Patent Publication Number: US-4258201-A

Title: Process for the manufacture of carbamates

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
     This application is related to my co-pending application Ser. No. 7,105, filed Jan. 29, 1979, entitled &#34;Promoted Method for Producing Carbamates&#34;, filed on even date herewith, the disclosure of which is hereby incorporated by reference. 
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     This invention relates to the preparation of carbamates, and more specifically to the preparation of carbamates by the direct carbonylation of primary and secondary amines. 
     2. Description of the Prior Art 
     Carbamates, which are also referred to herein as &#34;urethanes&#34;, are industrial chemicals of enormous significance, and much research has been performed in search of economical processes for their manufacture. One such process involves the formation of a primary amine such as aniline from the corresponding organic nitro compound (e.g., nitrobenzene) and reaction of the resulting primary amine with phosgene to form a carbamyl chloride salt which is then thermally decomposed to the corresponding isocyanate. Recovery and reaction of the isocyanate with an alcohol yeilds the carbamate. Due to the high toxicity of phosgene, and to the corrosive nature of systems in which the chloride ion is employed, alternative processes have been sought which would remove these disadvantages. 
     Accordingly, a large number of processes were developed to carbonylate an organic nitro compound with carbon monoxide in the presence of an organic hydroxy compound and certain catalyst systems to obtain the corresponding urethane. Exemplary references to these processes and their catalyst systems are as follows: (1) U.S. Pat. Nos. 3,338,956 (carbonyls of metals of Groups VI-B, VII-B and VIII); 3,448,140 (complex compound of a transition metal having atomic number of 21 to 29, 39 to 47 and 71 to 79, inclusive, containing ligands of P, As, or Sb); 3,467,694 (noble metal and a Lewis acid); 3,531,512 (palladium and a Lewis acid); 3,644,462 (noble metal halide and primary, secondary or tertiary amine); 3,895,054 (Se, S or Te); 3,956,360 (Se, S or Te); 3,993,685 (tertiary amine and a platinium group metal or compound thereof); 4,052,437 (rhodium oxide); and 4,080,365 (Se+base+aromatic amino or urea promoter); (2) British Pat. Nos. 1,089,132 (metal carbonyls of Groups VI-B, VII-B and VIII and multivalent metals or their salts); 1,469,222 (palladium group metal halide and a nitrogen-containing heterocyclic compound); and 1,485,108 (Se); and (3) French Patent of Addition No. 2,008,365, as cited in 73 Chem. Abs. 66 302p (1970) (palladium, Al 2  O 3  or Fe 2  O 3 ). 
     While the above processes allow direct formation of carbamates from nitro-compounds, a one-step process for converting amines to carbamates would also be useful. 
     Direct carbonylation of aromatic amines to carbamates in significant yields has not heretofore been achieved. Indeed, it was long believed that carbonylation of such amines only yields ureas or formamides. Thus, Hagelloch, Ber., vol. 83, 258 (1950) reacted aniline and COS in ethanol to form low yields (1-3%) of 1,3-diphenyl urea, and German Patent 863,800 (1953) converted aniline to high yields of urea and/or N-substituted formamides with CO in the presence of nickel iodide, powder nickel or cobalt (activated with MgO or SiO 2 ) as catalyst. 
     U.S. Pat. No. 3,099,689 obtained formamides by reaction of aniline with CO in the presence of organometallic compounds of metals of Groups IVB, VB, VIB, VIIB or VIII of the Periodic Table. 
     U.S. Pat. No. 4,052,454 formed unsymmetrical ureas by the reaction of nitrogeneous organic compounds with aniline, carbon monoxide and sulfur or selenium and certain bases, and British Pat. No. 1,275,702 produced ureas from primary or secondary mono- or diamines by reaction with CO in the presence of Se. N. Sonoda et al., J. Amer. Chem. Soc., vol. 92 (23), p. 6344 (1971) obtained very high yields of urea from ammonia or aliphatic amines, CO and O 2  in the presence of Se, and K. Kondo et al., J. Chem. Soc. Chem. Comm., 307 (1972) obtained stiochiometric yields of urea by carbonylation of aromatic amines with CO, O 2  and Se, employing a strongly basic tertiary amine, such as triethyl amine, as co-catalyst. 
     R. A. Franz et al., 26 J. Orq. Chem. 3309 (1961) found that tertiary aliphatic amines, KOH and CaO or MgO in methanol were urea catalysts in the reaction of aromatic amines with CO and S. U.S. Pat. No. 2,877,268 disclosed obtention of &#34;excellent yields&#34; of urea by use of alkaline catalysts with a dissociation constant of greater than 1×10 -10  : tertiary alkyl amines of 1 to 18 carbon atoms, quaternary ammonium hydroxides, alkaline earth metal and alkali metal hydroxides, alkaline and alkali metal salts (such as sodium oleate), MgO (in methanol), Ca (in methanol) and certain substituted aryl and aralkyl amines. Similarly, diuredides were obtained in Canadian Pat. No. 634,690 by reacting aromatic diamines with CO, S and certain aliphatic or aromatic secondary amines in methanol. 
     Thio-derivatives of amines have also been produced by carbonylations. U.S. Pat. No. 3,636,104 formed N, N&#39;-diaryl thioureas by reacting aniline with CS 2  in pyridine or alcohol with the addition of S or H 2  O. Alkylamine salts of N-alkyl thiocarbamic acid were prepared in U.S. Pat. No. 2,655,534 by reacting COS and a primary or secondary aliphatic amine. U.S. Pat. Nos. 3,392,197 and 3,539,587 prepared substituted thioureas and monothiocarbamates from primary and secondary amines employing CO and sulfur or sulfur compounds. Thiocarbamates have also been prepared by reaction of amines and disulfides in equimolecular ratio with carbon monoxide in the presence of selenium catalysts and triethylamine. See P. Koch, Tetrahedron Letters No. 25, pp. 2087-2088 (1975); West German Patent Publication No. 2,617,917, 86 Chem. Abs. 43426 m (1977). 
     In attempting to carbonylate amines to a carbamate product, F. Baiocchi, et al., 21 J. Org. Chem. 1546 (1956) prepared methyl-N-phenyl carbamate in low yield (27-30%, based on aniline charged) by reacting aniline and COS in methanol employing either zinc peroxide, di-tert-butyl peroxide or O 2  to induce the reaction. Magnesium peroxide was found to be not operative, and other peroxides (H 2  O 2  in H 2  O and cumen hydroperoxide in methanol, with and without sodium methoxide), yielded very large amounts of 1, 3-diphenyl urea. Netherlands Pat. No. 94,613 converted aliphatic primary and secondary amines to urethanes by reaction with CO in the presence of alcohols and stoichiometric amounts of certain cupric compounds, which were reduced to the cuprous state, and required reoxidation, as by O 2 , to regenerate the cupric reactant. 
     R. A. Franz et al., 28 J. Org. Chem. 585 (1963) also obtained urethanes from aniline, COS and methanol in the presence of triethyl amine, but could not achieve urethane yields greater than about 13.5%. Even using a carefully controlled, multi-step process, urethane yields greater than 25% were not obtained by Franz et al. under any combination of experimental conditions. Stoichiometric reaction of certain metal acetates (Hg +2 , Tl +3  and Cu +2 ) in T. Saegusa, et al., Tetrahedron Letters No. 42, pp. 4123-4126 (1967) with piperidine, CO and CH 3  OH did not greatly improve urethane yields. Use of the metal acetates of Ag +1 , Cd +2  and Zn +2  gave only trace product, even after 98 hours of reaction. 
     Higher urethane yields have been provided by U.S. Pat. Nos. 3,384,655 (issued in 1968 to Anderson et al.) and 3,629,311 (issued in 1971 to Anderson et al.) and K. Kondo, et al., Chem. Letters, pp. 373-374 (Chem. Soc. Japan 1972). In the Anderson et al. process, a secondary (or a mixture of secondary and teritary) amine is first reacted with COS and an alcohol to form an adduct containing the urea, COS and alcohol, followed by a low temperature oxidation of the adduct with O 2 , optionally in the presence of soluble Fe, Ni, Co, Cu, Hg, Pd, Pt or Au halide, sulfate or nitrate promoters, to form the desired urethane, elemental sulfur and water. Kondo et al. reacted a primary amine, CO, Se and methanol in the presence of triethylamine, followed by oxidation with O 2  of the foregoing mixtures, to yield the urethane, and to form a Se precipitate and water. However, the required use of O 2  (or peroxides as in the Baiocchi process) is industrially severely disadvantageous due to the ease with which aniline is oxidized to a wide variety of by-products and due to the obvious explosive hazards associated with mixtures of oxygen, carbon monoxide and alcohol. The explosive hazards require careful attention to temperature controls and use of expensive processing equipment. A further disadvantage to the use of oxygen is the by-product water which is formed and which then reacts with the carbamate to form a urea. To avoid the urea problem, water absorbing agents must be added and additional care must be taken to use anhydrous reactants to avoid further urea being formed. Both of these precautions require added processing expense. 
     SUMMARY OF THE INVENTION 
