Light irradiation utilization system, photoreaction method and photoreaction device

Abstract

To provide an optimal light irradiation system capable of clarifying characteristics of photoreaction thereof.SOLUTION: A light irradiation utilization system is for a purpose of bringing an action by light energy to an irradiation target body. The light irradiation utilization system executes a plural times of intermittent light irradiation with on-off frequency of the light irradiation changed, in the same total light volume to the irradiation target body to determine an optimal light irradiation frequency to obtain a desired result.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a light irradiation utilization system, a light reaction method, and a light reaction device, including an analysis method thereof, for the purpose of bringing about an action of light energy on an irradiated object. [Background technology]

[0002] Light irradiation is used for lighting, as well as in various fields such as chemical reactions, sterilization, optical communications, image formation, beauty, and treatment of injuries and diseases. Among these uses of light irradiation, "use of light irradiation for the purpose of bringing about an action of light energy on the irradiated subject," such as chemical reactions and sterilization, has recently started to increase, and the scope of application has been expanded to beauty and treatment of injuries and diseases, and studies for full-scale use are becoming more active. Among these, in photoreactions, which are the origin of light utilization, some studies have been conducted using not only constant light but also pulsed light that is irradiated intermittently. Pulsed light irradiation has been used to study the reaction kinetic effects of photoreactions (see Non-Patent Document 1), and the relationship between the frequency of pulsed light irradiation and the yield of photoreaction products has been studied (see Non-Patent Document 2). However, for example, this photoreaction is still far from being put into practical use, such as mass production. On the other hand, light, which is the basis of these, has various physical properties in addition to the above-mentioned pulsed light, that is, the temporal control of light. For example, energy control such as wavelength, and even intensity, which is the number of photons that affect the irradiated object per unit area or unit volume, that is, a parameter that can be said to be the spatial control of light. Controlling these and using an optimal light source is useful not only for the revolutionary evolution of photoreactions, such as the creation and acquisition of products that could not be obtained by previous methods, but also for scale-up, that is, mass production. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Katsuya Ishiguro and 1 other, Journal of the Society of Organic Synthetic Chemistry, 1999, Vol. 57, pp. 857-866 [Non-Patent Document 2] Thomas P. Nicholls and 3 others, Chemical Communications, 2018, Vol. 54, pp. 4589-4592 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention aims to achieve optimal use by controlling the physical properties of light, aiming at revolutionary evolution in the use of light and practical application in the sense of so-called social implementation. In particular, the first priority is placed on temporal control, that is, controlling the parameters of pulsed light that is irradiated intermittently, rather than irradiating light continuously. Below, the meaning of this will be explained using the photoreaction, which is the origin of the concept, as an example. Since photoreaction is a combination of many phenomena, it is important to control the time and timing of irradiation in order to utilize light more optimally. Furthermore, when a combination of multiple phenomena is related to a relaxation process, it is extremely important to control the off state of light. The relaxation process includes not only the process in which an electronically excited object returns to the ground state, but also the process in which a phenomenon indirectly obtained by the influence of light returns to a state in which there was no light irradiation, such as the formation and dissociation of an association, the formation and dissociation of a solvation, the generation and disappearance of an intermediate, the decay associated with the lifetime of the generated species, and the diffusion process associated with all of them. However, as a conventional example, the use of intermittent light in consideration of the lifetime of the intermediate is very effective, and examples of using periodic light in photoreactions have been reported, such as in the above-mentioned Non-Patent Documents 1 and 2. However, the current situation is that the effects and effective methods of using such intermittent light have not yet been fully examined, and there is room for consideration of effective methods of using intermittent light in photoreactions (especially comprehensive evaluation of time control at multiple frequencies, etc.).

[0005] Secondly, by controlling the energy, i.e. the wavelength of the light source, it is expected that the optimization of the photoreaction and the creation of new products will be achieved. Although the studies to date have used white light as the light source, and the phenomenon of utilizing the optical properties of LEDs has been studied, such as by simply expressing blue light in the case of LEDs, there have been few examples that have focused on this, and it cannot be denied that there has been a lack of study. In terms of technology, light sources (LEDs) of various wavelengths have become easily available recently, and the ground has been laid for detailed studies. Furthermore, from the viewpoint of optical properties, using only excitation at a specified wavelength not only makes it easier to control the amount of excited species, for example, but also, for example, the amount and lifetime of excited species differ between excitation of allowed transitions and excitation of forbidden transitions, which is thought to affect the subsequent reaction. Therefore, controlling the energy is thought to be one of the effective means of precisely controlling photoreactions. It is expected that combining these methods will produce even more new benefits. Thirdly, spatial control of light is considered. In actual experiments, photoreactions are carried out in a finite space. Since light is given from a light source, it is always directional and anisotropic. From the viewpoint of mass production, it is important to make this uniform. On the other hand, by distributing light spatially and temporally, it is possible to change reactive species into a largely non-equilibrium state by suddenly changing from high light density to low light density. In this way, new products can be created. However, the main focus of the previous methods was to deliver a large amount of light at any rate, and naturally, the amount of light was excessive near the light source, and side reactions such as light pollution, i.e., excessive reactions, could not be prevented. Therefore, it is possible to design the irradiation so that the light is irradiated from a position where it hits evenly in space. For example, one method is to carry out the reaction system in a direction other than the direction of irradiation of the light source, reduce the thickness of the reaction system (the distance light passes) so that the attenuation of light is small, and use a flow-type reaction system instead of a batch system. It is also possible to prevent light pollution such as side reactions as much as possible by using time control to compensate for the attenuation. From the above, aiming to control these light parameters and verifying photoreactions with multiple parameters will clarify the characteristics of the photoreaction, which can reveal characteristics that have been overlooked up until now, so it can be said to be a new analysis method for photoreactions. Furthermore, this verification makes it possible to design optimal (desired) photoreactions. This also makes it possible to reexamine existing photoreactions, allowing each reaction to be reevaluated. From the above, we believe that this system, including this analysis method, will enable a redefinition of photoreactions.

