Silica-based zinc catalysts, their preparation and use in the alkoxycarbonylation of amines

Abstract

The present invention relates to silica-based heterogeneous zinc compounds which are suitable as catalysts in the reaction of amines with dialkyl carbonates to produce carbamates. The catalysts have the formula [SiO.sub.2]CH.sub.2CHRXCOOZn[Y], wherein [SiO.sub.2] represents a silica carrier selected from the group consisting of ordered mesoporous silica and irregular amorphous narrow pore silica, R represents a moiety selected from the group consisting of hydrogen, CH.sub.3, and CH.sub.2CH.sub.3, preferably hydrogen, X is an aliphatic chain of 2 to 11 carbon atoms that optionally comprises ether moieties and [Y] represents a mono anion. The invention is also directed towards a method for the preparation of the aforementioned compounds and towards method for the alkoxycarbonylation of amines.

Claims

1. A silica-based zinc compound of the formula
[SiO.sub.2]CH.sub.2CHRXCOOZn[Y] wherein [SiO.sub.2] represents a silica carrier selected from the group consisting of ordered mesoporous silica and irregular amorphous narrow pore silica, said silica carrier [SiO.sub.2] being covalently bound to the terminal CH.sub.2 group of CH.sub.2CHRXCOOZn[Y]; R represents a moiety selected from the group consisting of hydrogen, CH.sub.3, and CH.sub.2CH.sub.3; X is an aliphatic chain of 2 to 11 carbon atoms that comprises one or more ether moieties; and [Y] represents a mono anion.

2. The silica-based zinc compound according to claim 1, wherein X is an aliphatic chain of 2 to 9 carbon atoms that comprises one or more ether moieties.

3. The silica-based zinc compound according to claim 2, wherein X is CH.sub.2O(CH.sub.2).sub.2.

4. The silica-based zinc compound according to claim 1, wherein said compound (a) has a structure A in which the mono anion [Y] comprises a carboxylate group, the carboxylate oxygen atoms coordinating to the zinc atom and the carboxylate carbon atom being covalently connected to the silica carrier [SiO.sub.2] via a chain of the same structure as CH.sub.2CHRX, or (b) has a structure B in which the mono anion [Y] is not covalently connected to the [SiO.sub.2] carrier, or (c) exists as a mixture of structures A and B.

5. The silica-based zinc compound according to claim 4, wherein the mono anion of structure B is selected from the group consisting of chloride, bromide, iodide, acetate, naphthenate, octanoate, propionate, salicylate, pivalate, acrylate, p-chlorobenzoate, phenolate, formate, chloroacetate, acetylacetonate, oxalate, and trifluoroacetate.

6. The silica-based zinc compound according to claim 5, wherein the mono anion of structure B is acetate.

7. The silica-based zinc compound according to claim 1, wherein the ordered mesoporous silica is selected from the group consisting of SBA-1, SBA-2, SBA-3, SBA-6, SBA-8, SBA-11, SBA-12, SBA-15, SBA-16, MCM-41, MCM-48, and FSM-16, and the irregular amorphous narrow pore silica is a silica gel with an average pore diameter in the range of 2.5 nm to 7.5 nm, and particle sizes in the range of 35-500 m.

8. A method for producing the silica-based zinc compound according to claim 1, comprising: A) reacting an unsaturated carboxylic acid of the formula CH.sub.2CRXCOOH, where R represents a moiety selected from the group consisting of hydrogen, CH.sub.3, and CH.sub.2CH.sub.3 and X is an aliphatic chain of 2 to 11 carbon atoms that comprises one or more ether moieties, with a trialkyloxy silane or triaryloxy silane or mixed alkyl-aryloxy trisubstituted silane in the presence of a catalyst to yield a silicon-containing addition product; B) impregnating a silica carrier selected from the group consisting of ordered mesoporous silica and irregular amorphous narrow pore silica with a solution of the silicon-containing addition product in a solvent to yield a silica-based carboxylic acid; and C) ion-exchanging the silica-based carboxylic acid with a zinc salt to yield the silica-based zinc compound.

9. The method according to claim 8, wherein the zinc salt is selected from the group consisting of zinc(II) chloride, bromide, iodide, acetate, naphthenate, octanoate, propionate, salicylate, pivalate, acrylate, p-chlorobenzoate, phenolate, formate, chloroacetate, acetylacetonate, oxalate, and trifluoroacetate.

10. A method of producing carbamate compounds, comprising reacting an organic amine with a dialkyl carbonate in the presence of a catalyst, wherein the catalyst is the silica-based zinc compound according to claim 1.

11. The method according to claim 10, wherein the dialkyl carbonate is selected from the group consisting of propyl carbonate, ethyl carbonate, and methyl carbonate.

12. The method according to claim 10, wherein the reaction of the organic amine with the dialkyl carbonate is carried out at a molar ratio of organic amine to Zn catalyst ranging from 10:1 to 20:1.

13. The method according to claim 10, wherein the reaction of the organic amine with the dialkyl carbonate is carried out at a temperature ranging from 150 C. to 200 C. for a reaction time ranging from 0.5 h to 6 h.

14. The method according to claim 10, wherein the organic amine is an aromatic amine selected from the group consisting of aniline, 2,4-diamino-N-phenylaniline, o-, m-, and p-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 1,2,4,5-tetraaminobenzene, 4-methoxy-m-phenylenediamine, 4-amino-N-phenylaniline, 2-amino-N-methylaniline, N-isobutyl-p-phenyldiamine, o-, m-, and p-xylylenediamine, N-isoamyl-p-phenylenediamine, N-benzyl-p-phenylenediamine, N-cyclohexyl-p-diphenylenediamine, N,N-di(n-propyl)-p-phenylenediamine, N-(n-butyl)-N-benzyl-p-phenylenediamine, N,N-dibenzyl-p-phenylenediamine, N-ethyl-m-phenylenediamine, N-ethyl-o-phenylenediamine, N-methyl-m-phenylenediamine, N,N-diethyl-p-phenylenediamine, N-methyl-N-(n-propyl)-p-phenylenediamine, 4,4-oxydianiline, 4,4-ethylenedianiline, 2,4-bis(4-aminobenzyl)aniline, 4,4-methylenebis(N,N-dimethylaniline); 4,4-methylenebis(N-methylaniline); benzidine; N,N,N,N-tetramethylbenzidine, bis(3,4-diaminophenyl)methane, bis(3-methyl-4-aminophenyl)methane, 2,2-, 2,4- or 4,4-methylene dianiline, 1,6-hexamethylene diamine, isophorone diamine, (2-aminocylohexyl)-(4-aminocylohexyl)-methane, bis-(4-aminocyclohexyl)-methane and mixtures of the aforementioned organic amines.

15. The method according to claim 14, wherein the organic amine is selected from the group consisting of aniline, 2,4-diaminotoluene, 2,6-diaminotoluene, and mixtures thereof or wherein the organic amine is selected from the group consisting of 2,2-, 2,4-, 4,4-methylene dianiline, and mixtures thereof.