     According to the improved process of the present invention, carbamates are produced by contacting an organic primary or secondary amine, in the substantial absence of reactive oxygen, with a source of carbon-monoxide, an organic compound containing at least one hydroxyl group and a source of sulfur, selenium or tellurium, in the presence of an effective amount of a catalyst selected from the group consisting of non-halide compounds and complexes of metals of Groups IVB, VB, VIB, VIIB, VIII, IB and IIIA of the Periodic Table. 
     The process of the present invention can achieve surprisingly high yields of carbamate, and has been found to produce the carbamate in selectivities of up to about 90% and more. The process can also produce only very small amounts of uresa, formamides and other by-products. 
     Further, the present invention can achieve the above advantages using very low concentrations of the above metal catalysts, thereby avoiding the requirement of prior art processes in which stoichiometric levels of metal reactants were used. Importantly, the present invention removes the requirement of using molecular O 2  or a peroxidic reactant to effect the formation of the carbamate product, minimizing the safety hazards and urea-formation problems attending the use of such reactants. 
     DETAILED DESCRIPTION OF THE INVENTION 
     Any organic primary or secondary amine capable of being converted to an organic carbamate may be employed as a reactant. Aliphatic amines, alicyclic amines and aromatic amines are operable. These amines include primary amines of the formula RNH 2  wherein R is alkyl, aryl, alkaryl, aralkyl, and cycloalkyl, and secondary amines of the formula RNH(R&#39;) wherein R and R&#39; are independently selected from the group consisting of alkyl, aryl, alkaryl, aralkyl and cycloalkyl. Also included as operable organic amines are primary and secondary amines containing fused rings and heterocyclic substituents. The primary and secondary amines may be substituted or unsubstituted, and when substituted preferably contain inert substituents such as alkyl, aryl, alkaryl, aralkyl, cycloalkyl, halogen (Cl, Br, F and I) cyano, tertiary amino, carboxyl, esters, ethers and thioether groups. Preferably, the amine reactant contains no substitution by OH--, &gt;C═O (i.e., ketonic or aldehydic) or sulfonic acid groups since such groups interfere with the desired carbonylation reaction to the selected carbamates. The foregoing suitable hydrocarbon substituents to the R and R&#39; groups can themselves be substituted by one or more amino groups. Exemplary of such amino substituted hydrocarbyl substituents to the R and R&#39; groups are amino-substituted aralkyls (e.g., ##STR1## and the like), amino-substituted alkyl (e.g., H 2  NCH(CH 3 )--, H 2  NC 2  H 5  --and the like) and amino-substituted alkaryls (e.g., ##STR2## and the like). 
     Also included as reactants in this invention are amines of the formula R(NH 2 ) m  wherein R is as defined above and wherein m is an integer of from 2 to 5, preferably of from 2 to 3. Thus, aliphatic, alicyclic and aromatic diamines, such as ethylenediamine, hexamethylenediamine and other homologues and isomers of 2 to 10 carbon atoms are operable. The aromatic diamines include phenylenediamine, toluenediamine and naphthylenediamine. Phenylenetriamine also is operable. Polymeric amines having repeating polymer units based on any of the above amines can also be used (e.g., polymeric methylene dianiline). 
     Examples of R and R&#39; substituents of the amines of each of the above formulas are alkyl radicals derived from straight and branched-chained alkanes of from 1 to 20, preferably from 1 to 12, carbon atoms (such as methyl, ethyl, isopropyl, butyl, decyl, dodecyl, isostearyl, and the like); aryl of 6 to 18, preferably 6 to 12, carbon atoms (such as phenyl, naphthyl, anthryl and the like), alkaryl and aralkyl of 7 to 24, preferably 7 to 12, carbon atoms (such as benzyl, tolyl, p-butyl phenyl, dihexylphenyl; isostearyl phenyl, and the like) and cycloalkyl of 3 to 12 carbon atoms (such as cyclohexyl, cyclopentyl, cyclobutyl, cyclododecyl and the like). 
     Typical examples of suitable amines which can be reacted to form carbamates include the following primary amines such as aniline, tolyl amines, xylyl amines, naphthyl amines, anthryl amines, benzyl amine, 1- or 2-bromoethyl benzyl amine, cyclohexylamine, bis-aminoaryl-substituted alkylenes (e.g., compounds of the formula ##STR3## wherein Z&#39; is alkylene of 1 to 6 carbon atoms, such as methylene, ethylene, trimethylene, tetramethylene and the like), the diamino toluenes and the like. 
     Especially preferred as amines in the process of this invention are primary amines of up to 14 carbon atoms. Most preferred are aromatic primary mono- and di-amines of from 6 to 13 carbon atoms. Examples of most preferred monoamines are aniline, and of most preferred diamines are 2,4-diamino-toluene and 4,4&#39;-methylene dianiline. 
     The source of the carbon monoxide employed as reactant in this invention is not critical and thus carbon monoxide can be employed, in gaseous or liquid form, as a pure material, or in admixtures with other materials which do not adversely affect the desired reaction. For example, carbon monoxide gas can be employed in admixture with materials normally found in synthesis gas (generally containing from about 50 to 80 volume % CO), such as hydrogen, CO 2  and the like. Of course, inert gases such as N 2 , Ar and the like can be employed. The carbon monoxide can also be introduced to the reaction zone in a chemically combined form with one or more of the desired components of the catalyst system. For example, the carbon monoxide can be chemically combined with sulfur as carbonyl sulfide or chemically combined with a metal component of the catalyst system as a metal carbonyl which under the conditions of the reaction will release carbon monoxide for reaction in the process with the desired amine. Such metal carbonyls are known materials and include Co, Mn and Fe carbonyls. Thus, as used herein, the term &#34;source of carbon monoxide&#34; is intended to refer to CO or a chemically combined or complexed form thereof which releases CO under the conditions of the reaction. Preferred sources of carbon monoxide are CO, COS, COSe, COTe, and metal carbonyls, with COS and mixtures of COS and CO being especially preferred. 
     The reaction is preferably conducted in the substantial absence of &#34;reactive oxygen&#34;, that is, the amount of molecular oxygen, and organic and inorganic peroxides in the reaction zone, whether dissolved, suspended, or in the gaseous state, shuld be less than 1 weight percent, and preferably less than about 0.1 weight percent, of amine reactant charged to the reaction zone. 
     Organic compounds containing at least one hydroxyl group suitable for use in the process in the present invention include mono- or polyhydric alcohols containing primary, secondary or tertiary hydroxyl groups and mixtures thereof. The alcohols can be aliphatic or aromatic and can bear other substituents in addition to hydroxyl groups, but the substituents should, except as hereinafter defined, preferably be non-reactive with carbon monoxide under the process conditions. 
     Generally, the hydroxyl group-containing compounds comprise compounds of the formula Z(OH) n  wherein n is 1 or more and preferably from 1 to 3, and Z is an optionally substituted aryl, aliphatic, cycloaliphatic or araliphatic group, preferably containing from 1 to 20 carbon atoms, more preferably from 1 to 7 carbon atoms. The group Z can therefore be alkyl, cycloalkyl, alkylene, cycloalkylene, aryl, or aralkyl, which groups can be substituted by alkyl, alkoxy, aryl or aryloxy groups normally containing up to 7 carbon atoms, and derivatives of the foregoing in which one or more carbon atoms are substituted by oxygen, nitrogen or sulfur atoms. The foregoing groups can also be substituted by sulfoxide, sulfone, amide, or carboxylic ester groups. 
     Exemplary hydroxyl group-containing compounds are monohydric alcohols such as methanol, ethanol, n-propanol, sec-propanol, n-iso- and tert-butanol, amyl alcohol, hexyl alcohol, lauryl alcohol, cetyl alcohol, benzyl alcohol, chlorobenzyl alcohol, methoxy benzyl alcohol, methoxy ethanol, butoxy ethanol, cyclohexyl alcohol, phenol and the like. Exemplary polyhydric compounds include diols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol, triols such as glycerol, trimethylolpropane, hexanetriol, tetrols such as pentaerythritol and the like. Ethers of the foregoing polyols can also be employed provided that at least one OH group remains unetherified. The etherifying group in such ether alcohols normally will contain up to 4 carbon atoms and are preferably selected from the group consisting of alkyl, cycloalkyl or aralkyl groups which can themselves be substituted. 
     Especially suitable hydroxy-containing compounds are the lower alkanols. Exemplary of such especially suitable compounds are methanol, ethanol, n-propanol, isopropanol, butanol, sec-butanol, isobutanol, ethylene glycol, glycerol and trimethylol propane. 