[0006] The present invention has been made in consideration of the above-mentioned current situation, and aims to provide an optimal light irradiation system, and further to provide a system that clarifies the characteristics of the photoreaction. [Means for solving the problem]

[0007] The present inventor has studied the optimal light irradiation system, and has found that by changing the frequency in intermittent light irradiation in which light irradiation is repeatedly turned on and off, and by studying multiple such systems and by changing the wavelength of light irradiation, the effect of light irradiation on the irradiated body changes, and the resulting product changes. It has also been found that by changing the frequency of intermittent light irradiation and the wavelength of light irradiation and performing multiple photoreactions, it is possible to determine the optimal light irradiation conditions for obtaining the desired results, and that specific reaction results can be obtained by performing light irradiation with a specific frequency or wavelength. The present inventor has also developed a reaction device suitable for evaluating the results of such photoreactions in which the frequency of intermittent light irradiation and the wavelength of light irradiation are changed, and further found that systematic data obtained from multiple such systems are suitable for finding the characteristics of photoreactions, and has found a new analysis method using the data, which has led to the present invention.

[0008] That is, the present invention is as follows. [1] A light irradiation utilization system for the purpose of bringing about an effect of light energy on an irradiated object, characterized in that the system performs multiple intermittent light irradiations on the irradiated object with different on / off frequencies under the same total light intensity, and determines the optimal light irradiation frequency for obtaining the desired result.

[0009] [2] A light irradiation utilization system for the purpose of bringing about an effect of light energy on an irradiated object, the utilization system being characterized in that the irradiated object is irradiated with intermittent light with an on / off frequency of light irradiation of 1 Hz or less.

[0010] [3] A photoreaction method in which a reaction raw material is intermittently irradiated with light to cause a reaction, the photoreaction method being characterized in that the reaction raw material is subjected to a plurality of intermittent light irradiations with different on / off frequencies under the same total light intensity, and an optimal light irradiation frequency for obtaining a desired result is determined.

[0011] [4] A photoreaction method in which a reaction raw material is reacted by intermittently irradiating it with light, the photoreaction method being characterized in that the reaction raw material is intermittently irradiated with light having an on / off frequency of 1 Hz or less.

[0012] [5] A method for producing a compound using a photoreaction in which a reaction raw material is intermittently irradiated with light, comprising the steps of: The method for producing a compound includes a step of irradiating the reaction raw materials with intermittent light multiple times at different on / off frequencies under the same total light intensity, thereby determining the optimal frequency of light irradiation for obtaining the desired result, and a step of irradiating the reaction raw materials with light of the determined frequency.

[0013] [6] A method for producing a compound using a photoreaction in which a reaction raw material is intermittently irradiated with light, the method comprising the step of intermittently irradiating the reaction raw material with light having an on / off frequency of 1 Hz or less.

[0014] [7] A reaction apparatus used for photoreaction in which a reaction raw material is intermittently irradiated with light, the reaction apparatus comprising a plurality of reaction vessels, a power source, a plurality of waveform generating circuits capable of controlling the frequency of the irradiated light, and a plurality of light sources, all of which are directly connected to the power source through different waveform generating circuits, and the light sources are arranged so that light from different light sources is directly irradiated to each of the plurality of reaction vessels, making it possible to carry out photoreactions in multiple reaction vessels at the same time.

[0015] [8] A light irradiation utilization system for the purpose of bringing about an effect of light energy on an irradiated object, the utilization system being characterized in that the reaction raw material is irradiated with light of multiple different wavelengths and the optimal wavelength of light irradiation for obtaining a desired result is determined.

[0016] [9] A light irradiation utilization system for the purpose of bringing about an effect of light energy on an irradiated object, characterized in that the system irradiates the irradiated object with light having a peak wavelength within 50 nm around the wavelength of the absorption edge of the optical absorption spectrum of the irradiated object.

[0017]

[10] A light irradiation utilization system for the purpose of bringing about an effect of light energy on an irradiated object, the utilization system being characterized in that the irradiated object is irradiated with light of a wavelength capable of primarily exciting forbidden transitions in the optical absorption spectrum of the irradiated object.

[0018]

[11] A photoreaction method for reacting a reaction material by irradiating it with light, the photoreaction method being characterized in that the reaction material is irradiated with light of a plurality of different wavelengths and an optimal wavelength of light irradiation for obtaining a desired result is determined.

[0019]

[12] A photoreaction method for reacting a reaction material by irradiating the reaction material with light, the photoreaction method being characterized in that the reaction material is irradiated with light having a peak wavelength within 50 nm of the wavelength of the absorption edge of the optical absorption spectrum of the reaction material.

[0020]

[13] A photoreaction method for reacting a reaction material by irradiating the reaction material with light, the photoreaction method being characterized in that the reaction material is irradiated with light of a wavelength capable of primarily exciting forbidden transitions in the optical absorption spectrum of the reaction material.

[0021]

[14] A method for producing a compound using a photoreaction in which a reaction raw material is irradiated with light, the method comprising the steps of: irradiating the reaction raw material with light of a plurality of different wavelengths; determining an optimal wavelength of light irradiation for obtaining a desired result; and irradiating the reaction raw material with light of the determined wavelength.

[0022]

[15] A method for producing a compound using a photoreaction in which a reactant is irradiated with light, the method comprising the step of irradiating the reactant with light having a peak wavelength within 50 nm of the wavelength of the absorption edge of the optical absorption spectrum of the reactant.

[0023]

[16] A method for producing a compound using a photoreaction in which a reactant is irradiated with light, the method comprising the step of irradiating the reactant with light of a wavelength capable of primarily exciting a forbidden transition in the optical absorption spectrum of the reactant.