Description

DETAILED DESCRIPTION

(1) The invention will now be described in greater detail referring inter alia to the different embodiments described in short above. It is to be understood that different embodiments may be combined with each in any conceivable manner unless the technical context suggests otherwise.

(2) In one preferred embodiment of the silica-based zinc compound of the invention, X is an aliphatic chain of preferably 2 to 9 carbon atoms that optionally comprises ether moieties. More preferred, X is selected from the group consisting of (CH.sub.2).sub.2, (CH.sub.2).sub.9, and CH.sub.2O(CH.sub.2).sub.2. Most preferred, X is CH.sub.2O(CH.sub.2).sub.2. In all embodiments of the silica-based zinc compound of the invention, it is preferred that R shall be hydrogen. Most preferred, X is CH.sub.2O(CH.sub.2).sub.2 and [SiO.sub.2] is irregular amorphous narrow pore silica.

(3) Irrespective of the precise nature of the chain X, the catalyst of the invention preferably (a) has a structure A in which the mono anion [Y] comprises a carboxylate group, the carboxylate oxygen atoms coordinating to the zinc atom and the carboxylate carbon atom being covalently connected to the silica carrier [SiO.sub.2] via a chain of the same structure as CH.sub.2CHRX, or (b) has a structure B in which the mono anion [Y] is not covalently connected to the [SiO.sub.2] carrier, or (c) exists as a mixture of structures A and B.

(4) It is to be understood that the variants (a) and (b) are meant to describe alternatives, i.e. variant (a) excludes structure B (i.e. within the limits of analytical detection) and variant (b) excludes structure A (again within the limits of analytical detection). See the examples for a visualization of both structures. In variant (a), within the limits of analytical detection refers to the absence of free (i.e. not covalently connected to the [SiO.sub.2] carrier) carboxylate anions (derived from the ZnY.sub.2 precursorsee below for details, which is a zinc carboxylate in variant (a)) as determined by ion chromatography (see examples for details) in the final catalyst. In variant (b), within the limits of analytical detection means that in the final catalyst all mono anions [Y] (which may or may not be carboxylate anions in variant (b)) are free mono anions as defined above, again as determined by ion chromatography (see examples for details).

(5) In the variants (b) and (c), the mono anion [Y] in structure B is preferably selected from the group consisting of chloride, bromide, iodide, acetate, naphthenate, octanoate, propionate, salicylate, pivalate, acrylate, p-chlorobenzoate, phenolate, formate, chloroacetate, acetylacetonate, oxalate, and trifluoroacetate. Acetate is the most preferred mono anion [Y] in this embodiment. (The mono anion of structure B corresponds to the anion of the zinc salt used in Step C) of the preparation method; see below.)

(6) As regards the silica carrier [SiO.sub.2] in [SiO.sub.2]CH.sub.2CHRXCOOZn[Y], the invention comprises two alternatives: (1) The silica carrier is chosen from ordered mesoporous silica. In this alternative, SBA-1, SBA-2, SBA-3, SBA-6, SBA-8, SBA-11, SBA-12, SBA-15, SBA-16, MCM-41, MCM-48 or FSM-16 are preferred starting materials to be converted to the covalently bound [SiO.sub.2] in the silica-based zinc compound, with mesostructured SBA-15 silica (2D hexagonal structure, channelled, particle size <150 m) being a particularly suitable silica carrier starting material to be converted to the covalently bound [SiO.sub.2] in the silica-based zinc compound. The terms SBA (Santa Barbara amorphous), MCM (Mobil composition of matter) and FSM (folded sheet material), including their respective denotations 1, 2 and the like, are well-known in the art. Reference is made to Ordered Nanoporous Structure (authors: Shen, J.; Chu, B.; Liu, Y.) in Handbook of Nanophysics: Functional Materials; Sattler, K. D., Ed.; CRC Press: Boca Raton, 2011; Vol. 5, chapter 10, especially pages 10-4, 10-8, and 10-9. In the context of this invention, all values for particle size are to be understood as referring to values as explained under no. III below. (2) The silica carrier is chosen from irregular amorphous narrow pore silica. In this alternative, (in particular high-purity grade) silica gel with an average pore diameter in the range of 2.5 nm to 7.5 nm, such as silica gel 60 with an average pore diameter of 60 (6.0 nm), and particle sizes in the range of 35-500 m is a preferred starting material to be converted to the covalently bound [SiO.sub.2] in the silica-based zinc compound. More particularly, commercially available silica gel fractions having producer-specified particle sizes of 35-70 m, 40-63 m, 63-200 m, 150-250 m or 250-500 m are preferred starting materials to be converted to the covalently bound [SiO.sub.2] in the silica-based zinc compound, with silica gel 60 230-400 mesh ASTM having an average pore diameter of 6.7 nm, a specific surface area of 435 m.sup.2/g, a pore volume of 0.73 mL/g, and a particle size of 40-63 m being a particularly suitable silica carrier starting material to be converted to the covalently bound [SiO.sub.2] in the silica-based zinc compound. In the context of this invention, all values for pore volume are to be understood as referring to values as determined by the Barrett-Joyner-Halenda (BJH) method as described in more detail later on in this description under no. II below. Particle sizes being in the range of 35-500 m (or in any preferred range within these boundaries) means that all particles of other sizes have been removed within the limits of analytical detection (sieving analysis; see also below under no. III).

(7) Silica carriers as described above are commercially available and/or can be prepared according to literature-known protocols. Preferred textural parameters as determined following the IUPAC technical report of 1994 (recommendations for characterization of porous solids, see Pure Appl. Chem. 1994, 66, 1739) by Brunauer-Emmett-Teller (BET) adsorption isotherm (for specific surface area; see also no. I below) and Barrett-Joyner-Halenda (BJH) method (for average pore diameter and pore volume) in N.sub.2 are:

(8) For silica carrier (1):

(9) 500 m.sup.2/g<specific surface area<1000 m.sup.2/g and

(10) 0.9 mL/g<pore volume<1.1 mL/g for silica carrier (1).

(11) For silica carrier (2):

(12) 300 m.sup.2/g<specific surface area<500 m.sup.2/g and

(13) 0.5 mL/g<pore volume<0.8 mL/g for silica carrier (2).

(14) Descriptions of the Applicable Measurement Methods are Provided in the Following:

(15) I. Specific Surface Area:

(16) Nitrogen isotherms at 77 K were measured on a Quantachrome Autosorb iQ analyzer. Prior to the analysis, the samples were degassed in vacuum at 120 C. for 12 h. The BET method was applied to calculate the specific surface area by using the calculations originally described by Brunauer, Emmett and Teller in J. Am. Chem. Soc. 1938, 60, 309.

(17) II. Total Pore Volume and the Average Pore Diameter:

(18) The desorption branch of the nitrogen isotherms determined as described under no. I were used to calculate the total pore volume and the average pore diameter by using the calculations described by Barrett, Joyner and Halenda in J. Am. Chem. Soc. 1951, 73, 373.

