KR101912840B1 - Covalent Triazine Framework-based Heterogenized Catalysts for Carbonylation and Method of Preparing Lactone Using the Same - Google Patents
Covalent Triazine Framework-based Heterogenized Catalysts for Carbonylation and Method of Preparing Lactone Using the Same Download PDFInfo
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Abstract
The present invention relates to an inhomogeneous catalyst using a CTF for preparing a heterogeneous carbonylation catalyst by inserting a covalent bond to a metal ion such as bypyridine in a skeleton of CTF as a ligand, As the heterogeneous catalyst, propylene oxide (PO) can be produced as? -Butyrolactone while exhibiting high selectivity and can be easily separated from the product and easily reused. .
Description
The present invention relates to a covalent triazine framework (CTF) -based inhomogeneous carbonylation reaction catalyst and a method for preparing lactone using the catalyst. More particularly, the present invention relates to a method for preparing a lactone using a metal ion such as bypyridine , A heterogeneous carbonylation catalyst is prepared, and a lactone is prepared using the resulting catalyst. The covalently bonded triazine structure is easily separated from the product and can be reused several times. Based heterogeneous carbonylation reaction catalyst and a process for preparing lactone using the same.
β- lactone is a biodegradable naturally occurring (Muller, H.-M. et al, Angew Chem, Int Ed 1993, 32, 477;........ Sudesh, K. et al, Prog Polym Sci 2000, 25, 1503) and thermoplastic polyester (Gerngross, TU et al, Sci Am 2000, 283 (2...), 36-41;. Bronco, S. et al, Macromolecules 1994, 27, 4436; Jiang , Z. et al., J. Am. Chem . Soc . 1995, 117 , 4455). Many synthetic methods are available for the preparation of? -Lactones (Nozaki, K. et al., J. Am. Chem . Soc . 1995, 117, 9911; Chang, B.-H. et al., J. Polym .. Prepr (.... .. Am Chem Soc, Di v Polym Chem) 1995, 36 (2), 146; Yokouchi, M. et al, J. Polym Sci 1976, 14, 81;... Kurcok, P. et al., Macromolecules 1992, 25, 2017; Hori, Y. et al., Macromolecules 1993, 26, 5533). Among them, catalytic ring-opening carbonylation reaction of epoxide is attracting much attention because it can produce enantiopure β-lactone.
For the past several decades, the Co 2 (CO) 8 precursor has been reported to catalyze the epoxide as a lactone in the carbonylation reaction (Drent, E. et al., Chem . Abstr . 1994, 120, 191517; et al., J. Org . Chem . 2001, 66, 5424-5426; Khumtaveeporn, K. et al., Acc . Chem . Res. 1995, 28, 414; Davoli, P. et al., J. Org . Chem . 1999, 64, 518). Recently, Coates et al. (Salph) M (THF) 2 ] [Co (CO) 4 ] (salph = N, N'-o-phenylene bis (3,5-di- tert- butylsalicylideneimine), which is a homogeneous wetting agent Lewis acid- , M = Al 3 + , Cr 3 + ) acts as a catalyst in the reaction of converting the epoxide to lactone and has shown the best performance in epoxide-carbonylation catalysts (Getzler YD et al., J. Am. Chem . Soc ., 2002, 124, 1174; Kramer, J. W et al., Org . Lett ., 2006, 8, 3709). However, it is difficult to separate the products and the disadvantage of poor recovery of the catalyst gives a considerable limitation to practical use. In order to solve such problems, it has been confirmed that the active sites of the homogeneous catalyst are inhomogeneous on the solid support thus far developed, which is easy to separate and has high catalytic efficiency.
