another by one or more substituents selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, O(C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl, O(C.sub.3-C.sub.12)-cycloalkyl, S(C.sub.1-C.sub.12)-alkyl, S(C.sub.3-C.sub.12)-cycloalkyl, COO(C.sub.1-C.sub.12)-alkyl, COO(C.sub.3-C.sub.12)-cycloalkyl, CONH(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.3-C.sub.12)-cycloalkyl, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.3-C.sub.12)-cycloalkyl, N[(C.sub.1-C.sub.12)-alkyl].sub.2, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl, (C.sub.3-C.sub.20)-heteroaryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl-O(C.sub.1-C.sub.12)-alkyl, COOH, OH, SO.sub.3H, NH.sub.2, halogen.

PROCESS FOR THE PREPARATION OF ESTERS BY MEANS OF CARBONYLATION OF ETHERS

The invention relates to a process comprising the process steps of: a) initially charging an ether having from 3 to 30 carbon atoms; b) adding a phosphine ligand and a compound comprising Pd, or adding a comprising Pd and a phosphine ligand; c) feeding in CO; d) heating the reaction mixture, with conversion of the ether; wherein the phosphine ligand is a compound of formula (I)

##STR00001## where m and n are each independently 0 or 1; R.sup.1, R.sup.2, R.sup.3, R.sup.4 are each independently selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.20)-heteroaryl; at least one of the R.sup.1, R.sup.2, R.sup.3, R.sup.4 radicals is a (C.sub.3-C.sub.20)-heteroaryl radical; and R.sup.1, R.sup.2, R.sup.3, R.sup.4, if they are (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl or (C.sub.3-C.sub.20)-heteroaryl, may each independently be substituted by one or more substituents selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, O(C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl, O(C.sub.3-C.sub.12)-cycloalkyl, S(C.sub.1-C.sub.12)-alkyl, S(C.sub.3-C.sub.12)-cycloalkyl, COO(C.sub.1-C.sub.12)-alkyl, COO(C.sub.3-C.sub.12)-cycloalkyl, CONH(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.3-C.sub.12)-cycloalkyl, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.3-C.sub.12)-cycloalkyl, N[(C.sub.1-C.sub.12)-alkyl].sub.2, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl, (C.sub.3-C.sub.20)heteroaryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl-O(C.sub.1-C.sub.12)-alkyl, COOH, SO.sub.3H, NH.sub.2, halogen; and wherein no alcohol is added to the reaction mixture.

PROCESS FOR THE PREPARATION OF ESTERS BY MEANS OF CARBONYLATION OF ETHERS

The invention relates to a process comprising the process steps of: a) initially charging an ether having from 3 to 30 carbon atoms; b) adding a phosphine ligand and a compound comprising Pd, or adding a comprising Pd and a phosphine ligand; c) feeding in CO; d) heating the reaction mixture, with conversion of the ether; wherein the phosphine ligand is a compound of formula (I)

##STR00001## where m and n are each independently 0 or 1; R.sup.1, R.sup.2, R.sup.3, R.sup.4 are each independently selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.20)-heteroaryl; at least one of the R.sup.1, R.sup.2, R.sup.3, R.sup.4 radicals is a (C.sub.3-C.sub.20)-heteroaryl radical; and R.sup.1, R.sup.2, R.sup.3, R.sup.4, if they are (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl or (C.sub.3-C.sub.20)-heteroaryl, may each independently be substituted by one or more substituents selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, O(C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl, O(C.sub.3-C.sub.12)-cycloalkyl, S(C.sub.1-C.sub.12)-alkyl, S(C.sub.3-C.sub.12)-cycloalkyl, COO(C.sub.1-C.sub.12)-alkyl, COO(C.sub.3-C.sub.12)-cycloalkyl, CONH(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.3-C.sub.12)-cycloalkyl, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.3-C.sub.12)-cycloalkyl, N[(C.sub.1-C.sub.12)-alkyl].sub.2, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl, (C.sub.3-C.sub.20)heteroaryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl-O(C.sub.1-C.sub.12)-alkyl, COOH, SO.sub.3H, NH.sub.2, halogen; and wherein no alcohol is added to the reaction mixture.