[0024]

[17] A reaction apparatus used for photoreaction in which reaction raw materials are irradiated with light, the reaction apparatus comprising a plurality of reaction vessels, a power source, and a plurality of light sources each irradiating light of a different wavelength, all of the light sources being directly connected to the power source, and the light sources being arranged so as to directly irradiate light from a different light source to each of the plurality of reaction vessels, thereby making it possible to carry out photoreactions in a plurality of reaction vessels at the same time. Effect of the Invention

[0025] The light irradiation utilization system of the present invention changes the effect on the irradiated body by controlling the on / off frequency and wavelength of the irradiated light, and can be used in various fields that use light irradiation, such as the agricultural field such as plant factories, the fisheries field such as aquaculture, the medical field such as phototherapy, the beauty field such as anti-aging, and the chemical field such as photochemical reactions, which are the origin of all of these. The photoreaction method of the present invention, in which the light irradiation utilization system of the present invention is applied to a photoreaction, is a method for determining the optimal light irradiation conditions for obtaining a desired result from the results of a photoreaction in which the on / off frequency or wavelength of the irradiated light is changed. This method can be used to control reaction results, such as optimizing the yield of a specific product or controlling selectivity, and is also a useful method for capturing the characteristics of a photoreaction. [Brief description of the drawings]

[0026] [Figure 1] FIG. 1 is a schematic diagram showing the configuration of a photoreactor (time control) of the present invention. [Diagram 2] FIG. 2 is a diagram showing the UV-vis absorption spectrum in acetonitrile of anthraquinone used as a photocatalyst in the examples. [Diagram 3] FIG. 2 is a graph showing the light frequency dependence of the yields of the mono-adduct (mono-substitution product) and the di-adduct (di-substitution product) in the photoreaction of Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] The present invention will be described in detail below. In addition, a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

[0028] The light irradiation utilization system, photoreaction method, compound production method, and photoreaction device of the present invention include those related to the frequency of intermittent light irradiation (time control) and those related to the wavelength of light irradiation (wavelength control). In the following, the time-controlled light irradiation utilization system, the photoreaction method, the compound production method, and the photoreaction device will first be described, and then those using wavelength control will be described. The preferred light irradiation conditions in the light irradiation utilization system of the present invention described below are also preferred light irradiation conditions in the photoreaction method and compound production method of the present invention. The time control and the wavelength control may be performed independently or in conjunction with each other, but it is preferable to perform them in conjunction with each other. In that case, the order does not matter, but it is more preferable to perform the wavelength control first and then the frequency control.

[0029] 1. Light irradiation system (time control) The time-controlled light irradiation utilization system of the present invention performs multiple intermittent light irradiations with different on / off frequencies for the irradiated object under the same total light amount, and determines the optimal light irradiation frequency to obtain the desired result. By making the total light amount the same, in principle, both the quality of the product (e.g., the production ratio caused by selectivity) and the quantity (e.g., the yield) will be the same, but by controlling the time, at least one of these can be changed, making it possible to approach more desired conditions. As described above, the effect of light irradiation on the irradiated object can be changed by changing the on / off frequency of light irradiation. By performing multiple intermittent light irradiations with different frequencies under the same total light intensity and comparing the results, it is possible to determine the optimal frequency of light irradiation to selectively produce the desired result. The scope of application of the light irradiation utilization system of the present invention is not particularly limited, and the system can be used in any field in which light irradiation is performed for the purpose of bringing about an effect of light energy on an irradiated object, such as chemical reactions, sterilization, image formation, beauty treatment, and treatment of injury or disease. The term "action due to light energy" as used herein includes any chemical or physical action that occurs in an irradiated object as a result of light irradiation.

[0030] In the time-controlled light irradiation utilization system of the present invention, the number of intermittent light irradiations with different on / off frequencies is not particularly limited, and may be performed at least at two different frequencies, but the more different frequencies there are, the more optimal light irradiation conditions can be found to obtain the desired results, so it is preferable that the number of types of frequencies used is three or more. More preferably, it is five or more, and even more preferably, it is ten or more. And, it is preferable that the frequency width at both ends is at least three digits or more. More preferably, it is five or more, and even more preferably, it is ten or more. The frequency range used is not particularly limited, but in order to fully confirm the effect of the frequency of intermittent light irradiation, the low frequency side is preferably 10 Hz or less, more preferably 1 Hz or less, and even more preferably 0.1 Hz or less. As shown in the examples, 0.001 Hz or less is even more preferable. The high frequency side is preferably 100 Hz or more, more preferably 1000 Hz or more, and even more preferably 10000 Hz or more as shown in the examples.

[0031] When checking the effect of the frequency of intermittent light irradiation, the total amount of light irradiated needs to be constant, and it is preferable to keep the on / off ratio (duty ratio) of light irradiation constant. It is also possible to find a composite effect by periodically using a plurality of duty ratios, which is also one of the inventions. However, it is preferable for the analysis to be constant, and the on / off ratio is not particularly limited as long as it is constant, and can be appropriately set within the range of 99.99 / 0.01 to 0.01 / 99.99, preferably 99.9 / 0.1 to 0.1 / 99.9, more preferably 99 / 1 to 1 / 99, and even more preferably 90 / 10 to 10 / 90.

[0032] The present invention also includes a light irradiation utilization system that performs intermittent light irradiation on an irradiated object with a low on / off frequency of 1 Hz or less. In photoreactions, the reaction substrate is sufficiently consumed after a certain time from the start of the reaction, and the reaction reaches an equilibrium state and is completed, but there are various reactions, such as those in which by-products are observed only at the beginning of the reaction, and those in which the main product is produced at a high rate at the beginning of the reaction and the by-product is produced at a high rate at the end. If intermittent light irradiation is performed on such reactions with a sufficiently long off time, the state at the beginning of the photoreaction can be repeated, and by-products that cannot usually be isolated can be obtained, or conversely, the selectivity of the main product can be improved, which is a reaction result that cannot be obtained by continuous light irradiation. Intermittent light irradiation with a low frequency of on / off frequency of 1 Hz or less is an intermittent light irradiation condition for obtaining reaction results that cannot be obtained by such continuous light irradiation, and the reaction shown in the examples below has a result in which the selectivity of the main product is improved. The low-frequency intermittent light irradiation may have an on / off frequency of 1 Hz or less, preferably 0.1 Hz or less, and more preferably 0.01 Hz or less.