In recent years, CTFs (covalent triazine frameworks) with high surface area, stability, large pore volume, and structural tunability have been reported in heterogeneous catalyst supports (Cote, A. et al., Science 2005 , 310, 1166; Uribe-Romo, al, J. Am Chem Soc 2011, 133, 11478;.... Kandambeth, S. et al, J. Am Chem Soc 2012, 134, 19524;..... Ding, YS et al, J. Am. Chem . Soc ., 2011 , 133, 19816) (Beaudoin, D. et al., J. Nat. Chem . 2013 , 5 , 830; Katekomol, P. et al., Chem. , 25, 1542; Chan-Thaw , CE et al, Abstr Pap Am Chem Soc 2010, 240;....... Chan-Thaw, CE et al, Nano Lett . 2010, 10, 537; Kailasam, K. et al., Chem . Mater. 2010, 22, 428; Hug, S. et al., J. Mater. Chem . 2012, 22, 13956). In particular, as shown in
Accordingly, the present inventors have made intensive efforts to solve the problem of difficulty in mass production of? -Lactone through epoxidized carbonylation because of difficulty in separating and reusing the homogeneous catalyst from the product. As a result, 2] + and [Co (CO) 4] - ions immobilized on the CTF by the non-homogenization was non-homogeneous catalyst [bpy-CTF-Al (OTf ) 2] [Co (CO) 4] is at least 90% higher selectivity It is confirmed that propylene oxide (PO) can be prepared as? -Butylolactone, easily separated from the product, and does not decrease the catalytic activity even when it is reused in the carbonylation reaction. It was completed.
An object of the present invention is to provide a catalyst which has a catalytic efficiency equal to or higher than that of a conventional catalyst including a homogeneous system, is stable to an acid, a base and a temperature and is easy to separate from a product, Catalyst and a method for producing the same.
In order to achieve the above object, the present invention provides a covalent bond organic structure in which a frame ligand forms a cavity and is bonded to each other; And wherein the covalent bond coordinated to an organic structure [M 1 (L 1) n (L 2) m] and [M 2 (L 3) x (CO) y] and wherein the covalently linked organic structure to the CTF (Covalent Triazine Framework), and, M 1 and M 2 are each independently selected from Al, Cr, Fe, Co, Ti, W, Si, Ir, Pt, Pd, Ru, Th, Ni, Cu, V, Au, Re, Zr , or Mo is, L 1 and L 2 are each independently selected from OTf - (trifluoromethane sulfonate), Cl -, I -, ClO 4 -,
(A) coordinating a transition metal compound represented by [M 1 (L 1 ) n (L 2 ) m ] in a covalently bonded organic structure in which a frame ligand forms a cavity and is bonded to each other; And (b) reacting the covalently linked organic structure coordinates as [M 1 (L 1) n (L 2) m] [M 2 (L 3) x (CO) y] a metal compound containing a to L 1 and a portion of L 2 [M 2 (L 3 ) x (CO) y], and including the step of replacing in the covalently bonded organic structure is (covalent Triazine Framework) CTF,
The present invention also provides a process for producing a lactone, which comprises carbonylating an epoxide and carbon monoxide using the catalyst to produce a lactone.
The carbonylation reaction catalyst according to the present invention has a catalytic efficiency equal to or higher than that of a conventional catalyst including a homogeneous system and can be easily separated from the product, is stable to an acid, a base and a temperature, Is used as a carbonylation reaction catalyst using carbon dioxide, which is useful for mass production of? -Lactone.
1 is a homogeneous catalyst [(salph) Al (THF) 2] [Co (CO) 4] (3) Structure (a) and heterogeneous catalyst [bpy-CTF-Al (OTf ) 2] in the [Co (CO ) 4] (a view of the structure (b) 4) (white in carbon, blue: nitrogen, pink: aluminum, bright red: (OTf), violet blue: cobalt and dark red: oxygen, hydrogen is omitted box).
2 is a view showing FT-IR spectrum of bpy-CTF according to the present invention.
FIG. 3 (a) is a nitrogen adsorption and desorption isotherm of bpy-CTF according to the present invention, and FIG. 3 (b) is a graph showing the pore size of a sample.
