Method for producing organic compounds

Abstract

The method for producing an organic compound according to the present invention comprises reacting a starting compound using a catalyst in the presence of a gas phase and a liquid phase comprising an organic phase and an aqueous phase, thereby producing the organic compound. The method includes stirring the liquid phase under the stirring conditions of a unit stirring power of 0.5 kW / m3 to 3.5 kW / m3 inclusive and a stirring-blade tip speed of 1.10 m / s or higher.

Description

Technical Field

[0001] The present invention relates to a method for producing an organic compound.

Background Art

[0002] Conventionally, stirring conditions for efficiently producing organic compounds have been studied. For example, in Patent Document 1, in a reaction vessel having a stirrer, when the stirring speed is n [rpm] and the diameter of the stirring blade is d [m], n × d 3 / 2 A method for producing an aromatic cyanate ester is described in which the reaction is carried out under conditions where the value is 8 or more.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] There was room for improvement in the conventional stirring conditions. In particular, improvement of the stirring conditions is required when producing an organic compound using a reaction system involving not only a liquid phase but also a gas phase.

[0005] Therefore, an object of the present invention is to provide a production method suitable for improving the yield of an organic compound.

Means for Solving the Problems

[0006] The present invention provides A method for producing an organic compound by reacting a starting compound using a catalyst in the presence of a gas phase and a liquid phase containing an organic phase and an aqueous phase, where the unit stirring power is 0.5 kW / m 3 or more and 3.5 kW / m 3 or less, and including stirring the liquid phase under stirring conditions where the tip speed of the stirring blade is 1.10 m / s or more. [Effects of the Invention]

[0007] According to the present invention, a manufacturing method suitable for improving the yield of organic compounds can be provided. [Brief explanation of the drawing]

[0008] [Figure 1] Figure 1 is a schematic cross-sectional view showing an example of a stirring device used in the method for producing organic compounds according to this embodiment. [Figure 2] Figure 2 is a cross-sectional view of a stirring apparatus illustrating an example of a method for producing an organic compound according to this embodiment. [Figure 3] Figure 3 is a graph showing the stirring conditions for Examples 1 to 12 and Comparative Examples 1 to 2. [Modes for carrying out the invention]

[0009] A method for producing an organic compound according to a first aspect of the present invention is: A method for producing an organic compound by reacting a starting compound with a catalyst in the presence of a gas phase and a liquid phase containing an organic phase and an aqueous phase, The unit stirring power is 0.5 kW / m². 3 More than 3.5kW / m 3 The following includes stirring the liquid phase under stirring conditions where the tip speed of the stirring blade is 1.10 m / s or higher.

[0010] In a second embodiment of the present invention, for example, in the method for producing an organic compound according to the first embodiment, the tip velocity of the stirring blade is 1.8 m / s or more.

[0011] In a third aspect of the present invention, for example, in the method for producing an organic compound according to the first or second aspect, the unit stirring power is 2.8 kW / m 3 The following applies:

[0012] In a fourth aspect of the present invention, for example, in a method for producing an organic compound according to any one of the first to third aspects, the rotation speed under the stirring conditions is 10 rpm or more and 1200 rpm or less.

[0013] In a fifth aspect of the present invention, for example, in a method for producing an organic compound according to any one of the first to fourth aspects, the liquid phase is 0.05 L or more and 7000 L or less.

[0014] In a sixth aspect of the present invention, for example, in a method for producing an organic compound according to any one of the first to fifth aspects, the proportion of the organic phase in the liquid phase is 5% by volume or more and 60% by volume or less.

[0015] In the seventh aspect of the present invention, for example, in the method for producing an organic compound according to any one of the first to sixth aspects, the temperature of the liquid phase in the reaction is 40°C or higher and 100°C or lower.

[0016] In the eighth aspect of the present invention, for example, in the method for producing an organic compound according to any one of the first to seventh aspects, the stirring is performed using a stirring blade, and in a stationary state, the interface between the aqueous phase and the organic phase is in contact with the stirring blade.

[0017] In the ninth aspect of the present invention, for example, in the method for producing an organic compound according to any one of the first to eighth aspects, the reaction is a reversible reaction.

[0018] In a tenth embodiment of the present invention, for example, in a method for producing an organic compound according to any one of the first to ninth embodiments, the organic phase includes the catalyst and the aqueous phase includes the starting compound.

[0019] In the eleventh embodiment of the present invention, for example, in a method for producing an organic compound according to any one of the first to tenth embodiments, the gas phase includes a gas that can react with the starting compound.

[0020] In a twelfth embodiment of the present invention, for example, in the method for producing an organic compound according to the eleventh embodiment, the gas contains hydrogen, and the reaction is a hydrogenation reaction of the starting compound.

[0021] In the 13th aspect of the present invention, for example, in the method for producing an organic compound according to the 12th aspect, the starting compound is at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate, and a formate is synthesized from the starting compound by the reaction.

[0022] In the 14th aspect of the present invention, for example, in the method for producing an organic compound according to any one of the 1st to 13th aspects, the catalyst is a metal catalyst.

[0023] In the 15th aspect of the present invention, for example, in the method for producing an organic compound according to the 14th aspect, the metal catalyst contains ruthenium.

[0024] In the 16th aspect of the present invention, for example, in the method for producing an organic compound according to any one of the 1st to 15th aspects, the organic phase contains toluene.

[0025] In the 17th aspect of the present invention, for example, in the method for producing an organic compound according to any one of the 1st to 16th aspects, the unit stirring power is 0.5 kW / m 3 or more and 2.0 kW / m 3 or less.

[0026] In the 18th aspect of the present invention, for example, in the method for producing an organic compound according to any one of the 1st to 17th aspects, the unit stirring power is 1.5 kW / m 3 or less.

[0027] Hereinafter, the details of the present invention will be described, but the following description is not intended to limit the present invention to specific embodiments.

[0028] (Method for Producing Organic Compound) The method for producing an organic compound of the present embodiment is a method for producing an organic compound by reacting a starting compound using a catalyst in the presence of a gas phase and a liquid phase containing an organic phase and an aqueous phase. The method for producing an organic compound of the present embodiment has a unit stirring power of 0.5 kW / m 3 or more and 3.5 kW / m 3The following stirring conditions are used, and the stirring blade tip speed is 1.10 m / s or higher, to stir the liquid phase. The aqueous phase is a phase containing an aqueous solvent, the organic phase is a phase containing an organic solvent, and the gas phase is a phase containing a gas. In this specification, aqueous solvents and organic solvents are sometimes collectively referred to as solvents. In this specification, the liquid phase containing the organic phase and the aqueous phase is sometimes referred to as the reaction solution.

[0029] Unit stirring power is the stirring power per unit volume of the liquid phase. The tip velocity of the stirring blade is given by the formula: rotational speed n(s). -1 The value is calculated as ) × impeller diameter d(m) × π. Rotation speed n is the number of rotations of the impeller per second. Impeller diameter d is the diameter of the circle traced by the tip of the impeller.

