Patent Application
20200061596
This application claims priority under 35 U.S.C. § 119 to Korean Patent Application No. 10-2018-0100230 filed on Aug. 27, 2018 in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference in its entirety.
The present invention relates to a method for producing a methyl N-phenyl carbamate using a zinc-imidazole complex mixed catalyst, and more specifically to a technology for preparing a zinc-imidazole complex mixed catalyst and producing a methyl N-phenyl carbamate in high yield with high selectivity in the presence of the catalyst.
Aromatic carbamates are valuable intermediates that are used in the production of herb medicines, dyes, pharmaceuticals, and isocyanates as units for polyurethane synthesis.
Isocyanates as monomers for polyurethanes are usually produced by reacting corresponding amines with phosgene. However, the reactant phosgene is known as a highly toxic substance that causes environmental pollution and safety problems. Under such circumstances, methods for producing isocyanates without using phosgene have been investigated in various aspects. Reductive carbonylation of nitrobenzene [J. Mol. Catal. A: Chem. (2001) 9; J. Mol. catal. A: Chem. (2006) 64], oxidative carbonylation of aniline [Green Chem. (2011) 3406; J. Catal. (1999) 526], and methoxycarbonylation of amines with dimethyl carbonate (U.S. Pat. No. 4,268,683) are known as typical methods for isocyanate production without using phosgene. The products of these methods are aromatic carbamates that can be used to synthesize isocyanates through thermal decomposition.
Reductive carbonylation of nitrobenzene and oxidative carbonylation of aniline are limited in that carbon monoxide (CO), which is also a toxic gas, is used, high temperature (130-250° C.) and high pressure (40-80 bar) conditions are required, and noble metal catalysts (Ru, Pd, Rh, and Se) are used. In contrast, methoxycarbonylation of amines with dimethyl carbonate is advantageous in that the reaction proceeds under milder conditions and environmentally friendly dimethyl carbonate is used.
In addition, methoxycarbonylation of amines with dimethyl carbonate produces methanol as a by-product, which can be reused for dimethyl carbonate production through oxidative carbonylation. Representative catalysts for this method are relatively inexpensive metals such as Zn and Pb.
U.S. Pat. No. 3,763,217 describes a method for preparing a carbamate by reacting an amine with an alkyl carbonate under reflux in the presence of a Lewis acid catalyst such as uranyl nitrate. However, this method requires a long reaction time of 18-24 hours and has the problems of low conversion rate and selectivity (˜20%).
Further, U.S. Pat. No. 4,268,683 reported a method for synthesizing a carbamate using a halide or an organic acid salt of Sn(II) or Zn(II) as a Lewis acid catalyst. Particularly, the use of zinc acetate as a catalyst for methyl N-phenyl carbamate synthesis achieved a selectivity of 99.8% at a temperature of 140° C. and a pressure of 0.88 MPa. However, according to a study conducted by Feng Li et al., the use of zinc acetate for methyl N-phenyl carbamate production suffers from difficulty in separating and recovering the product and the zinc acetate is converted to zinc oxide by reaction with by-produced methanol, losing its catalytic activity (Applied Catalysis A: General 475 (2014) 355).
In attempts to solve these problems, heterogeneous catalysts such as Al/MCM-41, ZnO—TiO2, and ZrO2/SiO2 were developed (Ind. Eng. Chem. Res. 2006, 45, 4892). However, the yields are still limited to ˜60-80% and a detailed description of the reuse of the catalysts is not sufficiently found in the literature.
Zeolitic imidazole frameworks (ZIFs) are structures produced from Zn compounds and imidazole compounds. ZIFs are structurally similar to zeolite and have good thermal stability and large surface area. ZIFs are generally used in membranes for the separation of CO2, hydrogen, and methane, EO/CO2 coupling, and transesterification. However, to our knowledge, attempts to produce methyl N-phenyl carbamates using ZIFs have never been reported to date.
The present inventors have found that a zinc-imidazole complex mixed catalyst prepared in a one-pot process can be used as a reusable catalyst for methyl N-phenyl carbamate production.
The present invention has been accomplished based on this finding.
The present invention has been made in view of the above problems, and it is one object of the present invention to provide a zinc-imidazole complex mixed catalyst that can be reused due to its high reaction yield and good stability, and a method for preparing the catalyst.
It is a further object of the present invention to provide a method for producing a methyl N-phenyl carbamate in high yield with high selectivity in the presence of the zinc-imidazole complex mixed catalyst.