4 is a SEM image (a) and an EDS mapping result (bd) of 2 in
5 is [3 CTF-bpy-Al ( OTf)] according to the present invention + [KCo (CO) 4] (A) and, [CTF-bpy-Al ( OTf) 2] + - [Co (CO) 4 ] (B).
6 (b) is an SEM photograph of the
7 is a graph showing the FTIR spectra of KCo (CO) 4 , 2 and 4 according to the present invention.
8 is a diagram showing the 3D structure of the
Figure 9 is a diagram showing possible mechanisms for PO carbonylation and acetone production from common intermediates.
FIG. 10 is a nitrogen adsorption and desorption isotherm of 4 according to the present invention, and FIG. 3 (b) is a graph showing the pore size of the sample.
11 is an FT-IR spectrum of the
12 is a diagram showing the SEM image and the EDS element mapping result of the
13 is a 1 H-NMR spectrum of the
14 is a 1 H-NMR spectrum of the
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein and the experimental methods described below are well known and commonly used in the art.
The COF (Covalent Organic Framework) is stable at a temperature of 400 ° C or higher, has a porosity of 1000 m 3 / g or more, and the pore radius can be 2 nm or more. A portion of the COF skeleton capable of acting as a ligand to a metal ion such as bypyridine can be covalently inserted, and the homogeneous organometallic compound can be homogenized using the covalent bond. The COF system was used to homogenize the iridocatalytic hydrogenation reaction of Ir organic compounds and to report the implementation of heterogeneous catalysts with the same activity as homogeneous catalysts.
The present inventors Fig. 1 (b) as shown in, devised a {Al (OTf) 2} [ Co (CO) 4] non-homogenized in bpy-CTF system, and [(salph) Al (THF) 2] [ Co (CO) 4 ] (3) As shown in the homogeneous catalyst (FIG. 1A), it provides a similar N 2 O 2 coordination environment for Al 3 + cations and Co anions.
Thus, in one aspect, the present invention provides a covalently bonded organic structure in which the frame ligands form a cavity and are bonded together; And wherein the covalent bond coordinated to an organic structure [M 1 (L 1) n (L 2) m] and [M 2 (L 3) x (CO) y] and wherein the covalently linked organic structure to the CTF (Covalent Triazine Framework), and, M 1 and M 2 are each independently selected from Al, Cr, Fe, Co, Ti, W, Si, Ir, Pt, Pd, Ru, Th, Ni, Cu, V, Au, Re, Zr , or Mo, L 1 and L 2 are trifluoromethane sulfonate (OTf), L 3 is cyclopentadiene, pentamethylcyclopentadiene, triphenylphosphine, cyclooctadiene, Benzene, ethylene diamine, acetylacetonate or a derivative thereof, and n, m, x and y are each independently an integer of 0 to 6 , and 2? N + m? 4, 2? x + y < / = 6. < / RTI >
(A) coordinating a transition metal compound represented by [M 1 (L 1 ) n (L 2 ) m ] in a covalently bonded organic structure in which a frame ligand forms a cavity and is bonded to each other; And (b) reacting the covalently linked organic structure coordinates as [M 1 (L 1) n (L 2) m] [M 2 (L 3) x (CO) y] a metal compound containing a to L 1 and a portion of L 2 [M 2 (L 3 ) x (CO) y], and including the step of replacing in the covalently bonded organic structure is (covalent Triazine Framework) CTF,
In the present invention, the frame ligand is a ligand commonly used in covalent organic structures and is not limited as long as the transition metal can coordinate. Examples thereof include biphenyl, phenyl, naphthalene, pyrene, thiophene, pyridine, pyrrole, phosphine, phosphinine, ), Triphenyl amine, phorpyrrine, biphenyl, biphyridine, biphosphinine, bipyrrole, phenylpyridine, bipyrimidine ( bipyrimidine, biimidazole, bithiophene, and derivatives thereof.