[0030] In the manufacturing method of this embodiment, the reaction of the starting compounds proceeds by bringing the liquid phase into contact with the gas phase through stirring. For example, the reaction mixture is stirred using a stirring device equipped with a stirring blade. At this time, by ensuring that the tip speed of the stirring blade is 1.10 m / s or higher, the droplets of the organic phase and the aqueous phase, as well as the bubbles of the gas phase, are refined to suit the progress of the gas-liquid reaction. Furthermore, the unit stirring power is 0.5 kW / m 3 More than 3.5kW / m 3 The reaction mixture is sufficiently circulated under the following conditions. This enables contact between the gas phase and the liquid phase suitable for the progress of the gas-liquid reaction. Here, the unit stirring power is 3.5 kW / m². 3 When the turbine is larger and the blade tip velocity is 1.10 m / s or higher, droplet miniaturization and circulation of the liquid phase become dominant, and the frequency of contact between liquid phases increases compared to contact between gas and liquid phases. This tends to make the reverse reaction of the reaction to synthesize the target organic compound more likely to occur. Therefore, it is not suitable for improving yield. Also, the unit stirring power is 0.5 kW / m 3If the stirring speed is less than 1.10 m / s, the ability to circulate the entire reaction solution is insufficient, preventing sufficient contact between the gas phase and the liquid phase, and tending to reduce the yield. Also, if the stirring blade tip speed is less than 1.10 m / s, the atomization of droplets and bubbles is insufficient, preventing sufficient contact between the gas phase and the liquid phase, and tending to reduce the yield. Therefore, by satisfying the above stirring conditions, the manufacturing method of this embodiment can produce organic compounds in an improved yield.

[0031] In the method for producing organic compounds according to this embodiment, the reaction of the starting compound can be carried out, for example, as follows. First, a reaction solution containing an organic phase and an aqueous phase, and a gas phase are prepared. In the reaction solution, the organic phase may contain a catalyst, and the aqueous phase may contain the starting compound.

[0032] Next, prepare a reaction vessel and a stirring device equipped with a stirring blade, and introduce the gas phase and reaction liquid into the reaction vessel.

[0033] The reaction is carried out by rotating the stirring blade to achieve the above stirring conditions and stirring the reaction mixture. As an example, the starting compound reacts with the gas contained in the gas phase. If the gas contains hydrogen, the reaction of the starting compound is typically a hydrogenation reaction. However, the reaction of the starting compound is not limited to a hydrogenation reaction, and may also be a reduction reaction, dehydration condensation reaction, hydrolysis reaction, etc. In the method for producing the organic compound of this embodiment, the gas phase may contain hydrogen, and the hydrogenation reaction of the starting compound by hydrogen may proceed.

[0034] The reaction of the starting compound is, for example, a reversible reaction. As described above, the manufacturing method of this embodiment uses a unit stirring power of 3.5 kW / m 3 The following steps tend to suppress the progress of the reverse reaction, which is considered one of the factors that reduce yield. Therefore, the production method of this embodiment can particularly improve yield when the reaction of the starting compound is a reversible reaction.

[0035] The unit stirring power is, for example, 3.3 kW / m². 3 The following are also acceptable: 3.0 kW / m 3Below, 2.8kW / m 3 Below, 2.5kW / m 3 Below, 2.3kW / m 3 Below, 2.0kW / m 3 Below, 1.9kW / m 3 Below, 1.8kW / m 3 Below, 1.7kW / m 3 Below, 1.6kW / m 3 Below, 1.5kW / m 3 Below, 1.4kW / m 3 Below, 1.3kW / m 3 Furthermore, 1.2 kW / m 3 The following may also apply: The unit stirring power is, for example, 0.508 kW / m³. 3 It may be greater than or equal to 0.54 kW / m 3 The above is 0.6 kW / m 3 More than 0.65kW / m 3 More than 0.7kW / m 3 More than 0.8kW / m 3 More than 0.9kW / m 3 Furthermore, 1.0 kW / m 3 The above is also acceptable. The unit stirring power is, for example, 0.5 kW / m 3 More than 3.3kW / m 3 Below, 0.508kW / m 3 Above 3.0kW / m 3 Below, 0.6kW / m 3 More than 2.8kW / m 3 It may also be less than 0.5 kW / m 3 More than 1.8kW / m 3 Below, 0.508kW / m 3 More than 1.5kW / m 3 Below, 0.6kW / m 3 More than 1.5kW / m 3 The following is also acceptable.

[0036] The blade tip velocity may be, for example, 1.20 m / s or more, 1.30 m / s or more, 1.40 m / s or more, 1.50 m / s or more, 1.60 m / s or more, 1.70 m / s or more, 1.80 m / s or more, and even 1.90 m / s or more. There is no particular upper limit to the blade tip velocity, but for example, it is 5.00 m / s or less.

[0037] The rotational speed of the impeller per minute is not particularly limited, but may be, for example, 10 rpm or more, 100 rpm or more, 200 rpm or more, 300 rpm or more, 400 rpm or more, 450 rpm or more, 485 rpm or more, 500 rpm or more, 600 rpm or more, 650 rpm or more, and even 670 rpm or more. The rotational speed of the impeller per minute may be, for example, 1200 rpm or less, 1100 rpm or less, 1000 rpm or less, 970 rpm or less, 900 rpm or less, 800 rpm or less, and even 750 rpm or less. The rotational speed of the impeller per minute may be, for example, 10 rpm or more and 1200 rpm or less, 100 rpm or more and 1100 rpm or less, and 300 rpm or more and 1000 rpm or less.

[0038] The reaction mixture may be heated while it is being stirred. This accelerates the synthesis reaction of the organic compound.

[0039] The temperature of the reaction solution is not particularly limited, but to ensure the reaction proceeds efficiently, the reaction solution may be heated to, for example, 30°C or higher, 40°C or higher, 50°C or higher, 60°C or higher, or even 70°C or higher. From the viewpoint of energy efficiency, the reaction solution is preferably 200°C or lower, more preferably 150°C or lower, and even more preferably 100°C or lower, less than 100°C, or even less than 90°C. The temperature of the reaction solution in the reaction of the starting compound is, for example, 40°C or higher and less than 100°C, 40°C or higher and less than 100°C, 40°C or higher and 90°C or lower, or 65°C or higher and less than 100°C. For example, the gas phase, aqueous phase, and organic phase may be heated to 90°C or to 70°C.

[0040] The duration of the synthesis reaction is not particularly limited. That is, the stirring time is not particularly limited. The reaction time is not particularly limited from the viewpoint of ensuring sufficient reactivity, but for example it may be 0.5 hours or more, 1 hour or more, 1.5 hours or more, 2 hours or more, 3 hours or more, 6 hours or more, 12 hours or more, 24 hours or more, 48 hours or more, 60 hours or more, and even 100 hours or more. The upper limit of the reaction time is not particularly limited, and for example it may be 1000 hours or less, 800 hours or less, 300 hours or less, 200 hours or less, 100 hours or less, 50 hours or less, and even 20 hours or less.

[0041] The reaction pressure (gas pressure in the reaction vessel) is not particularly limited, but from the viewpoint of improving yield, it may be, for example, 0.1 MPa or higher, 0.2 MPa or higher, 0.5 MPa or higher, 1 MPa or higher, 4 MPa or higher, 4.5 MPa or higher, 5 MPa or higher, or even 7 MPa or higher. The upper limit of the reaction pressure is not particularly limited, and may be, for example, 50 MPa, 20 MPa or 10 MPa.

[0042] The obtained organic compound is dissolved in the aqueous phase, for example. After stirring, the organic phase and aqueous phase may be recovered and separated. Since the aqueous phase and organic phase can be separated by a simple method, the organic compound can be easily recovered. In addition, expensive metal catalysts tend to be reusable without losing their catalytic activity. High productivity can be achieved by reusing the catalyst.

[0043] The manufacturing method of this embodiment is suitable for improving the yield of organic compounds in catalyst-assisted reactions in the presence of a gas phase, an aqueous phase, and an organic phase. The yield is preferably 70% or higher, and may be 75% or higher, or even 80% or higher. The upper limit of the yield is not particularly limited, and is, for example, 99%.

