Patent Application
20200360911
The present disclosure relates to a ligand for ruthenium complex formation, a ruthenium complex catalyst, a preparation method thereof, and use thereof.
A following shell higher olefin process (SHOP) is a method of synthesis of linear α-olefin obtained from petrochemical raw materials as developed in 1977.
The shell higher olefin process has a problem in that the linear α-olefin has a wide distribution such that 41% of 4 to 8 carbon atoms, 40.5% of 10 to 18 carbon atoms and 18.5% of 20 or greater carbon atoms are obtained. For example, the shell higher olefin process has a low synthesis yield of 1-decene. In addition, this SHOP requires a high temperature of 60 to 300 degrees C. and a high pressure of 30 to 200 bar.
In order to overcome these drawbacks, research and development of ruthenium complex catalysts in olefin metathesis is vigorous.
Known ruthenium complex catalysts include the 2005 Nobel Prize-winning Grubbs catalyst (Yves Chauvin, Robert H. Grubbs and Richard R. Schrock).
For the production of linear α-olefin, natural seed oils may be used instead of petroleum based raw material.
For example, a method for synthesizing a linear α-olefin obtained from a renewable seed oil raw material is as follows.
Methyl oleate may undergo cross metathesis with ethylene. C═C double bond is decomposed by ethenolysis of the methyl oleate. Thus, the desired linear α-olefin may be synthesized.
Unlike the SHOP (Shell Higher Olefin Process) as described above, the synthesis yield of a single 1-decene is high in this cross metathesis. Further, unlike the SHOP (Shell Higher Olefin Process) as described above, the cross metathesis reaction using the Ru catalyst has an advantage that the reaction may be carried out under a low temperature of 40° C. to 100° C. and a low pressure of about 10 bar.
Further, the ruthenium complex catalyst may be N-heterocyclic carbene (NHC) ligand. Since the ruthenium complex with asymmetrically substituted N-heterocyclic carbene ligands exhibits a high selectivity to a cross-metathesis product compared to a by-product from the self-metathesis, the ruthenium complex with asymmetrically substituted N-heterocyclic carbene ligands has been identified as a promising catalyst for ethenolysis (Yann Schrodi, Thay Ung, Angel Vargas, Garik Mkrtumyan, ChoonWoo Lee, Timothy M. Champagne, Richard L. Pederson, Soon Hyeok Hong_Clean: Soil, Air, Water, 2008, 36, 669). Stabilization of methylidene intermediates has been suggested as a key factor in improving catalyst activity. It is known that additional electron donating ligands can help stabilize these methylidene intermediates (Vanessa M. Marx, Alexandra H. Sullivan, Mohand Melaimi, Scott C. Virgil, Benjamin K. Keitz, David S. Weinberger, Guy Bertrand, and Robert H. Grubbs_Angew. Chem. Int. Ed. 2015, 54, 1919).
The stability of the methylidene species was compared.
However, a phosphine ligand (Soon Hyeok Hong, Anna G. Wenzel, Tina T. Salguero, Michael W. Day, and Robert H. Grubbs_J. Am. Chem. Soc. 2007, 129, 7961) is degraded by phosphine. Thus, the phosphine-free catalyst is more stable than the phosphine ligand. Accordingly, the present inventors have studied the phosphine-free catalyst having the stability.
Imidazo [1,5-a]pyridine-3-ylidene (mPy), which was first reported in 2005, is a candidate for a structurally asymmetric NHC ligand and has various electronic characteristics.
Thus, the present inventors have repeatedly studied the effect of the asymmetric Impy-based ligand structure change on the activity, selectivity and stability of the catalyst. We have acquired a novel ruthenium complex ligand and ruthenium complex which has a high activity as a catalyst , and has a high selectivity to formation of terminal olefins in ethenolysis of methyl oleate and has high stability.
A purpose of the present disclosure is to provide a novel ruthenium complex ligand and ruthenium complex which has a high activity as a catalyst, and has a high selectivity to formation of terminal olefins in ethenolysis of methyl oleate and has high stability.