(19) III. Particle Size Values:

(20) Particle size values are regularly stated by the corresponding commercial source of the silica carrier. Usually, these values are reliable and can be referred to without limitation. In case of doubt, particle sizes as determined by dry sieve analysis as specified in DIN 66165 (version of April 1987), carried out with a vibratory sieving machine, are authoritative. Sieving can also be used to prepare fractions of silica carrier having a specific particle size range that is not commercially available.

(21) The present invention is also directed towards a method for producing a catalyst compound according to the invention, comprising the steps of: A) Reacting an unsaturated carboxylic acid of the formula CH.sub.2CRXCOOH, wherein X and R have the meanings as described above, with a trialkyloxy silane or triaryloxy silane or mixed alkyl-aryloxy trisubstituted silane in the presence of a catalyst to yield the corresponding silicon-containing addition product; B) Impregnating a silica carrier selected from the group consisting of ordered mesoporous silica and irregular amorphous narrow pore silica with a solution of the silicon-containing addition product in a solvent to yield a silica-based carboxylic acid; C) Ion-exchanging the silica-based carboxylic acid with a zinc salt.

(22) The invention is also directed to a silica-based zinc compound obtainable by the aforementioned method.

(23) The addition Step A) can be described by the following equation:
CH.sub.2CRXCOOH+(ZO).sub.3SiH.fwdarw.(ZO).sub.3SiCH.sub.2CHRXCOOH,

(24) wherein Z represents the alkyl and/or aryl residues of the alkyloxy, aryloxy or mixed alkyl-aryloxy silane. The residue Z is preferably selected from the group consisting of methyl, ethyl, and phenyl. The catalyst used in Step A) is preferably selected from the group consisting of PtO.sub.2, H.sub.2PtCl.sub.6, Pt(PPh.sub.3).sub.4, and Pt/C. As regards process conditions, Step A) is preferably carried out as follows:

(25) Under an inert atmosphere, trisubstituted silane (1 equiv.) is added dropwise to a mixture of unsaturated carboxylic acid (1 equiv.) and catalyst (0.001 equiv.) in dry THF at 0 C. The mixture is stirred at 0 C. for 6 h followed by another 10 h at room temperature. Then, the mixture is filtered under an inert atmosphere and the filtrate evaporated in vacuo to give the corresponding silane carboxylic acid.

(26) The solvent used in Step B) is preferably selected from the group consisting of toluene, benzene, cyclohexane, and hexane. The impregnation step B) can be described by the following equation and is preferably carried out as follows:
SiO.sub.2+(ZO).sub.3SiCH.sub.2CHRXCOOH.fwdarw.[SiO.sub.2]CH.sub.2CHRXCOOH+3ZOH.

(27) Previously dried (120 C. overnight) silica support SiO.sub.2 is impregnated with a solution of the previously obtained silane carboxylic acid in dry toluene. The overall volume of the final solution is chosen such that it is equal to the total pore volume of the silica gel carrier used. The impregnation is carried out by slowly adding the silane carboxylic acid solution over the silica support while stirring vigorously with a vortex stirrer (3000 rpm). Once the addition is complete, the material is left at room temperature for 3 h and is then heated for 15 h at 120 C. in vacuo (10 mbar). The material is then sequentially washed with toluene, dichloromethane, hexane, and diethyl ether and dried for 3 h at 120 C. in vacuo (10 mbar).

(28) It is to be understood that after completion of the impregnation step the silicon of the intermediate silicon-containing addition product (ZO).sub.3SiCH.sub.2CHRXCOOH is considered an integral part of the silica carrier [SiO.sub.2] of the silica-based carboxylic acid. In the latter compound, the silica carrier is covalently bound to the terminal methylene group of CH.sub.2CHRXCOOH, this being indicated by the spelling [SiO.sub.2] in the context of this invention.

(29) The zinc salt used in Step C) is preferably selected from the group consisting of zinc(II) chloride, bromide, iodide, acetate, naphthenate, octanoate, propionate, salicylate, pivalate, acrylate, p-chlorobenzoate, phenolate, formate, chloroacetate, acetylacetonate, oxalate, and trifluoroacetate (salts of the type ZnY.sub.2, Y being the respective anion of the salt). The ion exchange step C) can be described by the following equation and is preferably carried out as follows:

(30) ##STR00003##

(31) [Y] represents the anion of the salt ZnY.sub.2 in its state bound to [SiO.sub.2]CH.sub.2CHRXCOOZn. This bonding of [Y] involves ionic bonding to zinc. In certain embodiments of the invention, this bonding of [Y] may also involve covalent bonding to the carrier [SiO.sub.2] (see Scheme 1 for illustration). However, such covalent bonding does not necessarily occur in all embodiments of the invention. Whether or not covalent bonding of the type shown in Scheme 1 is involved depends on the nature of ZnY.sub.2 and on the nature of the precursor [SiO.sub.2]CH.sub.2CHRXCOOH. Thus, the designation [Y] indicates possible differences in the anion in its state bound to [SiO.sub.2]CH.sub.2CHRXCOOZn.sup.+, but it also encompasses embodiments in which the anion in its state bound to [SiO.sub.2]CH.sub.2CHRXCOOZn.sup.+ is identical to the anion Y.sup. of ZnY.sub.2.

(32) The resulting carboxylic acid containing material is subjected to ion exchange employing aqueous zinc salt solutions. To a portion of the latter material, a zinc salt solution, for example a zinc acetate solution (0.4 M; 40 mL; 20 mL/g), is added, the mixture is then heated with stirring at 65 C. for 1 h, and the aqueous solution is filtered off and discarded. This process is repeated two more times with the zinc salt solution. The zinc-containing material is thoroughly washed with deionized water, filtered and dried for 3 h at 120 C. in vacuo (10 mbar).

(33) Since the silicon of the intermediate silicon-containing addition product (ZO).sub.3SiCH.sub.2CHRXCOOH is considered an integral part of the silica carrier of the silica-based carboxylic acid obtained in the impregnation step, it is also considered an integral part of the silica carrier [SiO.sub.2] of the silica-based zinc compound obtained in the ion exchange step, i.e. it is also considered an integral part of the silica carrier [SiO.sub.2] of the silica-based zinc compound of the invention.

(34) A further aspect of the invention is a method of producing carbamate compounds, comprising the step of reacting an organic amine with a dialkyl carbonate in the presence of a catalyst, wherein the catalyst is the silica-based zinc compound of the invention as described above.

(35) The dialkyl carbonate is preferably selected from the group consisting of propyl, ethyl, and methyl carbonate, the latter being particularly preferred.

(36) The reaction of the organic amine with the dialkyl carbonate is preferably carried out at a molar ratio of organic amine to Zn catalyst ranging from 10:1 to 20:1.

(37) As regards process conditions, the reaction of the organic amine with the dialkyl carbonate is carried out at a temperature ranging from 150 C. to 200 C. for a reaction time ranging from 0.5 h to 6 h, preferably at a temperature ranging from 180 C. to 190 C. for a reaction time ranging from 1 h to 4 h, a temperature ranging from 180 C. to 190 C. and a reaction time from 1.5 h to 2.5 h, in particular 2 h being most preferred. The reaction time refers to the time the reaction is allowed to proceed after the desired temperature has been reached.