[0033] 2. Photoreaction method (time control) The time-controlled photoreaction method of the present invention is a photoreaction method in which reaction raw materials are intermittently irradiated with light to cause a reaction, in which the reaction raw materials are subjected to a plurality of intermittent light irradiations with different on / off frequencies under the same total light intensity, and the optimal light irradiation frequency for obtaining the desired result is determined. The above non-patent documents 1 and 2 also examine the use of pulsed light irradiation in photoreactions and the relationship between the frequency of pulsed light irradiation and the yield of photoreaction products, but non-patent document 1 does not examine multiple frequencies in the first place, and does not compare them. Non-patent document 2 examines three frequencies, but the maximum and minimum frequencies are only in two digits, which makes it impossible to fully grasp the characteristics of the photoreaction and optimize it. In fact, non-patent document 2 does not describe in detail the frequency dependence and optimal value. Originally, each elementary process has its own time scale. For example, the luminescence lifetime of a photocatalyst is nanoseconds for singlet and microseconds for triplet. In addition, there are various theories about the lifetime of radicals, but it has been reported that it is on the 10 microsecond scale. Diffusion is expected to have an even slower time scale, and the non-equilibrium state, which is the initial process of the reaction, is in units of seconds to minutes. Since the reciprocal of these is the frequency, it is considered desirable to perform light irradiation with different frequencies over a time width of at least three digits, or even about 10 digits, as mentioned above, in order to capture all the phenomena of the photoreaction and determine the optimal light irradiation frequency. Such a study is not found in Non-Patent Documents 1 and 2, and as far as we know, the present invention is believed to be the first to do so.

[0034] The present invention also provides a photoreaction method in which the reaction raw materials are intermittently irradiated with light to cause a reaction, the photoreaction method being a photoreaction method in which the reaction raw materials are intermittently irradiated with light at an on / off frequency of 1 Hz or less. This corresponds to the non-equilibrium state, which is the initial process of the reaction shown above, and is realized by repeating it to efficiently collect them. In this case, as shown above, an on / off ratio is required that maintains a sufficient off time for the reaction system to return to the initial state, and an on / off ratio of 1:99 or more as in the embodiment is preferable, and considering a realistic light irradiation time, 10:90 is more preferable. As mentioned above, if the off-time of the light irradiation is long enough, it may be possible to obtain a product that is observed only before the reaction reaches equilibrium, or conversely, the production of by-products may be suppressed and the selectivity of the desired product may be improved. Thus, the photoreaction method of performing intermittent light irradiation with an off frequency of 1 Hz or less is a reaction method of great technical significance in that it may be possible to obtain reaction results that cannot be obtained by normal light irradiation.

[0035] The reaction using the photoreaction method of the present invention may be any photoreaction in which reaction raw materials are irradiated with light to cause a reaction. Examples of photoreactions include photodecomposition reactions such as decarbonylation of carbonyl compounds and denitrogenation of azo compounds; photoisomerization reactions such as cis- and trans-photoisomerization of double bonds; photosubstitution reactions such as halogenation of alkanes and substitution reactions of substituents on aromatic compounds; photo(cyclization)addition reactions such as the cycloaddition reaction of alkadienes and alkenes; photodimerization reactions such as the dimerization of anthracene; photopolymerization reactions; photorearrangement reactions that involve nucleophilic rearrangement, electrophilic rearrangement, sigmatropic rearrangement, or radical rearrangement; photooxidation reactions such as the Diels-Alder oxidation reaction and the ene reaction; photoreduction reactions such as the photoreduction of aromatic ketones, photoring-expansion reactions such as the Dowd-Beckwith reaction, and photoinduced cross-coupling reactions using transition metal catalysts.

[0036] 3. Compound manufacturing method (time control) By using the time-controlled photoreaction method of the present invention, it is possible to determine the conditions of light irradiation so that a large amount of the target product is produced, and perform the photoreaction to efficiently obtain the target product. Such a production method, that is, a method for producing a compound using a photoreaction in which a reaction raw material is intermittently irradiated with light, which includes a step of performing a plurality of intermittent light irradiations with different on / off frequencies of light irradiation under the same total light amount on the reaction raw material, determining the optimal light irradiation frequency for obtaining the desired result, and a step of performing light irradiation with the determined frequency on the reaction raw material, is also one of the present inventions. Furthermore, as described above, there is technical significance in carrying out a photoreaction by irradiating a low-frequency light having an on / off frequency of 1 Hz or less, and a method for producing a compound using such a photoreaction, that is, a method for producing a compound using a photoreaction in which a reaction raw material is intermittently irradiated with light, the method including a step of intermittently irradiating the reaction raw material with light having an on / off frequency of 1 Hz or less, is also one of the present inventions. In this case, as described above, an on / off ratio is required that maintains a sufficient off time for the reaction system to return to the initial state, and an on / off ratio of 1:99 or more as in the examples is preferable, and considering a realistic light irradiation time, 10:90 is more preferable.

[0037] The time-controlled compound production method of the present invention may include other steps as long as it includes the above steps. Examples of other steps include a step of separating the obtained product from other components in the reaction solution, a step of purifying the reaction product, etc.