A ligand for the ruthenium complex formation in accordance with the present disclosure has a following Chemical Formula:
A ruthenium complex catalyst according to the present disclosure has a following Chemical Formula:
The ruthenium complex catalyst for ruthenium complex formation according to the present disclosure have the high catalyst activity, high selectivity, and stability.
The ruthenium complex catalyst according to the present disclosure can exhibit the high selectivity to the formation of terminal olefins in the ethenolysis of methyl oleate. As a result, the production efficiency of the terminal olefin can be improved.
The present disclosure is described in more detail below.
The present inventors have considered that the ruthenium complex with asymmetrically substituted N-heterocyclic carbene ligand exhibits a high selectivity to the cross-metathesis product compared to the by-products from self-metathesis. In conjunction with this consideration, we have studied the asymmetric ImPy-ruthenium complex catalysts.
Thus, the present inventors have completed a ligand for ruthenium complex formation, the ligand having following [Chemical Formula 1a] and [Chemical Formula 1b].
The ligand for ruthenium complex formation with a structure of the Chemical Formula 1a according to the present disclosure may include an asymmetric structure. In this connection, the asymmetric structure may mean that sizes of R1 and R2 are different from each other. In detail, R1 may include an atom or an atomic group smaller than that of R2. In the Chemical Formula 1a, due to the asymmetric structure where R1 has a smaller size than R2, the ligand for ruthenium complex formation with a structure of the Chemical Formula 1a may have the high selectivity. In this connection, the selectivity may mean that a proportion of the cross-metathesis product is higher than a portion of the by-product from the self-metathesis. Thus, the ligand for ruthenium complex formation according to the Chemical Formula 1a may bind with the ruthenium to be used as a catalyst for ethenolysis.
In the ligand for ruthenium complex formation with the structure according to Chemical Formula 1a, R1 and R2 may electronically and/or sterically influence the ruthenium since R1 and R2 may be placed at a close distance from the ruthenium atom or the atomic group bonded to ruthenium. Thus, in the ligand for ruthenium complex formation with a structure according to Chemical Formula Ia, R1 and R2 were determined under electronic and stereo control.
R1 may be F or methyl. The halogen element other than F increases the bond length with cyclic carbon and the size of the element is large and thus has the increased steric repulsion, to lower the selectivity of the reaction. Further, alkyl groups other than methyl may have the increased steric repulsion during ruthenium complex catalyst formation, thereby to reduce the selectivity of the reaction.
R2 may include substituted or unsubstituted aryl. For example, R2 may comprise a substituted aryl of 9 to 12 carbon atoms.
Each of R3, R4, R5 and R6 may represent one selected from a group consisting of hydrogen, a halogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. For example, each of R3, R5, and R6 may include hydrogen. For example, R4 may include one selected from a group consisting of H, t-Bu, MeO, and Cl.
The structure of R2 will be described in detail with reference to a following Chemical Formula 1b:
In the Chemical Formula 1b, each of R1, R3, R4, R5, and R6 are the same as in Chemical Formula 1a described above.
Each of R7, R8, R9, R10, and R11 may be selected from a group consisting of hydrogen or a linear or branched alkyl group having 1 to 8 carbon atoms. For example, each of R7, R8, R9, R10, and R11 may include one selected from hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms.
For example, R7 may include any one selected from ethyl, isopropyl, and t-butyl. For example, each of R8, R9, and R10 may include hydrogen. For example, R11 may be any one selected from methyl, ethyl, and isopropyl.
In the Chemical Formula 1b, R7 and R11 may have the same or different substituents. Specifically, the carbon number of R7 may be the same as the carbon number of R11, or the carbon number of R7 may be larger than the carbon number of R11. In one example, R7 and R11 may each be isopropyl. Alternatively, R7 and R11 may each be ethyl. In one example, R7 may be ethyl and R11 may be methyl. Alternatively, R7 may be isopropyl and R11 may be hydrogen. Alternatively, R7 may be t-butyl and R11 may be hydrogen.
