Preparation of carbamates from aromatic amines and organic carbonates

BACKGROUND OF THE INVENTION
Lewis acids have been disclosed in U.S. Pat. No. 3,763,217 as being suitable catalysts for reacting an organic carbonate with an aromatic amine to prepare carbamates.
It has been unexpectedly discovered that zinc and divalent tin salts provide the desired carbamates in higher yields and/or selectivity than the particular Lewis acids disclosed by Brill in U.S. Pat. No. 3,763,217.
SUMMARY OF THE INVENTION
The present invention pertains to an improvement in a process for preparing a carbamate from an organic carbonate and an aromatic amine in the presence of a catalytic quantity of a Lewis acid under suitable reaction conditions to produce said carbamate wherein the improvement comprises employing as the Lewis acid a zinc or divalent tin halide or a zinc or divalent tin salt of a monovalent organic compound having a pKa value of at least about 2.8, preferably from about 4 to about 10 and is soluble in the reaction mixture at the reaction conditions.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Suitable organic carbonates which can be employed in the process of the present invention include the alkyl, aryl or alkyl aryl esters of carbonic acid. The ester group can be an alkyl group having up to about 12 carbon atoms, preferably a lower alkyl group containing up to about 6 carbon atoms or the ester group can be an aryl group containing up to about 10 carbon atoms.
Particularly suitable organic carbonates are the cyclic and acyclic organic carbonates such as for example ethylene carbonate, propylene carbonate, styrene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dihexyl carbonate, methyl ethyl carbonate, methyl butyl carbonate, diphenyl carbonate, methyl phenyl carbonate, mixtures thereof and the like.
Any aromatic amine having a conjugate pKa value of from about 3.5 to about 5.5 is suitable for use herein with those amines having a conjugate pKa value of from about 4 to about 5.4 being preferred.
Suitable such aromatic amines include those represented by the formulas ##STR1## wherein each R is independently hydrogen or a hydrocarbyl or hydrocarbyloxy group containing up to about 8 carbon atoms, preferably up to about 4 carbon atoms, A is a divalent hydrocarbon group having from 1 to about 10 carbon atoms, preferably from 1 to about 6 carbon atoms, n has a value of zero or 1 and x has an average value of from about 1.1 to about 10, preferably from about 2 to about 4.
Particularly suitable amines include, for example, aniline, o-, m- or p-toluidine, 2,4-xylidine, 3,4-xylidine, 2,5-xylidine, 4-ethylaniline, 3-propylaniline, 1,3-diaminobenzene, 2,4-diaminotoluene, 2,6-diaminotoluene, 4,4'-diamino-diphenyl methane, 2,4,4'-triamino-diphenyl ether, 2,6-diamino naphthalene, 4,4'-bis-methylene diphenylamine, o-, m- or p-anisidine mixtures thereof and the like.
Suitable catalysts which can be employed herein include zinc or divalent tin salts of monovalent organic compounds having a pKa value above about 2.8, preferably from about 4 to about 10 and are soluble in the reaction mixture at the reaction conditions.
Suitable such catalysts include, for example, zinc acetate, zinc propionate, zinc octoate, zinc naphthenate, zinc benzoate, zinc pivalate, zinc stearate, zinc itaconate, zinc p-chlorobenzoate, zinc methoxide, zinc phenolate, zinc acetylacetonate, zinc chloride, stannous chloride, stannous octoate, mixtures thereof and the like.
When the organic carbonate is a cyclic organic carbonate, such as, for example, ethylene carbonate, a zinc or divalent tin salt of trifluoroacetic acid can be employed, even though trifluoroacetic acid has a pKa value below about 2.8.
The reaction is generally conducted at a temperature of from about 80.degree. C. to about 300.degree. C., preferably from about 120.degree. C. to about 250.degree. C. and most preferably from about 130.degree. C. to about 200.degree. C. for a time sufficient to complete the reaction depending upon the particular catalyst, reactants and temperature employed. Usually around 150.degree. C., the time is from about one hour to about six hours, preferably from about two hours to about four hours. The reaction generally should be conducted under conditions at which none of the reactants or desired product undergo decomposition.
The quantity of catalyst employed usually depends upon the activity of the particular catalyst. Usually from about 0.001 mole to about 0.2 mole, preferably from about 0.005 mole to about 0.05 mole of catalyst per mole of reactant present in a stoichiometric quantity is suitable.
The reactants can be employed on an equimolar basis or one may be present in an excess of the other up to about a 20, preferably from about one to about five moles in excess of the other. It is preferred that the organic carbonate reactant be employed in excess of the aromatic amine.
Uses for the desired carbamate reaction product is suitably discussed by Rosenthal et al in U.S. Pat. Nos. 3,919,279, 3,919,280 and 3,962,302, all of which are incorporated herein by reference.

The following examples are illustrative of the present invention but are not to be construed as to limiting the scope thereof in any manner.
EXAMPLES 1-73 AND COMPARATIVE EXPERIMENTS A-P
In the following examples and comparative experiments, aniline and dimethyl carbonate were premixed employing an excess of the carbonate and a quantity of the mixture was then mixed with catalyst and poured into a stainless steel cylindrical container, 15/8" internal diameter, and 21/4" internal depth with a wall thickness of 3/16". A stainless steel lid screwed over the reactor with a polytetrafluoroethylene O-ring being used as a seal. Mounted on the lid using stainless steel pipe fittings and parts were a pressure gauge, a pressure relief valve, and a needle valve.
