Zinc cluster compounds and their use as catalysts in the reaction of amines with dialkyl carbonates

Abstract

The present invention relates to metallic zinc cluster compounds which are suitable as catalysts in the reaction of amines with dialkyl carbonates to produce carbamates. The invention is also directed towards a method for the alkoxycarbonylation of amines. The cluster compound has a general formula which may be written as [M(O.sub.2CR).sub.2].sub.x.[MO].sub.y.[H.sub.2O].sub.z, wherein M is Zn, R is an unsubstituted or substituted aromatic, cycloaliphatic, linear aliphatic, or other organic rest, x is 1, y is x is 1, y is 0.03 to 26.0 and z is >0.00 to 17.0.

Claims

1. A compound of the formula
[Zn(O.sub.2CR).sub.2].sub.x.[ZnO].sub.y.[H.sub.2O].sub.z, wherein R is selected from the group of C.sub.6H.sub.5, o-, m- and p-C.sub.6H.sub.4OMe, o-, m- and p-C.sub.6H.sub.4OH, p-C.sub.6H.sub.4NH.sub.2, p-C.sub.6H.sub.4NO.sub.2, p-C.sub.6H.sub.4Br, o- and p-C.sub.6H.sub.4CO.sub.2, 2-pyrrolidinyl, heptadecanyl and/or CH.sub.2CH(OH)CO.sub.2; x is 1, y is 0.03 to 3.0 and z is >0 to 3.0.

2. The compound of claim 1, wherein R is para-C.sub.6H.sub.4OCH.sub.3 and wherein the zinc content as determined by thermogravimetric analysis is 20.0% to 45.0%.

3. The compound of claim 1, wherein R is para-C.sub.6H.sub.4OCH.sub.3 and wherein the carbon content as determined by elemental analysis is 30.0% to 48.0%.

4. A method for producing the compound of claim 1, comprising the steps of: A) providing an aqueous solution comprising a carboxylic acid HO.sub.2CR and a base, wherein R is an unsubstituted or substituted aromatic, cycloaliphatic, or linear aliphatic organic rest; B) providing an aqueous solution comprising a dissolved zinc salt; and C) combining the solutions of step A) and step B).

5. The method of claim 4, wherein the zinc salt is zinc sulfate and/or zinc sulfate heptahydrate.

6. The method of claim 4, wherein the base in step A) is sodium hydrogen carbonate and/or sodium hydroxide.

7. The method of claim 4, wherein during step C) the solution of step A) is added to the solution of step B).

8. The method of claim 4, wherein during step C) the solution of step A) has a temperature of 30 C. to 90 C.

9. The method of claim 4, wherein during step C) the solution of step B) has a temperature of 18 C. to 30 C.

10. The method of claim 4, further comprising waiting after step C) for 30 minutes to 1500 minutes before isolating the compound.

11. A method of producing carbamate compounds, comprising the step of reacting an organic amine with a dialkyl carbonate in the presence of a catalyst comprising the compound of claim 1.

12. The method of claim 11, wherein the organic amine is an aromatic amine selected from the group of 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, 4,4oxydianiline, 4,4ethylenedianiline, 2,4-bis(4-aminobenzyl)aniline, 4,4methylenebis(N,N-dimethylaniline); 4,4methylenebis(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-aminocyclohexyl)-(4-aminocyclohexyl)-methane and/or bis-(4-aminocyclohexyl)-methane.

13. The compound of claim 1, wherein x is 1, y is 0.5 to 1.0, and z is 0.50 to 1.0.

14. The method of claim 11, wherein x is 1, y is 0.5 to 1.0, and z is 0.50 to 1.0.

15. The compound of claim 3, wherein R is para-C.sub.6H.sub.4OCH.sub.3 and wherein the carbon content as determined by elemental analysis is 40.0 and 45.0.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIGS. 1-5 are analytical spectra of the catalyst according to example 1; and

(2) FIGS. 6 and 7 illustrate the results of reactions of example 4.