[0044] The stirring device, reaction solution, gas phase, and catalyst used in the method for producing the organic compound of this embodiment will be described in detail below.

[0045] (Agitation device) Figure 1 is a schematic cross-sectional view showing an example of a stirring device used in the method for producing organic compounds according to this embodiment. The stirring device 100 comprises a reaction vessel 10 and a stirring blade 20, the stirring blade 20 being attached to a stirring shaft 21. The reaction vessel 10 contains a reaction liquid 30. The stirring blade 20 and the stirring shaft 21 may be an integrated unit. The stirring device 100 may further have one or more openings (not shown) for supplying the gas phase and the reaction liquid 30 (organic phase and aqueous phase) to the interior.

[0046] The shape of the stirring blade 20 is not particularly limited. Examples of stirring blades 20 include anchor blades, turbine blades, paddle blades, or large blades. Examples of large blades include Fullzone® blades (Shinko Environmental Solutions Co., Ltd.) and Maxblend® blades (Sumitomo Heavy Industries Process Equipment Co., Ltd.). The stirring blade 20 may also be an anchor blade or a turbine blade.

[0047] The diameter d of the stirring blade is not particularly limited as long as it satisfies the above stirring conditions and the stirring blade 20 fits inside the reaction vessel 10.

[0048] In a stationary state, the ratio h / L1 of the length h of the stirring blade 20 to the distance L1 from the inner bottom 10a of the reaction vessel 10 to the liquid surface 30a of the reaction liquid 30 (i.e., the height of the liquid surface 30a in the reaction vessel 10) may be 5% or more and 95% or less, or 5% or more and 50% or less. The length h of the stirring blade 20 is the blade length of the stirring blade 20 in the direction of the stirring shaft 21 (axis direction of rotation), as shown in Figure 1. The stirring blade 20 is an anchor blade, and the ratio h / L1 may be 50% or more and 90% or less.

[0049] As shown in Figure 2, it is preferable that the interface 33 between the aqueous phase 31 and the organic phase 32 and the stirring blade 20 are in contact when the reaction is standing still. That is, when the reaction is standing still, the distance L2 from the inner bottom 10a of the reaction vessel 10 to the interface 33 is preferably greater than the distance from the inner bottom 10a of the reaction vessel 10 to the bottom (one end in the axial direction) of the stirring blade 20, and smaller than the distance from the inner bottom 10a to the top (the other end in the axial direction) of the stirring blade 20. It is more preferable that the proportion of the organic phase in the reaction solution 30 is 5% by volume or more and less than 50% by volume, and that the interface 33 and the stirring blade 20 are in contact when the reaction is standing still.

[0050] In a stationary state, the ratio L3 / L2 of the distance L3 from the inner bottom 10a of the reaction vessel 10 to the axial center 20c of the stirring blade 20 (i.e., the height of the axial center 20c of the stirring blade 20 in the reaction vessel 10) to the distance L2 from the inner bottom 10a of the reaction vessel 10 to the interface 33 (i.e., the height of the interface 33 in the reaction vessel 10) is preferably 0.5 or more and 1.8 or less, more preferably 0.7 or more and 1.5 or less, even more preferably 0.8 or more and 1.2 or less, and particularly preferably 0.9 or more and 1.1 or less. The axial center 20c of the stirring blade 20 is set to half the length h of the stirring blade 20, as shown in Figure 2. 1 / 2 This is the position where it is divided. The axial direction is typically aligned with the vertical direction. That is, the direction of the stirring shaft 21 is typically aligned with the vertical direction. In a stationary state, the reaction vessel 10 is positioned so that the liquid surface 30a and the interface 33 extend horizontally.

[0051] The volume of the reaction vessel 10 is not particularly limited and can be appropriately selected according to the scale of production. For example, the volume of the reaction vessel 10 is 0.3 L or more and 10,000 L or less.

[0052] (Reaction solution) The reaction solution 30 includes an aqueous phase and an organic phase.

[0053] The volume of the reaction solution 30 is not particularly limited, but may be, for example, 0.05 L or more and 7000 L or less, 0.05 L or more and 5000 L or less, 0.05 L or more and 1000 L or less, 0.08 L or more and 500 L or less, 0.08 L or more and 100 L or less, 0.08 L or more and 50 L or less, 0.08 L or more and 20 L or less, 0.1 L or more and 20 L or less, 0.5 L or more and 20 L or less, 1.0 L or more and 20 L or less, 1.4 L or more and 20 L or less, 0.08 L or more and 1.4 L or less, or 1.4 L or more and 1000 L or less.

[0054] The aqueous phase contains an aqueous solvent. The aqueous phase may further contain the starting compound.

[0055] Examples of aqueous solvents include water, methanol, ethanol, ethylene glycol, glycerin, and mixtures thereof, with water being preferred from the viewpoint of low environmental impact.

[0056] The aqueous phase may contain an aqueous solvent and the starting compound.

[0057] The starting compound is, for example, an inorganic substance. Examples of inorganic substances include carbon dioxide, bicarbonates, and carbonates. That is, the starting compound may be at least one selected from the group consisting of carbon dioxide, bicarbonates, and carbonates.

[0058] Examples of bicarbonates and carbonates include alkali metal and alkaline earth metal carbonates or bicarbonates. Examples of bicarbonates include sodium bicarbonate and potassium bicarbonate, with potassium bicarbonate being preferred from the viewpoint of high solubility in water. That is, in this embodiment, the starting compound preferably contains potassium bicarbonate as the bicarbonate. Examples of carbonates include sodium carbonate, potassium carbonate, sodium potassium carbonate, and sodium sesquicarbonate.

[0059] Bicarbonates and carbonates can be produced by the reaction of carbon dioxide with a base. For example, bicarbonates or carbonates may be produced by introducing carbon dioxide into a basic solution.

[0060] There are no particular restrictions on the solvent of the basic solution used in the production of bicarbonates or carbonates, but examples include water, methanol, ethanol, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, benzene, toluene, and mixed solvents thereof. It is preferable that the solvent contains water, and more preferably water. There are no particular restrictions on the base used in the basic solution, as long as it can react with carbon dioxide to produce bicarbonates or carbonates, and hydroxides are preferred. Examples include lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, potassium hydroxide, sodium hydroxide, diazabicycloundecene, and triethylamine. Among the above, hydroxides are preferred, potassium hydroxide and sodium hydroxide are more preferred, and potassium hydroxide is even more preferred.

[0061] The base content in the basic solution is not particularly limited, as long as it is sufficient to produce bicarbonate and carbonate. From the viewpoint of ensuring the amount of formate produced, the base content is preferably 0.1 mol or more, more preferably 0.5 mol or more, and even more preferably 1 mol or more per liter of aqueous solvent. From the viewpoint of reaction efficiency, it is preferably 30 mol or less, more preferably 20 mol or less, and even more preferably 15 mol or less. However, if it exceeds the solubility of the aqueous phase, the solution will be suspended.

[0062] The ratio of carbon dioxide to base used in the reaction between carbon dioxide and a base is preferably 0.1 or higher in molar ratio, more preferably 0.5 or higher, and even more preferably 1.0 or higher, from the viewpoint of producing carbonate from carbon dioxide. Furthermore, from the viewpoint of carbon dioxide utilization efficiency, it is preferably 8.0 or lower, more preferably 5.0 or lower, and even more preferably 3.0 or lower. The ratio of carbon dioxide to base used is expressed as molar amount of CO2 (mol) / molar amount of base (mol). By setting the ratio of carbon dioxide to base used within the above range, the excessive input of carbon dioxide can be suppressed, unreacted carbon dioxide can be minimized, and the final conversion efficiency of formic acid can be easily improved.