After charging the mixture to the reactor, the lid was sealed by tightening down on the polytetrafluoroethylene O-ring and the reactor was immersed in a hot fluidized sand bath thermostatically controlled at 140.degree. C. in the center of the bath. The reactor was heated 10 to 15 minutes then shaken to mix the contents. Then heating was continued for the desired time. After cooling the contents were analyzed for yields of carbamate and by-products.
The quantity of reactants, catalysts, reaction conditions and results are given in the following Table I.
TABLE I EX- % CON- AMPLE pKa.sup.12 OF DIMETHYL CON- REACTION VERSION OR ORGANIC CAR- REACTION DITIONS PRODUCTS WEIGHT OF EXPT. CATALYST COM- ANILINE BONATE TIME TEMP. PRESS..sup.14 MPC.sup.1 NMA.sup.2 DPU.sup.3 RATIO ANILINE NO. TYPE g/mole POUND g/mole g/mole Hrs. .degree.C. psi(kg/cm.sup.2) g/mole g/mole g/mole MPC/NMA TO MPC.sup.10 1 zinc acetate 0.46 /0.0025 4.74 18.6/0.2 27.2/0.3 2 140 200 (14) 14.94/0.0988 1.02 /0.0095 1.3 /0.0064 14.65/1 49.4 2 zinc acetate 0.46 /0.0025 4.74 18.6/0.2 27.2/0.3 8 140 210 (15) 18.28/0.1209 1.62 /0.0151 1.21 /0.0060 11.28/1 60.45 3 zinc acetate 0.46 /0.0025 4.74 18.6/0.2 27.2/0.3 13 140 220 (15) 22.55/0.1492 2.03 /0.0189 1 /0.0049 11.11/1 74.6 4 zinc acetate 0.46 /0.0025 4.74 18.6/0.2 27.2/0.3 22 140 170 (12) 23.32/0.1543 1.85 /0.0173 0.72 /0.0036 12.61/1 77.15 5 zinc naphthenate.s up.4 0.41 /0.0005 U.A..sup.11 5 /0.0537 25 /0.2775 1 140 170 (12) 2.7 /0.0179 0.2 /0.0019 0.2 /0.0010 13.5 /1 33.3 A uranium trioxide 0.143 /0.0005 N.A..sup.13 5 /0.0537 25 /0.2775 2 140 130 (9) 0.12/0.0008 0.55 /0.0051 0.02 /0.0001 0.22/1 1.49 B uranium trioxide 0.143 /0.0005 N.A. 5 /0.0537 25 /0.2775 5 140 150 (11) 0.3 /0.002 0.93/0.0087 0.17 /0.0008 0.32/1 3.72 6 zinc naphthenate.sup.4 2.043 /0.0025 U.A. 5 /0.0537 25 /0.2775 2 140 110 (8) 7.5 /0.0496 0.1 /0.0009 0.44 /0.0022 75 /1 92.36 C uranium trioxide 0.715 /0.0025 N.A. 5 /0.0537 25 /0.2775 2 140 150 (11) 0.07/0.0005 0.2 /0.0019 0 /0 0.35/1 0.93 D uranium dioxide 0.4 /0.0015 N.A. 5 /0.0537 25 /0.2775 2 140 150 (11) 0.16/0.0011 0.35 /0.0033 0.13 /0.006 0.46/1 2.05 7 zinc naphthenate.sup.5 0.327 /0.0005 U.A. 5 /0.0537 25 /0.2775 1 140 160 (11) 2.32/0.0153 0.17 /0.0016 0.26 /0.0013 13.65/1 28.49 8 zinc salt of synthetic acids.sup.6 0.41 /0.0005 U.A. 5 /0.0537 25 /0.2775 1 140 160 (11) 2.41/0.0159 0.12 /0.0011 0.34 /0.0017 20.08/1 29.61 9 zinc tallate.sup.7 0.409 /0.0005 U.A. 5 /0.0537 25 /0.2775 1 140 160 (11) 3.87/0.0256 0.23 /0.0021 0.31 /0.0015 16.83/1 47.67 10 zinc neodecanoate.sup.8 0.2043/0.0005 U.A. 5 /0.0537 25 /0.2775 1 140 160 (11) 1.38/0.0091 0.17 /0.0016 0.06 /0.0003 8.12/1 16.95 11 zinc octoate.sup.9 0.182 /0.0005 4.85 5 /0.0537 25 /0.2775 1 140 160 (11) 2.65/0.0175 0.26 /0.0024 0.26 /0.0013 10.19/1 32.59 12 zinc salt of synthetic acids.sup.6 1.021 /0.0025 U.A. 5 /0.0537 25 /0.2775 2 140 110 (8) 6.7 /0.0443 0.16 /0.0015 0.15 /0.0007 41.88/1 82.5 13 zinc salicylate 0.98 /0.0025 3.00 5 /0.0537 25 /0.2775 2 140 110 (8) 0.5 /0.0033 0.76 /0.0071 0.20 /0.0010 0.66/1 6.15 14 zinc pivalate 1.34 /0.005 5.02 5 /0.0537 25 /0.2775 2 140 200 (14) 7.05/0.0466 0.13 /0.0012 0.12 /0.0006 54.23/1 86.78 15 zinc pivalate 