(38) The method according to this invention may for example use aliphatic, cycloaliphatic or aromatic amines or a mixture of two or more amine compounds as a starting material. The aromatic amine is a compound having at least one aromatic ring and at least one amino group bound to the aromatic ring. When the aromatic amine has more than one aromatic ring, the rings may be condensed or joined by at least one common ring member, a bond between a ring member of each aromatic ring or a divalent moiety. The divalent moiety preferably comprises C, O, S or N, more preferably from 1 to 6 C atoms. In a preferred embodiment, the divalent moiety is methylene.

(39) At least one substituent of an aromatic amine is an amino group. Preferably at least two substituents, preferably up to four substituents, and even more preferably two substituents, are amino groups. The amino groups are preferably primary or secondary amino groups, and more preferably primary amino groups. Preferably, at least one amino group is in the 2-, 4- or 6-position, more preferably at least one amino group is in the 2-position, relative to a purely C,H-substituent, preferably a methyl group, substituent on at least one, preferably only one, aromatic ring. More preferably, amino groups are present in the 2- and the 4- or 6-position of at least one, preferably only one, aromatic ring.

(40) In general, examples for aromatic amines include:

(41) ##STR00004##

(42) wherein R is hydrogen, halogen, linear or branched C1-C12 alkyl, linear or branched C1-C12 alkoxy, linear or branched C1-C12 alkoxyalkyl, or C1-C12 alkylamino; R.sup.1 and R.sup.2 are independently hydrogen, or linear or branched C1-C12 alkyl; k is an integer 2-4.

(43) Other examples include:

(44) ##STR00005##

(45) wherein R is hydrogen, halogen, linear or branched C1-C12 alkyl, linear or branched C1-C12 alkoxy, linear or branched C1-C12 alkoxyalkyl, or C1-C12 alkylamino; R.sup.1 and R.sup.2 are independently hydrogen, or linear or branched C1-C12 alkyl; 1 is an integer 2-4; and the substituents R and NR.sup.1R.sup.2 can be present at any position of the naphthalene ring.

(46) Further examples include:

(47) ##STR00006##

(48) wherein R is hydrogen, halogen, linear or branched C1-C12 alkyl, linear or branched C1-C12 alkoxy, linear or branched C1-C12 alkoxyalkyl, or C1-C12 alkylamino; R.sup.1 and R.sup.2 are independently hydrogen, or linear or branched C1-C12 alkyl; X is linear or branched C1-C6 alkylene, O, S, NR; m and n is 0 or an integer 1-3 and m+n2; and p is 0 or 1.

(49) In another embodiment of this method the organic amine is an aromatic amine selected from the group of 2,4-diamino-m-phenylaniline, o-, m-, and p-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 1,2,4,5-tetraaminobenzene, 4-methoxy-m-phenylenediamine, 4-amino-N-phenylaniline, 2-amino-N-methylaniline, N-isobutyl-p-phenyldiamine, o-, m-, and p-xylylenediamine, N-isoamyl-p-phenylenediamine, N-benzyl-p-phenylenediamine, N-cyclohexyl-p-diphenylenediamine, N,N-di(n-propyl)-p-phenylenediamine, N-(n-butyl)-N-benzyl-p-phenylenediamine, N,N-dibenzyl-p-phenylenediamine, N-ethyl-m-phenylenediamine, N-ethyl-o-phenylenediamine, N-methyl-m-phenylenediamine, N,N-diethyl-p-phenylenediamine, N-methyl-N-(n-propyl)-p-phenylenediamine, 4,4-oxydianiline, 4,4-ethylenedianiline, 2,4-bis(4-aminobenzyl)aniline, 4,4-methylenebis(N,N-dimethylaniline); 4,4-methylenebis(N-methylaniline); benzidine; N,N,N,N-tetramethylbenzidine, bis(3,4-diaminophenyl)methane, bis(3-methyl-4-aminophenyl)methane, 2,2-, 2,4- or 4,4-methylene dianiline, 1,6-hexamethylene diamine, isophorone diamine, (2-aminocylohexyl)-(4-aminocylohexyl)-methane and/or bis-(4-aminocyclohexyl)-methane.

(50) In a particularly preferred embodiment of this method the amine is selected from 2,4-diaminotoluene, 2,6-diaminotoluene, and mixtures thereof. Most preferred is a technical mixture such as 80% 2,4-diaminotoluene and 20% 2,6-diaminotoluene.

(51) In another preferred embodiment of this method the amine is selected from 2,2-, 2,4-, 4,4-methylene dianiline, and mixtures thereof.

(52) An advantage of the method for producing carbamates according to the invention is the reusability of the catalyst. The silica-based zinc compound of the invention that is used as catalyst can be removed from the reaction mixture (preferably by filtration), washed (preferably with the same solvent as used for the alkoxycarbonylation reaction, i.e. dimethyl carbonate, followed by acetone), dried (preferably at a temperature ranging from 100 C. to 150 C. and a pressure ranging from 0.001 bar.sub.(abs.) to 1.00 bar.sub.(abs)). Reusing the catalyst in this way is particularly preferred for catalysts in which the chain X comprises ether moieties, more particularly preferred for XCH.sub.2O(CH.sub.2).sub.2, and most preferred for XCH.sub.2O(CH.sub.2).sub.2 and [SiO.sub.2]=irregular amorphous narrow pore silica.

(53) The present invention will now be described with reference to the following examples without wishing to be limited thereto.

EXAMPLES

A. Preparation of Silica-Based Zinc Compounds

Example A.1: Preparation of Irregular Amorphous Narrow Pore [SiO.SUB.2.](CH.SUB.2.).SUB.3.O(CH.SUB.2.).SUB.2.COOZn[Y]

(54) Under an inert atmosphere, triethoxysilane (3.39 g, 97%, 20.0 mmol) was added dropwise to a mixture of 3-allyloxypropionic acid (2.74 g, 95%, 20.0 mmol), dry THF (3.0 mL) and PtO.sub.2 (4.6 mg, 0.02 mmol) at 0 C. The mixture was stirred at 0 C. for 6 h followed by another 10 h at RT. After the reaction was complete, the mixture was filtered through a PTFE syringe filter and the filtrate evaporated in vacuo to give the corresponding alkoxy silane carboxylic acid (5.83 g). A minor by-product, whose structure was determined to be the corresponding cyclic ester by .sup.1H-NMR analysis, was also observed (16%). This reaction mixture was used without any further purification.

(55) .sup.1H NMR: 11.26 (s, 1H), 3.67 (q, 6H, J=7.0 Hz), 3.59-3.51 (m, 2H), 3.33-3.24 (m, 2H), 2.49-2.42 (m, 2H), 1.61-1.46 (m, 2H), 1.07 (t, 9H, J=7.0 Hz), 0.55-0.42 (m, 2H) ppm; .sup.13C{.sup.1H}NMR: 176.3, 73.1, 65.5, 58.2, 34.6, 22.6, 18.0, 6.2 ppm; .sup.29Si{.sup.1H} NMR: 49.4 ppm.