[0063] The reaction temperature in the reaction that produces a bicarbonate or carbonate by the reaction of carbon dioxide with a base is not particularly limited, but it is preferably 0°C or higher, more preferably 10°C or higher, and even more preferably 20°C or higher, in order to dissolve carbon dioxide in the aqueous phase. It is also preferably 100°C or lower, more preferably 80°C or lower, and even more preferably 40°C or lower.

[0064] The reaction time in the reaction between carbon dioxide and a base to produce a bicarbonate or carbonate is not particularly limited, but from the viewpoint of ensuring a sufficient amount of bicarbonate or carbonate produced, it is preferably 0.5 hours or more, more preferably 1 hour or more, and even more preferably 2 hours or more. Also from the viewpoint of cost, it is preferably 24 hours or less, more preferably 12 hours or less, and even more preferably 6 hours or less.

[0065] The proportion of the aqueous phase in reaction solution 30 may be 40% by volume or more and 95% by volume or less, 45% by volume or more and 90% by volume or less, 50% by volume or more and less than 95% by volume, 50% by volume or more and 90% by volume or less, 50% by volume or more and 80% by volume or less, or 80% by volume or more and 95% or less.

[0066] The organic phase contains an organic solvent. The organic phase may further contain a catalyst. Preferably, the organic phase contains a catalyst and a solvent that dissolves the catalyst and makes it homogeneous.

[0067] Examples of organic solvents include toluene, benzene, xylene, propylene carbonate, dioxane, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, methylcyclohexane, cyclopentyl methyl ether, and mixed solvents thereof. From the viewpoint of separation from aqueous solvents, it is preferable to include toluene or dioxane, and more preferable to include toluene.

[0068] The proportion of the organic phase in the reaction solution 30 may be 5% to 60% by volume, 5% to less than 50% by volume, 10% to 55% by volume, 10% to 50% by volume, 20% to 50% by volume, or 5% to 20% by volume. According to the manufacturing method of this embodiment, an organic compound can be produced in good yield regardless of the proportion of the organic phase.

[0069] (gas phase) The gas phase contains a gas. The gas phase may contain at least a portion of the raw materials. The gas phase may contain a gas that can react with the starting compound. This gas may include, for example, hydrogen.

[0070] As hydrogen sources, for example, hydrogen generated during the iron smelting process or hydrogen generated during the soda production process can be used. Hydrogen generated from the electrolysis of water can also be utilized.

[0071] The gas phase may contain the starting compound. For example, if the starting compound is carbon dioxide, the gas phase may contain the starting compound.

[0072] Carbon dioxide may be pure carbon dioxide gas or a mixture with other components. Other components may include inert gases such as nitrogen and argon, water vapor, and other components found in exhaust gases. The ratio of hydrogen to carbon dioxide used may be equal on a molar basis, but an excess of hydrogen is preferable.

[0073] (catalyst) In the method for producing organic compounds according to this embodiment, the catalyst is, for example, a metal catalyst. The metal catalyst includes, for example, ruthenium.

[0074] In the method for producing organic compounds according to this embodiment, it is preferable to use at least one compound selected from the group consisting of metal complexes represented by the following general formula (1A), their tautomers, stereoisomers, and salts thereof, as a catalyst.

[0075] [ka]

[0076] (In general formula (1A), X represents an atomic group containing typical elements from groups 13 to 15 that can coordinate with M. Each Q independently represents a bridging structure containing typical elements from groups 14 to 16 that connects Y and X. Y represents an atomic group containing typical elements from groups 14 to 16 that can independently coordinate with M, and M represents a metal atom. Z represents a halogen atom or a hydrogen atom. n represents 0 to 3, If multiple Ls exist, each L independently represents a neutral or anionic ligand.

[0077] In this specification, "group n" means "group n of the periodic table."

[0078] Typical elements of groups 13 to 15 of the periodic table in X include boron, carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, oxygen, sulfur, and selenium. Boron, carbon, silicon, germanium, tin, nitrogen, phosphorus, and arsenic are preferred, carbon, nitrogen, phosphorus, and sulfur are more preferred, and carbon or nitrogen is even more preferred.

[0079] X may be an atomic group with a valency of 0 to 1. Examples of atomic groups represented by X include alkyl groups, alkenyl groups, alkoxy groups, aromatic rings, and heterocycles, which may have substituents or be bonded with other substituents to form a ring.

[0080] Examples of alkyl groups in X include linear, branched, cyclic, substituted, or unsubstituted alkyl groups. Preferably, the alkyl group in X is an alkyl group having 1 to 30 carbon atoms, such as a methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, n-octyl group, eicosyl group, or 2-ethylhexyl group, and is preferably an alkyl group having 6 or fewer carbon atoms, and is preferably a methyl group.

[0081] Examples of alkenyl groups in X include linear, branched, cyclic substituted, or unsubstituted alkenyl groups. Preferably, the alkenyl group in X is a C2 to C30 alkenyl group, such as a vinyl group, n-propenyl group, i-propenyl group, t-butenyl group, n-octenyl group, etc., and it is preferable that the alkenyl group has 6 or fewer carbon atoms.

[0082] Examples of alkoxy groups in X include linear, branched, cyclic substituted or unsubstituted alkyloxy groups. Preferably, examples of alkoxy groups in X include substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, and 2-methoxyethoxy groups.

[0083] Examples of aromatic rings in X include phenyl rings and naphthyl rings.

[0084] Examples of heterocyclic rings in X include pyrrolidine rings, piperidine rings, pyrroline rings, imidazoline rings, imidazolidine rings, pyrrole rings, imidazole rings, pyridine rings, pyrimidine rings, triazine rings, quinoline rings, and quinazoline rings.

[0085] The group of atoms represented by X, which has a valency of 0 to 1, preferably represents a group of atoms that includes a heteroaromatic ring formed with two carbon atoms and a nitrogen atom. These groups may have substituents, or they may bond with other substituents to form a ring.

[0086] The 0-1 valent atomic group represented by X is preferably a pyrroline ring, pyridine ring, imidazoline ring, pyrimidine ring, or triazine ring, more preferably a pyridine ring or triazine ring, and even more preferably a pyridine ring.

[0087] When the 0- to 1 valent atomic group represented by X has substituents, examples of substituents include substituent group A, where alkyl groups are preferred and methyl groups are more preferred.

[0088] The bridging structure between Y and X represented by Q, which includes typical elements from groups 14 to 16 of the periodic table, may have a double bond, a monocyclic or fused ring structure, or substituents.

[0089] Q can be made to have various structures, but for example, the number of atoms in the part between Y and X is preferably 1 to 5, more preferably 1 to 4, even more preferably 1 to 3, and particularly preferably 1 to 2.

[0090] The atoms in the portion between Y and X described above are not particularly limited, but carbon atoms, nitrogen atoms, phosphorus atoms, oxygen atoms, and sulfur atoms are preferred, carbon atoms, nitrogen atoms, and oxygen atoms are more preferred, carbon atoms and oxygen atoms are even more preferred, and carbon atoms are particularly preferred.

[0091] Q may have a monocyclic structure. In other words, the bridging structure represented by Q may include a cyclic structure.