     The process of the present invention also employs in the reaction zone as reactant a &#34;source of sulfur, selenium or tellurium&#34;, i.e., a member selected from the group consisting of elemental sulfur, selenium and tellurium, and compounds and complexes thereof. When elemental sulfur, selenium or tellurium are employed, the selected element is preferably used in powdered form. Suitable sulfur compounds which can be employed include organic or inorganic sulfur compounds, exemplary of which are hydrogen sulfide, carbonyl sulfide, sulfur dichloride and the like. Illustrative organic sulfur compounds include the polysulfides having 3 or more S atoms and up to 20 carbon atoms per molecule, e.g., diethyl polysulfide, dioctyl polysulfide, and the like. Similarly, suitable selenium compounds include selenium dioxide, selenium trioxide as well as mixtures of the oxides, selenium oxychloride, titanium diselenide, selenium disulfide, sodium selenite, zinc selenite, zinc selenide, tungsten selenide, selenium sulfide, selenic acid and carbonyl selenide. Polyselenides such as diethyl polyselenide and dibutylpolyselenides can also be used. Illustrative tellurium compounds which may be employed include tellurium metal, tellurium oxides, hydrogen telluride, carbonyl telluride and the like. 
     In the practice of this invention when a source of sulfur is employed in the reaction zone, it has been found that best results are achieved when the reaction zone contains COS and H 2  S in a COS to H 2  S molar of at least 2:1, and more preferably at least 2.5:1. Likewise, when a Se or Te source is employed in the reaction zone, COSe and H 2  Se, or COTe and H 2  Te, are preferably present in the reaction zone in a molar ratio of COS to H 2  Se (or COTe to H 2  Te) of at least 2:1, and more preferably at least 2.5:1. Such H 2  S, H 2  Se and H 2  Te compounds will be formed as by-product in the reaction. If the amounts of COS, COSe or COTe which are formed in situ in the reaction zone is not sufficient to attain the above molar ratios in the preferred embodiment, additional amounts of the COS, COSe or COTe can be added directly to the reaction zone, to supplement that which is formed in situ. 
     The foregoing sulfur, selenium and tellurium sources and/or the below-disclosed catalysts, can be self-supported or can be deposited on a support or carrier for dispersing the catalyst to increase its effective surface. Alumina, silica, carbon, barium sulfate, calcium carbonate, asbestos, bentonite, diatomaceous earth, fuller&#39;s earth, organic ion exchange resins and analagous materials are useful as carriers for this purpose. Selenium, sulfur or tellurium containing molecular sieves can also be employed as well as complexes of selenium, sulfur or tellurium. 
     Especially preferred for use in this invention are sulfur sources, most especially COS or elemental sulfur. 
     The catalysts which are suitable for use in the process of this invention comprise at least one member selected from the group consisting of non-halide compounds and complexes of metals of Groups IVB, VB, VIB, VIIB, VIII, IB and IIIA of the Periodic Table. Therefore, catalysts which are useful in this invention include compounds and complexes of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Al, Ga, In and Tl. The compound or complex containing any of the foregoing metals can be inorganic or organic, and mixed salts of the above metals can also be used. Exemplary of suitable inorganic salts are the oxides, hydroxides, sulfides, silicates, sulfates, phosphates, arsenides, arsenates, nitrates, carbonates, and the like. 
     Preferred catalysts of this invention are members selected from the group consisting of inorganic compounds of non-noble metals of Group VIII (i.e., Fe, Co or Ni) and inorganic compounds of metals of Groups VIIB (i.e., Mn, Tc and Re) and IIIA (i.e., Al, Ga, In and Tl) of the Periodic Table. 
     Mixed metal salts can also be used such as the aluminates, titanates, chromates, molybdates, tungstates, gallates and thallates, of any of the foregoing catalyst metals. 
     The activity of the above catalysts can be further enhanced by incorporating therein or thereon one or more promoters comprising compounds of metals of Groups IA or IIA of the Periodic Table, i.e., Li, Be, Na, Mg, K, Ca, Rb, Sr, Cs and Ba, the oxides and hydroxides of these metals being preferred. Most preferably the promoter comprises an oxide or hydroxide of Ba, Sr or Cs. When employed, these promoters will generally be used in an amount of from about 0.1 to 20, and preferably from about 1 to 10, weight percent of the metal promoter cation based on the catalyst metal ion. 
     Illustrative of inorganic metal salts which can be employed as catalysts are MoS 2 , V 2  S 3 , ReS 2 , CuS, Cu 2  S, Tl 2  SiO 3 , Cs 3  PO 4 , Cs 2  TiO 3 , BaMoO 4 , SrMO 4 , BaAl 2  O 4 , BaO.CoMoO 4 , BaCrO 4 , Na 2  Ga 2  O 4 , Na 2  WO 4 , MnS, ReSO 4 , PtO, Tl 2  SO 4 , ZrO 2 , HfO 2 , Nb 2  O 3 , Ta 2  O 5 , Ru(NO 3 ) 3 , K 2  O.VWO 4  , IrO, NiS, AgO, Al 2  O 3 , InO, In 2  O 3 , CsMnO 4 , CsFe(SO 4 ) 2  and the like. Illustrative of mixed metal salts are CoWO 4 , Tl 2  O.CoMO 4 , CoMO 4 , Al 2  (CrO 4 ) 3 , NiGa 2  O 4 , FeTlO 4 , NiMO 4  and the like. 
     Especially preferred catalysts are inorganic compounds containing oxides of a Group IIIA or VIIB metal together with a non-noble metal of Group VIII, (such as CoMoO 4 , NiWO 4 , FeCrO 3 , CoAl 2  O 3 , NiTlO 4  and the like) most preferably also containing a promoter of Group IA or IIA (such as BaO.CoMoO 4 , SrO.NiWO 4 , CsO.CoMoO 4 , SrO.-FeCrO 4  and the like). 
     The above catalysts can be pre-treated, if desired, to incorporate the S, Se or Te in the catalyst by contacting the catalyst with a member of the group consisting of hydrogen sulfide, hydrogen selenide and hydrogen telluride, preferably in gaseous form, at elevated temperature to form a catalyst which is chemically combined with the S, Se or Te. This pretreatment step can be performed at a wide variety of temperatures, and generally will be effected at a temperature of from about 150° to 600° C., preferably from about 200° to 400° C. Lower and higher temperatures can also be used. Pressures are not critical and will generally be up to about 1,000 psig or higher. The catalysts can be treated with the selected hydrogen compound for any convenient period, which will generally vary from about 10 to 600 minutes, preferably from about 30 to 180 minutes. 
     A wide variety of organic solvents can also be employed in the reaction zone. Suitable organic solvents include alkanes such as cyclohexane, hexane, octane and the like; aromatic solvents such as benzene, toluene, xylene; nitrile solvents such as acetonitrile and benzonitrile; amide type solvents such as N, N-dimethyl formamide and N, N-dimethyl acetamide; aliphatic, alicyclic or aromatic sulfoxide and sulfone solvents, such as dimethyl sulfoxide; aliphatic halogenated hydrocarbons such as 1, 1,2-trichloro-1, 2, 2-trifluoroethane; halogenated aromatic hydrocarbons such as monochlorobenzene, dichlorobenzene and trichlorobenzene; esters; and ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and the like. The ether compounds, for example can be aliphatic, aromatic or heterocyclic, and they can also be either mono or polyethers, or combinations of these compounds. When the hydroxy-containing organic compound is a liquid under reaction conditions, it sometimes can function as a solvent and is generally preferred. The solvent can also comprise an organic base such as tertiary amines, heterocyclic compounds, amidines, imines and mixtures thereof. Exemplary of suitable tertiary amines are those having the general formula LNL&#39;(L&#34;), wherein L, L&#39; and L&#34; are independently selected from the group consisting of alkyl of 1 to 20 carbon atoms, aryl of 6 to 18 carbon atoms, alkaryl and aralkyl of 7 to 20 carbon atoms and cycloalkyl of from 3 to 12 carbon atoms. Preferred are the tertiary amines wherein L, L&#39; and L&#34; are each alkyl of from 1 to 4 carbon atoms. Suitable illustrative tertiary amines are tri-n-propyl amine, tri-ethyl amine, dimethylethyl amine, dimethylpropyl amine, dimethylbenzyl amine, and the like. Suitable heterocyclic compounds include those containing at least one nitrogen atom in the cyclic moiety. Exemplary of such nitrogen-containing basically reacting compounds are pyridine, pyridazine, pyrimidine, pyrazine, piperazine, triazines, tetrazines, pyrrole, isopyrrole, pyrazole, imidazole, quinolines, and the like. Especially preferred nitrogen-containing compounds are pyridine and the dialkylamino pyridines. Suitable amidines are those having the formula A 1  A 2  C=NA 3  wherein A 1 , A 2  and A 3  are independently selected from the group consisting of hydrogen alkyl of 1 to 20 carbon atoms, aryl of 6 to 18 carbon atoms, aralkyl or alkaryl of 1 to 20 carbon atoms, cycloalkyl of 3 to 12 carbon atoms, alkenyl of 2 to 20 carbon atoms, alkynyl of 2 to 20 carbon atoms and heterocyclic groups (containing N-, S- or O- atoms) of 3 to 5 carbon atoms. Suitable amidines are those having the formula ##STR4## wherein A 4 , A 5  and A 6  are independently selected from the group consisting of hydrogen, alkyl 1 to 20 carbon atoms, aryl 6 to 18 carbon atoms, alkaryl or aralkyl 7 to 20 carbon atoms, alkenyl 2 to 20 carbon atoms, alkynyl 2 to 20 carbon atoms, cycloalkyl 3 to 12 carbon atoms, and heterocyclic 3 to 5 carbon atoms. 
