Journal of Catalysis 184, 526–534 (1999) A rticle ID jcat.1999.2458, available online at http://www.idealibrary.com on Oxidative Carbonylation of Aromatic Amines by Selenium Compounds H oon Sik Kim,∗ ,1 Yong Jin Kim,∗ H yunjoo Lee,∗ Sang D euk Lee,∗ and Chong Shik Chin† ∗ CFC A lternatives R esearch Center, Korea Institute of Science and Technology, P.O. B ox 131, Cheongrayng, Seoul 130-650, Korea; and †D epartm ent of Chem istry, Sogang University, Seoul 121-742, Korea E -mail: khs@kist.re.kr R eceived November 30, 1998; revised February 8, 1999; accepted February 14, 1999 Various factors affecting the oxidative carbonylation of aromatic amines were investigated in the presence of a catalyst system comprising SeO2 and alkali metal carbonate. An active catalyst, K2SeO3 was obtained from the reaction of SeO2 and K2CO3 in methanol and the activity was tested. The effects of added alkali metal salts, solvents, aromatic amine substrates, molar ratio of aniline to catalyst, temperature, and pressure on the catalytic activity were studied. The activation energy of the carbonylation of aniline was evaluated as 17.0 kcal/mol. The highest turnover frequency was found to be 2082/h at aniline/catalyst = 12,800. A plausible mechanism for the carbonylation of aniline to diphenyl urea and phenyl carbamate has c 1999 Academic Press also been proposed. ° 1 2R NH 2 + CO + O 2 → R NH C(== O )NH R + H 2 O , 2 [1] R NH C(== O )NH R + R ′ O H → R NH 2 + R NH C(== O )O R ′ , [2] 1 R NH 2 + CO + O 2 + R ′ O H → R NH C(== O )O R ′ + H 2 O , 2 [3] 1. INTRODUCTION Carbamates are important materials as precursors for preparing isocyanates since they produce isocyanates and alcohols in good yields by thermal cracking (1, 2). Carbamates are commercially manufactured by reacting phosgene with the corresponding primary amine (3). U nfortunately, this conventional process possesses several disadvantages such as the use of highly toxic phosgene, the formation of large quantities of corrosive hydrogen chloride as a secondary product, and, furthermore, the presence of difficult-to-remove hydrolyzable chlorine compounds. A ccordingly, there have been numerous attempts to produce carbamates by using non-phosgene methods (4–10). O ne of the approaches is the catalytic oxidative carbonylation of an amine with carbon monoxide and oxygen in the presence of an alcohol and an appropriate catalyst. A number of effective catalyst systems have been reported for preparing carbamates via oxidative carbonylation of amines (11–13). G roup 8–10 transition metals and copper are commonly used catalysts for this purpose (14–16). Selenium and selenium compounds have also been demonstrated as catalysts in the carbonylation of aliphatic and alicyclic amines, but the catalysts show extremely low activity toward the carbonylation of aromatic amines (17–18). 1 In the previous communication, we reported that a catalyst comprising SeO 2 and alkali metal carbonate was highly effective for the oxidative carbonylation of aniline to produce phenyl carbamate and diphenyl urea as illustrated in E qs. [1–3] (19). (R = phenyl, R ′ = C 1–C 4). The synthesis of substituted ureas has also been extensively studied due to their importance in the chemical industry as precursors of carbamates, pigments, and resins, and the non-phosgene methods for converting substituted ureas to the corresponding carbamates are well established in the literature (20–23). In this paper, various aspects of the oxidative carbonylations of aromatic amines are investigated by using a new catalyst system comprising SeO 2 and alkali metal carbonate, and a plausible mechanism is presented. To whom correspondence should be addressed. 