1.34 /0.005 5.02 5 /0.0537 25 /0.2775 4 140 200 (14) 7.84/0.0519 0.15 /0.0014 0.06 /0.0003 52.27/1 96.65 16 zinc benzoate 0.77 /0.0025 4.17 5 /0.0537 25 /0.2775 1 140 140 (10) 4.57/0.030 2 0.22 /0.0021 0.26 /0.0013 20.77/1 56.24 17 zinc benzoate 0.77 /0.0025 4.17 5 /0.0537 25 /0.2775 2 140 140 (10) 7.26/0.048 0.28 /0.0026 0.22 /0.0011 25.93/1 89.39 18 zinc stearate 1.581 /0.0025 U.A. 5 /0.0537 25 /0.2775 2 140 150 (11) 5.31/0.0351 0.12 /0.0011 0.15 /0.0007 44.25/1 65.36 19 zinc acrylate 0.519 /0.0025 4.25 5 /0.0537 25 /0.2775 2 140 150 (11) 6.72/0.0445 0.10 /0.0009 0.58 /0.0028 67.20/1 82.87 20 zinc parachlorobenzoate 0.950 /0.0025 4.03 5 /0.0537 25 /0.2775 2 140 160 (11) 6.73/0.0445 0.55 /0.0051 0.15 /0.0007 12.24/1 82.87 21 zinc phenoxide 0.63 /0.0025 10.00 5 /0.0537 25 /0.2775 5 140 140 (10) 1.8 /0.0119 0.13 /0.0012 0.12 /0.0006 13.85/1 22.16 22 stannous octoate 1.02 /0.0025 4.85 5 /0.0537 25 /0.2775 2 140 110 (8) 2.2 /0.0145 0.39 /0.0036 0.27 /0.0013 5.64/1 27.11 23 zinc oxyacetate 0.66 /0.0025 4.74 5 /0.0537 25 /0.2775 1 140 110 (8) 4.9 /0.0324 0.03 /0.0003 0.15 /0.0007 143 /1 60.34 24 zinc oxyacetate 0.66 /0.0025 4.74 5 /0.0537 25 /0.2775 2 140 110 (8) 7.1 /0.0470 0.15 /0.0014 0.12 /0.0006 47 /1 87.52 25 zinc oxyacetate 0.66 /0.0025 4.74 5 /0.0537 25 /0.2775 4 140 120 (8) 7.3 /0.0483 0.18 /0.0017 0.072/0.0004 41 /1 89.94 26 zinc oxyacetate 0.66 /0.0025 4.74 5 /0.0537 25 /0.2775 6 140 120 (8) 7.7 /0.0509 0.28 /0.0026 0.14 /0.0007 28 /1 94.79 27 zinc acetate 0.46 /0.0025 4.74 5 /0.0537 25 /0.2775 1 140 160 (11) 6.04/0.04 0.02 /0.0002 0.1 /0.0005 302 /1 74.49 28 zinc acetate 0.46 /0.0025 4.74 5 /0.0537 25 /0.2775 2 140 170 (12) 7.1 /0.047 0.024/0.0002 0.1 /0.0005 296 /1 87.52 29 zinc acetate 0.46 /0.0025 4.74 5 /0.0537 25 /0.2775 4 140 140 (10) 7.5 /0.0496 0.02 /0.0002 0.03 /0.0001 375 /1 92.36 30 zinc acetate 0.46 /0.0025 4.74 5 /0.0537 25 /0.2775 6 140 125 (9) 8.1 92.36 0.02 /0.0002 0.06 /0.0003 405 /1 99.81 31 zinc acetate dihydrate 0.55 /0.0025 4.74 5 /0.0537 25 /0.2775 1 140 140 (10) 6.1 /0.0404 0.24 /0.0022 0.18 /0.0009 25 /1 75.23 32 zinc acetate dihydrate 0.55 /0.0025 4.74 5 /0.0537 25 /0.2775 2 140 160 (11) 7.0 /0.0463 0.27 /0.0025 0.15 /0.0007 26 /1 86.22 33 zinc acetate dihydrate 0.55 /0.0025 4.74 5 /0.0537 25 /0.2775 4 140 200 (14) 7.3 /0.0483 0.33 /0.0031 0.03 /0.0001 22 /1 89.94 34 zinc acetate dihydrate 0.55 /0.0025 4.74 5 /0.0537 25 /0.2775 6 140 200 (14) 7.5 /0.0496 0.24 /0.0022 0.06 0.0003 31 /1 92.36 35 zinc chloride 0.34 /0.0025 N.A. 5 /0.0537 25 /0.2775 1 140 150 (11) 0.58/0.0038 1.14 /0.0106 0.21 /0.0010 0.5 /1 7.08 36 zinc chloride 0.34 /0.0025 N.A. 5 /0.0537 25 /0.2775 2 140 200 (14) 1.86/0.0123 1.47 /0.0137 0.03 /0.0001 1.3 /1 22.91 37 zinc chloride 0.34 /0.0025 N.A. 5 /0.0537 25 /0.2775 4 140 200 (14) 2.76/0.0183 1.00 /0.0093 0.06 /0.0003 2.7 /1 17.32 38 zinc chloride 0.34 /0.0025 N.A. 5 /0.0537 25 /0.2775 6 140 200 (14) 3.12/0.020 6 0.6 /0.0056 0.06 /0.0003 5.2 /1 34.08 39 zinc propionate 0.53 /0.0025 4.88 5 /0.0537 25 /0.2775 1 140 80 (6) 6.71/0.0444 0.12 /0.0011 0.12 /0.0006 56 /1 38.36 40 zinc propionate 0.53 /0.0025 4.88 5 /0.0537 25 /0.2775 2 140 140 (10) 7.59/0.0502 0.12 /0.0011 0.07 /0.0003 61 /1 