Further, the present The inventor completed a ruthenium complex catalyst with [Chemical Formula 2a] and [Chemical Formula 2b]. The ruthenium complex catalyst with [Chemical Formula 2a] and [Chemical Formula 2b] may be formed by combining the ruthenium with the ligand for the ruthenium complex formation having the structure of [Chemical Formula 1a] and [Chemical Formula 1b]:
Since the ruthenium complex catalyst of the Chemical Formula 2a is a phosphine-free complex, instability due to decomposition may be removed. Further, the ruthenium complex catalyst of the Chemical Formula 2a is stable because R1 of the heterobicyclic ligand containing nitrogen can form a stable coordination with a metal center of Ru.
In the Chemical Formula 2a, R1, R3, R4, R5, and R6 are the same as in the Chemical Formula 1a as described above.
The structure of R2 will be described in detail with reference to the following Chemical Formula 2b:
In the Chemical Formula 2b, R7, R8, R9, R10 and R11 are the same as described above with reference to the Chemical Formula 1b.
More specifically, the present disclosure is described in detail below.
A cross-metathesis reaction with ethylene known as ethenolysis, has recently attracted much attention in terms of the selective synthesis of terminal olefins from renewable seed oils.
Referring to
The ethylene-based metathesis reaction is also called ethenolysis, and refers to a reaction that decomposes internal olefins to be converted to terminal olefin groups. This reaction has also been proposed as a new method for producing linear alpha olefins from oils present in nature, not via the petrochemistry. The present inventors have studied the reaction conversion, selectivity and catalyst reactivity using the methyl oleate.
In detail, we describe the ethenolysis of methyl oleate (1) and ruthenium metathesis catalyst.
Terminal olefins (so-called linear alpha-olefins; 2 and 3 in
Recent studies are focusing on the structural variation of the NHC ligand in order to achieve the selectivity to the desired α-olefins (2 and 3 in
The Grubbs-Hoveyda second-generation catalyst (6 in
In the ruthenium complex catalyst, the three-dimensional asymmetric substitution pattern of the N-heterocyclic carbene (NHC) ligand has been found to be very important for α-olefin selective ethenolysis. The lack of stereoscopic interactions on one side may favor “non-productive” metathesis of the alpha-olefin product and the methylidene intermediate to regenerate the same methylidene intermediate.
Imidazo[1,5-a]pyridin-3-ylidene carbine (ImPy), which was first reported independently by JM Lassaletta and F. Glorius in 2005, is a bicyclic variant of a typical imidazoylidene NHC. The ImPy ligand has an inherently asymmetric structure and is known to carry more electron donors than imidazolyliden NHC. Thus, the present inventors thought that the Ru-ImPy catalyst could be a good candidate for an efficient and selective ethenolysis reaction. Further, the R1 substituent of ImPy may be located close to the Ru metal center. For example, when R1 is fluorine, the Ru-F distance is expected to be short enough in terms of Ru-F bond interactions, which is not the case for other ruthenium metathesis catalysts with fluorinated NHC. The ImPy ligand (ImPy-Ru, 10) and ruthenium complex have not been reported.
In a following description, we refer to
DIBAL-H reduction of 2-pyridinecarboxylate derivatives (12a, 12g and 12h) yielded fluoropyridine carboxaldehyde (13a, 13g and 13h) with good separation yield. Alternatively, lithiation of 2-bromobipyridine (12f) followed by reaction with DMF yielded fluoropyridine carboxaldehyde (13f).
Next, imine formation (14a-14i) with aniline followed by cyclization with AgORf and chloromethyl pivalate provided the ImPy ligand with good overall separation yield (Christian Burstein, Christian W. Lehmann and Frank Glorius, Tetrahedron, 2005, 61, 6207).
ImPy containing chlorine atoms and methyl groups (10i to 10k) was synthesized from 6-chloropyridinecarboxaldehyde (13i, SI) and 6-methylpicolinecarboxaldehyde (13k, SI).
The Ru catalysts (10b, 10c, 10d, 10e, 10f, 10h, 10i, 10h, and 10k) were synthesized by the exchange reaction between free carbene made with the base and the phosphine ligand of the first generation Grubbs-Hoveyda catalyst.