PROCESS FOR THE ALKOXYCARBONYLATION OF ETHERS

The invention relates to a process comprising the following process steps: a) introducing an ether having 3 to 30 carbon atoms; b) adding a phosphine ligand and a compound which comprises Pd, or adding a complex comprising Pd and a phosphine ligand; c) adding an alcohol; d) supplying CO; e) heating the reaction mixture, the ether being reacted for form an ester; where the phosphine ligand is a compound of formula (I)

##STR00001##

where
m and n are each independently 0 or 1;
R.sup.1, R.sup.2, R.sup.3, R.sup.4 are each independently selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.20)-heteroaryl;
at least one of the R.sup.1, R.sup.2, R.sup.3, R.sup.4 radicals is a (C.sub.3-C.sub.20)-heteroaryl radical;
and
R.sup.1, R.sup.2, R.sup.3, R.sup.4, if they are (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl or (C.sub.3-C.sub.20)-heteroaryl,
may each independently be substituted by one or more substituents selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, O(C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl, O(C.sub.3-C.sub.12)-cycloalkyl, S(C.sub.1-C.sub.12)-alkyl, S(C.sub.3-C.sub.12)-cycloalkyl, COO(C.sub.1-C.sub.12)-alkyl, COO(C.sub.3-C.sub.12)-cycloalkyl, CONH(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.3-C.sub.12)-cycloalkyl, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.3-C.sub.12)-cycloalkyl, N[(C.sub.1-C.sub.12)-alkyl].sub.2, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl, (C.sub.3-C.sub.20)-heteroaryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl-O(C.sub.1-C.sub.12)-alkyl, COOH, OH, SO.sub.3H, NH.sub.2, halogen.

PROCESS FOR THE ALKOXYCARBONYLATION OF ETHERS

The invention relates to a process comprising the following process steps: a) introducing an ether having 3 to 30 carbon atoms; b) adding a phosphine ligand and a compound which comprises Pd, or adding a complex comprising Pd and a phosphine ligand; c) adding an alcohol; d) supplying CO; e) heating the reaction mixture, the ether being reacted for form an ester; where the phosphine ligand is a compound of formula (I)

##STR00001##

where
m and n are each independently 0 or 1;
R.sup.1, R.sup.2, R.sup.3, R.sup.4 are each independently selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl, (C.sub.3-C.sub.20)-heteroaryl;
at least one of the R.sup.1, R.sup.2, R.sup.3, R.sup.4 radicals is a (C.sub.3-C.sub.20)-heteroaryl radical;
and
R.sup.1, R.sup.2, R.sup.3, R.sup.4, if they are (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, (C.sub.6-C.sub.20)-aryl or (C.sub.3-C.sub.20)-heteroaryl,
may each independently be substituted by one or more substituents selected from (C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.12)-cycloalkyl, (C.sub.3-C.sub.12)-heterocycloalkyl, O(C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl-(C.sub.6-C.sub.20)-aryl, O(C.sub.3-C.sub.12)-cycloalkyl, S(C.sub.1-C.sub.12)-alkyl, S(C.sub.3-C.sub.12)-cycloalkyl, COO(C.sub.1-C.sub.12)-alkyl, COO(C.sub.3-C.sub.12)-cycloalkyl, CONH(C.sub.1-C.sub.12)-alkyl, CONH(C.sub.3-C.sub.12)-cycloalkyl, CO(C.sub.1-C.sub.12)-alkyl, CO(C.sub.3-C.sub.12)-cycloalkyl, N[(C.sub.1-C.sub.12)-alkyl].sub.2, (C.sub.6-C.sub.20)-aryl, (C.sub.6-C.sub.20)-aryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl-O(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl, (C.sub.3-C.sub.20)-heteroaryl-(C.sub.1-C.sub.12)-alkyl, (C.sub.3-C.sub.20)-heteroaryl-O(C.sub.1-C.sub.12)-alkyl, COOH, OH, SO.sub.3H, NH.sub.2, halogen.

PROCESS FOR THE ALKOXYCARBONYLATION OF OLEFINS IN A MEDIUM HAVING A LOW BRØNSTED ACID CONCENTRATION

Process comprising the following process steps: a) introducing an ethylenically unsaturated compound; b) adding a ligand-metal complex comprising Pd and a bidentate phosphine ligand, or adding a bidentate phosphine ligand and a compound which comprises Pd; c) adding an alcohol; d) supplying CO; e) heating the reaction mixture, the ethylenically unsaturated compound being reacted to form an ester, where the reaction mixture is admixed with less than 0.1 mol %, based on the amount of substance of the ethylenically unsaturated compound, of Brnsted acids having an acid strength of pKa 3, characterized in that the phosphine ligand is substituted on at least one phosphorus atom by at least one heteroaryl radical.

PROCESS FOR THE ALKOXYCARBONYLATION OF OLEFINS IN A MEDIUM HAVING A LOW BRØNSTED ACID CONCENTRATION

Process comprising the following process steps: a) introducing an ethylenically unsaturated compound; b) adding a ligand-metal complex comprising Pd and a bidentate phosphine ligand, or adding a bidentate phosphine ligand and a compound which comprises Pd; c) adding an alcohol; d) supplying CO; e) heating the reaction mixture, the ethylenically unsaturated compound being reacted to form an ester, where the reaction mixture is admixed with less than 0.1 mol %, based on the amount of substance of the ethylenically unsaturated compound, of Brnsted acids having an acid strength of pKa 3, characterized in that the phosphine ligand is substituted on at least one phosphorus atom by at least one heteroaryl radical.