DETAILED DESCRIPTION

(3) Taking into account the economic importance of carbamates as isocyanate precursors, it is highly desirable to provide new robust and functionalizable catalysts for the preparation of carbamates in high yield and with low amounts of by-products. Thus, the objective of the present invention is to provide new metallic clusters based on zinc and carboxylic acids, which are efficient and selective catalysts in the reaction of amines with dialkyl carbonates to produce carbamates. The invention is also directed towards a method for the alkoxycarbonylation of amines. According to the present invention this objective has been achieved by a compound of the formula:
[Zn(O.sub.2CR).sub.2].sub.x.[ZnO].sub.y.[H.sub.2O].sub.z wherein R is an unsubstituted or substituted aromatic, cycloaliphatic, linear aliphatic, or other organic rest and x is 1, y is 0.03 to 26.0 and z is >0.00 to 17.0.

(4) In contrast to the tetranuclear zinc clusters of the prior art discussed above, the compounds according to the invention contain OH groups. These are present in the form of crystal water (i.e. water that constitutes part of the molecular structure and cannot be removed without destruction) and/or bound to Zn (ZnOH moiety).

(5) The compounds according to the invention can be described as zinc clusters. Without wishing to be bound to a theory, the following structure is proposed (by way of example for R=p-C.sub.6H.sub.4CO.sub.2.sup.:

(6) ##STR00003##

(7) As will be shown in greater detail in the following description these zinc clusters efficiently mediate the methoxycarbonylation of amines, in particular MDA and TDA.

(8) Suitable aryl groups which do not contain heteroatoms include, for example, phenyl and 1- and 2-naphthyl.

(9) Suitable hetaryl groups include, but are not limited to, 5-12 carbon-atom aromatic rings or ring systems containing 1-3 rings, at least one of which is aromatic, in which one or more, e.g., 1-4 carbon atoms in one or more of the rings can be replaced by oxygen, nitrogen or sulfur atoms. Each ring typically has 3-7 atoms. For example, R can be 2- or 3-furyl, 2- or 3-thienyl, 2- or 4-triazinyl, 1-, 2- or 3-pyrrolyl, 1-, 2-, 4- or 5-imidazolyl, 1-, 3-, 4- or 5-pyrazolyl, 2-, 4- or 5oxazolyl, 3-, 4- or 5-isoxazolyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-isothiazolyl, 2-, 3 or 4-pyridyl, 2-, 4-, 5- or 6-pyrimidinyl, 1,2,3-triazol-1-,-4- or -5-yl, 1,2,4-triazol1-,-3- or -5-yl, 1- or 5-tetrazolyl, 1,2,3-oxadiazol-4- or -5-yl, 1,2,4-oxadiazol-3- or -5-yl, 1,3,4-thiadiazol-2- or -5-yl, 1,2,4-oxadiazol-3- or -5-yl, 1,3,4-thiadiazol-2- or -5-yl, 1,3,4-thiadiazol-3- or -5-yl, 1,2,3-thiadiazol-4- or -5-yl, 2-, 3-, 4-, 5- or 62H-thiopyranyl, 2-, 3- or 4-4H-thiopyranyl, 3- or 4-pyridazinyl, pyrazinyl, 2-, 3-, 4-, 5-, 6- or 7-benzofuryl, 2-, 3-, 4-, 5-, 6- or 7-benzothienyl, 1-, 2-, 3-, 4-, 5-, 6- or 7indolyl, 1-, 2-, 4- or 5-benzimidazolyl, 1-, 3-, 4-, 5-, 6- or 7-benzopyrazolyl, 2-, 4-, 5-, 6- or 7-benzoxazolyl, 3-, 4-, 5-6- or 7-benzisoxazolyl, 1-, 3-, 4-, 5-, 6- or 7benzothiazolyl, 2-, 4-, 5-, 6- or 7-benzisothiazolyl, 2-, 4-, 5-, 6- or 7-ben-1,3oxadiazolyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-quinolinyl, 1-, 3-, 4-, 5-, 6-, 7-, 8-isoquinolinyl, 1-, 2-, 3-, 4- or 9-carbazolyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-acridinyl, or 2-, 4-, 5-, 6-, 7- or 8-quinazolinyl, or additionally optionally substituted phenyl, 2- or 3-thienyl, 1,3,4-thiadiazolyl, 3-pyrryl, 3-pyrazolyl, 2-thiazolyl or 5-thiazolyl, etc. For example, B can be 4-methyl-phenyl, 5-methyl-2-thienyl, 4-methyl-2thienyl, 1-methyl-3-pyrryl, 1-methyl-3-pyrazolyl, 5-methyl-2-thiazolyl or 5-methyl-1,2,4-thiadiazol-2-yl.