(56) Then, 4.40 g of silica gel (irregular amorphous narrow pore, 40-63 m particle size, pore volume: 0.73 mL/g, 435 m.sup.2/g, average pore diameter 6.7 nm, Merck) previously dried (120 C. overnight) were impregnated with a solution of the previously obtained 3-(3-(triethoxysilyl)propoxy)propanoic acid (1.94 g, 84%, 5.57 mmol) and dry toluene (ca. 2 mL toluene; the overall volume of the final solution was 3.2 mL). The impregnation was carried out by slowly adding the alkoxy silane carboxylic acid solution over the silica support while stirring vigorously with a vortex stirrer (3000 rpm). Once the addition was complete, the material was left at RT for 3 h and then heated for 15 h at 120 C. in vacuo (10 mbar). The material was then sequentially washed with toluene, dichloromethane, hexane, and diethyl ether (20 mL each) and dried for 3 h at 120 C. in vacuo (10 mbar) to yield 5.68 g of a white powder.

(57) The resulting carboxylic acid containing material was subjected to ion exchange employing aqueous zinc acetate solutions. To a portion of 2.0 g of the latter material, a zinc acetate solution (0.4 M; 40 mL; 20 mL/g) was added, the mixture was then heated with stirring at 65 C. for 1 h and the aqueous solution was filtered off and discarded. This process was repeated two more times with a zinc acetate solution, as that indicated above. The zinc-containing material was thoroughly washed with deionized water (850 mL), filtered and dried for 3 h at 120 C. in vacuo (10 mbar) to yield 1.8 g of a white powder corresponding to the [SiO.sub.2](CH.sub.2).sub.3O(CH.sub.2).sub.2COOZn[Y]_material, whose zinc content was determined to be 0.78 mmol [Zn]/g, (complexometric titration with EDTA).

Characterization Data of [SiO.SUB.2.](CH.SUB.2.).SUB.3.O(CH.SUB.2.).SUB.2.COOZn[Y]

(58) TGA (air, 30-550 C., 5 C./min): mass loss at 80 C. (2.62%) and 270 C. (9.14%); XRPD (2 range 5-70): no diffraction peaks observed; BET surface area analysis (N.sub.2 adsorption-desorption isotherm): 0.46 mL/g total pore volume, 290 m.sup.2/g specific surface area; complexometric titration: 0.78 mmol [Zn]/g; ion chromatography: 0.014 mmol ACO.sup. groups/g (<2% of ACO.sup. groups with respect to [Zn] present in the modified SiO.sub.2); .sup.13C CP-MAS NMR: 182.1, 73.1, 67.2, 37.0, 23.0, 8.6 ppm; .sup.29Si CP-MAS NMR: 51.2, 59.4, 68.3, 94.1, 104.0, 113.3 ppm; FT-IR (ATR, solid, v/cm.sup.1): 2945 (out-of-phase stretch CH.sub.2), 2882 (in-phase stretch CH.sub.2), 1568 (asym. stretch COO), 1445 (deformation CH.sub.2), 1420 (sym. stretch COO), 1054 (asym. stretch SiOSi); zinc content: 0.78 mmol [Zn]/g.

(59) Repetitions of the reactions described above yielded products with the same spectroscopic and analytical data and with the following zinc contents:

(60) Batch #2: 0.75 mmol [Zn]/g

(61) Batch #3: 0.79 mmol [Zn]/g

(62) Average value: 0.77 mmol [Zn]/g; standard deviation: 0.02 mmol [Zn]/g.

(63) The analytical data (ion exchange) available for [SiO.sub.2](CH.sub.2).sub.3O(CH.sub.2).sub.2COOZn[Y] indicates predominantly (98 mass percent, based on the total mass of the silica-based zinc compound) a structure of type A, i.e. a structure in which the mono anion [Y] comprises a carboxylate group, the carboxylate oxygen atoms coordinating to the zinc atom and the carboxylate carbon atom being covalently connected to the silica carrier [SiO.sub.2] via a chain of the same structure as CH.sub.2CHRX. A minor amount (2 mass percent, based on the total mass of the silica-based zinc compound) exists in structure of type B, the mono anion [Y] being acetate (the counter ion of the zinc salt used in the ion exchange step). Thus, the catalyst [SiO.sub.2](CH.sub.2).sub.3O(CH.sub.2).sub.2COOZn[Y] when prepared as described above is of variant (c). The predominant structure of type A may be visualized as follows:

(64) ##STR00007##

(65) Scheme 1: Possible structure of type A of [SiO.sub.2](CH.sub.2).sub.3O(CH.sub.2).sub.2COOZn[Y] catalyst. It should be noted that the extract of the structure of the silica carrier [SiO.sub.2] shown here is not to be understood as limiting. Deviations therefrom are possible.

(66) The less dominant structure of type B may be visualized as follows:

(67) ##STR00008##

(68) Scheme 2: Possible structure of type B of [SiO.sub.2](CH.sub.2).sub.3O(CH.sub.2).sub.2COOZn[Y] catalyst. It should be noted that the extract of the structure of the silica carrier [SiO.sub.2] shown here is not to be understood as limiting. Deviations therefrom are possible.

Example A.2: Preparation of Irregular Amorphous Narrow Pore [SiO.SUB.1.](CH.SUB.2.).SUB.4.COOZn[Y]

(69) 5-(Triethoxysilyl)pentanoic acid was prepared following the same experimental protocol as that described above for Example 1, with the following amounts of reagents: triethoxysilane (4.32 g, 97%, 25.0 mmol), pent-4-enoic acid (2.50 g, 25.0 mmol), dry THF (3.0 mL) and PtO.sub.2 (5.7 mg, 0.025 mmol).

(70) Along with the desired compound, the corresponding cyclic ester was also observed as a minor by-product (4%). The alkoxy silane carboxylic acid was obtained as an oil (6.44 g, 96%, 23.4 mmol, 94% yield) and used without any further purification.

(71) .sup.1H NMR: 11.34 (s, 1H), 3.72 (q, 6H, J=7.0 Hz), 2.29-2.20 (m, 2H), 1.64-1.52 (m, 2H), 1.45-1.32 (m, 2H), 1.12 (t, 9H, J=7.0 Hz), 0.61-0.49 (m, 2H) ppm; .sup.13C{.sup.1H} NMR: 179.5, 58.2, 33.6, 27.8, 22.2, 18.1, 10.0 ppm; .sup.29Si{.sup.1H} NMR: 45.4 ppm.

(72) 5-(Triethoxysilyl)pentanoic acid was attached to SiO.sub.2 following the same experimental protocol as that described for Example 1, with the following amounts of reagents: Silica gel (4.09 g, irregular amorphous narrow pore, 40-63 m particle size, pore volume: 0.73 mL/g, 435 m.sup.2/g, average pore diameter 6.7 nm, Merck) previously dried (120 C. overnight), 5-(trimethoxysilyl)pentanoic acid (2.00 g, 96%, 7.25 mmol) and dry toluene (ca. 1.7 mL toluene; the overall volume of the final solution was 3.0 mL). The COOH-containing silica gel was obtained as a white powder (5.19 g).