[0092] If Q has a monocyclic structure, the monocyclic structure may be directly bonded to Y and X in general formula (1A), or a divalent substituent may be sandwiched between the monocyclic structure and Y and / or Z in general formula (1A). Examples of the divalent substituent include alkylene groups having 1 to 5 carbon atoms, alkenylene groups having 2 to 5 carbon atoms, heteroatoms such as oxygen atoms and sulfur atoms, or these being bonded in series.

[0093] Q preferably represents CH2, NH, or O independently, and CH2 and NH may have further substituents, with CH2 or NH being more preferably representing Q.

[0094] Q may have a fused ring structure. In other words, the cross-linked structure represented by Q may include a fused ring structure.

[0095] If Q has a fused ring structure, the fused ring structure may be directly bonded to Y and X in general formula (1A), or a divalent substituent may be sandwiched between the fused ring structure and Y and / or X in general formula (1A). The above divalent substituent is the same as the divalent substituent sandwiched between the monocyclic structure and Y and / or X in general formula (1A) described above.

[0096] Q may have substituents. If Q does not have either a monocyclic or fused ring structure, the substituent is a substituent on the portion of Q in a ring structure comprising Q, Y, X, and M in general formula (1A).

[0097] If Q has a monocyclic or fused ring structure, the substituent is a substituent of the monocyclic or fused ring structure, or a substituent of the portion of Q in a ring structure composed of Q, Y, X, and M in general formula (1A).

[0098] The substituents that Q may have may, for example, have heteroatoms, or may be other atoms or groups of atoms.

[0099] Examples of substituents having the heteroatom include alkoxy groups having 1 to 18 carbon atoms, arylalkoxy groups having 7 to 18 carbon atoms, aryloxy groups having 6 to 18 carbon atoms, acyl groups having 2 to 18 carbon atoms, alloyl groups having 7 to 18 carbon atoms, dialkylamino groups having 2 to 18 carbon atoms, oxygen atoms, sulfur atoms, and the like.

[0100] Examples of other atoms or groups of atoms include aromatic groups having 3 to 18 carbon atoms, alkyl groups having 1 to 18 carbon atoms, halogen atoms, and the like. Examples of aromatic groups include aryl groups having 6 to 20 carbon atoms, such as phenyl, xylyl, naphthyl, and biphenyl.

[0101] The number of carbon atoms in Q is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less.

[0102] Y may be a group of atoms with a valency of 0 to 1. Each Y independently represents a group of atoms with a valency of 0 to 1, containing typical elements from groups 14 to 16 of the periodic table that can coordinate to M, and may further have substituents. Preferred typical elements from groups 14 to 16 of the periodic table are carbon atoms, nitrogen atoms, phosphorus atoms, arsenic atoms, oxygen atoms, sulfur atoms, and selenium atoms; more preferably carbon atoms, nitrogen atoms, phosphorus atoms, and arsenic atoms; even more preferably nitrogen atoms and phosphorus atoms; and particularly preferably phosphorus atoms.

[0103] In general formula (1A), it is preferable that both Y atoms represent either a nitrogen atom or a phosphorus atom, or that one Y atom represents a phosphorus atom and the other Y atom represents a nitrogen atom.

[0104] When the 0-1 valent atomic group represented by Y has substituents, examples of substituents include substituent group A, which are preferably alkyl groups or aryl groups, and more preferably ethyl groups, t-butyl groups, or phenyl groups.

[0105] M represents a metal atom, and examples include elements from groups 8 to 11 of the periodic table, such as iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, and gold. Among these, iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, or copper are preferred, ruthenium, rhodium, iridium, nickel, or palladium are more preferred, ruthenium, rhodium, iridium, or palladium are even more preferred, and ruthenium (Ru) is particularly preferred.

[0106] Z preferably represents a halogen atom, and more preferably a chlorine atom.

[0107] n represents an integer between 0 and 3, and M represents the number of ligands coordinating to the metal atom. From the viewpoint of catalyst stability, n is preferably 2 or 3.

[0108] If multiple Ls exist, each L independently represents a neutral or anionic ligand.

[0109] Examples of neutral ligands represented by L include ammonia, carbon monoxide, phosphines (e.g., triphenylphosphine, tris(4-methoxyphenyl)phosphine), phosphine oxides (e.g., triphenylphosphine oxide), sulfides (e.g., dimethyl sulfide), sulfoxides (e.g., dimethyl sulfoxide), ethers (e.g., diethyl ether), nitriles (e.g., p-methylbenzonitrile), heterocyclic compounds (e.g., pyridine, N,N-dimethyl-4-aminopyridine, tetrahydrothiophene, tetrahydrofuran), and the like, with triphenylphosphine being preferred.

[0110] Examples of anionic ligands represented by L include hydride ions (hydrogen atoms), nitrate ions, cyanide ions, etc., with hydride ions (hydrogen atoms) being preferred.

[0111] In general formula (1A), it is preferable that X represents a heterocycle, Q represents CH2, NH, or O, Y represents a phosphorus atom, and M represents ruthenium.

[0112] Furthermore, it is preferable that Z represents a chlorine atom, n represents 1 to 3, and L independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.

[0113] In the method for producing organic compounds according to this embodiment, it is preferable that the metal complex represented by general formula (1A) is the metal complex represented by the following general formula (2A).

[0114] [ka]

[0115] (In general formula (2A), X1 represents a heteroaromatic ring formed with two carbon atoms and a nitrogen atom, which may have substituents or be bonded to other substituents to form a ring. Q1 independently represents CH2, NH, or O, and CH2 and NH may have further substituents. Each Y1 independently represents either a phosphorus atom or a nitrogen atom. R independently represents an alkyl group, an aryl group, or an aralkyl group, which may further have substituents. M represents a metal atom. Z represents a halogen atom or a hydrogen atom. n represents 0 to 3, If multiple Ls exist, each L independently represents a neutral or anionic ligand.

[0116] In general formula (2A), M, Q1, Z, n, and L are equivalent to M, Q, Z, n, and L in general formula (1A), respectively, and the preferred ranges are also the same.

[0117] The heteroaromatic ring formed with the two carbon atoms and nitrogen atom represented by X1 is preferably a pyrroline ring, a pyridine ring, an imidazoline ring, a pyrimidine ring, or a triazine ring, more preferably a pyridine ring or a triazine ring, and even more preferably a pyridine ring.

[0118] Substituents that X1 may have include the substituent group A, where alkyl groups are preferred and methyl groups are more preferred.

[0119] Y1 represents either a phosphorus atom or a nitrogen atom, and both Y1 atoms may represent either a nitrogen atom or a phosphorus atom, or one Y1 atom may represent a phosphorus atom and the other Y1 atom may represent a nitrogen atom. It is preferable that both Y1 atoms are either nitrogen atoms or phosphorus atoms, and it is even more preferable that both Y1 atoms are nitrogen atoms.

[0120] The alkyl group represented by R can be a linear, branched, cyclic, substituted, or unsubstituted alkyl group. Preferably, the alkyl group represented by R is an alkyl group having 1 to 30 carbon atoms, such as a methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, n-octyl group, eicosyl group, or 2-ethylhexyl group. From the viewpoint of catalytic activity, it is preferable that the alkyl group has 12 carbon atoms or less, preferably an ethyl group or a t-butyl group, and more preferably a t-butyl group.

[0121] The aryl group represented by R can be a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, or an o-hexadecanoylaminophenyl group. Preferably, it is an aryl group having 12 carbon atoms or less, and more preferably a phenyl group.

[0122] If R has further substituents, examples of substituents include substituent group A, which preferably consists of a methyl group, an ethyl group, an i-propyl group, a t-butyl group, or a phenyl group, and more preferably an ethyl group, an i-propyl group, or a t-butyl group.