According to one representative aspect of the present invention, there is provided a zinc-imidazole complex mixed catalyst including a first zinc-imidazole complex and a second zinc-imidazole complex wherein the first zinc-imidazole complex is represented by Formula 1:
Zn(A)x′ (1)
Zn(A)x″(OAc)y (2)
Preferably, x′ is 2, x″ is 1, and y is 1.
According to a further representative aspect of the present invention, there is provided a method for preparing the zinc-imidazole complex mixed catalyst including the first zinc-imidazole complex represented by Formula 1 and the second zinc-imidazole complex represented by Formula 2, the method including (A) reacting a zinc precursor with an imidazole precursor and (B) activating the reaction mixture.
Preferably, in step (A), a zinc precursor is mixed with an imidazole precursor in a first solvent and the mixture is allowed to react at a temperature of 100 to 150° C. for 12 to 48 hours.
Preferably, in step (B), the reaction mixture is precipitated in a second solvent and the precipitate is collected and dried at a temperature of 180 to 200° C. for 1 to 5 hours.
The zinc precursor is preferably a zinc salt, more preferably zinc acetate.
The imidazole precursor is preferably selected from imidazole, 2-chloromethylimidazole, imidazole-2-carboxylic acid, 2-phenylimidazole, benzimidazole, 2-methylimidazole, and mixtures thereof.
The zinc precursor is preferably allowed to react with the imidazole precursor in a molar ratio of 1:1-4.
Preferably, the first solvent and the second solvent may be the same as or different from each other and are each independently selected from N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, vinylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, hexamethylphosphoramide, and mixtures thereof.
According to another representative aspect of the present invention, there is provided a method for producing a methyl N-phenyl carbamate, including (C) reacting an aromatic amine with dimethyl carbonate in the presence of the zinc-imidazole complex mixed catalyst.
The reaction is preferably carried out at a temperature of 100 to 250° C. for 1 to 5 hours.
The aromatic amine is preferably allowed to react with the dimethyl carbonate in a molar ratio of 1:5-40.
The zinc-imidazole complex mixed catalyst is preferably added in an amount of 1 to 20% by weight, based on the weight of the aromatic amine.
The aromatic amine is preferably selected from aniline, phenylenediamine, methylenediphenyldiamine, toluenediamine, and mixtures thereof.
Exemplary embodiments of the present invention enable the preparation of a zinc-imidazole complex mixed catalyst that can be reused due to its high reaction stability.
In addition, the use of the zinc-imidazole complex mixed catalyst leads to a marked improvement in the production yield of a methyl N-phenyl carbamate with high selectivity.
These and/or other aspects and advantages of the invention will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
Several aspects and various embodiments of the present invention will now be described in more detail.
One aspect of the present invention provides a zinc-imidazole complex mixed catalyst including a first zinc-imidazole complex and a second zinc-imidazole complex wherein the first zinc-imidazole complex is represented by Formula 1:
Zn(A)x′ (1)
Zn(A)x″(OAc)y (2)
More preferably, x′ is 2, x″ is 1, and y is 1.
The zinc-imidazole complex mixed catalyst of the present invention can be used for the production of a methyl N-phenyl carbamate and can be used for the reaction of an aromatic amine and dimethyl carbonate.
A further aspect of the present invention provides a method for preparing a zinc-imidazole complex mixed catalyst including (A) reacting a zinc precursor with an imidazole precursor and (B) activating the reaction mixture wherein the zinc-imidazole complex mixed catalyst includes a first zinc-imidazole complex represented by Formula 1:
Zn(A)x′ (1)
Zn(A)x″(OAc)y (2)
In step (A), a zinc precursor is mixed with an imidazole precursor in a first solvent and the mixture is allowed to react in an open space at a temperature of 100 to 150° C. for 12 to 48 hours. The reaction temperature lower than 100° C. may be insufficient for the reaction to proceed due to insufficient chemical bonding energy between the zinc precursor and the imidazole precursor. Meanwhile, the reaction temperature exceeding 150° C. may cause deformation of the organic compound imidazole.
The zinc precursor is preferably a zinc salt. The zinc salt is preferably selected from zinc acetate, zinc nitrate, zinc oxalate, zinc halides, and mixtures thereof. More preferably, the zinc salt is zinc acetate (Zn(OAc)2).
The imidazole precursor is preferably selected from imidazole, 2-chloromethylimidazole, imidazole-2-carboxylic acid, 2-phenylimidazole, benzimidazole, 2-methylimidazole, and mixtures thereof.
The first solvent is preferably a polar compound having a boiling point of at least 150° C. More preferably, the first solvent is selected from N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, vinylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, hexamethylphosphoramide, and mixtures thereof.