The ImPy-Ru complex was synthesized as follows with the fluorinated ImPy ligand precursor (15a-15h). After in-situ deprotonation of imidacopyridinium salts (15a-15h) using potassium hexamethyldisilazide (KHMDS), the resulting product reacts with RuCl2(PCy3)(═CH-o-OiPrC6H4)(S1) to produce Grubbs-Hoveyda-type Ru complex with the ImPy ligand (10a-10k) at a reasonable separation yield ((a) S. F. Monsaert, F. W. C. Verpoort, Eur. Pat. 300 2011091980, 2011; S. F. Monsaert, F. W. C. Verpoort, WO 2011/091980 A1; S. F. Monsaert, F. W. C. Verpoort, PCT/EP2011/000300, 2011, (b) B. J. van Lierop, A. M. Reckling, J. A. M. Lummiss, and D. E. Fogg, ChemCatChem 2012, 4, 2020).
Complex (10i) containing a chlorine atom instead of fluorine was synthesized in a similar manner. These chelated benzylidene complexes (10a-10k) are stable under atmospheric conditions (air and moisture). These complexes were characterized by nuclear magnetic resonance spectroscopy (NMR), high resolution mass spectrometry (HRMS) and X-ray crystallography. The single crystal suitable for X-ray crystallography was grown by slow diffusion of hexane through the catalyst solution in dichloromethane at 25° C.
Among the synthesized catalysts, 10f (the second structure from the left in
Ru—F interactions may be identified on solid phase from X-ray analysis. The Ru—F interactions are believed to be involved in stabilizing the ruthenium methylidene intermediates.
Referring to
The selected coupling length (A) and coupling angle(°) are as follows.
For 10c: Ru—C1=1.956(5)A, Ru═C19=1.822(5)A, Ru—F1=2.688(3) A, Ru—O(1)=2.282(3)A, N1—C1—N1=101.8(3)°, C11—Ru—C12=154.13(5)°,
For 10f: Ru—C1=1.972(5)A, Ru═C28=1.803(5)A, Ru—F1=2.700(3) A, Ru—O1=2.274(3)A, N1—C1—N2=102.4(4)°, C11—Ru—C12=155.13(6)°,
For 10j: Ru—Cl=1.967(3)A, Ru—C17=1.840(3)A, Ru—C13=2.7194(8)A, Ru—O1=2.294(2)A, N1—C1—N2=102.0(2)°, C11—Ru—C12=165.43(3)°,
For 101: Ru—Cl=1.972(4)A, Ru═C21=1.831(3)A, Ru—C8=2.925(3)A, Ru—O1=2.300(3)A, N1—C1—N2=101.4(3)°, C11—Ru—C12=162.32(4)°.
Hereinafter, the present disclosure will be described in more detail through a concrete example.
The catalyst performance of the prepared ImPy-Ru complex was evaluated in the methyl oleate ethenolysis reaction.
The evaluation results are shown in Table 1.
Initial results in 10c (item 3) show that the structural asymmetry of the ImPy ligand results in an alpha-olefin selectivity, compared to the selectivity exhibited by other Grubbs-Hoveyda type Ru catalysts containing symmetric NHC. To investigate the steric effect of the ImPy ligand, the F-ImPy-Ru complexes (10a-10e and 10k) was tested in terms of ethenolysis reaction, using 100 ppm catalyst thereof at 60° C. and 150 psi ethylene. The complexes 10a and 10b show the higher conversion and turnover number compared to the complex 10c. However, probably because the steric hindrance is reduced on the same side, the complexes l0a and 10b exhibited a lower selectivity to the end products (2 and 3) compared to the products (4 and 5) of the self-and secondary-metathesis reactions (items 1, 2 and 3 in the table 1).
Control of the steric bulk of the same-side N-aryl group results in higher selectivity in ethenolysis. The use of mono-ortho-substituted N-aryl groups (10d and 10e) improved the turnover number to 2200 and 3400 while maintaining a high selectivity of 82% and 79% (items 4 and 5).
When the mono-ortho-substituted N-aryl groups are used, there may be a space for coordination of the olefins. A larger ortho substituent appears to be better for overall catalyst efficiency (R4 =t-Bu vs i-Pr) when a mono-substituted aryl (R3 =H) is used.