(10) Suitable alkyl groups and alkyl portions of groups, e.g., alkoxy, etc. throughout include methyl, ethyl, propyl, butyl, etc., including all straight-chain and branched isomers such as isopropyl, isobutyl, sec-butyl, tert-butyl, etc.

(11) The term cycloaliphatic, as used herein, refers to cyclic structures with or without alkyl substituents such that, for example, C4 cycloaliphatic includes methyl substituted cyclopropyl groups as well as cyclobutyl groups. The term cycloaliphatic, as used herein also includes saturated heterocyclic groups.

(12) Suitable halogen groups for substitution include F, Cl, Br, and/or I, from one to persubstitution (i.e. all H atoms on a group replaced by a halogen atom) being possible where an alkyl group is substituted by halogen, mixed substitution of halogen atom types also being possible on a given moiety.

(13) The parameter y in the formula [Zn(O.sub.2CR)2].sub.x.[ZnO].sub.y.[H.sub.2O].sub.z is preferably 0.03 to <3.0, more preferred 0.25 to 2.0 and most preferred 0.5 to 1.0. The parameter z in the formula is preferably 0 to 3.0, more preferred 0.25 to 1.50 and most preferred 0.50 to 1.0.

(14) The present invention will be described with reference to further embodiments and aspects. They may be combined freely unless the context clearly indicates otherwise.

(15) In one embodiment of the compound according to the invention R is selected from the group of C.sub.6H.sub.5, o-, m- and p-C.sub.6H.sub.4OMe, o-, m- and p-C.sub.6H.sub.4OH, p-C.sub.6H.sub.4NH.sub.2, p-C.sub.6H.sub.4NO.sub.2, p-C.sub.6H.sub.4Br, o- and p-C.sub.6H.sub.4CO.sub.2.sup., 2-pyrrolidinyl, heptadecanyl and/or CH.sub.2CH(OH)CO.sub.2.sup..

(16) In another embodiment of the compound according to the invention R is para-C.sub.6H.sub.4OCH.sub.3 and the zinc content as determined by thermogravimetric analysis is 20.0% to 45.0%, preferably 23.0% to 30.0%.

(17) In another embodiment of the compound according to the invention R is para-C.sub.6H.sub.4OCH.sub.3 and the carbon content as determined by elemental analysis is 30.0% to 48.0%, preferably 40.0% to 45.0%.

(18) The present invention is also directed towards a method for producing a compound according to the invention, comprising the steps of:

(19) A) providing an aqueous solution comprising a carboxylic acid HO.sub.2CR and a base, wherein R is an unsubstituted or substituted aromatic, cycloaliphatic, linear aliphatic, or other organic rest;

(20) B) providing an aqueous solution comprising a dissolved zinc salt;

(21) C) combining the solutions of step A) and step B) and optionally adding extra water.

(22) Regarding the rest R in the carboxylic acid in A), the same comments as already outlined above in connection with the compound according to the invention apply. For reasons of brevity they are not repeated here.

(23) The base used in step A) should of course be sufficiently strong to at least partially deprotonate the carboxylic acid HO.sub.2CR.

(24) After combining the solutions of A) and B) the precipitated desired zinc compound can be recovered, washed and dried.

(25) For solution A) the concentration of the carboxylic acid HO.sub.2CR is preferably 0.25 M to 0.60 M and the concentration of the base is preferably 0.39 M to 0.76 M. For solution B) the concentration of zinc ions is preferably 0.13 M to 0.51 M. After combining the solutions A) and B) and optionally adding extra water, the concentration of zinc is preferably 0.04 M to 0.26 M.

(26) An example for typical concentrations is: solution A) 0.5 M of carboxylic acid and 0.75 M of base, and for solution B) 0.31 M of Zn. After combination of A) and B) [Zn] is 0.14 M without adding extra water and 0.09 M after addition of extra water.

(27) In one embodiment of the method according to the invention R is selected from the group of C.sub.6H.sub.5, o-, m- and p-C.sub.6H.sub.4OMe, o-, m- and p-C.sub.6H.sub.4OH, p-C.sub.6H.sub.4NH.sub.2, p-C.sub.6H.sub.4NO.sub.2, p-C.sub.6H.sub.4Br, o- and p-C.sub.6H.sub.4CO.sub.2.sup., 2-pyrrolidinyl, heptadecanyl and/or CH.sub.2CH(OH)CO.sub.2.sup..