82.68 41 zinc propionate 0.53 /0.0025 4.88 5 /0.0537 25 /0.2775 4 140 150 (11) 7.88/0.0521 0.12 /0.0011 0.06 /0.0003 66 /1 97.02 42 zinc propionate 0.53 /0.0025 4.88 5 /0.0537 25 /0.2775 6 140 150 (11) 8 /0.0529 0.12 /0.0011 0.006/0.0000 67 /1 98.51 43 stannous chloride 0.474 /0.0025 N.A. 5 /0.0537 25 /0.2775 1 140 70 (5) 0.57/0.0038 0.51 /0.0048 0.018/0.0001 1.1 /1 7.08 44 stannous chloride 0.474 /0.0025 N.A. 5 /0.0537 25 /0.2775 2 140 90 (6) 3.43/0.0227 0.93 /0.0087 0.066/0.0003 3.7 /1 42.27 45 stannous chloride 0.474 /0.0025 N.A. 5 /0.0537 25 /0.2775 4 140 100 (7) 4.94/0.0327 0.72 /0.0067 0.072/0.0004 6.9 /1 60.89 46 stannous chloride 0.474 /0.0025 N.A. 5 /0.0537 25 /0.2775 6 140 190 (13) 2.94/0.0194 1.02 /0.0095 0.072/0.0004 2.9 /1 36.13 E antimony trichloride 0.57 /0.0025 N.A..sup.13 5 /0.0537 25 /0.2775 1 140 80 (6) 0.69/0.0046 0.45 /0.0042 0.21 /0.0010 1.5 /1 8.57 F antimony trichloride 0.57 /0.0025 N.A. 5 /0.0537 25 /0.2775 2 140 120 (8) 1.25/0.0083 0.26 /0.0024 0.27 /0.0013 4.8 /1 15.46 G antimony trichloride 0.57 /0.0025 N.A. 5 /0.0537 25 /0.2775 4 140 150 (11) 1.52/0.0101 1.29 /0.0120 0.18 /0.0009 1.2 /1 18.81 H antimony trichloride 0.57 /0.0025 N.A. 5 /0.0537 25 /0.2775 6 140 190 (13) 1.93/0.0128 1.32 /0.0123 0.18 /0.0009 1.5 /1 23.84 47 zinc acetate 0.0917/0.0005 4.74 5 /0.0537 25 /0.2775 1 140 120 (8) 3.2 /0.0212 0.24 /0.0022 0.15 /0.0007 13 /1 39.48 48 zinc acetate 0.0917/0.00 05 4.74 5 /0.0537 25 /0.2775 2 140 120 (8) 5.8 /0.0384 0.36 /0.0034 0.18 /0.0009 16 /1 71.51 49 zinc acetate 0.0917/0.0005 4.74 5 /0.0537 25 /0.2775 4 140 120 (8) 6.4 /0.0423 0.4 /0.0037 0.15 /0.0007 16 /1 78.77 50 zinc acetate 0.0917/0.0005 4.74 5 /0.0537 25 /0.2775 6 140 120 (8) 7.2/0.0476 0.4 /0.0037 0.06 /0.0003 18 /1 88.64 51 zinc propionate 0.106 /0.0005 4.88 5 /0.0537 25 /0.2775 1 140 40 (3) 0.47/0.0031 0.07 /0.0007 0 /0 6.7 /1 5.77 52 zinc propionate 0.106 /0.0005 4.88 5 /0.0537 25 /0.2775 2.5 140 60 (4) 2.79/0.0185 0.11 /0.0010 0.28 /0.0014 25 /1 34.45 53 zinc propionate 0.106 /0.00054.88 5 /0.0537 25 /0.2775 4 140 110 (8) 4.47/0.0296 0.10 /0.0009 0.45 /0.0022 45 /1 55.12 54 zinc propionate 0.016 /0.0005 4.88 5 /0.0537 25 /0.2775 6 140 105 (7) 6.62/0.0438 0.03 /0.0003 0.10 /0.0005 221 /1 81.56 55 zinc naphthenate 0.41 /0.0005 U.A. 5 /0.0537 25 /0.2775 1 140 140 (10) 3. /0.0198 0.18 /0.0017 0.15 /0.0007 17 /1 36.87 56 zinc naphthenate 0.41 /0.0005 U.A. 5 /0.0537 25 /0.2775 2 140 140 (10) 5.15/0.0341 0.21 /0.0020 1.23 /0.0061 25 /1 63.5 57 zinc naphthenate 0.41 /0.0005 U.A. 5 /0.0537 25 /0.2775 4 140 140 (10) 6.59/0.0436 0.54 /0.0050 0.15 /0.0007 12 /1 81.19 58 zinc naphthenate 0.41 /0.0005 U.A. 5 /0.0537 25 /0.2775 6 140 140 (10) 6.99/0.0462 0.30 /0.0028 0.06 /0.0003 23 /1 86.03 59 zinc acetate 1.03 /0.0056 4.74 18.6/0.2 18 /0.2 25.2 80 0 (0) 0.6 /0.004 0.2 /0.0019 0 /0 3 /1 2.0 I uranium trioxide 1.6 /0.0056 N.A. 18.6/0.2 18 /0.2 25.2 80 0 (0) 0 /0 0 100 /0 -- -- J uranium trioxide 1.6 /0.0056 N.A. 18.6/0.2 18 /0.2 25.2 80 0 (0) 0.1 /0.0007 0 /0 0 /0 -- 0.35 K uranium trioxide 1.6 /0.0056 N.A. 18.6/0.2 18 /0.2 48 80 0 (0) 0.22/0.0015 0.4 /0.0037 0.12 /0.0006.55/1 0.75 60 zinc octoate.sup.9 1.83 /0.0056 4.85 18.6/0.2 18 /0.2 24.8 80 0 (0) 6.7 /0.0443 0.4 /0.0037 0.2 /0.001 17 /1 22.15 L uranium dioxide 1.51 /0.0056 N.A. 18.6/0.2 18 /0.2 24.8 80 0 (0) 0 /0 0 /0 0 /0 -- -- 61 zinc acetate 1.61 /0.0088 4.74 18.6/0.2 18 /0.2 21 80 0 (0) 0.5 /0.0033 0 /0 0 /0 -- 1.65 M antimony trichloride 1.50 /0.0088 N.A. 18.6/0.2 18 /0.2 21 80 0 (0) 4.1 /0.0271 0.7 /0.0065 0.6 /0.003 5.9 /1 13.55 N UO.sub.2 (NO.sub.3).sub.2 . 