526 0021-9517/99 $30.00 c 1999 by A cademic Press Copyright ° A ll rights of reproduction in any form reserved. 2. EXPERIMENTALS 2.1. Chem icals A mines, selenium metal, selenium dioxide, and alkali metal carbonates were purchased from A ldrich Chemical Co. and used without further purification. Solvents were all reagent grade and distilled from appropriate drying agents under a nitrogen atmosphere prior to use. O ver 99% purity of carbon monoxide and oxygen were obtained from Samsung Fine Chemical Co. and D aesung O xygen Co., respectively. 527 CA R BO NYLATIO N O F A NILINE 2.2. Instrum entation G as chromatographic analyses were made for both gas and liquid samples. G as samples were analyzed using a G ow-Mac gas chromatography equipped with a thermal conductivity detector and a Carbosphere column (6 ft). Liquid samples were analyzed using a Young-In 680D gas chromatography equipped with a flame ionization detector and a H P-1 capillary column (0.32 µm × 50 m). Mass spectral analyses were carried out employing a H P 5890A G C/H P 5917A MS detector. U rea analysis was carried out on a Waters H PLC using 4.6 × 150 mm H yersil O D S column and U V detector (254 nm). Shimadzu (XR D 6000) diffractometer with a nickel-filtered Cu K α excitation source was employed to obtain XR D patterns for all the catalyst samples. The X-ray source was operated at 30 kV and 40 mA with scanning rate 2◦ /min. Compound identification was accomplished by the comparison of measured spectra of the samples with those of reference samples or JCPD S powder diffraction file data. 2.3. Carbonylation R eaction A ll carbonylation reactions were conducted in a Parr 100 or 300 ml stainless steel bomb with a magnetic drive stirrer and an electrical heater. R eactions were carried out at 1000 rpm stirring rates to minimize mass transfer of O 2/CO mixture gas as a limitation to the reaction rates. Toluene was used as an internal standard due to the presence of high boiling insoluble materials in the reaction mixture, such as urea. The reactor was purged with nitrogen followed with O 2/CO mixture gas and then pressurized to about 4.08 MPa with O 2/CO mixture (molar ratio of O 2/CO = 20/80). The bomb was then heated with agitation to a specified reaction temperature with the addition of O 2/CO mixture gas from a reservoir tank (ballast tank) to maintain a specified pressure. The drop in pressure in the ballast tank was recorded by means of a pressure transducer and a recorder, which provides a convenient method for observing the progress of the reaction. A fter the reaction, the bomb was cooled to room temperature. Product mixtures were analyzed by G C, H PLC, and G C–MS. Solid catalyst mixtures were characterized by XR D. 2.4. A lcoholysis of N,N ′-D iphenyl Urea 2.4.1. Under N 2 atm osphere. A 100 ml stainless Parr reactor was charged with 20 mmol diphenyl urea, 25 ml methanol, 1 g toluene as an internal standard, and catalyst (SeO 2/K 2CO 3). The reactor was purged with nitrogen and then heated to 130 or 170◦ C with agitation. A fter 2 h of reaction, the bomb was cooled to room temperature and the product mixture was analyzed by G C and H PLC. 2.4.2. Under (O 2/CO ) pressure. A 100 ml stainless Parr reactor was charged with 20 mmol diphenyl urea, 25 ml methanol, 1 g toluene as an internal standard, and catalyst (SeO 2/K 2CO 3). The reactor was purged with nitrogen and then with O 2/CO mixture gas and was then pressurized to about 4.08 MPa with O 2/CO mixture (molar ratio of O 2/CO = 20/80). The bomb was then heated with agitation to a specified reaction temperature (130 or 170◦ C) with the addition of O 2/CO mixture gas from a reservoir tank. A fter the reaction, the bomb was cooled to room temperature and vented, and the product mixture was removed for analysis. 