[0123] In general formula (2A), it is preferable that X1 represents a pyridine ring or a triazine ring, Q1 represents CH2, NH, or O, Y1 represents a phosphorus atom, R represents an ethyl group, a t-butyl group, or a phenyl group, and M represents ruthenium.

[0124] Furthermore, it is preferable that Z represents a chlorine atom, n represents 1 to 3, and L independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.

[0125] In the method for producing organic compounds according to this embodiment, it is preferable that the metal complex represented by general formula (2A) is the metal complex represented by the following general formula (3A).

[0126] [ka]

[0127] (In general formula (3A), R0 represents a hydrogen atom or an alkyl group. A independently represents CH, CR5, or N, and R5 represents an alkyl group, aryl group, aralkyl group, amino group, hydroxyl group, or alkoxy group. Each Q1 independently represents CH2, NH, or O, and CH2 and NH may have further substituents. Y1 represents a phosphorus atom or a nitrogen atom. Each R independently represents an alkyl group, an aryl group, or an aralkyl group, which may further have substituents. M represents a metal atom. Z represents a halogen atom or a hydrogen atom. n represents 0 to 3, If multiple Ls exist, each L independently represents a neutral or anionic ligand.

[0128] In general formula (3A), Y1, R, Q1, M, Z, n, and L are equivalent to Y1, R, Q1, M, Z, n, and L in general formula (2A), respectively, and the preferred ranges are also the same.

[0129] In general formula (3A), R0 represents a hydrogen atom or an alkyl group. Examples of alkyl groups represented by R0 include linear, branched, cyclic, substituted, or unsubstituted alkyl groups. Preferably, the alkyl group represented by R0 is an alkyl group having 1 to 30 carbon atoms, such as a methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, n-octyl group, eicosyl group, or 2-ethylhexyl group. From the viewpoint of ease of raw material procurement, it is preferable that the alkyl group has 6 carbon atoms or less, and it is preferable that it is a methyl group.

[0130] In general formula (3A), R0 is preferably a hydrogen atom or a methyl group.

[0131] A independently represents CH, CR5, or N, and R5 represents an alkyl group, aryl group, aralkyl group, amino group, hydroxyl group, or alkoxy group.

[0132] The alkyl group represented by R5 can be a linear, branched, cyclic substituted, or unsubstituted alkyl group. Preferably, the alkyl group represented by R5 is an alkyl group having 1 to 30 carbon atoms, such as a methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, n-octyl group, eicosyl group, or 2-ethylhexyl group. From the viewpoint of ease of raw material procurement, it is preferable that the alkyl group has 12 carbon atoms or less, and is preferably a methyl group.

[0133] The aryl group represented by R5 can be a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, or an o-hexadecanoylaminophenyl group. Preferably, it is an aryl group having 12 carbon atoms or less, and more preferably a phenyl group.

[0134] The aralkyl group represented by R5 can be a substituted or unsubstituted aralkyl group having 30 or fewer carbon atoms, such as a trityl group, benzyl group, phenethyl group, tritylmethyl group, diphenylmethyl group, naphthylmethyl group, etc., and preferably an aralkyl group having 12 or fewer carbon atoms.

[0135] The alkoxy group represented by R5 is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, ethoxy group, isopropoxy group, t-butoxy group, n-octyloxy group, or 2-methoxyethoxy group.

[0136] In general formula (3A), it is preferable that X1 represents a pyridine ring or a triazine ring, Q1 represents CH2, NH, or O, Y1 represents a phosphorus atom, R represents an ethyl group, a t-butyl group, or a phenyl group, and M represents ruthenium.

[0137] Furthermore, it is preferable that Z represents a chlorine atom, n represents 1 to 3, and L independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.

[0138] In the method for producing the organic compound of this embodiment, the metal complex represented by general formula (3A) is preferably a ruthenium complex represented by the following general formula (4A).

[0139] Ruthenium complexes represented by general formula (4A) are soluble in organic solvents and insoluble in water, making them suitable catalysts in the production of organic compounds. Ruthenium complexes represented by general formula (4A) are suitable, for example, in the production of formate. Since the formate produced by the reaction is readily soluble in water, the reaction can be easily separated from the catalyst in a two-phase system, making it easier to separate and recover the catalyst and formate from the reaction system, enabling the production of formate in high yield and facilitating the reuse of expensive catalysts.

[0140] [ka]

[0141] (In general formula (4A), R0 represents a hydrogen atom or an alkyl group, Each Q1 independently represents CH2, NH, or O, and CH2 and NH may have further substituents. Each R1 independently represents an alkyl group or an aryl group (however, if Q1 represents NH or O, at least one of R1 represents an aryl group). A independently represents CH, CR5, or N, and R5 represents an alkyl group, aryl group, aralkyl group, amino group, hydroxyl group, or alkoxy group. Z This represents a halogen atom, n represents 0 to 3, If multiple Ls exist, each L independently represents a neutral or anionic ligand.

[0142] In general formula (4A), R0, A, Q1, Z, L, and n are equivalent to R0, A, Q1, Z, L, and n in general formula (3A), respectively, and the preferred ranges are also the same.

[0143] The alkyl group and aryl group represented by R1 are equivalent to the alkyl group and aryl group represented by R in general formula (3A), respectively, and the preferred ranges are also the same.

[0144] Metal complexes represented by general formulas (1A) to (4A) may produce stereoisomers depending on the coordination mode and conformation of the ligands, but they may also be a mixture of these stereoisomers or a single pure isomer.

[0145] Metal complexes represented by general formulas (1A) to (4A) can also be used if they are prepared by known methods. Known methods include, for example, those described in E. Pidko et al., ChemCatChem 2014, 6, 1526-1530.

[0146] The following compounds are examples of ruthenium complexes represented by general formula (4A). In the compounds listed below, Et represents an ethyl group, tBu represents a tert-butyl group, and Ph represents a phenyl group.

[0147] [ka]

[0148] [ka]

[0149] [ka]

[0150] The amount of catalyst (preferably a ruthenium complex) used is not particularly limited. From the viewpoint of fully exhibiting the catalytic function, the amount of catalyst used is preferably 0.1 μmol or more, more preferably 0.5 μmol or more, and even more preferably 1 μmol or more per liter of organic phase solvent. From the viewpoint of cost, it is preferably 1 mol or less, more preferably 10 mmol or less, and even more preferably 1 mmol or less per liter of organic phase solvent. Furthermore, from the viewpoint of suppressing a decrease in catalytic efficiency, it may be 500 μmol or less, 400 μmol or less, or 100 μmol or less per liter of organic phase solvent. When two or more catalysts are used, the total amount used is within the above range.

[0151] (phase transfer catalyst) The method for producing the organic compound in this embodiment may also use a phase transfer catalyst that facilitates the transfer of substances between the aqueous phase and the organic phase. Examples of phase transfer catalysts include quaternary ammonium salts, quaternary phosphates, macrocyclic polyethers such as crown ethers, nitrogen-containing macrocyclic polyethers such as cryptands, nitrogen-containing linear polyethers, polyethylene glycol and its alkyl ethers. Among these, quaternary ammonium salts are preferred from the viewpoint that the transfer of substances between the aqueous solvent and the organic solvent is easy even under mild reaction conditions.