(28) In another embodiment of the method according to the invention the zinc salt is zinc sulfate and/or zinc sulfate heptahydrate.

(29) In another embodiment of the method according to the invention the base in step A) is sodium hydrogen carbonate and/or sodium hydroxide.

(30) In another embodiment of the method according to the invention, during step C) the solution of step A) is added to the solution of step B). This can be undertaken in a batch-wise, drop-wise or continuous fashion.

(31) In another embodiment of the method according to the invention, during step C) the solution of step A) has a temperature of 30 C. to 90 C., preferably 40 C. to 60 C.

(32) In another embodiment of the method according to the invention, during step C) the solution of step B) has a temperature of 18 C. to 30 C., preferably 20 C. to 25 C.

(33) In another embodiment of the method according to the invention, after step C) it is waited for a time period of 30 minutes to 1500 minutes before the product is isolated, preferably 60 minutes to 180 minutes.

(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 comprises a compound of the formula
[Zn(O.sub.2CR).sub.2].sub.x.[ZnO].sub.y.[H.sub.2O].sub.z wherein R is an unsubstituted or substituted aromatic, cycloaliphatic, linear aliphatic, or other organic rest and x is 1, y is 0.03 to 26.0 and z is >0.00 to 17.0.

(35) The parameter y in the formula [Zn(O.sub.2CR).sub.2].sub.x.[ZnO].sub.y.[H.sub.2O].sub.z is preferably 0.03 to <3.0, more preferred 0.25 to 2.0 and most preferred 0.5 to 1.0. The parameter z in the formula is preferably >0 to <3.0, more preferred 0.25 to 1.50 and most preferred 0.50 to 1.0.

(36) Regarding the rest R, the same comments as already outlined above in connection with the compound according to the invention apply. For reasons of brevity they are not repeated here. The same holds for the parameters y and z including their preferred ranges.

(37) In particular, a zinc compound according to the invention may be used as a catalyst.

(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 hydrocarbon group, 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. In general, examples for aromatic amines include:

(40) ##STR00004##
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.
Other examples include:

(41) ##STR00005##
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.
Further examples include:

(42) ##STR00006##
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.

(43) In one embodiment of this method in the catalyst compound R is selected from the group of C.sub.6H.sub.5, o-, m- and p-C.sub.6H.sub.4OMe, o-, m- and p-C.sub.6H.sub.4OH, p-C.sub.6H.sub.4NH.sub.2, p-C.sub.6H.sub.4NO.sub.2, p-C.sub.6H.sub.4Br, o- and p-C.sub.6H.sub.4CO.sub.2.sup., 2-pyrrolidinyl, heptadecanyl and/or CH.sub.2CH(OH)CO.sub.2.sup..

(44) In another embodiment of this method the organic amine is an aromatic amine selected from the group of 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, 4,4oxydianiline, 4,4ethylenedianiline, 2,4-bis(4-aminobenzyl)aniline, 4,4methylenebis(N,N-dimethylaniline); 4,4methylenebis(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-aminocyclohexyl)-(4-aminocyclohexyl)-methane and/or bis-(4-aminocyclohexyl)-methane.

(45) In another embodiment of this method the amine is a mixture of 2,4-toluylene diamine and 2,6-toluylene diamine. Preferably this is a technical mixture such as 80% 2,4-TDA and 20% 2,6-TDA.

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

EXAMPLES

Example 1: Catalyst Preparation

(47) Batch 1:

(48) A mixture of 4-methoxybenzoic acid (7.66 g, 99%, 49.8 mmol) and sodium hydrogen carbonate (6.45 g, 76.8 mmol) in distilled water (100 mL) was heated until all the solid had dissolved. A solution of zinc sulfate heptahydrate (7.27 g, 99%, 25.0 mmol) in distilled water (80 mL) was prepared. The first solution was added to the second while the first one was at 50 C. and the second one at RT. A white compound precipitated immediately forming a dense suspension. Distilled water (RT, 100 mL) was added and the mixture was allowed to stand for 1.5 h, during which it was gently shaken from time to time. The reaction was worked up when the precipitate settled on the bottom of the reaction flask.