2.5. Synthesis of K 2SeO 3. In a 100 ml 3-neck flask, K 2CO 3 (40 mmol) was reacted with SeO 2 (40 mmol) dissolved in 25 ml methanol at room temperature for 1 h. A s soon as the K 2CO 3 was added to the methanolic solution of SeO 2, CO 2 started to evolve. R emoval of the solvent in vacuum gave a white solid. The white compound was characterized as K 2SeO 3 by elemental analysis [found, Se (38.1% ), K (37.8% ); calculated, Se (38.5% ), K (38.5% )] and XR D results after several recrystallizations from diethyl ether/methanol solvent (yield: 87% ). 3. RESULTS AND DISCUSSION SeO 2-catalyzed oxidative carbonylations of aromatic amines were performed in various solvents in the presence of an alkali metal carbonate promoter. The effects of promoter, substrate, temperature, and pressure of O 2/CO on the carbonylation of aniline were evaluated. In order to ensure that the catalyst retains its original activity, several experiments on the reusability of the catalyst were carried out. A plausible reaction mechanism of the oxidative carbonylation of aniline catalyzed by K 2SeO 3 was also proposed. 3.1. E ffect of A dded A lk ali M etal Salt SeO 2-catalyzed oxidative carbonylation of aniline was carried out in the presence of various alkali metal salts. The reactions were performed in methanol at 130◦ C and 6.80 MPa (O 2/CO = 20/80) and the results are listed in Table 1. The addition of alkali metal halide, nitrite, nitrate, or sulfate was found to be ineffective for the carbonylation of aniline. U nlike other alkali metal salts, the presence of the alkali metal carbonate enabled the carbonylation of aniline to proceed very rapidly. A mong the alkali metal carbonate, the activity was found in the order SeO 2/Cs2CO 3 ∼ = SeO 2/R b 2CO 3 > SeO 2/K 2CO 3 > SeO 2/ Na 2CO 3 > SeO 2/Li2CO 3, suggesting that the solubility and basicity of alkali metal carbonate might play an important role (19). It is interesting to note that only alkali metal carbonate is the active promoter among the alkali metal salt tested. It is presumed that the reaction of SeO 2 with alkali metal salts such as halide, nitrite, nitrate, and sulfate may not produce active alkali metal containing selenium 528 KIM E T A L. TABLE 1 Effect of Alkali Metal Salts on the Oxidative Carbonylation of Anilinea Selectivity (% ) Catalyst A lkali metal salts Conversion (% ) SeO 2 SeO 2 SeO 2 SeO 2 SeO 2 SeO 2 SeO 2 K 2Se 2O 5 K 2SeO 3 SeO 2 SeO 2 None KBr KI KNO 3 KNO 2 K 2SO 4 K 2CO 3 None None K 2CO 3/KI d K 2CO 3/K 2SO 4e N.R . N.R . N.R . N.R . N.R . N.R . 97.5 95.4 95.0 67.1 63.4 Carbamate b U rea c lation of aniline, implying that both K 2SeO 3 and K 2Se 2O 5 may act as active species. The role of alkali metal carbonate and the reason for the activity of alkali metal containing selenium compound in the oxidative carbonylation of aromatic amine is described in the previous communication (19). 3.3. E ffect of Solvent 49.2 27.2 30.5 9.5 8.4 50.3 72.0 68.8 80.4 78.6 a Conditions: aniline 40 mmol, SeO 2 0.2 mmol, K 2CO 3 1 mmol, methanol 25 ml, toluene 1 g (internal standard), temperature 130◦ C, pressure 6.80 MPa (O 2/CO = 20/80), reaction time 2 h. b Carbamate: methyl-N -phenyl carbamate. c U rea: N ,N ′-diphenyl urea. d KI 0.2 mmol. e K 2SO 4 0.2 mmol. compound. A nother possibility is that halide, nitrite, nitrate, or sulfate anion left in the catalyst or reaction mixture may act as a detrimental poison. In fact, the activity of a catalyst composed of SeO 2 and K 2CO 3 was decreased significantly by the addition of K 2SO 4 or KI. Table 2 shows the effect of solvent on the conversion of aniline. In nonpolar solvents like n-hexane, benzene, and