The [M 2 (L 3) x (CO) y] is [Co (CO) 4] - , [Fe (CO) 5] -, [Mn (CO) 5] -, [Co (IMD) (CO) 2 ] - [Co (CP * ) (CO)] - or [Co (CP * ) (CO) 2 ] - .
The method for preparing the carbonylation reaction catalyst according to the present invention may be carried out by a hydrothermal synthesis method, a solvent method, a microwave method, or a solvent thermal synthesis method.
A preferred embodiment of the CTF-based inhomogeneous carbonylation reaction catalyst according to the present invention may be a compound represented by [bpy-CTF-Al (OTf) 2 ] [Co (CO) 4 ].
In addition, the production method of the CTF-based non-homogeneous system carbonylation reaction the catalyst is (a) bipyridinyl form a cavity, and the [bpy-CTF-Al (OTf ) 3] by the addition of Al (OTf) 3 in CTF bonded to each other ; And (b) [bpy-CTF- Al (OTf) 3] KCo (CO) a OTf negative ions are Co (CO) 4] was added to 4-a [bpy-CTF-Al (OTf ) replacing the anion-2 ] [Co (CO) 4 ].
In the present invention, PO was also carbonylated with? -Butylolactone using a catalyst having excellent catalytic conversion of [bpy-CTF-Al (OTf) 2 ] [Co (CO) 4 ], an inhomogeneous catalyst , It was confirmed that it was easy to separate and recover the catalyst.
Accordingly, the present invention relates to a process for producing a lactone, which comprises carbonylating an epoxide and carbon monoxide in a solvent using the carbonylation catalyst, thereby producing a lactone.
The lactone may be represented by the following formula (1).
[Chemical Formula 1]
Wherein R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of hydrogen, straight-chain or branched-chain alkyl, allyl, alkenyl, vinyl, aryl, alkylether, Alkylether, alkylether, arylester, arylester, alkylester, arylester, cyclic ether, cyclic ester, thiol, silyl, amine, amide amido, nitro, cyano, thioether, thioalkyl, sulphonyl, halogen or hydroxy, wherein alkyl is an alkyl having 1 to 20 carbon atoms And allyl, alkenyl and vinyl have 2 to 20 carbon atoms and aryl has 6 to 40 carbon atoms.
In the present invention, the epoxide may be selected from the group consisting of ethylene epoxide, propylene oxide, epichlorohydrin, epibromohydrin, 1,2-epoxybutane (1,2- epoxybutane, 2-vinyloxirane, cyclooctene oxide, 1,2-epoxy-1-carbonitrile, 1,2-epoxy N-butyl glycidylether, 2,3-epoxypropyl phenyl ether, or styrene oxide. The term " alkylene oxide " .
The solvent may be selected from the group consisting of dimethoxyethane (DME), tetrahydrofuran, dioxane, diglyme, tetraethylene glycol dimethylether, diethylether, 2- (2-methoxyethoxy) ethanol, and anisole.
In the process for producing lactones according to the present invention, the reaction can be carried out at a temperature of 22 to 120 ° C, preferably 60 to 90 ° C, and a CO pressure of 0.1 to 30.0 MPa, preferably a CO pressure of 5.0 to 8.0 MPa.
The
[Reaction Scheme 1]
KCo (CO) 4 prepared for replacing one OTf anion with an externally added [Co (CO) 4 ] - anion is reacted with 2 methanol solution at room temperature to form a black precipitate.
Carbonylation of PO using a catalyst was carried out in a stainless steel tube reactor containing a weakly polar solvent (dimethoxyethane, DME), the best solvent for carbonylating the epoxide to lactone, resulting in a selectivity of 90% PO is converted to? -Butyrolactone.
Also, after simple filtration, the catalyst (4) is separated from the reaction mixture and the recovered catalyst is still active and can act as a catalyst for further carbonylation. In addition, the activity and selectivity of the catalyst are comparable to those of the homogeneous catalyst.