(49) The reaction mixture was then filtered over a glass frit. The residue was washed with water (325 mL) and EtOH (125 mL) and dried on the filter. Finally it was washed with DCM (225 mL) and dried overnight in a vacuum oven at 120 C. and 1 mbar. A finely dispersed white powder is obtained. The zinc content of this material was estimated at 25.6% using thermogravimetric analysis (TGA; air, 30-1000 C.). Yield: 5.5 g, 86%.

(50) .sup.1H NMR (DMSO-d.sub.6) 7.91 (d, J=8.3 Hz, 12H, ArH), 6.92 (d, J=8.4 Hz, 12H, ArH), 3.77 (s, 18H, OCH.sub.3); .sup.13C NMR (DMSO-d.sub.6) 172.5 (q), 162.1 (q), 131.9 (t), 127.1 (q), 113.5 (t), 55.6 (p); FT-IR (neat, cm.sup.1): 3554, 2938, 2837, 1605, 1590, 1547, 1511, 1458, 1389, 1313, 1298, 1249, 1171, 1145, 1103, 1024, 848, 779, 699, 642, 623, 563, 502, 455; thermogravimetric analysis (TGA; N.sub.2, 30-500 C., 10 C./min): mass loss between 40 and 230 C. (3.01%) and >320 C.; differential scanning calorimetry (DSC; N.sub.2, 30-500 C., 10 C./min): phase transitions at 190 C. (endothermic, accompanied by mass loss) and 306 C. (endothermic, m.p.); purity calculation based on DSC (based on peak at 306 C.): 99.3%; zinc content (TGA, air, 30-1000 C., 10 C./min, residue is assumed to consist entirely of ZnO): 25.6%; Anal. calcd. for [Zn(O.sub.2CC.sub.6H.sub.4-p-OCH.sub.3).sub.2].sub.1[ZnO].sub.0.65[H.sub.2O].sub.0.62: C, 44.51; H, 3.56; Zn, 24.99. found: C, 44.53; H, 3.56.

(51) Repetitions of the reaction described above yielded products with the same spectroscopic data and the following elemental analyses:

(52) Batch 2:

(53) Anal. calcd. for [Zn(O.sub.2CC.sub.6H.sub.4-p-OCH.sub.3).sub.2].sub.1.[ZnO].sub.0.59.[H.sub.2O].sub.0.99: C, 44.33; H, 3.72; Zn, 24.08. found: C, 44.29; H, 3.72. Zinc content (TGA): 25.4%.

(54) Batch 3:

(55) Anal. calcd. for [Zn(O.sub.2CC.sub.6H.sub.4-p-OCH.sub.3).sub.2].sub.1.[ZnO].sub.0.60[H.sub.2O].sub.0.86: C, 44.39; H, 3.67; Zn, 24.22. found: C, 44.52; H, 3.67. Zinc content (TGA): 24.9%.

(56) Batch 4:

(57) Anal. calcd. for [Zn(O.sub.2CC.sub.6H.sub.4-p-OCH.sub.3).sub.2].sub.1.[ZnO].sub.0.97.[H.sub.2O].sub.0.50: C, 42.18; H, 3.32; Zn, 28.27. found: C, 42.21; H, 3.32. Zinc content (TGA): 28.6%.

(58) Analytical spectra of the catalyst according to example 1 are shown in FIGS. 1 to 5. The .sup.1H NMR, .sup.13C (APT) NMR and IR spectra, which are shown in FIGS. 1, 2 and 3, respectively, appear to indicate that the obtained product is zinc para-methoxybenzoate. However, thermal analysis (TGA and DSC, FIG. 4) shows loss of mass around 190 C. [TGA of zinc para-methoxybenzoate does not show loss of mass at this temperature], as well as a different melting point [306 C. instead of 278 C. for zinc para-methoxybenzoate]. Also the XRPD spectrum (FIG. 5) is different than that of zinc para-methoxybenzoate. Together, these data confirm the results of elemental analysis, that a material different from zinc para-methoxybenzoate has been obtained.

Example 2: Methoxycarbonylation of Aromatic Amines with Dimethyl Carbonate (DMC)

(59) The catalytic results presented below are based on a series of reactions using four different batches of the catalyst and a minimum of two reactions per catalyst batch. Each reaction was analyzed in duplo or triplo.