toluene, aniline was not carbonylated at all in the presence of a catalyst consisting of SeO 2 and K 2CO 3 (K 2CO 3/SeO 2 = 5), while in polar solvents like methanol, ethanol, isopropyl alcohol, n-propanol, sec-butyl alcohol, TH F, and D MF, high conversion of aniline was obtained. It is surprising to note that K 2Se 2O 5 and K 2SeO 3, ionic products obtained from the reactions of SeO 2 and K 2CO 3 in methanol, were able to carbonylate aniline even in nonpolar solvents such as n-hexane, benzene, and toluene. These results strongly indicate that the active species are ionic and the formation of such ionic active species is favored in polar solvent. Surprisingly, unlike in other C 1–C 4 alcohol, the catalyst comprising SeO 2 and K 2CO 3 showed very little activity in tert-butyl alcohol solvent, and it is believed that the steric hindrance of tert-butyl alcohol prohibits the formation of active species such as K 2Se 2O 5 and K 2SeO 3. This is supported by the experimental result that the reaction by K 2Se 2O 5 and K 2SeO 3 3.2. A lk ali M etal Containing Selenium Com pounds We reported that the reaction of K 2CO 3 with 2 equiv of SeO 2 in methanol produced KSeO 2(O CH 3) and K 2Se 2O 5 (19). K 2SeO 3 was similarly prepared by the 1 : 1 reaction of K 2CO 3 with SeO 2 in methanol and the compound was characterized by XR D and elemental analysis. A s shown in Fig. 1, the XR D pattern is in good agreement with that of K 2SeO 3 in the JCPD S H andbook. SeO 2 reacts with methanol to give (CH 3O )Se( == O )(O H ) and (CH 3O ) 2Se(O H ) 2 (19), and the subsequent reaction of K 2CO 3 with equivalent of (CH 3O ) 2Se(O H ) 2 would produce K 2SeO 3 as in E qs. [4–7]: SeO 2 + CH 3 O H → (CH 3 O )Se(== O )(O H ), [4] (CH 3 O )Se(== O )(O H ) + CH 3 O H → (CH 3 O )2 Se(O H )2 , [5] (CH 3 O )2 Se(O H )2 + K 2 CO 3 → (CH 3 O )2 Se(O K)2 + H 2 O + CO 2 , [6] (CH 3 O )2 Se(O K)2 → K 2 SeO 3 + (CH 3 )2 O . [7] Like K 2Se 2O 5, K 2SeO 3 also showed the similar activity to the catalyst composed of SeO 2 and K 2CO 3 in the carbony- FIG. 1. XR D patterns of A –D. 529 CA R BO NYLATIO N O F A NILINE TABLE 2 Effect of Solvents on the Oxidative Carbonylation of Aniline a Selectivity (% ) Catalyst Solvent SeO 2/K 2CO 3 SeO 2/K 2CO 3 SeO 2/K 2CO 3 SeO 2/K 2CO 3 SeO 2/K 2CO 3 SeO 2/K 2CO 3 SeO 2/K 2CO 3 SeO 2/K 2CO 3 SeO 2/K 2CO 3 SeO 2/K 2CO 3 SeO 2/K 2CO 3 K 2SeO 3 K 2SeO 3 K 2SeO 3 Methanol E thanol n-Propanol Isopropyl alcohol sec-Butyl alcohol TH F D MF tert-Butyl alcohol n-H exane Benzene Toluene tert-Butyl alcohol Toluene Benzene Conversion (% ) Carbamate b U rea c 97.5 95.7 94.6 92.8 91.4 96.7 95.4 1.1 N.R . N.R . N.R . 97.8 80.4 85.6 49.2 35.2 15.3 9.1 2.1 — — tr. 50.3 63.4 83.7 89.7 96.8 98.8 98.6 — 0.9 — — 98.1 98.6 98.5 a Conditions: aniline 40 mmol, SeO 2 0.2 mmol, K 2CO 3 1 mmol, solvent 25 ml, toluene 1 g (internal standard), temperature 130◦ C, pressure 6.80 MPa (O 2/CO = 20/80), reaction time 2 h. b Carbamate: methyl-N -phenyl carbamate. c U rea: N ,N ′-diphenyl urea. in tert-butyl alcohol proceeded as fast as in other C 1–C 4 alcohols. In separate experiments, the reaction of SeO 2 with K 2CO 3 in TH F and D MF at room temperature also produced K-containing selenium compounds by elemental and XR D analyses, but the full characterization of these compounds was not successful. Like K 2Se 2O 5 and K 2SeO 3, these unidentified compounds also show high catalytic activity for the carbonylation of aniline in nonpolar solvents, again supporting the assumption that the nature of active species is ionic and such ionic active species are favorably formed in polar solvents. toward the reductive and oxidative carbonylations of nitrobenzene that were carried out in methanol at 130◦ C for 2 h. The carbonylation of aromatic diamine such as 2,4diaminotoluene and 4,4′-methylenedianiline is important in the chemical industry because the resulting carbonylated products, diurea and/or dicarbamate, can be directly used as intermediates of TD I (toluene diisocyanate) and MD I (methylenediphenyl diisocyanate). 