Therefore, the catalyst according to the present invention is easily separated from the product and can be reused many times. This result implies that the heterogeneous catalyst (4) can perform sustainable epoxide-carbonylation on an industrial scale.
[Example]
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for illustrating the present invention and that the scope of the present invention is not construed as being limited by these embodiments.
Air and water sensitive compounds were tested in a glove box in dry argon atmosphere. Tetrahydrofuran (THF) and 1,2-dimethoxyethane (DME) were refluxed on sodium benzoquinone and distilled under N 2 atmosphere. Pentan was obtained from Sigma-Aldrich. Stirring the propylene oxide over CaH 2 and distilled under a N 2 atmosphere. Sinyang Gas Company's product was used as the research grade grade 99.99% pure carbon monoxide. Co 2 (CO) 8 is a aldrich Co., Al (OTf) 3, and the anhydride is Alfa-aesar Inc. 3,5-di - tert - butyl salicylaldehyde (3,5-di- tert -butylsalicylaldehyde) is TCI chemicals were used. NaCo (CO) 4 and [(salph) Al (THF) 2 ] + [Co (CO) 4 ] - were synthesized (Getzler et al., J. Am. Chem . Soc . ). NMR spectra were recorded on a TMS basis using Bruker advance IV (1 H NMR, 300 MHz). All new compounds were analyzed using standard spectroscopy. IR spectra were collected on a Nicolet iS 50 (Thermo Fisher Scientific) spectrometer. All carbonylation reactions were performed in a 100 mL stainless steel reactor and controlled with a pressure gauge and a pressure relief valve. Scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS) were measured on JEOL LTD (JAPAN) JEM-7610F operating at an accelerating voltage of 15.0 kV.
Both
X-ray diffraction (XPS) was performed using a concentric hemispherical analyzer on ESCA 2000 (VG microtech) at a pressure of ~ 3x10 -9 mbar using Al Ka (hγ = 1486.6 eV) as an excitation source. photoelectron spectroscopy.
1 H NMR spectra were measured on a Bruker 400 MHz spectrometer at 298 K and chemical shifts were taken based on the TMS peak. The conversion of PO, β-lactone and acetone was quantified using naphthalene as an internal standard. All carbonylation reactions were carried out in a well-ventilated hood equipped with a carbon monoxide detector (see MSDS for proper handling of CO).
Manufacturing example One: [ bpy - CTF - Al (OTf) 2 ] [ Co (CO) 4 ] [aluminum Tris ( Trifluoromethane burnt Sulfonate )] ([ bpy - CTF - Al (OTf) 2 ] [ Co (CO) 4 ] [Aluminum tris ( trifluoromethane sulfonate)], 4) of synthesis
bpy - The CTF (1) synthesis
Park, K. et al., ChemSus Chem . 2015, 8, 3410 and Hug, S. et al., J. Mater. Chem . 2012, 22, 13956.
The compound 5,5'-dicyano-2,2'-bipyridine (0.11 g, 0.04 mmol) and zinc chloride (0.33 g, 2.4 mmol) was injected into a 1 mL ampoule (10 nos). The ampoules were sealed under vacuum and heated from 400 ° C in a furnace at a heating rate of 60 ° h -1 . After 48 hours, the furnace was cooled to room temperature. The crude product was crushed well and stirred with 250 mL of water for 3 hours. The black solid was filtered off and washed with water and acetone. The resulting black solids were reflux overnight in 1M HCl (250mL), filtered, and washed each with 1M HCl (3X100ml), H 2 O (3X100ml), THF (3X100ml) and acetone (3X100 ml). The resulting solid was dried at 200 < 0 > C under vacuum for 16 hours. Yield = 0.57 g. This was confirmed by FTIR spectroscopy (FIG. 2).