The zinc precursor is preferably allowed to react with the imidazole precursor in a molar ratio of 1:1-4 for the synthesis of the mixed catalyst. As described previously, the zinc precursor may be a zinc salt. When the imidazole precursor is allowed to react with the zinc salt in an equivalent ratio of 4:1, the first zinc-imidazole complex and the second zinc-imidazole complex can be prepared in a one-pot process. A conventional zinc-imidazole framework (ZIF) forms an ideal structure in which zinc and imidazole are present in a 1:2 ratio. In this framework, the Lewis acid sites of zinc are completely hindered by imidazole. In contrast, according to the method of the present invention, the equivalent ratio of the imidazole to the zinc is limited to <4:1 to induce the synthesis of a combination of the first zinc-imidazole complex and the second zinc-imidazole complex.
In step (B), the reaction mixture is activated. Specifically, the reaction mixture is precipitated in a second solvent and the precipitate is collected and dried at a temperature of 180 to 200° C. for 1 to 5 hours. Outside the drying temperature and time ranges, there is a risk that satisfactory activation of the reaction mixture may not be achieved.
The second solvent may be the same as or different from the first solvent. Specifically, the second solvent is selected from N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, vinylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, hexamethylphosphoramide, and mixtures thereof.
The polar first solvent may remain attached to the surface of the catalytically active species even after the reaction. The activation step is carried out to remove the attached polar solvent from the catalytically active species. The activation solvent is an aromatic amine or diamine used for methoxycarboxylation and corresponds to the imidazole precursor. That is, the reactant imidazole precursor is used as the activation solvent, thus avoiding the need for subsequent washing. This is effective in terms of processing and cost.
The most preferred conditions for the method of the present invention are as follow: (i) the zinc precursor is mixed with the imidazole precursor in the first solvent and the mixture is allowed to react in an open space at a temperature of 100 to 150° C. for 12 to 48 hours (step (A)); (ii) N,N-dimethylformamide is used as the first and second solvents; and (iii) the zinc precursor is allowed to react with the imidazole precursor in a molar ratio of 1:1-4. When the conditions (i) and (iii) are all met, the use of the resulting catalyst for methyl N-phenyl carbamate production drastically reduces the total yield of methylation by-products to less than 5%. If one or more of the conditions (i) to (iii) are not met, the total yield of methylation by-products is 20% or more, which is at least four times higher than that obtained when the catalyst prepared under the conditions defined above is used.
Another aspect of the present invention provides a method for producing a methyl N-phenyl carbamate, including (C) reacting an aromatic amine with dimethyl carbonate in the presence of the zinc-imidazole complex mixed catalyst.
The reaction is preferably carried out at a temperature of 90 to 250° C. for 1 to 5 hours. If the reaction temperature is lower than 90° C., the production of a sufficient amount of the desired methyl N-phenyl carbamate cannot be expected. As the reaction temperature decreases, the reaction time increases undesirably. Outside the temperature and time ranges, the production yield of the desired product is considerably lowered. More preferably, the reaction is carried out at a temperature of 150 to 250° C. for 1 to 2 hours. Within these ranges, the highest yield of the desired product is obtained.
The aromatic amine is preferably selected from aniline, phenylenediamine, methylenediphenyldiamine, toluenediamine, and mixtures thereof.
The molar ratio of the aromatic amine to the dimethyl carbonate is preferably in the range of 1:5-40. Within this range, the yield of the desired product is markedly improved. Outside this range, an increase in yield by the action of the catalyst cannot be expected.
The dimethyl carbonate acts as a methylation agent in the reaction with the aromatic amine. Various methylation products are synthesized through the following reaction pathways.
According to the present invention, the total yield of the methylation products can be limited to less than 5%, as described previously.
The zinc-imidazole complex mixed catalyst is preferably added in an amount ranging from 1 to 20% by weight, based on the weight of the aromatic amine. Outside this range, the yield of the desired methyl N-phenyl carbamate is considerably lowered. More preferably, the amount of the zinc-imidazole complex mixed catalyst is in the range of 5 to 15% by weight, based on the weight of the aromatic amine. Within this range, the yield of the desired product is kept constant or increases.
The present invention will be explained in more detail with reference to the following examples. However, these examples are not to be construed as limiting or restricting the scope and disclosure of the invention. It is to be understood that based on the teachings of the present invention including the following examples, those skilled in the art can readily practice other embodiments of the present invention whose experimental results are not explicitly presented. Such modifications and variations are intended to come within the scope of the appended claims.
The experimental results of the following examples, including comparative examples, are merely representative and the effects of the exemplary embodiments of the present invention that are not explicitly presented hereinafter can be specifically found in the corresponding sections.