[0038] 4. Photoreactor (time control) The present invention also provides a reaction apparatus for photoreaction in which a reaction raw material is intermittently irradiated with light, the reaction apparatus including a plurality of reaction vessels, a power source, a plurality of waveform generating circuits capable of controlling the frequency of the irradiated light, and a plurality of light sources, all of which are directly connected to the power source through different waveform generating circuits, and the light sources are arranged so that light from different light sources is directly irradiated to each of the plurality of reaction vessels, and the photoreaction apparatus is capable of performing photoreaction in a plurality of reaction vessels at one time, which enables a significant time saving and highly accurate data acquisition. In general, photoreactions are susceptible to environmental influences such as temperature and humidity, and in order to eliminate these influences as much as possible and to confirm the influence of the frequency of intermittent light irradiation on photoreactions purely, it is preferable to perform multiple photoreactions using different frequencies at once under the same environment. In the photoreaction device (time control) of the present invention, multiple light sources are connected to a power source through different waveform generating circuits, and each light source can perform intermittent light irradiation with different frequencies at once. In addition, since all light sources are connected to one same power source, no difference occurs in the power supply. As a result, by using the photoreaction device (time control) of the present invention, it is possible to confirm the influence of the frequency of intermittent light irradiation on photoreactions purely. This makes it possible to collect highly accurate data in a short time. The photoreaction using the photoreaction device of the present invention is a method that allows the frequency development of photoreactions to be seen at once from the viewpoint that reactions that capture the characteristics of various physical phenomena can be observed by changing the frequency. It can be said that the photoreaction device of the present invention is a device that combines the necessary accuracy and the acquisition of a large amount of data in a short time. An outline of such a photoreaction device is shown in FIG. 1. The light sources and waveform generating circuits used here are identical to a level that allows for calibration, and have data sheets that allow for calibration.

[0039] The number of reaction vessels in the photoreaction device (time control) is not particularly limited, but the more photoreactions using different frequencies, the more optimal light irradiation conditions can be found to obtain the desired results, so the number is preferably 3 or more, more preferably 5 or more, and even more preferably 10 or more. The number of light sources and the number of waveform generating circuits are preferably the same as the number of reaction vessels.

[0040] The light source used in the reaction device of the present invention is not particularly limited, but an LED or an organic LED is preferred since it can accurately irradiate light according to a signal of the frequency sent from the waveform generating circuit and the on / off ratio of the irradiated light.

[0041] In addition, the above-mentioned photoreactor (time control) preferably has a facility for keeping the temperature of all reaction vessels the same in order to eliminate the effect of the outside air temperature on the reaction. Equipment that can keep all reaction vessels at the same temperature and irradiate light independently without being affected by other light can be, for example, a combination of a metal block that can house all reaction vessels and a thermostatic facility (water bath) that can house it. Since light irradiation is performed intermittently, it is necessary to shield the lights so that they do not interfere with each other, and a metal block is also effective for achieving this. A metal block that is hollowed out in the shape of a reaction vessel and has a path through which a heat transfer medium can circulate inside is a suitable example of a method that can block light and maintain uniformity in temperature.

[0042] The reaction apparatus of the present invention may include other elements in addition to the reaction vessels, the power source, the waveform generating circuit capable of controlling the frequency of the irradiated light, the light source, and the equipment for maintaining the same temperature of all the reaction vessels. The other elements include an oscilloscope for checking the waveform of the current flowing through the light source, a shielding member for covering the reaction vessels and the light source to block light other than the light from the light source, and the like.

[0043] 5. Light irradiation system (wavelength control) The wavelength-controlled light irradiation utilization system of the present invention irradiates a target object with light of a plurality of different wavelengths, and determines the optimum wavelength of light irradiation for obtaining a desired result. As described above, the effect of light irradiation on the irradiated object can be changed not only by changing the on / off frequency of light irradiation, but also by changing the wavelength of light irradiation. By performing multiple light irradiations with different wavelengths and comparing the results, it is possible to determine the optimal wavelength of light irradiation to selectively produce the desired result. The scope of application of the light irradiation utilization system (wavelength control) of the present invention is not particularly limited, as is the case with the above-mentioned light irradiation utilization system (time control), and can be used in any field in which light irradiation is performed for the purpose of bringing about an effect of light energy on an irradiated object, such as chemical reactions, sterilization, image formation, beauty, and treatment of injuries and diseases. Similarly, "action due to light energy" includes any chemical or physical action that occurs in an irradiated object as a result of light irradiation.

[0044] In the wavelength-controlled light irradiation utilization system of the present invention, the number of light irradiations with different wavelengths is not particularly limited, and at least two different wavelengths may be used, but the more different wavelengths there are, the more optimal light irradiation conditions can be found to obtain the desired results, so it is preferable that the number of wavelengths used is two or more, more preferably three or more, and even more preferably four or more. The wavelength range of the light source used is not particularly limited, but is preferably determined based on the absorption spectrum of the reaction system in order to fully confirm the effect of the wavelength of light irradiation. The long wavelength side is a light source having a spectrum with a maximum value of 50 nm on the longest wavelength side (absorption edge) among the wavelengths that have absorption, more preferably a maximum value of 30 nm, and even more preferably a maximum value of 15 nm. This is due to the half-width of the LED. On the other hand, the short wavelength side is preferably 400 nm or less in consideration of the ease of experimentation and the magnitude of absorption intensity. More preferably, it is 360 nm or less. The "absorption spectrum of the reaction system" mentioned here includes the absorption spectrum of the reaction substrate and the catalyst used in the reaction.

[0045] The present invention also includes a light irradiation utilization system that irradiates an object with light having a peak wavelength within 50 nm of the wavelength of the absorption edge of the light absorption spectrum of the object. Furthermore, the present invention also includes a light irradiation utilization system for irradiating an object with light having a wavelength capable of mainly exciting forbidden transitions in the light absorption spectrum of the object. The vicinity of the absorption edge is composed of absorption between limited levels, and for example, forbidden transitions due to odd-evenness, such as n → π*, and forbidden transitions due to spin forbidden involving triplets exist alone. Therefore, by irradiating light with a peak wavelength within 50 nm of the absorption edge wavelength, it is possible to excite only forbidden transitions, for example, and to generate limited excited species by taking advantage of this characteristic. Specifically, it is expected that small amounts of excited species can be generated for a long time. In such a case, the time distribution of excited species will be different, and it is expected that unusual products (selectivity) will be produced. The light used in a light irradiation utilization system that irradiates an irradiated object with light having a peak wavelength within 50 nm of the wavelength of the absorption edge of the optical absorption spectrum of the irradiated object depends on the half-width of the irradiating light source, but it may be a wavelength that is 50 nm away from the absorption edge of the optical absorption spectrum of the irradiated object on both the short-wavelength and long-wavelength sides, preferably a wavelength that is 30 nm away from the absorption edge on both the short-wavelength and long-wavelength sides, and more preferably a wavelength that is 15 nm away.