[ bpy - CTF - Al (OTf) 3 ] [aluminum Tris ( Trifluoromethanesulfonate )] ([ bpy -CTF-Al (OTf) 3 ] [Synthesis of Aluminum tris (trifluoromethanesulfonate)], 2)
A mixed solution of bpy-CTF (0.26 g) and Al (OTf) 3 (1.27 g, 2.67 mmol) in methanol (25 mL) was heated to 100 ° C in a hydrothermal reactor. After 24 hours, the reactor was cooled to room temperature and the black precipitate was filtered and washed with methanol (3 X 15 mL). The resulting solid was dried under vacuum for 8 hours. Yield = 0.28 g. (~ 1.246 g of Al (OTf) 3 was recovered from the filtrate).
Potassium cobalt Tetracarbonyl (potassium cobalt tetracarbonyl , KCo (CO) 4 ) Synthesis of
An excess of KOH (0.506 g, 9.036 mmol) was added to 15 mL of a THF solution of Co 2 (CO) 8 (1.031 g, 3.015 mmol) and the resulting brown solution was stirred at room temperature for 4 hours. The resulting pale yellow solution was filtered and the solvent was removed in vacuo to give a yellowish white precipitate (yield = 1.25 g).
[ bpy - CTF - Al (OTf) 2 ] [ Co (CO) 4 ] [aluminum Tris ( Trifluoromethane Sulphonate (Bpy-CTF-Al (OTf) 2 ] [ Co (CO) 4 ] [Aluminum tris ( trifluoromethane ulfonate ), 4) Synthesis of
A methanol solution (5 mL) of [bpy-CTF-Al (OTf) 3 ] (0.28 g) and KCo (CO) 4 (1.34 g, 6.38 mmol) was stirred at room temperature. During the reaction with methanol, the yellowish white of the KCo (CO) 4 solution turns red and then turns yellow, indicating an exogenous exchange of anion. After 24 hours the black precipitate was filtered off, washed with methanol (3 x 10 mL) and dried thoroughly. Yield = 0.291 g. IR = 1870 cm -1 . (~ 1.327 g of KCo (CO) 4 was recovered from the filtrate)
The
[Table 1]
Al (OTf) 3 was added to 1 in a methanol solution and refluxed in succession to give 0.57 wt% of metal immobilization (Table 2).
[Table 2]
The Al (OTf) thermal methods in order to increase the amount of 3 (hydrothermal method), a black precipitate of [bpy-CTF-Al (OTf ) 3] under very severe reaction conditions, be carried (2) is fixed to the first is generated. 2 shows an irregularly shaped block shape with an average size of> 35 (5) m (Reaction 1)
[Reaction Scheme 1]
4 (b) - (d)), it was confirmed that the aluminum, sulfur and fluorine elements were uniformly distributed in the ratio of about 1: 3: 9 throughout the structure from the EDS mapping results It can be seen that the
KCo (CO) 4 prepared for replacing one OTf anion with an externally added [Co (CO) 4 ] - anion is reacted with a methanol solution at room temperature to form a black precipitate (FIG. The IR spectrum of [bpy-CTF-Al (OTf) 2 Co (CO) 4 ] ( 4 ) shows a CO stretch peak at 1878 cm 1 , which corresponds to the carbonyl group in the tetrahedron [Co (CO) 4 ] , Indicating that the OTf has been successfully replaced with [Co (CO) 4 ] (Fig. 7). SEM photographs of the separated 4 are shown in Figs. 6 (a) and 6 (b), from which it can be seen that an irregular block shape is retained. Aluminum, fluorine, sulfur and cobalt elements uniformly distributed throughout the structure were identified through EDS mapping (Fig. 6 (c) and Fig. 6 (d)). ICP-OES (inductively coupled plasma- optical emission spectroscopy) through the Al and the content of Co was determined to be 3.76 and 2.67wt%, respectively ({Al (OTF) 2}, which accounts completely for the first and + [Co (CO ) 4 ] - units, the contents of Al and Co were 3.82 and 8.34 wt%, respectively. These values were smaller than the calculated values, indicating that each CTF ring was immobilized with one [Al (OTf) 2 Co (CO) 4 ] and two Al (OTf) 3 units, as shown in FIG.