6H.sub.2 O 1.5 /0.0030 N.A. 18.6/0.2 18 /0.2 23.5 80 0 (0) 2.6 /0.0172 0.6 /0.0056 0.13 /0.0006 4.3 /1 8.6 62 zinc octoate.sup.9 2.034 /0.0056 4.85 18.6/0.2 18 /0.2 2 200 400 (28) 16.36/0.1082 2.49 /0.0232 1.17 /0.0058 6.6 /1 54.1 63 stannous octoate 2.45 /0.0056 4.85 18.6/0.2 18 /0.2 2 200 550 (39) 8.45/0.0559 4.34 /0.0405 0.78 /0.0039 1.9 /1 27.95 O uranium trioxide 1.60 /0.0056 N.A. 18.6/0.2 18 /0.2 2 200 700 (49) 4.46/0.0295 6.37 /0.0594 0.67 /0.0033 0.7 /1 14.75 P uranium dioxide 1.51 /0.0056 N.A. 18.6/0.2 18 /0.2 2 200 650 (46) 4.54/0.0300 6.36 /0.0594 0.64 /0.0032 0.7 /1 15.0 64 zinc formate 0.48 /0.0025 3.77 5 /0.0537 25 /0.2775 2 200 450 (32) 2.9 /0.02 2.9 /0.027 0.09 /0.0004 1 /1 37.24 65 zinc chloroaceta te 0.636 /0.0025 2.85 5 /0.0537 25 /0.2775 2 200 280 (20) 2.31/0.0153 0.30 /0.00280 /0 7.7 /1 28.46 66 zinc trifluoroacetate 0.734 /0.0025 0.23 5 /0.0537 25 /0.2775 2 200 390 (27) 2.88/0.019 0.84 /0.0078 0.06 /0.0003 3.43/1 35.48 67 zinc octoate.sup.9 0.185 /0.0025 4.85 5 /0.0537 25 /0.2775 0.25 200 290 (20) 2.02/0.0134 0.41 /0.0038 0.35 /0.0016 85 24.88 68 zinc octoate.sup.9 0.185 /0.0025 4.85 5 /0.0537 25 /0.2775 0.50 200 290 (20) 4.32/0.029 0.67 /0.0063 0.35 /0.0016 6.45/1 53.22 69 zinc octoate.sup.9 0.185 /0.0025 4.85 5 /0.0537 25 /0.2775 1 200 300 (21) 6.51/0.043 0.70 /0.0065 0.07 /0.0003 9.3 /1 80.19 70 zinc octoate.sup.9 0.185 0.0025 4.85 5 /0.0537 25 /0.2775 2 200 300 (21) 6.66/0.044 0.54 /0.005 0.05 /0.0002 12.33/1 82.04 71 zinc thiodipropionic acid 0.604 /0.0025 U.A. 5 /0.0537 25 /0.2775 1 200 210 (15) 1.77/0.12 0.78 /0.0073 0.20 /0.0009 2.27/1 21.80 72 stannous chloride 0.474 /0.0025 N.A. 5 /0.0537 25 /0.2775 1 200 210 (15) 7.41/0.049 0.33 /0.003 0.13 /0.0006 22.45/1 91.28 73 zinc acetate 0.46 /0.0025 4.74 5 /0.0537 25 /0.2775 1 200 280 (20) 7.2 /0.048 0.21 /0.003 0.06 /0.0003 34.3 /1 88.7 .sup.1 MPC is methyl phenyl carbamate. .sup.2 NMA is Nmethyl aniline. .sup.3 DPU is diphenyl urea. .sup.4 zinc salt of a highly refined naphthenic acid containing 8% zinc and commercially available from Mooney Chemical, Inc. as a NapAll drier. .sup.5 zinc salt of a blend of synthetic domestic acid containing 10% zin and commercially available from Mooney Chemical, Inc. as a NapAll drier. .sup.6 zinc salt of a blend of synthetic domestic acid containing 8% or 16% zinc and commercially available from Mooney Chemicals, Inc. as a ChemAll drier. .sup.7 zinc salt of extrapale tall oil acids containing 8% zinc and commercially available from Mooney Chemicals, Inc. as a LinAll drier. .sup.8 zinc salt of a domestic, synthetic neodecanoic acid containing 16% zinc and commercially available from Mooney Chemicals, Inc. as a TenCem drier. .sup.9 a zinc salt of 2ethylhexanoic acid containing 18% zinc and commercially available from Mooney Chemicals, Inc. as a HexCem drier. .sup.10 Calculated by dividing moles of MPC produced by moles of aniline employed and multiplying by 100. .sup.11 U.A. means unavailable by the applicant (i.e. is not in the literature reviewed). .sup.12 pKa is the pKa value of the compound from which the catalyst was derived; e.g. for zinc acetate it is the value for acetic acid. .sup.13 N.A. means not applicable (i.e. not a derivative of an organic acid). .sup.14 Pressure indicated is gauge pressure.