60 g of N,N-dimethylformamide as a solvent and Zn(OAc)2 and benzimidazole in a molar ratio of 1:1.5 were placed in a flask. The reaction was allowed to proceed at 130° C. for 24 h. The resulting solid was collected by filtration. The solid was precipitated in N,N-dimethylformamide, collected, and dried under vacuum at 180° C. for 3 h to afford Zn(benzimidazole)1.6(OAc)0.4 as a zinc-imidazole complex mixed catalyst.
The catalyst was analyzed by Fourier-transform infrared (IR) spectroscopy and X-ray diffraction (XRD) and the results are shown in
Zinc-imidazole complex mixed catalysts were synthesized in the same manner as in Preparative Example 1, except that imidazole (Preparative Example 2), 2-chloromethylimidazole (Preparative Example 3), imidazole-2-carboxylic acid (Preparative Example 4), and 2-phenylimidazole (Preparative Example 5) were used instead of benzimidazole and the reaction conditions were changed as shown in Table 1.
Zinc-imidazole complex mixed catalysts were prepared in the same manner as in Preparative Example 1, except that the molar ratio of Zn(OAc)2 and benzimidazole and the reaction conditions were changed as shown in Table 1.
Methyl N-phenyl carbamate was produced using the zinc-imidazole complex mixed catalysts synthesized in Preparative Examples 1-5 by the following procedure. The reaction is shown as follows:
First, 0.11 g of each of the catalysts and 13.5 g (150 mmol) of dimethyl carbonate were placed in a batch reactor, and then 1.16 g (12.5 mmol) of aniline as a reactant was added thereto. The amount of the catalyst corresponded to 10 wt %, based on the weight of the aniline. The temperature of the reactor was raised to 190° C. The reaction was allowed to proceed with stirring at a rate of 500 rpm for 2 h to produce methyl N-phenyl carbamate.
The reaction mixture in the reactor was analyzed by gas chromatography to determine the conversion rate of the aniline and the yields (%) of methyl phenyl carbamate (MPC), methyl N-methyl phenyl carbamate (MMPC), methyl aniline (MA), and dimethyl aniline (DMA). The results are shown in Table 3 and
Methyl N-phenyl carbamate was produced in the same manner as in Examples 1-5, except that the zinc-imidazole complex mixed catalysts synthesized in Preparative Examples 6-9 were used.
Methyl N-phenyl carbamate was produced in the same manner as in Examples 1-5, except that the zinc-imidazole complex mixed catalysts were added in the amounts shown in Table 5.
The reaction mixtures in the reactors were analyzed by gas chromatography to determine the conversion rates of the aniline and the yields (%) of the products depending on the amounts of the catalysts. The results are shown in Table 5.
Methyl N-phenyl carbamate was produced in the same manner as in Examples 1-5, except that the reaction time was changed as shown in Table 6.
The reaction mixtures in the reactors were analyzed by gas chromatography to determine conversion rates (%), yields (%), and selectivities (%) depending on the reaction time. The results are shown in Table 6.
From the results in Table 6, it can be concluded that the yield of methyl N-phenyl carbamate gradually increases with increasing reaction time. The yield was above 70% from when the reaction time reached 2 h.
Methyl N-phenyl carbamate was produced in the same manner as in Examples 1-5, except that the reaction temperature was changed as shown in Table 7.
The reaction mixtures in the reactors were analyzed by gas chromatography to determine conversion rates (%), yields (%), and selectivities (%) depending on the reaction temperature. The results are shown in Table 7.
As can be seen from the results in Table 7, the reaction did not proceed thermodynamically at reaction temperatures of 90° C. or below. The temperature of 150° C. was sufficient for the reaction to proceed kinetically.
Methyl N-phenyl carbamate was produced in the same manner as in Examples 1-5, except that mixtures of Zn(benzimidazole)2 synthesized by reaction of ZnC12 and benzimidazole in a ratio of 1:2 and Zn(benzimidazoleXOAc) synthesized by reaction of Zn(OAc)2 and benzimidazole in a ratio of 1:1 were used in the weight ratios shown in Table 8.
Methyl N-phenyl carbamate was produced in the same manner as in Example 25, except that a single zinc-imidazole complex catalyst was used as shown in Table 8.
The procedure of Example 1 was repeated four times to determine the lifetimes of the catalysts. Specifically, after the lapse of 2 h, the reaction was stopped and analysis was performed for methyl N-phenyl carbamate. Thereafter, fresh dimethyl carbonate and aniline were placed in a batch reactor containing the catalyst. The experiment was conducted in quadruplicate. The results are shown in Table 9 and
The results in Table 9 and
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2018-0100230 | Aug 2018 | KR | national |