Nitrogen adsorption / desorption measurements were performed to determine the changes in pore volume and surface area due to immobilization (FIG. 10 and Table 1). In the case of the
, Using XPS (X-ray photoelectron spectroscopy) analysis of Al + 3 and Co -1 coordination environment at 4 to 4 to ensure that has a similar active site as a homogeneous catalyst (3). A homogeneous type catalyst (3) were compared, Al 3 + 2p 3/2 , Co - 1
Example One: Epoxide - Expanding the collar Carbonylation ( epoxide -ring expansion carbonylation)
In a glove box, a
Example 2: Regeneration of the catalyst (4)
After three runs, catalyst (4) was filtered, washed with 5 mL of DME and dried under vacuum for 6 hours. The catalyst (4, 0.029 g) was stirred with freshly formed yellowish KCo (CO) 4 (1.02 g, 4.86 mmol) in methanol (5 mL). After 24 h, the black precipitate was washed with methanol (2 x 5 mL) and dried for 8 h (Yield = 0.031 g) (~ 0.98 g KCo (CO) 4 was recovered from the filtrate).
Carbonylation of PO using a catalyst was carried out in a stainless steel tube reactor containing a weakly polar polar solvent (dimethoxyethane, DME), which is the best solvent for carbonylating the epoxide to lactone. Initially, carbonylation of PO was carried out by carbonylation of PO using DME of 50 占 폚 and CO of 6.0 MPa using reference standard (3) to obtain 91% of? -Butyrolactone and acetone as 9: 1 And were very similar to the reported results (Table 3, entry 1).
3, the activity of the prepared heterogeneous catalyst (4) was measured using the same reaction conditions of
[Table 3]
a Reaction with 2.5 mL of pressurized DME using CO at ambient temperature.
b S / C = 100. c S / C = 30.
d 1 H-NMR spectroscopy was carried out using naphthalene as an internal standard
e measured the unreacted epoxide residue rate of reaction of the 4 catalytic activity at different temperatures for 4 to a reduction in the growth and formation of acetone. When the temperature is raised to 70 캜 and 90 캜 (Fig. 4,
Based on the proposed mechanism of PO carbonylation (Fig. 9), the activation of PO by immobilization of Al < 3 + & gt ; cations initiated the catalytic cycle and the [Co (CO) 4 ] Alkyne-alkoxide and cobalt alkylate (b) are formed by nucleophilic attack. CO pores (4), which can be utilized at mild reaction temperatures, allow CO to migrate into the cobalt-alkyl bond and form the cobalt alkyl intermediate (c) easily to form? -Butyrolactone. However, at higher temperatures, the available CO pore (4) is limited and the rate of CO insertion into the Co-alkyl bond (b) may be slowed. Delayed CO insertion can result in the elimination of the β-hydride, resulting in enolate protonation (d) and tautomerization resulting in the main product, acetone (Table 3,
The catalyst (4) was then separated from the reaction mixture by simple filtration and washed with DME. The FT-IR analysis of the recovered catalyst shows a carbonyl peak at 1878 cm -1 indicating that the catalyst is still active and can act as a catalyst for further carbonylation (FIG. 11). Along with EDS analysis, SEM images show that aluminum, fluorine, sulfur, and cobalt are uniformly distributed throughout the sample (FIG. 12). However, from the results of ICP-OES analysis, the contents of Al and Co were 3.72 and 2.48 wt%, respectively, indicating that a small amount of [Co (CO) 4 ] - anion was removed from the catalyst (4). The recovered catalyst can be subjected to carbonylation at least three times under the same reaction conditions as the first cycle, as shown in Table 4. As compared to the first cycle, the catalytic activity in the recycle was maintained at about 92%. A slight reduction in activity may be due to partial release of [Co (CO) 4 ] - anions from the catalyst in the separation process. The relative amount of acetone to lactone during recycling increases. May be due to the release of [Co (CO) 4 ] anions while the amount of Al 3 + cations is unchanged, and more acetone may be formed due to further removal of β-hydrides. Co [CO (CO) 4 ] was continuously treated after the third cycle in order to confirm the reproducibility of the recovered catalyst with a relatively small amount of [Co (CO) 4 ]. The regenerated catalyst converts PO to p-butylolactone (90%) and showed a total conversion efficiency of 96%. This result confirms the possibility that the heterogeneous catalyst (4) maintains activity for efficient carbonylation and is an industrially useful catalyst.