EXAMPLES 74-98 AND COMPARATIVE EXPERIMENTS Q-U
Equimolar amounts of aniline and ethylene carbonate were mixed together. Then 10 gram quantities (5.14 g, 0.0552 mole aniline; 4.86 g, 0.0552 mole ethylene carbonate) of this mixture were weighed into each of a series of 4 dram (15 cc) glass vials. Various catalysts, one per vial, were then weighed into the vials and mixed. The vials were then placed, unsealed, in a metal block of a "Temp Blok" module heater with thermostatic control to hold any desired temperature and the mixture heated for the desired time. Small aliquots could be removed periodically and analyzed for the degree of carbamate formation, if any.
The various catalysts and quantity of catalyst, reaction conditions and results are given in Table II.
TABLE II__________________________________________________________________________ % CON-EX- pKa.sup.3 VER-AMPLE OF SIONOR OR- REACTION REACTION WEIGHT OF ANI-COMP. GANIC CONDITIONS PRODUCTS RATIO LINEEXPT. CATALYST COM- TIME TEMP. HENPC.sup.1 NHA.sup.2 HENPC/ TONO. TYPE g/mole POUND Hrs. .degree. C. g/mole g/mole NHEA HENPC.sup.5__________________________________________________________________________74 zinc acetate 0.2 /.0011 4.74 16 108 4.67/0.0258 0.84 /0.0061 5.56/1 46.7475 zinc acetate 0.2 /.0012 4.74 48 108 3.99/0.0220 1.24 /0.0090 3.22/1 39.86Q ferric chloride 0.2 /.0011 N.A..sup.4 40 108 2.79/0.0154 1.98 /0.0144 1.41/1 27.976 zinc salicylate 0.2 /.0025 3.00 36 108 2.26/0.0125 1.0 /0.0073 2.26/1 22.6477 zinc stearate 0.2 /.0003 U.A..sup.6 36 108 3.07/0.0169 1.47 /0.0107 2.09/1 30.6278 zinc acrylate 0.2 /.0015 4.25 36 108 2.33/0.0129 0.88 /0.0064 2.65/1 23.3779 zinc di(2-aminoethyl sulfide) 0.2 /.00092 N.A..sup.4 36 108 4.13/0.0228 1.05 /0.0077 3.93/1 41.380 zinc trifluoracetate 0.2 /.0011 0.23 36 108 4.13/0.0228 0.97/0.0071 4.26/1 41.381 stannous chloride 0.1 /.00053 N.A..sup.4 40 90 3.56/0.0196 1.11 /0.0081 3.21/1 35.51R stannous oxalate 0.1 /.00048 1.23 40 90 0.18/0.001 1.21 /0.0088 0.15/1 1.8182 zinc acetate 0.1 /.00055 4.74 40 90 3.36/0.0185 0.81 /0.0059 4.15/1 33.5183 zinc acetate 0.1 /.00055 4.74 40 90 4.97/0.0274 1.01 /0.0074 4.92/1 49.6484 zinc di(2-aminoethyl sulfide) 0.1 /.00046 N.A..sup.4 40 90 3.51/0.0194 0.51 /0.0037 6.88/1 35.1485 zinc di(2-aminoethyl sulfide) 0.1 /.00046 N.A..sup.4 40 90 5.05/0.0279 1.01 /0.0074 5.00/1 50.5486 zinc chloride 0.18/.0013 N.A..sup.4 44 90 3.09/0.0171 1.10 /0.0080 2.81/1 30.9887 zinc acetylacetonate 0.05/.0003 9.00 44 90 3.54/0.0195 1.02 /0.0074 3.47/1 35.3388 stannous laurate 0.2 /.0004 N.A..sup.4 44 90 0.10/0.0006 1.15 /0.0084 0.09/1 1.09S ferric chloride 0.02/.00011 N.A..sup.4 44 90 0.66/0.0036 1.21 /0.0088 0.55/1 6.5289 stannous octoate 0.4 /.0009 4.9 72 90 4.27/0.0236 