(60) ##STR00007##

(61) For reactions with TDA: 30 molar equivalents of DMC, 2.5 mol % Zn, T=190 C.

(62) For reactions with MDA: 25 molar equivalents of DMC, 1.0 mol % Zn, T=180 C.

(63) Reactions are performed in an autoclave. The reaction time of 2 h refers to the time the reaction is allowed to proceed after the desired temperature has been reached. Heating up the autoclave takes 50 min for reactions at 180 C. or 60 min for reactions at 190 C.

(64) The results are summarized in the following table:

(65) TABLE-US-00001 Average Yield biscarbamate Substrate (%) Number of reactions 2,4-TDA 96 1 12 2,6-TDA 69 5 10 2,4-/2,6-TDA 80:20 98 1/87 2 11 MDA 96 1 8

(66) The methoxycarbonylation of 2,6-TDA was found to give slightly lower yields and the reaction results displayed a larger standard deviation. Interestingly, when a 80:20 mixture of 2,4- and 2,6-TDA is used, both of the substrates behave better than when used on their own.

Example 3: Comparative Examples

(67) It should be recalled at this point that catalyst according to the invention ([Zn(O.sub.2CC.sub.6H.sub.4-p-OCH.sub.3).sub.2].sub.x.[ZnO].sub.y.[H.sub.2O].sub.z) presented a higher catalytic activity than observed for the isolated components when used as catalysts.

(68) ##STR00008##

(69) TABLE-US-00002 Zn(O.sub.2CC.sub.6H.sub.4p-OMe).sub.2: 80% ZnO: <1% Zn(OH).sub.2: <1%

(70) It is worth noting that, as a general rule, analytically pure aromatic zinc carboxylates (no ZnO or Zn(OH).sub.2 moieties) give rather poor yields in the methoxycarbonylation of TDA:

(71) TABLE-US-00003 Yield of 2,4-TDA-BCMe Catalyst (%) Zn(O.sub.2CC.sub.6H.sub.5).sub.2 85 Zn(O.sub.2CC.sub.6H.sub.4p-OCH.sub.3).sub.2 80 Zn(O.sub.2CC.sub.6H.sub.4p-NO.sub.2).sub.22H.sub.2O 87

Example 4: Kinetic Profiles

(72) A kinetic profile of the methoxycarbonylation of 2,4-TDA was made based on a series of independent reactions that were stopped at t=15, 30, 40, 45, 50, 60, 90, 135, 180, and 240 min. Reactions were performed in duplo (t=15, 90, 135, 180 and 240 min), triplo (t:=30 and 40 min) or quadruplo (t=45, 50 and 60 min). The results are summarized in the table below. Percentages given are molar fractions of starting material and products, as determined by HPLC using external standards (calibration curves).

(73) ##STR00009##

(74) TABLE-US-00004 2,4-TDA- 2,4-TDA- 2,4- T t (min) 2,4-TDA (%) MC-p-Me (%) MC-o-Me (%) TDA-BCMe (%) ( C.) 0 100 0 0 0 27 1 15 99.2 0.0 0.7 0.1 0.1 0.0 0.0 0.0 94 1 30 73.9 6.0 21.9 5.5 3.3 0.8 0.9 0.3 148 1 40 23.6 4.7 60.5 2.9 6.7 0.2 9.2 1.4 164 1 45 11.6 5.0 65.5 1.5 5.6 0.7 17.3 4.3 172 3 50 1.3 0.2 61.3 1.3 2.3 0.2 35.1 1.8 181 1 60 0.2 0.1 40.0 8.8 0.6 0.2 57.6 7.8 190 1 90 0.1 0.0 5.1 1.5 0.2 0.0 90.6 1.9 190 1 135 0.0 0.0 1.2 0.2 0.2 0.0 96.5 1.4 190 1 180 0.0 0.0 0.8 0.1 0.1 0.0 97.6 1.4 190 1 240 0.0 0.0 0.8 0.0 0.2 0.0 96.0 0.9 190 1

(75) This is also shown in FIG. 6.

(76) The maximum rate in the alkoxycarbonylation of 2,4-TDA mediated by the catalyst according to the invention is observed at 50 min. This catalyst shows a slightly higher maximum rate than the ones observed for Zn.sub.4O(OAc).sub.6 and for zinc acetate dihydrate (cf. FIG. 7).