     At higher temperatures and pressures the process of the invention can advantageously be carried out in an inert diluent. The preferred inert diluents are those in which the non-gaseous reactants are soluble, including some of the solvents mentioned about. Suitable inert diluents include aliphatic or aromatic hydrocarbons such as n-pentane or toluene, ethers, ketones and esters. 
     Water is detrimental to carbamate yields employing the process of this invention, and, therefore, it is preferred to employ substantially anhydrous reaction conditions and to employ as reactants those that are substantially anhydrous, although minor amounts of water introduced, for example, as water of hydration in any of the S, Se or Te sources or metal salts, can be introduced without marked effect on product yield or quality. In general, the amount of water in the reaction zone should be limited to a concentration of less than about 1 weight percent, based on the amine reactant charged to the reaction zone. To effect such desired low levels of water, a water absorbing agent can also be employed in the reaction zone. Suitable water absorbing agents are described in U.S. Pat. Nos. 3,384,655 and 3,629,311. However, use of such water absorbing agents will not generally be necessary since water is not a by-product of the reaction to the desired carbamate. As used herein, the term &#34;in the substantial absence of water&#34; is intended to refer to water concentrations of less than about 1 weight percent, based on the amine reactant charged to the reaction zone. 
     The invention is preferably carried out with at least equal molar amounts of the hydroxyl-containing compound, carbon monoxide and the amine reactant being present. Preferably, however, a molar excess of the hydroxy-containing compound is present. 
     The mole ratio of the S, Se or Te source to the amine reactant can vary over a wide range, e.g., from about 1:10 to 100:1. However, a somewhat more preferred range of moles of S, Se or Te source to amine is from about 1:1 to 10:1. It will be understood that with reference to the &#34;moles&#34; of S, Se or Te source it is meant the element selenium or sulfur and not the compound if the S, Se or Te source is a compound. Likewise with respect to the amine reactant, reference is to the active nitrogen containing group, e.g., the amine group. Thus if the amine reactant is diamino compound, for example, ethylenediamine, the number of moles would be one half, i.e., the equivalent ratio. 
     The catalysts of this invention will be generally used in an amount (calculated as the catalytically active metal) of at least about 1, and preferably at least about 10, weight percent of the amine reactant charged. While the catalyst can be used in larger concentrations, use of greater than about 50 weight percent will generally be uneconomical. Likewise, while less than 1 weight percent can be used, the reaction rate may be uneconomically low. 
     The monohydric hydroxyl-containing organic compounds will generally be used in at least an equimolar amount with the amine reactant, with the mole ratio of monohydric hydroxyl-compound to amine reactant preferably being from at least 2:1 to about 20:1, and most preferably from about 6:1 to 12:1. The amount of polyhydric alcohol which will be generally employed as the hydroxyl-containing organic compound can be determined from the foregoing mole ratios of monohydric alcohol to amine reactant and will, of course, be based on the number of reactive hydroxyl groups in each molecule of the alcohol, e.g., at least 0.5 mole of ethylene glycol will generally be used for each mole of amine reactant in the preparation of the corresponding N-phenyl carbamate derivative of ethylene glycol. 
     The amount of solvent is also not critical and, where used, will generally range from about 1 to 50 weight percent, and preferably from about 10 to 40 weight percent, of the reaction mixture. 
     The order of mixing the reactants is not critical and can be varied within the limitations of the equipment employed. A simple procedure is to charge the amine reactant, the organic compound containing at least one hydroxyl group, and the S, Se or Te source into the reaction vessel, introduce the proper amount of the source of carbon monoxide and then heat the mixture to obtain the desired reaction. A suitable pressure vessel, such as an autoclave, which is preferably provided with heating means and agitation means, such as a stirrer or an external rocking mechanism, is employed for the reaction. 
     Generally, the amount of gaseous carbon monoxide in the free space of the reactor is sufficient to maintain the desired pressure as well as to provide a reactant for the process. As the reaction progresses an additional source of carbon monoxide can be fed to the reactor either intermittently or continuously. Although greater and lesser amounts of the source of carbon monoxide can be employed if desired, generally the total amount of the source of carbon monoxide added during the reaction is between about 3 and about 50 moles and preferably between about 8 and about 15 moles of CO per non-cyclic group containing the active amine group of the amine reactant nitrogen atom. The highest carbon monoxide requirements are generally utilized in a process in which carbon monoxide gas is added continuously, but suitable recycle of carbon monoxide containing gas streams greatly reduces the overall consumption of carbon monoxide. 
     The reaction temperature is generally maintained in the range of from about 60° to about 250° and preferably from about 100° to 200° C., and more preferably from about 150° to 180° C. These temperature ranges permit a convenient rate of reaction to be achieved while avoiding undesirable side reactions. It will be understood, however, that any elevated temperatures below that at which the starting materials or the products decompose can be used. The reaction is carried out, as indicated above, at superatmospheric pressures which is normally between about 10 and about 500 atmospheres, although higher or lower reaction pressures can be employed if other reaction conditions are suitably adjusted. Preferably, however, only moderate carbon monoxide pressures in the range of about 10 to about 100 atmospheres are employed and the reaction is conveniently run at a temperature of below about 200° C. within this pressure range. 
     The process of the present invention can be carried out batchwise, semi-continuously or even continuously. The reaction time is dependent upon the nature of the reactants, temperature, pressure and the type of catalyst employed, as well as the type of equipment which is used. Normally the reaction time is less than 180 minutes and generally the effectiveness of the catalysts of this invention permits the reaction to be completed within a time period between about 10 minutes and about 75 minutes. 
     The process of this invention can be carried out in a vapor phase or a liquid phase, or partially in vapor and liquid phases in the reaction zone. 
     After the reaction has been completed in the batchwise practice of this invention, the temperature of the reaction mixture can be dropped to ambient temperature and the pressure vessel vented. The reaction product is then treated by conventional procedures, including filtration, distillation, or other suitable separation techniques, to effect separation of urethane from unreacted starting material, solvent, by-product, catalyst, etc. Urea by-products, if any, can be readily recovered and recycled to the reaction zone, if desired, to suppress formation of the urea by-product therein. 
     As indicated above, the amount of reaction by-products (e.g., formanilide and ureas when N-phenyl carbamates are the desired product) which are formed in the process of this invention is surprisingly low. While the amount of such N-containing by-products will vary, they will preferably be formed in a selectivity of less than 20 weight percent, more preferably less than 10 weight percent, and most preferably less than 5 weight percent, based on the amine reactant-reacted. 
     The process of this invention, therefore, preferably forms the desired carbamate product in a selectivity of at least 80 weight percent, more preferably at least 90 weight percent, and most preferably at least 95 weight percent, based on the amount of the amine reactant reacted. 
     The urethane products obtained by the invention contain one or more urethane groups and can be monomeric or polymeric in nature. Thus, the process of the invention can be adapted for the preparation of monourethanes from monoamine compounds and monohydroxy compounds and adopted from the preparation of polyurethanes from polyamine compounds and monofunctional hydroxy compounds. The resulting urethane products, in particular those urethanes containing not more than three urethane groups per molecule, can be converted to corresponding isocyanates by suitable means, including thermal and catalytic means. 
    