(73) The resulting carboxylic acid containing material was subjected to ion exchange following the same experimental protocol as that described for [SiO.sub.2](CH.sub.2).sub.3O(CH.sub.2).sub.2COOZn[Y], with the following amounts of reagents: COOH-containing silica gel (1.5 g) and aqueous zinc acetate (0.4 M; 30 mL; 20 mL/g). [SiO.sub.2](CH.sub.2).sub.4COOZn[Y] was obtained as a white powder (1.4 g).

Characterization Data for [SiO.SUB.2.](CH.SUB.2.).SUB.4.COOZn[Y]

(74) TGA (air, 30-550 C., 5 C./min): mass loss at 80 C. (2.36%) and 460 C. (9.35%); XRPD (2 range 5-70): no diffraction peaks observed; BET surface area analysis (N.sub.2 adsorption-desorption isotherm): 0.43 mL/g total pore volume, 282 m.sup.2/g specific surface area; complexometry: 1.00 mmol [Zn]/g, ion chromatography: 0.016 mmol ACO.sup. groups/g (<2% of ACO.sup. groups with respect to [Zn] present in the modified SiO.sub.2); FT-IR (ATR, solid, v/cm.sup.1): 2936 (out-of-phase stretch CH.sub.2), 2877 (in-phase stretch CH.sub.2), 1557 (asym. stretch COO), 1454 (deformation CH.sub.2), 1423 (sym. stretch COO), 1052 (asym. stretch SiOSi); zinc content: 1.00 mmol [Zn]/g.

Example A.3: Preparation of Ordered Mesoporous [SiO.SUB.2.](CH.SUB.2.).SUB.4.COOZn[Y]

(75) Previously obtained 5-(triethoxysilyl)pentanoic acid was attached to ordered mesoporous silica SBA15 following the same experimental protocol as that described for Example 1, with the following amounts of reagents: SBA15 silica gel (2.10 g, mesostructured [average pore diameter 5.8 nm,], pore volume: 0.94 mL/g, 656 m.sup.2/g, Aldrich) previously dried (120 C. overnight), 5-(trimethoxysilyl)pentanoic acid (1.26 g, 96%, 4.57 mmol) and dry toluene (ca. 1.0 mL toluene; the overall volume of the final solution was 1.9 mL). The COOH-containing silica gel was obtained as a white powder (2.65 g).

(76) The resulting carboxylic acid containing material was subjected to ion exchange following the same experimental protocol as that described for [SiO.sub.2](CH.sub.2).sub.3O(CH.sub.2).sub.2COOZn[Y], with the following amounts of reagents: COOH-containing silica gel (1.5 g) and aqueous zinc acetate (0.4 M; 30 mL; 20 mL/g). Ordered mesoporous [SiO.sub.2](CH.sub.2).sub.4COOZn[Y] was obtained as a white powder (1.4 g).

Characterization Data for Ordered Mesoporous [SiO.SUB.2.](CH.SUB.2.).SUB.4.COOZn[Y]

(77) TGA (air, 30-550 C., 5 C./min): mass loss at 80 C. (2.67%) and 460 C. (10.32%); XRPD (2 range 5-70): no diffraction peaks observed; BET surface area analysis (N.sub.2 adsorption-desorption isotherm): 0.56 mL/g total pore volume, 350 m.sup.2/g specific surface area; complexometric titration: 1.25 mmol [Zn]/g, ion chromatography: 0.015 mmol ACO.sup. groups/g (<2% of ACO.sup. groups with respect to [Zn] present in the modified SiO.sub.2); FT-IR (ATR, solid, v/cm.sup.1): 2935 (out-of-phase stretch CH.sub.2), 2868 (in-phase stretch CH.sub.2), 1557 (asym. stretch COO), 1457 (deformation CH.sub.2), 1423 (sym. stretch COO), 1056 (asym. stretch SiOSi); zinc content: 1.25 mmol [Zn]/g.

Example A.4: Preparation of Irregular Amorphous Narrow Pore [SiO.SUB.2.](CH.SUB.2.).SUB.11.COOZn[Y]

(78) 12-(Triethoxysilyl)dodecanoic acid was prepared following the same experimental protocol as that described above for Example 1, with the following amounts of reagents: triethoxysilane (2.56 g, 97%, 15.1 mmol), dodec-11-enoic acid (3.00 g, 15.1 mmol), dry THF (3.0 mL) and PtO.sub.2 (3.4 mg, 0.015 mmol). Along with the desired compound, the corresponding cyclic ester was also observed as a minor by-product (12%). The alkoxy silane carboxylic acid was obtained as an oil (5.32 g, 88%, 12.9 mmol, 86% yield) and used without any further purification.

(79) .sup.1H NMR: 11.54 (s, 1H), 3.71 (q, 6H, J=7.0 Hz), 2.26-2.18 (m, 2H), 1.57-1.46 (m, 2H), 1.36-1.26 (m, 2H), 1.26-1.14 (m, 14H), 1.11 (t, 9H, J=7.0 Hz), 0.56-0.47 (m, 2H) ppm; .sup.13C{.sup.1H} NMR: 179.4, 58.1, 33.9, 33.0, 29.4, 29.4, 29.3, 29.1, 29.1, 28.9, 22.6, 22.6, 18.1, 10.2 ppm; .sup.29Si{.sup.1H} NMR: 44.7 ppm.

(80) 12-(Triethoxysilyl)dodecanoic acid was attached to SiO.sub.2 following the same experimental protocol as that described for Example 1, with the following amounts of reagents: Silica gel (3.40 g, irregular amorphous narrow pore, 40-63 m particle size, pore volume: 0.73 mL/g, 435 m.sup.2/g, average pore diameter 6.7 nm, Merck) previously dried (120 C. overnight), 12-(triethoxysilyl)dodecanoic acid (1.48 g, 88%, 3.57 mmol) and dry toluene (ca. 1.6 mL toluene; the overall volume of the final solution was 2.5 mL). The COOH-containing silica gel was obtained as a white powder (4.12 g).

(81) The resulting carboxylic acid containing material was subjected to ion exchange following the same experimental protocol as that described for [SiO.sub.2](CH.sub.2).sub.3O(CH.sub.2).sub.2COOZn[Y], with the following amounts of reagents: COOH-containing silica gel (2.0 g) and aqueous zinc acetate (0.4 M; 40 mL; 20 mL/g). [SiO.sub.2](CH.sub.2).sub.11COOZn[Y] was obtained as a white powder (1.9 g).