0.73 /0.0053 5.85/1 42.75T aluminum trichloride 0.06/.00045 N.A..sup.4 72 90 1.58/0.0087 2.98 /0.0217 0.53/1 15.7690 zinc acetate 0.02/.00011 4.74 72 100 2.52/0.0139 1.66 /0.0121 1.52/1 25.1891 zinc acetate 0.5 /.0027 4.74 72 100 3.95/0.0218 0.72 /0.0052 5.49/1 39.4992 zinc acetate 0.1 /.00055 4.74 24 90 3.06/0.0169 0.6 /0.0047 4.78/1 30.6293 zinc acetate 0.3 /.0016 4.74 24 90 3.74/0.0206 0.525/0.0038 7.12/1 37.3294 zinc acetate 0.5 /.0027 4.74 24 90 3.96/0.0219 0.43 /0.0031 9.2/1 39.6795 zinc acetate 1.0 /0.0055 4.74 24 90 4.08/0.0225 0.36/0.0026 11.33/1 40.7696 zinc trifluoroacetate 0.2/0.0007 0.23 36 108 4.13/0.0228 1.11/0.0081 3.72/1 41.397 zinc formate 0.2 /0.001 3.75 36 108 4.46/0.0246 1.77/0.0129 2.52/1 44.57U zinc oxalate 0.2 /0.0001 1.23 36 108 0.19/0.001 3.47/0.0253 0.05/1 1.8198 zinc chloroacetate 0.2 /0.0008 2.85 36 108 2.17/0.0120 3.48/0.0254 0.62/1 21.74__________________________________________________________________________ .sup.1 HENPC is hydroxyethyl Nphenyl carbamate. .sup.2 NHEA is Nhydroxyethyl aniline. .sup.3 pKa is the pKa value of the compound from which the metal catalyst salt was derived; e.g. for zinc acetate, it is the value of acetic acid. .sup.4 N.A. means not applicable since the catalyst is a salt of a minera acid or a compound other than carboxylate. .sup.5 calculated by dividing moles of HENPC produced by moles of aniline employed and multiplying by 100. .sup.6 U.A. means unavailable by the applicant (i.e. is not in the literature reviewed).
EXAMPLE 99
A. Present invention employing zinc acetate as the catalyst
To a 500 ml reaction vessel fitted with a means for heating and reflux azeotrope removal, was added 180 g (2 moles) of dimethyl carbonate, 37.2 g (0.4 mole) of aniline and 9.2 g (0.05 mole) of anhydrous zinc acetate. The zinc acetate was completely soluble in the reaction mixture. The reaction mixture was refluxed for 6 hours while slowly taking off an azeotropic mixture of dimethyl carbonate and methanol. The reaction temperature was 96.degree. C. On cooling, no precipitate of diphenyl urea was observed and 203 g of solution remaining contained the following:
0.24 g (0.0012 mole) of diphenyl urea
38.0 g (0.2514 mole) of methyl phenyl carbamate
12.18 g (0.1308 mole) of aniline
1.0 g (0.0093 mole) of N-methyl aniline.
B. Comparative experiment employing antimony trichloride as the catalyst
In like manner as A above, 180 g (2 moles) dimethyl carbonate, 37.2 g (0.4 mole) aniline and 11.4 g (0.05 mole) antimony trichloride were employed. The antimony trichloride formed a dense white suspension of complex with aniline. The reaction temperature was 98.degree. C. On cooling, solid diphenyl urea separated. Upon filtering, 11.3 g of solid diphenyl urea was obtained. The filtrate was analyzed and found to contain:
1.2 g (Total=12.5 g, 0.0618 mole) of diphenyl urea
10.37 g (0.0686 mole) of methyl phenyl carbamate
2.0 g (0.0187 mole) of N-methyl aniline
11.86 g (0.13 mole) of aniline.
EXAMPLES 100 TO 113
These examples were prepared in the same manner as those for Examples 1-63 except that different amines were employed. The reactants, reaction conditions and results are given in the following Table III.