[0152] Examples of quaternary ammonium salts include methyltrioctylammonium chloride, benzyltrimethylammonium chloride, trimethylphenylammonium bromide, tributylammonium tribromide, tetrahexylammonium bisulfate, decyltrimethylammonium bromide, diallyldimethylammonium chloride, dodecyltrimethylammonium bromide, dimethyldioctadecylammonium bromide, tetraethylammonium tetrafluoroborane, ethyltrimethylammonium iodide, tris(2-hydroxyethyl)methylammonium hydroxide, tetramethylammonium acetate, tetramethylammonium bromide, and tetraethylammonium iodide, with methyltrioctylammonium chloride being preferred.

[0153] The amount of phase transfer catalyst used is not particularly limited. Preferably, the amount of phase transfer catalyst used is 0.1 mmol or more, more preferably 0.5 mmol or more, and even more preferably 1 mmol or more, per liter of the organic and aqueous solvents. From a cost viewpoint, it is preferable that the amount is 1 mole or less, more preferably 500 mmol or less, and even more preferably 100 mmol or less, per liter of the organic and aqueous solvents. When using two or more types of phase transfer catalysts, the total amount used should not exceed the above range.

[0154] (Other ingredients) In the manufacturing method according to this embodiment, antioxidants may be added to the reaction solution 30 as needed. Examples of antioxidants include phosphorus-based antioxidants, amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants. For example, those disclosed in Japanese Patent Application Publication No. 2016-44190 can be used as antioxidants. In addition, additives such as ultraviolet absorbers and light stabilizers may be added to the reaction solution 30 instead of, or together with, the antioxidants. For example, those disclosed in Japanese Patent Application Publication No. 2016-44190 can be used as additives. The organic phase may also contain antioxidants.

[0155] When using antioxidants, the amount used is adjusted, for example, to a range in which the antioxidant dissolves in reaction solution 30. From the viewpoint of allowing the antioxidant to fully exert its function, it is preferable that the amount of antioxidant used be 1 mmol or more per 1 L of solvent. From the viewpoint of reducing the cost of antioxidants, it is preferable that the amount of antioxidant used be 100 mmol or less per 1 L of solvent. One type of antioxidant may be used alone, or two or more types may be used in combination.

[0156] (Method of manufacturing formate) In the manufacturing method of this embodiment, formate may be synthesized by a hydrogenation reaction between a starting compound, which is at least one selected from the group consisting of carbon dioxide, bicarbonates, and carbonates, and hydrogen. Formate has the advantage of being easy to handle because it has a high hydrogen storage density, is safe, and is stable as a chemical substance, and allows for long-term storage of hydrogen and carbon dioxide. Formic acid can be produced by protonating at least a portion of the formate produced by the manufacturing method of the organic compound of this embodiment.

[0157] The formate salts and formic acid obtained in this way have a wide range of applications in various fields, such as silage additives, feed preservatives, leather tanning agents, textile dyes, rubber coagulants, antifreeze agents, cleaning agents and neutralizing agents for precision machinery, heavy metal precipitants, de-icing agents, cutting fluids, heat conduction fluids, lubricants, hydride ion sources, and hydrogen sources. [Examples]

[0158] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto. In the examples, formate salts were synthesized by hydrogenation of the starting compound using a catalyst, and the effect of improving the yield was evaluated.

[0159] [Catalyst synthesis] The catalyst was synthesized by the following procedure. First, under an inert atmosphere, 40 mg (0.1 mmol) of ligand A was added to a suspension of [RuHCl(PPh3)3(CO)] in THF (tetrahydrofuran) (5 mL), and the mixture was stirred and heated at 65°C for 3 hours to carry out the reaction. After that, it was cooled to room temperature (25°C). The resulting yellow solution was filtered, and the filtrate was evaporated to dryness under vacuum. The resulting yellow residual oil was dissolved in a very small amount of THF (1 mL), and hexane (10 mL) was slowly added to precipitate a yellow solid, which was then filtered. The filtrate was dried under vacuum to obtain catalyst 1, which is a yellow crystal shown below. In catalyst 1 and ligand A shown below, tBu represents a tertiary butyl group.

[0160] [ka]

[0161] 31 P{ 1 H}(C6D6):90.8(s), 1 H(C6D6):-14.54(t,1H,J=20.0Hz),1.11(t,18H,J=8.0Hz),1.51(t,18H,J=8.0Hz),2.88(dt,2H,J= 16.0Hz,J=4.0Hz),3.76(dt,2H,J=16.0Hz,J=4.0Hz),6.45(d,2H,J=8.0Hz),6.79(t,1H,J=8.0Hz). 13 C{ 1H}NMR(C6D6):29.8(s),30.7(s),35.2(t,J=9.5Hz),37.7(t,J=6.0Hz),37.9 (t,J=6.5Hz),119.5(t,J=4.5Hz),136.4(s),163.4(t,J=5.0Hz),209.8(s).

[0162] [Calculation of yield] In the following Examples 1-14 and Comparative Examples 1-2, the yield of formate (potassium formate) was calculated by the following method.

[0163] First, the amount of formate contained in the aqueous phase was quantified as follows: 100 μL of dimethyl sulfoxide was added as a reference substance to 100 μL of the aqueous phase discharged from the flow reactor, and dissolved in 500 μL of heavy water. A sample was prepared in this manner. NMR measurements were performed on this sample. From the obtained NMR spectrum, the amount of formate produced, X (mol), was calculated. Furthermore, based on the amount of formate produced, X (mol), and the total amount of carbon dioxide, bicarbonate, and carbonate used in the reaction, Z (mol) (in Examples 1-14 and Comparative Example 1-2 below, the amount of potassium bicarbonate), the yield (%) of formate was calculated using the following formula (1). Formate yield (%) = 100 × X / Z (1)

[0164] [Example 1] Under a nitrogen gas atmosphere, 1.12 L of water, 4.7 mol of potassium bicarbonate, 0.28 L of toluene, 70 μmol (250 μmol / L in the organic phase) of catalyst, and 15 mmol (54 mmol / L in the organic phase) of methyltrioctylammonium chloride were added to a reactor equipped with an anchor impeller. The impeller was positioned in the center of the reaction mixture. When the reactor was stationary, the interface between the organic and aqueous phases was in contact with the impeller. Subsequently, hydrogen gas was added to 7 MPa, the temperature was raised to 90°C, and the reaction was stirred under the stirring conditions shown in Table 1 until completion. The reaction time for Example 1 was 224 minutes. After cooling to room temperature, the pressure was carefully released. The reactor was then purged with nitrogen gas.

[0165] Under a nitrogen gas atmosphere, the reaction mixture was removed from the reactor, and the organic phase and aqueous phase were separated. The yield of formate was calculated using the aqueous phase according to the method described above.

[0166] [Example 2] The reaction was carried out in the same manner as in Example 1, except that the conditions were changed as shown in Table 1, and the yield was calculated.

[0167] [Example 3] The reaction was carried out in the same manner as in Example 1, except that the water was changed to 0.5 L, potassium bicarbonate to 2.1 mol, toluene to 0.5 L, catalyst to 30 μmol (60 μmol / L in the organic phase), and methyltrioctylammonium chloride to 27 mmol (54 mmol / L in the organic phase), and the conditions were changed as shown in Table 1. The yield was then calculated.

[0168] [Example 4] The reaction was carried out in the same manner as in Example 1, except that the water was changed to 0.064 L, potassium bicarbonate to 0.42 mol, toluene to 0.016 L, catalyst to 4 μmol (250 μmol / L in the organic phase), and methyltrioctylammonium chloride to 0.86 mmol (54 mmol / L in the organic phase), and the conditions were changed as shown in Table 1. The yield was then calculated.