Characterization Data for [SiO.SUB.2.](CH.SUB.2.).SUB.11.COOZn[Y]

(82) TGA (air, 30-550 C., 5 C./min): mass loss at 80 C. (2.05%) and 430 C. (16.36%); XRPD (2 range 5-70): no diffraction peaks observed; BET surface area analysis (N.sub.2 adsorption-desorption isotherm): 0.30 mL/g total pore volume, 268 m.sup.2/g specific surface area; complexometric titration: 0.81 mmol [Zn]/g, ion chromatography: 0.015 mmol ACO.sup. groups/g (<2% of ACO.sup. groups with respect to [Zn] present in the modified SiO.sub.2); FT-IR (ATR, solid, v/cm.sup.1): 2925 (out-of-phase stretch CH.sub.2), 2854 (in-phase stretch CH.sub.2), 1557 (asym. stretch COO), 1456 (deformation CH.sub.2), 1418 (sym. stretch COO), 1054 (asym. stretch SiOSi); zinc content: 0.81 mmol [Zn]/g.

Example A.5: Preparation of a Siliceous Catalyst without Zinc Groups (Comparison)

(83) With the aim of assessing the methoxycarbonylation background reaction mediated by the solid support (a siliceous material), (MeO).sub.3SiMe was grafted to irregular amorphous narrow pore silica gel following an identical procedure to that employed for covalently linking COOZn groups to the inorganic supports (see Example 1). Thus, a modified silica gel (SG-Me) was prepared by grafting identical amounts of (MeO).sub.3SiMe. The work-up and purification procedures employed were also the same than those employed for preparing the real catalysts. It should be noted that this material (SG-Me) is based on the same siliceous support and has the same functionalization degree as the real catalysts (with irregular amorphous narrow pore silica carriers), however it lacks zinc groups.

B. Alkoxycarbonylations of Aromatic Amines

(84) General Procedure

(85) The catalytic results presented below are based on a series of experiments employing the four different heterogeneous catalysts that have been prepared according to Examples A.1 to A.4 and the comparison catalyst prepared according to Example A.S. Catalytic assays were at least duplicated (a minimum of two reactions per catalyst and substrate were performed). Furthermore, two samples for HPLC quantitative analysis were made up for each reaction mixture and were analysed with the corresponding quantitative HPLC analytical method. The aromatic amines used as substrates were aniline, MDA and 2,4-TDA, as shown in the following scheme:

(86) ##STR00009##
Crude product mixtures derived from the methoxycarbonylation reaction of aniline were analyzed by NMR using internal standards whereas crude product mixtures derived from the methoxycarbonylation reaction of MDA and TDA were analyzed by quantitative HPLC analysis using calibration curves. The analytical conditions for MDA and 2,4-TDA derivatives were as follows:

(87) MDA-derivatives: Kromasil 100 C18 5 m 4.6150 column, RT, 1.0 mL/min, Injection=5 L, UV detection 254 nm, Eluent A:100 mL CH.sub.3CN, 900 mL H.sub.2O, 0.01M NH.sub.4Ac. Eluent B: 900 mL CH.sub.3CN, 100 mL H.sub.2O, 0.01M NH.sub.4Ac. Gradient: 0 min 60% A, 40% B; 15 min 60% A, 40% B; 25 min 100% B; 30 min Stop. Retention times: Rt(MDA)=4.1 min, Rt(MDA-MCMe)=6.4 min, Rt(MDA-MMe)=8.4 min, Rt(MDA-BCMe)=10.0 min, Rt(MDA-BMe)=19.0 min.

(88) 2,4-TDA-derivatives: Kromasil 100 C18 5 m 4.6150, RT, 1.0 mL/min, Injection=5 L, UV detection 225 nm, Eluent A:100 mL CH.sub.3CN, 900 mL H.sub.2O, 0.01M NH.sub.4Ac. Eluent B: 900 mL CH.sub.3CN, 100 mL H.sub.2O, 0.01M NH.sub.4Ac. Gradient: 0 min 100% A, 22 min 100% A; 48 min 80% A, 20% B; 60 min 55% A, 45% B; 80 min Stop. Retention times: Rt(2,4-TDA)=7.5 min, Rt(2,4-TDA-M-oMe)=15.0 min, Rt(2,4-TDA-M-pMe=20.0 min, Rt(2,4-TDA-MC-oMe)=22.4 min, Rt(2,4-TDA-MC-pMe)=30.8 min, Rt(2,4-TDA-BMe)=42.0 min, Rt(2,4-TDA-BCMe)=45.1 min.

(89) The reaction conditions that were used in the catalytic studies were based on the ones disclosed in WO 2014/187756 A1 (Example 2 in page 12, line 12), with the exception of the catalyst loading employed. The reaction conditions for each substrate are indicated below and catalyst loadings are expressed in molar ratio of dimethyl carbonate (DMC), amine and catalyst (based in [Zn] content). Aniline: molar ratio DMC:amine:catalyst=25:1:0.05, T=180 C. MDA: molar ratio DMC:amine:catalyst=25:1:0.05, T=180 C. 2,4-TDA: molar ratio DMC:amine:catalyst=30:1:0.10, T=190 C.

(90) In order to recover and reuse the catalysts after the alkoxycarbonylation reactions, the crude reaction mixtures were filtered. The recovered heterogeneous catalysts were washed with acetone, and the solid residue was dried at 120 C. prior to its reuse. The results are indicated in each case and are labelled as cycle #2 in the Tables that summarise the results on catalysis in Examples B.2 to B.6 below. In the methoxycarbonylation of MDA, considerable amounts of insoluble and non-analysable materials were formed. The catalysts were separated from the reaction mixture together with these MDA-derived insoluble compounds, which could not be separated from the catalyst during the catalyst recycling process. Thus, catalytic studies with recycled catalyst implied adding these impurities to the reaction mixture.

Examples B.1 and B.2 (Comparisons): Catalyst From Example A.5 and No Catalyst, Respectively

(91) The results are summarised in Table 1.

(92) TABLE-US-00001 TABLE 1 Methoxycarbonylation reactions using a blank catalyst (SG-Me, Example A.5) or no catalyst. Conver- High. Poss. Yield Reaction sion Yield (%) (%) Ex. conditions Substrate (%) (SD) (SD) .sup.[a] (SD) .sup.[b] B.1 190 C., 2 h, 2,4-TDA 73 8 <1 DMC, SG-Me as catalyst B.2 190 C., 2 h, 2,4-TDA 73 5 1 DMC No catalyst .sup.[a] Highest possible yield. Sum of the yield of the target biscarbamate and its intermediates. .sup.[b] Yield of the desired biscarbamate.

Example B.3: Irregular Amorphous Narrow Pore [SiO.SUB.2.](CH.SUB.2.).SUB.4.COOZn[Y] (of Example A.2) as Catalyst

(93) Table 2 summarises the results.

(94) TABLE-US-00002 TABLE 2 Methoxycarbonylation reactions using irregular amorphous narrow pore [SiO.sub.2](CH.sub.2).sub.4COOZn[Y] as the catalyst..sup.[a] High. Alk. Poss. Amines Conver- Yield Yield (%)/Alk. Ex. sion (%) (%) Carb. ( B.3.- Substrate Cycle (%) (SD) (SD) .sup.[b] (SD) .sup.[c] area %).sup.[d] 1 Aniline #1 >99 (0) 95 (0) 95 (0) 4/2 2 Aniline #2 >99 (0) 98 (0) 98 (0) 2/0 3 MDA #1 >99 (0) 57 (2) 42 (3) 4/29 4 MDA #2 97 (2) 54 (7) 32 (11) 7/23 5 2,4-TDA #1 >99 (0) 46 (1) 33 (2) 4/32 6 2,4-TDA #2 >99 (1) 36 (1) 11 (2) 18/28 .sup.[a]Values expressed as an average of all independent runs. Standard deviations are indicated in brackets. .sup.[b] Highest possible yield: sum of the yield of the target carbamate and its precursors (i.e. the corresponding monocarbamates). .sup.[c] Yield of the desired carbamate. .sup.[d]Sum of areas of alkylated carbamates.