[0046] 6. Photoreaction method (wavelength control) The wavelength-controlled photoreaction method of the present invention is a method in which a reaction raw material is irradiated with light of a plurality of different wavelengths, and the optimum wavelength of light irradiation for obtaining a desired result is determined. As described above, the wavelength of light irradiation can change the effect of light irradiation on the irradiated object, so by irradiating the reaction raw materials with light of multiple different wavelengths and checking the reaction results, the optimal wavelength of light irradiation to obtain the desired results can be determined.

[0047] The present invention also includes a photoreaction method in which the reactant is irradiated with light having a peak wavelength within 50 nm of the wavelength of the absorption edge of the light absorption spectrum of the reactant. Furthermore, the present invention also includes a photoreaction method in which an object to be irradiated is irradiated with light having a wavelength capable of mainly exciting forbidden transitions in the optical absorption spectrum of the reaction raw materials. As described above, by irradiating the reactant with light having a peak wavelength within 50 nm of the wavelength of the absorption edge of the optical absorption spectrum of the reactant, it is possible to generate only specific excitations such as forbidden transitions, which may result in the appearance of products (selectivity) that are different from normal. In this way, the photoreaction method in which the reactant is irradiated with light having a peak wavelength within 50 nm of the wavelength of the absorption edge of the optical absorption spectrum of the reactant, and the photoreaction method in which the reactant is irradiated with light having a wavelength that can mainly excite the forbidden transition of the optical absorption spectrum of the reactant, are reaction methods of great technical significance in that they may be able to obtain reaction results that cannot be obtained by normal light irradiation.

[0048] The reaction using the wavelength-controlled photoreaction method of the present invention may be any photoreaction in which a reaction raw material is irradiated with light to cause a reaction, and examples of the photoreaction include reactions similar to the photoreaction using the time-controlled photoreaction method described above.

[0049] 7. Compound manufacturing method (wavelength control) By using the wavelength-controlled photoreaction method of the present invention, it is possible to determine the conditions of light irradiation so that a large amount of the target product is produced, and perform the photoreaction to efficiently obtain the target product. Such a production method, that is, a method for producing a compound using a photoreaction in which a reaction raw material is irradiated with light, which includes a step of irradiating the reaction raw material with light of a plurality of different wavelengths, determining the optimal wavelength of light irradiation for obtaining the desired result, and a step of irradiating the reaction raw material with light of the determined wavelength, is also one of the present inventions. Furthermore, as described above, there is technical significance in performing a photoreaction in which the raw materials are irradiated with light having a peak wavelength within 50 nm of the wavelength of the absorption edge of the optical absorption spectrum of the raw materials, or in performing a photoreaction in which the raw materials are irradiated with light having a wavelength capable of mainly exciting a forbidden transition in the optical absorption spectrum of the raw materials, and a method for producing a compound using such a photoreaction, i.e., a method for producing a compound using a photoreaction in which the raw materials are irradiated with light, which includes a step of irradiating the raw materials with light having a peak wavelength within 50 nm of the wavelength of the absorption edge of the optical absorption spectrum of the raw materials, or a method for producing a compound using a photoreaction in which the raw materials are irradiated with light, which includes a step of irradiating the raw materials with light having a wavelength capable of mainly exciting a forbidden transition in the optical absorption spectrum of the raw materials, also constitutes one aspect of the present invention.

[0050] The method for producing a wavelength-controlled compound of the present invention may include other steps as long as it includes the above steps. Examples of other steps include a step of separating the obtained product from other components in the reaction solution, a step of purifying the reaction product, etc.

[0051] 8. Photoreactor (wavelength control) The present invention also relates to a reaction apparatus used for photoreaction in which reaction raw materials are irradiated with light, the reaction apparatus including a plurality of reaction vessels, a power source, and a plurality of light sources each irradiating light of a different wavelength, all of the light sources being directly connected to the power source, and the light sources being arranged so as to directly irradiate light from each of the plurality of reaction vessels, thereby making it possible to carry out photoreactions in a plurality of reaction vessels at one time. As mentioned above, photoreactions are generally susceptible to environmental influences such as temperature and humidity, so in order to confirm the pure effect of the wavelength of light irradiation on photoreactions, it is preferable to carry out multiple photoreactions using light of different wavelengths at once. In the photoreaction device (wavelength control) of the present invention, multiple light sources that irradiate light of different wavelengths are directly connected to a power source, so that each light source can irradiate light of different frequencies at once without being affected by other light sources. In addition, since all light sources are connected to one and the same power source, there is no difference in power supply. As a result, by using the photoreaction device (wavelength control) of the present invention, it is possible to confirm the pure effect of the wavelength of light irradiation on photoreactions. FIG. 1 is a schematic diagram of a time-controlled photoreaction device of the present invention, but the light source connected to the multiple waveform generating circuits in FIG. 1 is replaced with multiple light sources that irradiate light of different wavelengths, which corresponds to the schematic diagram of a wavelength-controlled photoreaction device of the present invention.

[0052] The number of reaction vessels in the photoreaction device (wavelength control) is not particularly limited, but the more photoreactions using different wavelengths, the more optimal light irradiation conditions can be found to obtain the desired results, so it is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. The number of light sources is preferably the same as the number of reaction vessels.

[0053] The light source used in the photoreaction device (wavelength control) is not particularly limited, and any light source capable of irradiating light of a desired wavelength may be used, for example, an LED or an organic LED.

[0054] Moreover, the photoreactor (wavelength control) preferably has a facility for keeping the temperatures of all reaction vessels at the same temperature in order to eliminate the effect of the outside air temperature on the reaction. Examples of equipment for keeping all the reaction vessels at the same temperature include a hot bath or a metal block capable of housing all the reaction vessels.

[0055] The reaction apparatus of the present invention may include other elements other than the reaction vessels, the power source, the light source, and the equipment for maintaining the same temperature of all the reaction vessels, such as a shielding member for covering the reaction vessels and the light source to block light other than the light from the light source. EXAMPLES

[0056] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, "%" means "% by mass".