    
     The process of this invention can be further illustrated by the following examples wherein parts are by weight unless otherwise indicated. In the examples, analysis of gas and liquid samples is performed by gas chromotography, with toluene being used in the liquid samples as internal standard. 
     In the Examples, the CoMoO 4  on alumina catalyst are 1/8 in pellets comprising 3.5 weight percent CoO, 10.0 weight percent MoO 4  on gamma-alumina (Strem Chemical Co.) having a surface area of 244 sq. m. per gm. The BaO.CoMoO 4  on alumina catalyst is prepared by admixing 25 grams of the above CoMoO 4  on alumina pellets with 75 cc of an aqueous solution containing dissolved therein 2.5 grams of BaOH.8H 2  O. the mixture is then placed in a rotovap at 50° C. to remove the water, and the resulting solids are heated for four hours at a temperature of from about 350° to 400° C. in an oven, to form the BaO.CoMoO 4  on alumina. All other catalysts in the Examples are used in powder form, 60-80 mesh. 
     In Examples 1-22 and 24-25, and elsewhere as stated, the COS:H 2  S, COSe:H 2  Se and COTe:H 2  Te molar ratios (as appropriate) in the reaction zone are at least 2:1. 
     In the Examples, carbamates yields and selectivities are based on the amounts of the amine reactant charged and reacted, respectively. 
     EXAMPLE 1 
     To a 200 cc Parr reactor provided with a glass liner (actual reactor volume with liner=134 cc) and a magnetic stirrer is charged, at room temperature, 5.1 grams aniline, 30 cc methanol and 0.5 gram of BaMoO 4  as catalyst. The reactor is sealed and then purged with gaseous nitrogen by means of a gas inlet tube and, also at room temperature, gaseous COS (5 grams) is pressured into the reactor following which CO is pressured into the reactor, to provide a pressure in the reactor of about 800 psig. The molar ratio of S:aniline in this example is about 1.5:1. The pressured reactor is then heated with stirring by means of an oil bath to a temperature of 180° C., which is measured externally to the reactor. This reaction temperature is maintained for five hours after which the oil bath is cooled to about 30° C. by passing cooling water through a copper tube which is immersed in the bath. The gas in the reactor is then vented and the vent gas and the liquid product mixture in the reactor are analyzed. Methyl N-phenyl carbamate is found to be present in a yield of about 34.5 weight percent, based on the aniline charged, and to have been formed in a selectivity of about 100 percent, based on aniline reacted. 
     EXAMPLE 2 
     Following the procedure of Example 1, 3.06 grams of aniline, 20 cc of methanol and 5 grams of COS are charged in separate runs with the desired catalyst to the reactor, thereby employing a sulfur to aniline molar ratio of about 2.5:1. The reaction is effected at a temperature of 180° C. for six hours, employing a CO pressure of 750 psig. Analysis of the effluent gas and liquid product mixture following the reaction period yields the data set forth in Table I below: 
     