(95) In comparison, the wide-pore supported catalyst described in Catal. Sci. Technol. 2015, 5, 109 and CN 102872912 A is said to give yields with aniline as reactant of up to 91.6%.

Example B.4: Ordered Mesoporous [SiO.SUB.2.](CH.SUB.2.).SUB.4.COOZn[Y] (of Example A.3) as Catalyst

(96) Table 3 summarises the results.

(97) TABLE-US-00003 TABLE 3 Methoxycarbonylation reactions using ordered mesoporous [SiO.sub.2](CH.sub.2).sub.4 COOZn[Y] as the catalyst..sup.[a] Aik. High. Poss. Amines (%)/ Ex. Conversion Yield (%) Yield (%) Aik. Carb. B.4.- Substrate Cycle (%) (SD) (SD) .sup.[b] (SD) .sup.[c] ( area %).sup.[d] 1 Aniline #1 >99 (0) 94 (0) 94 (0) 4/2 2 Aniline #2 >99 (0) 97 (0) 97 (0) 3/1 3 MDA #1 99 (1) 54 (2) 34 (6) 6/26 4 MDA #2 97 (2) 47 (5) 23 (1) 8/22 5 2,4-TDA #1 >99 (0) 43 (1) 28 (1) 5/40 6 2,4-TDA #2 96 (1) 38 (6) 12 (4) 17/31 .sup.[a]Values expressed as an average of all independent runs. Standard deviations are indicated in brackets. .sup.[b] Highest possible yield: sum of the yield of the target carbamate and its precursors (i.e. the corresponding monocarbamates). .sup.[c] Yield of the desired carbamate. .sup.[d]Sum of areas of alkylated carbamates.

Example B.5: Irregular Amorphous Narrow Pore [SiO.SUB.2.](CH.SUB.2.).SUB.11.COOZn[Y] (of Example A.4) as Catalyst

(98) Table 4 summarises the results.

(99) TABLE-US-00004 TABLE 4 Methoxycarbonylation reactions using irregular amorphous narrow pore [SiO.sub.2](CH.sub.2).sub.4COOZn[Y] as the catalyst..sup.[a] Aik. High. Poss. Amines (%)/ Ex. Conversion Yield (%) Yield (%) Aik. Carb. B.5.- Substrate Cycle (%) (SD) (SD) .sup.[b] (SD) .sup.[c] ( area %).sup.[d] 1 Aniline #1 >99 (0) 93 (0) 93 (0) 4/4 2 Aniline #2 >99 (0) 98 (0) 98 (0) 1/1 3 MDA #1 98 (0) 57 (0) 34 (1) 6/23 4 MDA #2 97 (2) 50 (2) 27 (6) 7/21 5 2,4-TDA #1 65 (1) 3 (1) <1 (0) 45/10 6 2,4-TDA #2 / .sup.[a]Values expressed as an average of all independent runs. Standard deviations are indicated in brackets. .sup.[b] Highest possible yield: sum of the yield of the target carbamate and its precursors (i.e. the corresponding monocarbamates). .sup.[c] Yield of the desired carbamate. .sup.[d]Sum of areas of alkylated carbamates.

Example B.6: Irregular Amorphous Narrow Pore [SiO.SUB.2.](CH.SUB.2.).SUB.3.O(CH.SUB.2.).SUB.2.COOZn[Y] (of Example A.1) as Catalyst

(100) Table 5 summarises the results.

(101) TABLE-US-00005 TABLE 5 Methoxycarbonylation reactions using irregular amorphous narrow pore [SiO.sub.2](CH.sub.2).sub.3O(CH.sub.2).sub.2COOZn[Y] as the catalyst..sup.[a] Aik. High. Poss. Amines (%)/ Ex. Conversion Yield (%) Yield (%) Aik. Carb. B.6.- Substrate Cycle (%) (SD) (SD) .sup.[b] (SD) .sup.[c] ( area %).sup.[d] 1 Aniline #1 >99 (0) 93 (0) 93 (0) 6/2 2 Aniline #2 >99 (0) 97 (0) 97 (0) 2/1 3 MDA #1 99 (0) 56 (3) 40 (4) 4/28 4 MDA #2 >99 (0) 68 (5) 57 (5) 2/24 5 2,4-TDA #1 >99 (0) 46 (2) 37 (1) 3/39 6 2,4-TDA #2 >99 (0) 67 (1) 55 (2) 1/26 .sup.[a]Values expressed as an average of all independent runs. Standard deviations are indicated in brackets. .sup.[b] Highest possible yield: sum of the yield of the target carbamate and its precursors (i.e. the corresponding monocarbamates). .sup.[c] Yield of the desired carbamate. .sup.[d]Sum of areas of alkylated carbamates.

(102) Recycled catalyst of Example A.1 mediated the methoxycarbonylation of 2,4-TDA with higher selectivity, reaching 55% and 67% yield of the desired biscarbamate and biscarbamate plus intermediates (i.e. 2- and 4-monocarbamates derived from 2,4-TDA; compare Examples B.6.5 and B.6.6 in Table 5). Despite containing MDA-derived impurities, recycled catalyst of Example A.1 gave slightly better results in the second cycle (for instance, yield in the desired biscarbamate increased from 40% in the first cycle to 57% in the second; compare entries B.6.3 and B.6.4 in Table 5).

(103) Zinc leaching after each catalytic cycle was also investigated for catalyst of Example A1, [SiO.sub.2](CH.sub.2).sub.3O(CH.sub.2).sub.2COOZn[Y]. As indicated in Table 6, zinc leaching was found to be negligible after two catalytic cycles, with leaching values around 1 mol % with respect to the original [Zn] loading present in the reaction.

(104) TABLE-US-00006 TABLE 6 [Zn] leaching in the methoxycarbonylation of 2,4-TDA..sup.[a] Leaching Entry Substrate Cycle (mol % [Zn]) .sup.[b] 1 2,4-TDA #1 1.1 2 2,4-TDA #2 0.8 .sup.[a][Zn] content determined by complexometric titration with EDTA as reagent and Eriochrome T as final point indicator. .sup.[b] Leaching expressed as mol % [Zn] respect to the initial Zn content in the catalyst.

Summary of Examples B.2 to B.6

(105) Total conversion of the substrates was observed for almost each combination of substrate and catalyst. The different catalysts prepared within this co-operation performed similarly in the alkoxycarbonylation of aniline. The four explored catalysts gave excellent results, with an average yield of 94% towards the corresponding carbamate.