[0057] Example 1 The following photoreaction was carried out.

[0058] [ka]

[0059] 1,3-dimethoxybenzene as the substrate, anthraquinone (AQN) as the photocatalyst, and sodium trifluoromethanesulfinate as the trifluoromethyl source were dissolved in acetonitrile in the amounts shown in formula (1), and the temperature was controlled in a water bath at 15°C to carry out a photoreaction for 20 hours. Regarding the light conditions, wavelength, intensity, and pulse characteristics (frequency and duty ratio), the wavelength of the light source was unified to 405 nm, and the intensity was unified to 235 mW at a distance of 2.0 cm from the light source, and the pulse characteristic conditions were changed as shown in entries 1 to 11 in Table 1 below. An LED was used as the light source. After 20 hours, a saturated aqueous solution of sodium carbonate was added to the reaction solution, and the mixture was extracted with ethyl acetate. The ethyl acetate phase was dried over magnesium sulfate, and then hexafluorobenzene was added. A small amount of the solution was dissolved in deuterated chloroform, 19 The yields of the produced compounds (compounds A to D represented by formula (1)) were calculated by FNMR. The yields of compounds A to D at this time are shown in Table 1 below.

[0060] [Table 1]

[0061] Example 2 The same reaction as in Example 1 was carried out by changing the light irradiation to continuous light and the wavelength of the light source to entries 1 to 5 in Table 2 below. The intensity of the light irradiation was 235 mW at a distance of 2.0 cm from the light source. The yield of the compound produced in the same manner as in Example 1 was calculated, and the results are shown in Table 2.

[0062] [Table 2]

[0063] As shown in Table 1, when light irradiation was performed with the duty ratio of intermittent light irradiation fixed and the frequency changed, the yield of the entire products A to D and the ratio of the products A to D produced varied depending on the frequency. In addition, in Example 1 in which the on / off duty ratio of light irradiation was set to 10:90 and the dark time was lengthened, the selectivity of compound B increased when intermittent light irradiation was performed at a low frequency of 1 Hz or less. In addition, it was found that the actual amount of the diadducts C and D was extremely reduced at 0.01 Hz or less. This can be seen as the selective production of the monoadduct. Furthermore, the total yields of the monoadducts (A+B) and diadducts (C+D) were calculated, and the frequency dependence was shown in Figure 3. From Figure 3, it is suggested that the ratio of the diadduct decreased at 0.1 Hz or less, and the overreaction was suppressed. From this result, the technical significance of performing intermittent light irradiation at a low frequency was confirmed. As shown in Table 2, when light irradiation was performed by changing the wavelength of light irradiation, the overall yield of products A to D and the ratio of the generated products A to D varied depending on the wavelength of light. In addition, when light irradiation was performed with a 448 nm LED, which has a peak wavelength about 20 nm longer than the absorption edge (around 430 nm) of the anthraquinone used as the photocatalyst, the selectivity of compound B was high and the generation of the diadduct was suppressed. This result confirmed the technical significance of irradiating light with a wavelength near the absorption edge of the reaction raw material. From the above, it was confirmed that the effects on the irradiated object differ depending on the on / off frequency and wavelength of light irradiation. Furthermore, by performing multiple reactions with different on / off frequencies and wavelengths of light irradiation, it was confirmed that the optimal frequency and wavelength for obtaining the desired results can be determined, and it is possible to obtain the desired product in the photoreaction with high yield and high selectivity. In addition, the frequency expansion over 10 digits shows that the selectivity of compound B varies. This indicates the characteristics of this photoreaction, and we believe that detailed analysis will reveal the details of the reaction process of this photoreaction. Therefore, it can be said that the new analytical method of performing such frequency expansion is meaningful.

[0064] Example 3 The photoreaction shown below was carried out under the same reaction conditions as in Example 1, except that 3,5-dimethoxypyridine was used as the substrate. The yields of the produced compounds (compounds A to C represented by formula (2)) were calculated in the same manner as in Example 1. The results are shown in Table 3.

[0065] [ka]

[0066] [Table 3]

[0067] From the results in Table 3, it can be seen that, in Example 3 as in Example 1, the production ratios of each of compounds A to C differ depending on the frequency of the irradiated light, even though the total amount of light is the same. For example, the production amount of compound A is almost the same at frequencies higher than 1 Hz, but gradually decreases on the low frequency side. Although no clear trends are observed for the B form and the C form, which is a diadduct, most of the experiments are average values ​​of multiple runs, and the variance in the results of each run was small, so it is believed that there is some scientific significance and this has been demonstrated. Moreover, the effect was also confirmed for heterocyclic compounds in Example 3. This suggests once again that the parameter frequency is a general factor that determines reactions, similar to factors that affect other reactions such as those in electronic systems.

[0068] Example 4 The experiment in entry 11 in Example 1 was carried out on a three-fold scale. The results are shown in Table 4.

[0069] [Table 4]

[0070] Comparative Example 1 The reaction was carried out on the same scale and under the same conditions as in Example 4, except that the light intensity was 1 / 10 and the reaction was carried out under continuous light. The results are shown in Table 5.

[0071] [Table 5]

[0072] Example 4 and Comparative Example 1 are reactions performed under the same conditions with the same total light amount. The difference is whether intermittent light or continuous light is used. Although the yield of Example 4 is inferior to that of entry 11 of Example 1, the value is higher than that of Comparative Example 1. This is considered to indicate that light reaches areas that cannot be reached with low-intensity light with intermittent light irradiation, and the reaction proceeds, and this result indicates that photoreaction using intermittent light is useful as a manufacturing method. From these results, it can be said that when the reaction scale is large, the intermittent use of high-intensity light is an effective method for delivering light uniformly and causing a uniform reaction. Specifically, this is as follows. In Example 4, the scale is three times that of Example 1. In this system, the light source position is one place to ensure the uniformity of light, and therefore in Example 4, the distance (depth) from the light source to the reaction solution is three times that of Example 1. In the case of this light intensity, if the scale is about twice, it is presumed that the same yield can be achieved in the case of the intermittent light irradiation proposed in this patent. Based on this idea, if the light intensity is increased, the distance from the light source to the reaction target can be made longer (deeper). Although the power source for light irradiation needs to be in one place, there can be multiple light sources as long as they are the same electrical system, and the number can be increased. By using these two elements, it can be said that the light irradiation system of this patent can design a reaction apparatus according to the desired production amount. Of course, the same can be said when continuous light is used, but the degree of freedom in designing the reaction apparatus is narrow, and as shown above, it is not realistic due to the increase in side reactions. As a result, it can be said that this method can be realized only by the reaction using intermittent light proposed in this patent.