In Me-ImPy-Ru (10k), 91% selectivity was obtained, but the turnover number was lower presumably due to increased steric hindrance (item 6).
The present inventors compared the activities of synthesized ruthenium complex catalysts with each other. The results of the activity analysis of the ruthenium complex catalysts indicated by 10a to 10k having different structures are shown in Table 1.
The effects from steric restrictions of various alkyls having N-aryl groups were compared and analyzed using the synthesized catalysts 10a to 10k at a 100 ppm content at 60° C. for 3 hours.
The complexes 10a and 10b showed higher conversion compared to the complex 10c. However, both the former catalysts showed the lower selectivity because of the reduced steric restrictions of the alkyl having the N-aryl group. The larger the steric restrictions of the alkyl having the N-aryl group, the higher the selectivity.
The complexes 10d and 10e showed higher conversion compared to the complex 10c and at the same time maintained high selectivity. This is presumably due to the fact that there is a proper space for the olefin access when the alkyl is substituted only into one ortho-site in the N-aryl group.
Therefore, when the N-aryl group has a large alkyl group at the ortho position, this exhibits better catalyst conversion. The 10k has the high selectivity as in the above catalysts satisfying the above conditions, but the catalyst efficiency of the 10k is low. This is expected due to the steric restriction of the methyl group of R1.
The reaction conditions in the experiment in Table 1 were based on the catalyst content (ppm), and C2H4 (150 psi, 99.95% purity). The conversion and selectivity at 60° C. for 3 hours were measured using tridecane as an internal standard and using GC.
The conversion is calculated as 100−[(final molar number 1)*100/[initial molar number 1]].
The selectivity is calculated as 100*(2+3 moles)/[(2+3 moles)+(2*4+5 moles)].
The yield is calculated as conversion*selectivity/100.
The turnover number is calculated as yield*(initial mole number 1/mole number of catalyst)/100.
The present inventors compared the activities of synthesized ruthenium complex catalysts with each other. The results of the activity analysis of the ruthenium complex catalysts represented by 10e to 10i having different structures are shown in Table 2.
The complex 10f with a sigma-donor functional group and tert-butyl functional group shows a higher conversion compared to the complex 10e. However, the complexes lOg and 10h with the pie-donor functional group shows the lower conversion. The complex 10i with chlorine group in R1 does not show activity.
Table 2 summarizes the backbone substitution effect of F-ImPy-Ru catalysts. The complex 10f containing the σ-donating t-Bu group in the backbone has 50% conversion and 4000 turnover number to improves the activity of the catalyst compared to the complex 10e (item 2 vs item 1).
However, the catalysts 10g and 10h exhibit the lower conversions (item 3 and 4 vs item 1) compared to the complex 10e. In the complexes 10g and 10h, the πdonating group appears to be ineffective because it exhibits a low turnover number.
The Cl-ImPy-Ru catalyst does not exhibit catalyst activity (item 5).
The reaction conditions in the experiment in Table 2 were based on the catalyst content (ppm), and C2H4 (150 psi, 99.95% purity). The conversion and selectivity at 60° C. for 3 hours were measured using tridecane as an internal standard and using GC.
The conversion is calculated as 100−[(final molar number 1)*100/[initial molar number 1]].
The selectivity is calculated as 100*(2+3 moles)/[(2+3 moles)+(2*4+5 moles)].
The yield is calculated as conversion*selectivity/100.
The turnover number is calculated as yield*(initial mole number 1/mole number of catalyst)/100.
The present inventors compared the activity of the 10f ruthenium complex catalyst. The results of the activity analysis by controlling the amount of catalyst of the ruthenium complex catalyst indicated by 10f and the temperature are shown in Table 3.
We have established the reaction conditions by controlling the amount of catalyst of ruthenium complex catalyst having the 10f structure and temperature. Thus, 6700 TON (turnover numbers) was obtained at a temperature of 60° C. using a catalyst amount of 20 ppm.
Table 3 summarizes the optimization of the reaction condition for catalyst loading and reaction temperature. The catalyst loading at 60° C. and the 200 ppm shows optimum catalyst performance (6700 turnover number, 71% selectivity).