TABLE III pKa.sup.6 OF DIMETHYL REACTION CONDITIONS % CONVERSION EXAMPLECATALYST O RGANICAMINE CARBONATE TIME TEMP. PRESS. DICARBAMATE OF AMINE TO NUMBERTYP Eg/mole COMPOUND TYPE g/mole g/mole Hrs. .degree. C. psi (kg/cm.sup.2) g/mole DICARBAMATE.sup.5 100.sup.1 zinc acetate 0.46 /0.0025 4.74 2,6-diaminotoluene 3.4 /0.0279 25 /0.2775 4 140 180 (13) 1.61/.00678 24.4 101 zinc acetate 0.46 /0.0025 4.74 2,6-diaminotoluene 3.4 /0.0279 25 /0.2775 4 140 240 (17) 2.37/.01 36.0 102 zinc octoate (18% Zn).sup.2 1.82 /0.005 U.A..sup.4 2,6-diaminotoluene 3.45 /0.0283 25 /0.2775 4 160 220 (15) 2.54/.0107 37.8 103 zinc octoate (18% Zn).sup.2 1.82 /0.005 U.A..sup.4 2,4-diaminoto luene 3.4 /0.0279 25 /0.2775 4 140 240 (17) 2.12/.0089 32.0 104 zinc octoate (18% Zn).sup.2 1.82 /0.005 U.A..sup.4 2,4-diaminotoluene 3.4 /0.0279 25 /0.2775 7 160 190 (13) 4.9 /.0206 74.0 105 zinc octoate (18% Zn).sup.2 1.82 /0.005 U.A..sup.4 2,4-diaminotoluene 3.45 /0.0283 25 /0.2775 4 160 220 (15) 3.92/.0165 58.3 106.sup.3 zinc acetate 0.46 /0.0025 4.74 2,4-diaminotoluene 3.4 /0.0283 25 /0.2775 4 140 140 (10) 1.22/.005 18.3 107.sup.7,8,9 zinc propionate 0.534/0.0025 4.88 p-toluidin e 5.75 /0.0537 32.8 /0.2775 4 140 110 ( 8) 6.42/.0387 72 108 zinc octoate (18% Zn).sup.2 0.363/0.001 4.85 2,4-diaminotoluene 3.05 /0.025 22.5/0.25 3 200 300 (21) 2.44/0.01 40 109.sup.7 zinc acetate 0.46 /0.0025 4.74 o-anisidine 6.2 /0.05 22.5/0.25 2 160 220 (15) 5.6 /0.031 62 110.sup.7 zinc acetate 0.46 /0.0025 4.74 m-anisidine 6.2 /0.005 22.5/0.25 2 160 220 (15) 6.6 /0.037 74 111.sup.7 zinc acetate 0.46 /0.0025 4.74 p-anisidine 6.2 /0.05 22.5/0.25 2 160 220 (15) 8.0 /0.044 88 112.sup.7,8,9,10 zinc octoate (18% Zn).sup.2 0.911/0.0025 U.A..sup.4 aniline 5 /0.0537 25 /0.212 2 200 180 (13) 4.8 /0.027 54 113.sup.11,12 zinc propionate 0.55 /0.0258 4.88 aniline 4 /0.043 23 /0.1073 5 140 110 (8) good yield -- .sup.1 also contained 25 grams of dioxane as a reaction diluent. .sup.2 a zinc salt of 2ethylhexanoic acid containing 18% zinc and commercially available from Mooney Chemicals, Inc., as a HexCem drier. .sup.3 Also contained 25 grams dimethyl ether of ethylene glycol as a reaction diluent. .sup.4 U.A. means unavailable by the applicant (i.e. is not in the literature reviewed). .sup.5 Calculated by dividing moles of dicarbamate produced by moles of amine employed and multiplying by 100. .sup.6 pKa is the pKa value of the compound from which the metal catalyst salt was derived; e.g. for zinc acetate, it is the value of acetic acid. .sup.7 Product was a monocarbamate instead of a dicarbamate. .sup.8 Employed diethyl carbonate instead of dimethyl carbonate. .sup.9 The results were approximated using the calibration curve for methyl phenyl carbamate. .sup.10 The wt. ratio of ethyl phenyl carbamate to undesired Nethyl aniline was 253 to 1. .sup.11 Employed diphenyl carbonate instead of dimethyl carbonate. .sup.12 Also employed 20 grams of acetonitrile as a reaction medium.
Zinc acetate was also found to be suitable for catalyzing the reaction between dimethyl carbonate and methylene dianiline, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, and an 80/20 mixture of 2,4-/2,6-diamino toluene.
Zinc naphthenate (80% Zn) was also found to be suitable for catalyzing the reaction between dimethyl carbonate and 2,6-diamino toluene and an 80/20 mixture of 2,4-/2,6-diamino toluene.
Zinc octoate (18% Zn) was found to not catalyze the reaction between dimethyl carbonate and 2,4,6-tribromoaniline.

Number	Name	Date
3763217	Brill	Oct 1973
3895054	Zajacek et al.	Jul 1975
3919279	Rosenthal et al.	Nov 1975
3919280	Rosenthal et al.	Nov 1975
3962302	Rosenthal et al.	Jun 1976

Preparation of carbamates from aromatic amines and organic carbonates

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Mukai et al., Chem. Absts., 87, 52961(e), 1977.
Olah, Friedel-Crafts and Related Reactions, vol. 1, Interscience Publishers, pp. 288-291 (1963).