                       TABLE I                                                     
______________________________________                                    
                             MPC*    MPC*                                 
Run                          %       %                                    
No.    Catalyst      (q)     Yield   Selectivity                          
______________________________________                                    
1      BaO . CoMoO.sub.4                                                  
                     1.0     50.1    --                                   
       on alumina.                                                        
2      BaAl.sub.2 O.sub.4                                                 
                     0.5     48.1    &gt;95                                  
3      CoMoO.sub.4   0.5     38.3    &gt;95                                  
       on alumina.                                                        
______________________________________                                    
 *&#34;MPC&#34; = methylN-phenyl carbamate.                                       
 
    
     EXAMPLE 3 FOR COMPARISON 
     The procedure of Example 2 is repeated except that catalyst is omitted from the reaction zone. After six hours of reaction at 180° C., the reactor effluent (i.e., both the vent, gas and liquid phases) is found to contain methyl N-phenyl carbamate in a yield of only 8.1 percent and a selectivity of only 18 percent. 
     EXAMPLE 4 
     Following the procedure of Example 1, 3.06 grams of aniline, 25 cc of methanol nad 5 grams of COS, providing a sulfur to aniline molar ratio of 2.5:1, is charged to the reactor. After six hours of reaction at 180° C. in separate runs with 0.5 gram of the indicated catalyst and employing a CO pressure of 750 psig, the effluent from each run is analyzed and the data thereby obtained are set forth in Table II below: 
     
                       TABLE II                                                    
______________________________________                                    
                    MPC         MPC                                       
Run                 %           %                                         
No.     Catalyst    Yield       Selectivity                               
______________________________________                                    
1       SrMoO.sub.4 44.7        84                                        
2       V.sub.2 S.sub.3                                                   
                    34.0        86                                        
3       TiS.sub.2   34.2        94                                        
4       Ti.sub.2 S.sub.3                                                  
                    43.5        93                                        
5       CuS         18.0        61                                        
6       MoS.sub.2   23.6        77                                        
7       WS.sub.2    18.0        64                                        
8       CrS         22.1        70                                        
______________________________________                                    
 
    
     EXAMPLE 5 
     Following the procedure of Example 1, 3.06 grams of aniline, 20 cc of methanol and a desired amount of the selected catalyst, together with two grams of powdered elemental sulfur is charged to the reactor, thereby providing a sulfur to aniline molar ratio of about 1.9:1. The reactor is sealed and purged with gaseous nitrogen and gaseous CO is then pressured into the reactor to provide an internal pressure of 1000 psig. The mixture is then allowed to react at a temperature of 180° C. for a period of six hours. The data thereby obtained in each run are set forth below in Table III. 
     