3.5. E ffect of M olar R atio of A niline/SeO 2 The effect of molar ratio of aniline/SeO 2 on the carbonylation of aniline was studied in the presence of SeO 2/K 2CO 3 at 130◦ C (K 2CO 3/SeO 2 = 5) and 6.80 MPa (O 2/CO = 20/80). The molar ratio of aniline to SeO 2 was varied in the range 50–25,600, and the results are shown in Fig. 2. The conversion of aniline remained almost constant at around 95% in the molar ratio range between 50 and 1600, and thereafter sharp decrease in conversion was observed. The selectivity of carbamate decreased as the molar ratio increased, whereas the selectivity of diphenyl urea increased with the increasing molar ratio. The maximum turnover frequency was found to be 2082/h at molar ratio of 12,800, indicating that our catalyst system comprising SeO 2 and K 2CO 3 is as active as Pd system reported by Fukuoka et al. (14). 3.6. E ffect of Tem perature and Pressure Figures 3 and 4 show the effects of temperature and pressure on the oxidative carbonylation of aniline to give phenyl carbamate and diphenyl urea in the temperature range 90–170◦ C at various pressure of O 2/CO (molar ratio of O 2/CO = 20/80) ranging from 2.04 to 6.80 MPa. A plot of TABLE 3 Oxidative Carbonylation of Various Aromatic Aminesa 3.4. E ffect of Substrate SeO 2-catalyzed oxidative carbonylations of aniline and substituted anilines were performed in methanol at 130◦ C in the presence of a promoter, K 2CO 3. A s shown in Table 3, aniline, o-toluidine, dimethyl anilines, 2,4,6-trimethylaniline, 2,4-diaminotoluene, and 4,4′-methylenedianiline were carbonylated to give high yields of corresponding carbamates and/or ureas while p-nitroaniline was not carbonylated at all under the same experimental condition. R elatively higher yield of carbamate was obtained in the carbonylation of aniline, but ureas were predominantly formed in the case of substituted aniline, possibly due to the electronic effect of substituents. It is not clear at the moment why the carbonylation of p-nitroaniline did not take place. H owever, it is likely that nitro group in p-nitroaniline played a certain role in quenching the catalytic activity of SeO 2/K 2CO 3. E xperimental results also show that the catalyst comprising SeO 2 and K 2CO 3 catalyst was inactive Selectivity (% ) A mine Conversion (% ) Carbamate b U rea c A niline o-Toluidine 4,4′-Methylenedianiline 2,4-D iaminotoluene 2,4-D imethylaniline 2,6-D imethylaniline 2,4,6-Trimethylaniline p-Nitroaniline p-Nitroaniline d Nitrobenzene Nitrobenzene d 97.5 96.4 95.2 94.1 98.9 99.1 97.6 N.R . N.R . N.R . N.R . 49.2 23.4 0.5 0.4 tr. tr. tr. 50.3 75.3 98.1 98.7 98.6 98.1 99.1 a Conditions: substrate 40 mmol, SeO 2 0.2 mmol, K 2CO 3 1 mmol, methanol 25 ml, toluene 1 g (internal standard), temperature 130◦ C, pressure 6.80 MPa (O 2/CO = 20/80), reaction time 2 h. b Carbamate: methyl-N -phenyl carbamate. c U rea: N ,N ′-diphenyl urea. d R eactions carried out in the absence of O 2, pressure 6.80 MPa. 530 KIM E T A L. FIG. 2. E ffect of molar ratio (aniline/SeO 2) on the oxidative carbonylation of aniline. Conditions: aniline 40 mmol, molar ratio (K 2CO 3/SeO 2 = 5), methanol 25 ml, toluene 1 g, temperature 130◦ C, pressure 6.80 MPa (O 2/CO = 20/80), reaction time 2 h. Carbamate, methyl-N -phenyl carbamate; urea, N ,N ′-diphenyl urea. FIG. 3. E ffect of temperature on the oxidative carbonylation of aniline. Conditions: aniline 40 mmol, SeO 2 0.2 mmol, K 2CO 3 1 mmol, methanol 25 ml, toluene 1 g, pressure 6.80 MPa, reaction time 2 h. Carbamate, methyl-N -phenyl carbamate; urea, N ,N ′-diphenyl urea. CA R BO NYLATIO N O F A NILINE 531 FIG. 4. E ffect of pressure on the oxidative carbonylation of aniline. Conditions: aniline 40 mmol, SeO 2 0.2 mmol, K 2CO 3 1 mmol, methanol 25 ml, toluene 1 g, temperature 130◦ C, reaction time 2 h. Carbamate, methyl-N -phenyl carbamate; urea, N ,N ′-diphenyl urea. −log rate vs 1/T is shown in Fig. 5, from which the value of activation energy, E a , was evaluated as 17.0 kcal/mol. The conversion of aniline increased with increasing temperature up to 130◦ C and then decreased with further FIG. 5. increase in temperature. The decrease in conversion at temperatures higher than 130◦ C can be rationalized by assuming that the rate of alcoholysis of diphenyl urea is higher than that of carbonylation of aniline, i.e., the rate A rrhenius plot. 532 KIM E T A L. TABLE 4 ′ Alcoholysis of N , N -Diphenyl Urea a Selectivity (% ) Pressure (MPa) Temp. ( ◦ C) Conversion (% ) Carbamate b A niline 0.1 (N 2) 0.1 (N 2) 6.80 (O 2/CO ) 6.80 (O 2/CO ) 130 170 130 170 60.5 96.2 25.5 67.5 49.2 49.2 82.8 75.9 50.4 50.5 16.7 23.7 a Conditions: N ,N ′-diphenyl urea 20 mmol, SeO 2 0.2 mmol, K 2CO 3 1 mmol, methanol 25 ml, toluene 1 g (internal standard), O 2/CO = 20/80, reaction time 2 h. b Carbamate: methyl-N -phenyl carbamate. of formation of aniline from diphenyl urea is higher than that of aniline disappearance by carbonylation at higher temperature (see E qs. [1–3]). The results on the alcoholysis of diphenyl urea at 130◦ C and 170◦ C are listed in Table 4. Table 4 shows that under atmospheric pressure of N 2 at 130◦ C, the 60.5% of diphenyl urea was converted into aniline and phenyl carbamate. When the reaction was conducted at 6.80 MPa of O 2/CO, however, the conversion dropped significantly from 60.5% to 25.5% . Such a pressure effect was also observed by Macho et al. (4). The selectivity of phenyl carbamate increased with the increase of temperature while the selectivity of diphenyl urea decreased, strongly indicating that diphenyl urea is an intermediate to the formation of phenyl carbamate. The effect of pressure on the conversion of aniline as shown in Fig. 4 seems to be less pronounced than that of temperature because the conversion reached over 85% as long as the pressure was maintained above 2.04 MPa of O 2/CO (O 2/CO = 20/80). H owever, the selectivity of phenyl carbamate was found to be more strongly dependent on the pressure as going from 8% at 2.04 MPa to 49% at 6.80 MPa even though the dependence was much less pronounced compared with that of temperature. In order to test the catalyst reusuability, the carbonylation reaction was performed for 2 h in the presence of a catalyst, SeO 2/K 2CO 3 at 130◦ C and 6.80 MPa of O 2/CO in methanol. A fter the reaction, the reaction solution was filtered to remove insoluble diphenyl urea. The resulting solution containing the catalyst was reused with a fresh charge of aniline. It was found that the catalyst retained its original activity even after four reuses. 