[0169] [Example 5] The reaction was carried out in the same manner as in Example 3, except that the conditions were changed as shown in Table 1, and the yield was calculated.

[0170] [Example 6] The reaction was carried out in the same manner as in Example 3, except that the stirring blades were changed to disk turbine blades and the conditions were changed as shown in Table 1, and the yield was calculated.

[0171] [Example 7] The reaction was carried out in the same manner as in Example 3, except that the stirring blades were changed to disk turbine blades and the conditions were changed as shown in Table 1, and the yield was calculated.

[0172] [Example 8] The reaction was carried out in the same manner as in Example 3, except that the stirring blades were changed to disk turbine blades and the conditions were changed as shown in Table 1, and the yield was calculated.

[0173] [Example 9] The reaction was carried out in the same manner as in Example 1, except that the stirring blades were changed to disk turbine blades and the conditions were changed as shown in Table 1, and the yield was calculated.

[0174] [Example 10] The reaction was carried out in the same manner as in Example 1, except that the stirring blade was changed to a Fullzone® blade (manufactured by Kobe Steel Environmental Solutions) and the conditions were changed as shown in Table 1, and the yield was calculated. The stirring blade was installed at a height that covered the entire reaction liquid.

[0175] [Example 11] The reaction was carried out in the same manner as in Example 1, except that the conditions were changed as shown in Table 1, and the yield was calculated.

[0176] [Example 12] The reaction was carried out in the same manner as in Example 1, except that the water was changed to 11.2 L, potassium bicarbonate to 56.0 mol, toluene to 2.8 L, catalyst to 700 μmol (250 μmol / L in the organic phase), and methyltrioctylammonium chloride to 151 mmol (54 μmol / L in the organic phase), and the conditions were changed as shown in Table 1. The yield was then calculated.

[0177] [Comparative Example 1] The reaction was carried out in the same manner as in Example 4, except that the amount of water was changed to 0.08 L and the amount of toluene to 0.02 L, and the conditions were changed as shown in Table 1. The yield was then calculated.

[0178] [Comparative Example 2] The reaction was carried out in the same manner as in Example 1, except that the stirring blade was changed to a Fullzone® blade (manufactured by Kobe Steel Environmental Solutions) and the conditions were changed as shown in Table 1, and the yield was calculated.

[0179] The results for Examples 1 to 12 and Comparative Examples 1 to 2 are shown in Table 1. In Table 1, the Froude number is given by the formula: impeller diameter d × rotational speed n 2 This value is calculated using the gravitational acceleration g. Reaction time is the time it takes for the reaction of the starting compounds to complete (time to reach equilibrium).

[0180] Figure 3 is a graph showing the stirring conditions for Examples 1 to 12 and Comparative Examples 1 to 2. The horizontal axis in the plot in Figure 3 represents the unit stirring power (unit: kW / m). 3 The vertical axis represents the blade tip velocity (unit: m / s). In Figure 3, the marker "○" indicates that the reaction solution temperature during the reaction was 90°C and the yield was 80% or higher, the marker "●" indicates that the reaction solution temperature during the reaction was 70°C and the yield was 80% or higher, the marker "◇" indicates that the yield was 75% or higher and less than 80%, and the marker "×" indicates that the yield was less than 75%. The plots for Examples 6 and 7 overlap, with Example 6 represented by the marker "◇" and Example 7 by the marker "●".

[0181] [Table 1]

[0182] The unit stirring power is 0.5 kW / m². 3 More than 3.5kW / m 3 Examples 1 to 12, which satisfy the stirring conditions below and have a blade tip velocity of 1.1 m / s or higher, showed higher yields compared to Comparative Examples 1 to 2. From Table 1, it can be seen that, when the reaction solution temperature is the same, a higher blade tip velocity tends to result in a higher yield.

[0183] [Example 13] The reaction was carried out in the same manner as in Example 1, except that the conditions were changed as shown in Table 2, and the yield was calculated.

[0184] [Example 14] The reaction was carried out in the same manner as in Example 13, except that the installation position (height) of the stirring blade was changed as shown in Table 2, and the yield was calculated.

[0185] The results for Examples 10 and 13 to 14 are shown in Table 2. In Table 2, "Reaction Liquid Level Height" is the distance L1 from the inside bottom of the reactor (reaction vessel) to the liquid surface of the reaction liquid. "Aqueous Phase-Organic Phase Interface Height" is the distance L2 from the inside bottom of the reactor (reaction vessel) to the liquid surface at the interface between the aqueous phase and the organic phase. "Ratio L3 / L2" is the ratio of the distance L3 from the inside bottom of the reactor (reaction vessel) to the axial center of the impeller to the distance L2. "Impeller Bottom Height" is the distance from the inside bottom of the reactor (reaction vessel) to the bottom of the impeller. "Time to Reach 80% Yield" is the time at which the absolute value of the formate yield reached 80%.

[0186] [Table 2]

[0187] Compared to Example 14, Example 13 showed a shorter time to reach an 80% yield. From the above, it can be seen that setting the position of the stirring blade so that it is in contact with the interface between the aqueous phase and the organic phase when stationary tends to increase the reaction rate. This is presumed to be because the surface area of ​​the interface between the organic phase and the gas phase during stirring increases, achieving gas-liquid phase contact suitable for the reaction. Furthermore, from the results of Example 10 and Example 13, it can be seen that the reaction rate can be improved without increasing the unit stirring power by adjusting the installation position of the stirring blade. From the above, it is suggested that even with an anchor blade, gas-liquid dispersion and gas-liquid phase contact can be achieved at a level greater than that of a full-zone blade. [Industrial applicability]

[0188] According to the method for producing organic compounds of this embodiment, for example, the target organic compound can be produced in an improved yield.

Claims

1. A method for producing an organic compound by reacting a starting compound with a catalyst in the presence of a gas phase and a liquid phase containing an organic phase and an aqueous phase, The unit stirring power is 0.5 kW / m 3 3.5kW / m or more 3 The following includes stirring the liquid phase under stirring conditions where the tip speed of the stirring blade is 1.10 m / s or more: The gas phase contains a gas that can react with the starting compound, and the reaction is a hydrogenation reaction of the starting compound. The starting compound is at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate, and the formate is synthesized from the starting compound by the reaction. The catalyst is a metal catalyst containing ruthenium. A method for producing organic compounds.

2. The method for producing an organic compound according to claim 1, wherein the tip velocity of the stirring blade is 1.8 m / s or more.

3. The aforementioned unit stirring power is 2.8 kW / m². 3 The method for producing the organic compound according to claim 1 is as follows:

4. The method for producing an organic compound according to claim 1, wherein, under the stirring conditions, the rotation speed is 10 rpm or more and 1200 rpm or less.

5. The method for producing an organic compound according to claim 1, wherein the liquid phase is 0.05 L or more and 7000 L or less.

6. The method for producing an organic compound according to claim 1, wherein the proportion of the organic phase in the liquid phase is 5% by volume or more and 60% by volume or less.

7. The method for producing an organic compound according to claim 1, wherein the temperature of the liquid phase in the reaction is 40°C or higher and 100°C or lower.

8. The stirring is performed using a stirring blade. A method for producing an organic compound according to claim 1, wherein, in a stationary state, the interface between the aqueous phase and the organic phase is in contact with the stirring blade.

9. The method for producing an organic compound according to claim 1, wherein the reaction is a reversible reaction.

10. A method for producing an organic compound according to claim 1, wherein the organic phase contains the catalyst and the aqueous phase contains the starting compound.

11. A method for producing an organic compound according to claim 1, wherein the organic phase contains toluene.

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