Table 4. recycling rate of the
a reaction conditions: DME = 2.5 mL, S / C = 30, CO = 6.0 Mpa, temperature = 50 DEG C
b Determined by 1 H-NMR spectroscopy.
In summary, the results of fixing the novel non-homogeneous based composite [bpy-CTF-Al (OTf ) 2] [Co (CO) 4] of Al (OTf) 3 to a shared organic structure and [Co (CO) 4] Were synthesized by exchanging [OTf] anions with anions. The heterogeneous catalyst (4) shows good activity at mild conditions (6.0 MPa and 50 ° C) and exhibits a high selectivity of 90% in ring extended carbonylation which converts PO to β-butylolactone. The activity and selectivity of homogeneous catalysts are comparable to those of homogeneous catalysts. In addition, the catalyst is easily separated from the product and can be reused many times. This result implies that the heterogeneous catalyst (4) can perform sustainable epoxide-carbonylation on an industrial scale.
While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereto will be. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.
Claims (13)
The covalent bond containing the [M 1 (L 1) n (L 2) m] and [M 2 (L 3) x (CO) y] coordinates to the organic structure,
The covalent organic structure is a Covalent Triazine Framework (CTF)
M 1 and M 2 are independently Al, Cr, Fe, Co, Ti, W, Si, Ir, Pt, Pd, Ru, Th, Ni, Cu, V, Au, Re, Zr,
L 1 and L 2 are trifluoromethane sulfonate (OTf)
L 3 is at least one selected from the group consisting of cyclopentadiene, pentamethylcyclopentadiene, triphenylphosphine, cyclooctadiene, benzene, ethylene diamine, acetylacetonate ) Or a derivative thereof,
n, m, x and y are each independently an integer of 0 to 6, and 2? n + m? 4 and 2? x + y? 6.
(a) coordinating a transition metal compound represented by [M 1 (L 1 ) n (L 2 ) m ] in a covalently bonded organic structure in which a frame ligand forms a cavity and is bonded to each other; And
(b) [M 1 (L 1) n (L 2) m] a covalently bonded organic structure coordinated [M 2 (L 3) x (CO) y] is reacted with a metal compound containing a L 1 and L to Replacing part of 2 with [M 2 (L 3 ) x (CO) y ]
The covalent organic structure is a Covalent Triazine Framework (CTF)
M 1 and M 2 are independently Al, Cr, Fe, Co, Ti, W, Si, Ir, Pt, Pd, Ru, Th, Ni, Cu, V, Au, Re, Zr,
L 1 and L 2 are trifluoromethane sulfonate (OTf)
L 3 is at least one selected from the group consisting of cyclopentadiene, pentamethylcyclopentadiene, triphenylphosphine, cyclooctadiene, benzene, ethylene diamine, acetylacetonate ) Or a derivative thereof,
n, m, x and y are each independently an integer of 0 to 6, and 2? n + m? 4, 2? x + y?
(a) adding Al (OTf) 3 to a CTF in which bipyridine forms a cavity and bonds to each other to produce [bpy-CTF-Al (OTf) 3 ], and bpy is bipyridine; And
(b) [bpy-CTF- Al (OTf) 3] is one OTf anion by the addition of KCo (CO) 4 [Co ( CO) 4] in - is replaced by the anion [bpy-CTF-Al (OTf ) 2 ] [Co (CO) 4 ]. ≪ / RTI >
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