The reaction conditions in the experiment of Table 3 were based on the catalyst content (ppm), and C2H4 (150 psi, 99.95% purity). The conversion and selectivity at 60 ° C. for 3 hours were measured using tridecane as an internal standard and using GC.
The conversion is calculated as 100−[(final molar number 1)*100/[initial molar number 1]].
The selectivity is calculated as 100*(2+3 moles)/[(2+3 moles)+(2*4+5 moles)].
The yield is calculated as conversion*selectivity/100.
The turnover number is calculated as yield*(initial mole number 1/mole number of catalyst)/100.
Item 5 of Table 3 refers to a reaction for 12 hours.
The present disclosure describes the synthesis of a novel ruthenium catalyst containing an asymmetric ImPy ligand (ImPy-Ru) and the application thereof to the catalytic ethenolysis of methyl oleate.
The effects of the ligand structure changes on the catalyst activity, selectivity and stability were investigated. The Ru-F interactions were identified using the solid state by X-ray analysis, and the Ru-F interactions could stabilize ruthenium methylidene intermediates.
The F-ImPy-Ru catalyst with an ortho-t-Bu-phenyl substituent on the ring nitrogen and a sigma donating t-Bu group on the pyridine backbone showed a high turnover number (up to 6700).
The ImPy-Ru catalyst exhibits the high selectivity (up to 86%) to the terminal olefin formation in the ethenolysis of methyl oleate.
The ruthenium complex according to [Chemical Formula 2a] and [Chemical Formula 2b] according to the present disclosure may be used as a catalyst in the olefin metathesis reaction. Thus, the production yield of the linear alpha-olefins through the olefin metathesis reaction can be improved.
That is, the ruthenium complex catalyst of the Present Example can exhibit selectivity of greater than 70% in the olefin metathesis reaction at 60° C. for 3 hours. For example, the ruthenium complex catalyst of the Present Example can exhibit selectivity of 75% to 86% to the terminal olefin formation in the ethenolysis of methyl oleate. For example, the ruthenium complex catalyst of the Present Example can exhibit 81% to 86% selectivity to terminal olefin formation in the ethenolysis of methyl oleate.
The ruthenium complex according to the present disclosure is not limited thereto, and may be utilized in various reactions such as an intramolecular ring-closing olefin metathesis reaction, an intermolecular olefin metathesis reaction, and an olefin metathesis polymerization reaction.
For example, referring to
For example, when using the ImPy-Ru complex according to the Example, the conversion in the intramolecular ring-closed metathesis reaction may be greater than 88%. For example, in the case of using the ImPy-Ru complex according to the Example, the conversion in the intramolecular ring-closed metathesis reaction may be greater than 92%. For example, in the case of using the ImPy-Ru complex according to Example, the conversion in the intramolecular ring-closed metathesis reaction may be from 92% to 99%.
Referring to
Table 4 summarizes optimization of reaction conditions for catalyst loading and reaction temperature. (73 conversion, 47% selectivity and 34% yield)
The reaction conditions in the experiments in Table 4 were based on the catalyst content (ppm), and C2H4 (150 psi, 99.95% purity). The conversion and selectivity at 60° C. for 3 hours were measured using tridecane as an internal standard and using GC.
In the ruthenium complex and cyclic alkyne compound reaction, the ring opening metathesis polymerization may have high activity and may allow competitive side reaction of ethenolysis.
In addition, linear a, w-diene can be competitively side-reacted via condensation polymerization while ethylene is removed. For example, referring to
For example, referring to
For example, the ruthenium complex catalyst according to the present disclosure may be used to improve the yield of the depolymerization or ethenolysis reaction of 1,4-polybutadiene.
For example, the ruthenium complex catalyst according to the present disclosure may be used to synthesize the linear diene compound such as 1,9-decadiene, 1,8-nonadiene, 1,7-octadiene, 1,6-heptadiene, 1,5-hexadiene, 1,4-pentadiene, and 1,3-butadiene using the depolymerization or ethenolysis reaction.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2018/007122 | 6/22/2018 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62523803 | Jun 2017 | US |