                       TABLE III                                                   
______________________________________                                    
                      MPC        MPC                                      
Run                   %          %                                        
No.     Catalyst (g)  Yield      Selectivity                              
______________________________________                                    
1       BaMoO.sub.4 0.5                                                   
                      43.9       96                                       
2       CoMoO.sub.4 0.75                                                  
                      22.5       46                                       
3       SrMoO.sub.4 0.84                                                  
                      48.3       100                                      
______________________________________                                    
 
    
     EXAMPLE 6 FOR COMPARISON 
     The procedure of Example 5 is repeated except that catalyst is omitted in the reaction zone. After six hours of reaction at 180° C., analysis of the effluent from the reactor shows methyl N-phenyl carbamate to have been formed in a yield of only about six percent, at a selectivity of only about 19 percent. 
     EXAMPLE 7 
     Following the procedure of Example 5, 1.02 gram of aniline, 20 cc of methanol, 0.5 gram of BaAl 2  O 4  as catalyst and 0.5 gram of powdered elemental sulfur, are charged to the reactor, to provide a sulfur to aniline molar ratio of about 1.4:1. Employing a CO pressure of 1000 psig, the mixture is allowed to react at 180° C. for six hours. Analysis of the reactor effluent shows methyl N-phenyl carbamate to be present in a yield of about 23.8 percent and to have been formed in a selectivity of greater than about 50 percent. 
     EXAMPLE 8 
     Following the procedure of Example 1, 3.06 grams of aniline, 16 cc of methanol, 10 cc dioxane and 2.0 gram of powdered elemental sulfur, together with 0.84 gram of SrMoO 4  as catalyst, are charged to the reactor, thereby providing a sulfur to aniline molar ratio of about 1.9:1. Using a CO pressure of 1000 psig, the mixture is allowed to react for six hours at 180° C. Analysis of the effluent from the reactor shows methyl N-phenyl carbamate to be present in a yield of about 35.8 percent and to have been formed in a selectivity of about 95 percent. 
     EXAMPLE 9 
     In separate runs, the procedure of Example 1 is repeated employing the desired amount of BaMoO 4  as catalyst, together with 3.06 grams of aniline, 16 cc of methanol, 10 cc of dioxane and 12 grams of COS, thereby providing a charge to the reactor containing a sulfur to aniline molar ratio of about 6.1:1. A CO pressure of about 250 psig, the mixture is allowed to react at 180° C. for a period of 19 hours. The effluent from each run is analyzed and the data thereby obtained are set forth below in Table IV. 
     
                       TABLE IV                                                    
______________________________________                                    
                      MPC        MPC                                      
Run                   %          %                                        
No.     Catalyst (q)  Yield      Selectivity                              
______________________________________                                    
1       BaMoO.sub.4 0.5                                                   
                      44.0       100                                      
2       BaMoO.sub.4 0.25                                                  
                      34.0        93                                      
______________________________________                                    
 
    
     EXAMPLE 10 
     The procedure of Example 1 is repeated except that a mixture charged to the reaction zone additionally contains 2 cc of pyridine. After reaction of the mixture at a CO pressure of 750 psig and a temperature of 180° C. for a period of five hours, the reaction effluent is found to contain methyl N-phenyl carbamate in a yield of about 43.0 percent and in a selectivity of about 80 percent. 
     EXAMPLE 11 
     In a series of runs the procedure of Example 1 is repeated employing a charge to the reactor comprising 3.06 grams of aniline, 16 cc of methanol and 0.5 gram of the indicated catalyst together with the indicated amounts of either COS or powdered elemental sulfur as a sulfur source. Employing a reaction temperature of 180° C., a mixture in each run is allowed to react for the indicated period of time under the desired CO pressure. The data thereby obtained are set forth below in Table V. 
     
                                           TABLE V                                 
__________________________________________________________________________
                Sulfur                                                    
                     S/N Reaction MPC MPC                                 
Run        Pyridine                                                       
                Source                                                    
                     Mole                                                 
                         Time CO  %   %                                   
No.                                                                       
   Catalyst                                                               
           (cc) q    Ratio                                                
                         (Hrs)                                            
                              (psig)                                      
                                  Yield                                   
                                      Selectivity                         
__________________________________________________________________________
1  BaMoO.sub.4                                                            
           5    COS,2.5                                                   
                      1.25                                                
                         18   500 55.4                                    
                                      74                                  
2  BaMoO.sub.4                                                            
           5    COS,5.0                                                   
                     2.5 5.5  500 61.1                                    
                                      98                                  
3  CoWO.sub.4                                                             
           10   COS,5.0                                                   
                     2.5 18   500 58.4                                    
                                      90                                  
4  BaO . CoMO.sub.4                                                       
           10   COS,5.0                                                   
                     2.5 18   500 61.6                                    
                                      87                                  
   on alumina                                                             
5  BaMoO.sub.4                                                            
           5    S,2.0                                                     
                     1.9 18    1000                                       
                                  53.3                                    
                                      96                                  
6  TiS.sub.2                                                              
           5    COS,5.0                                                   
                     2.5 6    750 36.6                                    
                                      57                                  
7  Ti.sub.2 S.sub.3                                                       
           5    COS,5.0                                                   
                     2.5 6    750 50.4                                    
                                      93                                  
__________________________________________________________________________
 
    
     EXAMPLE 12 
     Following the procedure of Example 1, there is charged to the reactor 3.06 grams of aniline, 10 cc of pyridine, 16 cc of ethanol and 2.5 grams of COS, thereby employing a sulfur to aniline molar ratio of about 1.25:1. At a CO pressure of 500 psig, the mixture is allowed to react at 180° C. for three hours in the presence of 0.5 gram of BaMoO 4  as catalyst. Analysis of the reaction effluent shows ethyl N-phenyl carbamate to be formed in a yield of about 37 percent and in a selectivity of about 100 percent. 
     EXAMPLE 13 
     Following the procedure of Example 1, separate runs are made employing a charge to the reactor of 3.06 grams of aniline, 5.0 grams of COS and 0.5 gram of BaMoO 4  as catalyst, together with 20 cc of the selected alcohol and the desired amount of pyridine. Thus, a sulfur to aniline molar ratio of 2.5:1 is used in each run. Employing a CO pressure of 750 psig, the reaction is performed at a temperature of 180° C. for 36 hours, after which the effluent of each is analyzed, thereby yielding the data set forth in Table VII below. 
     