3.7. E ffect of CO 2 The catalytic activity of SeO 2/K 2CO 3 was tested for the oxidation of CO to CO 2, and the effect of CO 2 on the oxidative carbonylation of aniline was investigated. It is reported that oxidation of CO to CO 2 takes place during the oxidative carbonylation of amines (24). A s most of the catalysts proposed in the literature, our catalyst system, SeO 2/K 2CO 3, also showed some catalytic activity toward the oxidation of CO to CO 2. The oxidative carbonylation of aniline (40 mmol) was performed in methanol (25 ml) at 130◦ C and 6.80 MPa (O 2/CO = 20/80) for 2 h. G C analysis of gas sample showed that 7.7% of CO consumed was oxidized to CO 2. Conversion of aniline and selectivity to methyl-N phenyl carbamate were 97.5% and 49.2% , respectively. In order to find out the effect of CO 2 formation on the carbonylation of aniline, the carbonylation reaction was conducted in the presence of added CO 2 using 6.80 MPa of CO 2/O 2/CO mixture gas (CO 2/O 2/CO = 12/18/70) instead of O 2/CO (O 2/CO = 20/80). G as chromatographic analysis of liquid sample gave 98.1% of conversion and 48.3% of selectivity, which were similar to those obtained from the above experiment performed without the presence of added CO 2. From these results, it is concluded that the oxidation of CO to CO 2 occurs in significant yield, but the effect of CO 2 formation on the carbonylation of aniline can be neglected. 3.8. Proposed M echanism Based on the experimental results, the mechanism of the oxidative carbonylation of aniline catalyzed by K 2SeO 3 is proposed in Scheme 1. A s described in the experimental section, the active species, K 2SeO 3 is formed by the reaction of SeO 2 with K 2CO 3. In a second step, aniline reacts with K 2SeO 3 to give amido complex II. A mido species II could take up one molecule of CO to form selenium carbonyl species, Se(O K) 2(CO )(O H )(NH Ph), and the subsequent insertion of CO into Se–N bond would produce carbamoyl complex III. The formation of carbamoyl species III seems to be a key step in the proposed mechanism. A ddition of one molecule of another aniline to species III and the subsequent elimination of diphenyl urea and H 2O give rise to selenium species IV (path A ). IV can also be produced by interaction of species III with one molecule of methanol and subsequent elimination of phenyl carbamate and H 2O (path B). Liberated diphenyl urea can be added to I, forming Se(O K) 2(O H )(NPhCO NH Ph), which, in turn, reacts with methanol to give phenyl carbamate, simultaneously regenerating species II (path C). The final step is the regeneration of K 2SeO 3 (I) by the interaction of species IV with molecular O 2. E ven though diphenyl urea was found to be easily converted into phenyl carbamate by reacting with methanol in the presence of SeO 2/K 2CO 3 catalyst, it cannot be concluded that diphenyl urea is the sole intermediate to the formation of phenyl carbamate. Phenyl carbamate also can be produced directly via a separate route such as path B other than the diphenyl urea route. 4. CONCLUSIONS Various factors affecting the oxidative carbonylation of aromatic amines were investigated in the presence of a new 533 CA R BO NYLATIO N O F A NILINE SCHEME 1. A plausible reaction mechanism of oxidative carbonylation of aniline catalyzed by K 2SeO 3. catalyst system comprising SeO 2 and alkali metal carbonate. The reaction of SeO 2 with K 2CO 3 in methanol produced active alkali metal containing selenium compounds, K 2SeO 3 and K 2Se 2O 5. The carbonylation reactions catalyzed by SeO 2/K 2CO 3 proceeded in polar solvents, like C 1–C 4 alcohols, TH F, and D MF, but not in nonpolar solvents such as n-hexane, benzene, and toluene. In contrast with SeO 2/K 2CO 3 catalyst, the use of alkali metal containing selenium compounds, K 2SeO 3 and K 2Se 2O 5, resulted in a high conversion of aniline, irrespective of the polarity of the solvent used. The activation energy calculated from the A rrhenius plot was evaluated as 17.0 kcal/mol, and the maximum turnover frequency was found to be 2082/h at 130◦ C with a molar ratio of aniline/SeO 2 = 12,800. The formation of phenyl carbamate was more strongly dependent on the temperature than on the pressure. 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