                       TABLE VII                                                   
______________________________________                                    
                                Carbamate                                 
Run     Pyridine                %                                         
No.     (cc)        Alcohol     Yield                                     
______________________________________                                    
1       10          DMAE*       50                                        
2       --          DMAE*       50                                        
3       --          Methyl**    50                                        
                    cellosolv                                             
______________________________________                                    
 ##STR5##                                                                 
 ##STR6##                                                                 
 
    
     EXAMPLE 14 
     The procedure of Example 4 is repeated in separate runs employing the catalysts indicated in Table VIII. Analysis of the effluent from each run yields the data set forth in Table VIII: 
     
                       TABLE VIII                                                  
______________________________________                                    
                      MPC         MPC                                     
Run                   %           %                                       
No.      Catalyst     Yield       Selectivity                             
______________________________________                                    
1        MnS          25          75                                      
2        ReS.sub.2    25          75                                      
3        PtO          30          80                                      
4        NiWO.sub.4   30          80                                      
5        FeCrO.sub.4  30          80                                      
6        Tl.sub.2 SiO.sub.3                                               
                      35          80                                      
7        Tl.sub.2 SO.sub. 4                                               
                      35          80                                      
______________________________________                                    
 
    
     EXAMPLE 15 
     The procedure of Example 5 is repeated except that 4.9 grams of powdered elemental selenium are employed instead of the elemental sulfur, thereby providing a selenium to aniline molar ratio of about 1.9:1. Essentially no difference in results over those achieved in Example 5 is noted. 
     EXAMPLE 16 
     The procedure of Example 5 is repeated except that 8.0 grams of powdered elemental tellurium are used instead of the elemental sulfur, to provide a tellurium to aniline molar ratio of about 1.9:1. Essentially no difference in results is noted. 
     EXAMPLE 17 
     The procedure of Example 5 is repeated except that 3.5 grams ortho-toluidine are used instead of aniline, and essentially no difference in results is noted in the formation of methyl-N-ortho-tolyl carbamate. 
     EXAMPLE 18 
     The procedure of Example 5 is repeated except that 2.4 grams of N-butylamine are used instead of aniline, and essentially no difference in results is noted in the formation of methyl-N-butylcarbamate. 
     EXAMPLE 19 
     The procedure of Example 5 is repeated except that 3.3 grams of cyclohexylamine are used instead of aniline, and essentially no difference in results is noted in the formation of methyl-N-cyclo hexyl carbamate. 
     EXAMPLE 20 
     The procedure of Example 13 is repeated except that the alcohol reactant comprises, in separate runs, cyclohexanol, benzyl alcohol and butyl alcohol, respectively, and essentially no difference is noted in the formation of cyclohexyl-N-phenyl carbamate, benzyl-N-phenyl carbamate and butyl-N-phenyl carbamate, respectively. 
     EXAMPLE 21 
     The procedure of Example 5 is repeated except that 2.1 grams of 2,4-toluene diamine are employed instead of aniline. SrMoO 4  (0.84 gram) is employed as the catalyst. After six hours of reaction at 180° C. the total conversion of NH 2  groups to the carbamate form is found to be 45%, at a selectivity to the monocarbamate ##STR7## of about 30% and at a selectivity to the bis-carbamate form ##STR8## of about 10%. 
     EXAMPLE 22 
     The procedure of Example 21 is repeated except that 3.3 grams of 4,4&#39;-methylene dianiline is used instead of toluene diamine, and essentially no difference is noted in the formation of the mono- and bis-methyl carbamate derived from the 4,4&#39;-methylene dianiline, e.g., ##STR9## 
     EXAMPLE 23 
     Following the procedure of Example 1, 3.06 grams of aniline, 20 cc of methanol and 0.5 gram of BaO.CoMoO 4  as catalyst, together with 1,000 psi CO and 200 psi H 2  S are charged to the reactor. Analysis of the materials in the reactor shows a COS:H 2  S mole ratio of 0.67:1. The mixture is then allowed to react to a temperature of about 180° C. for a period of 18 hours, thereby forming methyl-N-phenyl carbamate in a 10% yield. 
     The above procedure is repeated except that sufficient additional COS is pressured into the reactor to provide a COS:H 2  O molar ratio of 1.9:1. After the 18 hours of reaction time, the methyl-N-phenyl carbamate yield was increased to 20%. 
     In a third run, additional COS is pressured into the reactor to raise the COS:H 2  O molar ratio to 2.5:1. Analysis of the effluent following the 18 hours of reaction time shows methyl and phenyl carbamate to be formed in a yield of about 42% and in a selectivity of about 90%. 
     EXAMPLE 24 
     Following the procedure of Example 1, 3.06 grams of aniline, 15 cc of methanol, 1 gram of powdered elemental sulfur and 5 cc pyridine, together with 0.5 gram BaMoO 4 , are charged to the reactor, thereby providing a sulfur to aniline molar ratio of about 1:1. Using a CO pressure of 1,000 psig, and a reaction time of 5 hours at 160° C., the reaction effluent, upon analysis, is found to contain methyl-N-phenyl carbamate in a yield of about 31% and to have been formed in a selectivity of about 87%. 
     EXAMPLE 25 FOR COMPARISON 
     The procedure of Example 24 is repeated except that the BaMoO 4  catalyst is omitted from the reaction zone. After 5 hours of reaction at 160° C., the reaction effluent is found to contain methyl-N-phenyl carbamate in a yield of about 18% and to have been formed in a selectivity of about 52%. This indicates the large increase in yield and selectivities attributable to the inorganic catalysts of this invention. 
     EXAMPLE26 
     Following the procedure of Example 1, 1.02 grams of aniline, 10 cc of phenol and 1 gram of powdered elemental sulfur, together with about 0.5 gram of BaO.CoMoO 4  catalyst, are charged to the reactor, thereby providing a sulfur to aniline molar ratio of about 2.85:1. Using a CO pressure of 850 psig, and a reaction time of 6 hours at 150° C., the reaction effluent, upon analysis, is found to contain phenyl-N-phenyl carbamate in a yield of about 5%. 
     EXAMPLE 27 
     The procedure of Example 26 is repeated except that 10 cc of 2, 2, 2-trifluroethanol are used instead of the phenol. After the 6 hours of reaction time the reaction effluent is found to contain 2, 2, 2-trifluoroethyl-N-phenyl carbamate in a yield of about 5%. 
     It will be obvious that various changes and modifications can be made without departing from the invention, and it is intended, therefore, that all matter contained in the foregoing description shall be interpreted as illustrative only and not as limitative of the invention.