Claims

1. A system for utilizing light irradiation for the purpose of bringing about an action of light energy on an irradiated object, comprising: The system performs multiple intermittent light irradiations on the object under the same total light intensity, varying the on / off frequency of the light irradiation, and determines the optimal light irradiation frequency to obtain the desired results. A light irradiation utilization system.

2. A system for utilizing light irradiation for the purpose of bringing about an action of light energy on an irradiated object, comprising: The system performs intermittent light irradiation on the object to be irradiated with light having an on / off frequency of 1 Hz or less. A light irradiation utilization system.

3. A photoreaction method for intermittently irradiating a reaction raw material with light to cause a reaction, comprising the steps of: In this photoreaction method, the reaction raw materials are subjected to multiple intermittent light irradiations with different on / off frequencies under the same total light intensity, and the optimal light irradiation frequency for obtaining the desired results is determined. A photoreaction method comprising:

4. A photoreaction method for intermittently irradiating a reaction raw material with light to cause a reaction, comprising the steps of: The photoreaction method involves intermittently irradiating the reaction raw materials with light at an on / off frequency of 1 Hz or less. A photoreaction method comprising:

5. A method for producing a compound using a photoreaction in which a reaction raw material is intermittently irradiated with light, comprising the steps of: The method includes a step of irradiating the reaction raw materials with light intermittently by changing the on / off frequency of the light irradiation under the same total light amount, and determining an optimal light irradiation frequency for obtaining a desired result; and irradiating the reaction raw materials with light of a determined frequency. A method for producing a compound comprising the steps of:

6. A method for producing a compound using a photoreaction in which a reaction raw material is intermittently irradiated with light, comprising the steps of: The method includes a step of intermittently irradiating the reaction raw materials with light having an on / off frequency of 1 Hz or less. A method for producing a compound comprising the steps of:

7. A reaction apparatus used for a photoreaction in which a reaction raw material is intermittently irradiated with light, The reaction apparatus includes a plurality of reaction vessels, a power source, a plurality of waveform generating circuits capable of controlling the frequency of the irradiated light, and a plurality of light sources; All light sources are directly connected to the power supply through different waveform generating circuits, and The light sources are arranged so that each of the multiple reaction vessels is directly irradiated with light from a different light source, making it possible to carry out photoreactions in multiple reaction vessels at the same time. A photoreactor characterized by:

8. A system for utilizing light irradiation for the purpose of bringing about an action of light energy on an irradiated object, comprising: The utilization system irradiates the object with light of a plurality of different wavelengths and determines the optimum wavelength of light irradiation to obtain the desired result. A light irradiation utilization system.

9. A system for utilizing light irradiation for the purpose of bringing about an action of light energy on an irradiated object, comprising: The utilization system irradiates the object with light having a peak wavelength within 50 nm of the wavelength of the absorption edge of the light absorption spectrum of the object. A light irradiation utilization system.

10. A system for utilizing light irradiation for the purpose of bringing about an action of light energy on an irradiated object, comprising: The utilization system irradiates an object with light having a wavelength capable of mainly exciting forbidden transitions in the optical absorption spectrum of the object. A light irradiation utilization system.

11. A photoreaction method for irradiating a reaction raw material with light to cause a reaction, comprising the steps of: In this photoreaction method, the reaction raw materials are irradiated with light of a plurality of different wavelengths, and the optimum wavelength of light irradiation for obtaining the desired result is determined. A photoreaction method comprising:

12. A photoreaction method for irradiating a reaction raw material with light to cause a reaction, comprising the steps of: The photoreaction method involves irradiating the reactant with light having a peak wavelength within 50 nm of the wavelength of the absorption edge of the light absorption spectrum of the reactant. A photoreaction method comprising:

13. A photoreaction method for irradiating a reaction raw material with light to cause a reaction, comprising the steps of: The photoreaction method comprises irradiating the reactant with light having a wavelength capable of mainly exciting the forbidden transition in the optical absorption spectrum of the reactant. A photoreaction method comprising:

14. A method for producing a compound using a photoreaction in which a reaction raw material is irradiated with light, comprising the steps of: The method includes a step of irradiating a reaction material with light of a plurality of different wavelengths and determining an optimal wavelength of light irradiation for obtaining a desired result; and irradiating the reaction raw materials with light of a determined wavelength.

15. A method for producing a compound using a photoreaction in which a reaction raw material is irradiated with light, comprising the steps of: The method includes a step of irradiating the reactant with light having a peak wavelength within 50 nm of the wavelength of the absorption edge of the light absorption spectrum of the reactant. A method for producing a compound comprising the steps of:

16. A method for producing a compound using a photoreaction in which a reaction raw material is irradiated with light, comprising the steps of: The method includes the step of irradiating the reactant with light having a wavelength capable of primarily exciting forbidden transitions in the optical absorption spectrum of the reactant. A method for producing a compound comprising the steps of:

17. A reaction apparatus used for a photoreaction in which a reaction raw material is irradiated with light, The reactor includes a plurality of reaction vessels, a power source, and a plurality of light sources each emitting light of a different wavelength; All light sources are directly connected to a power source, and the light sources are arranged so that light from different light sources is directly irradiated to each of the multiple reaction vessels, making it possible to carry out photoreactions in multiple reaction vessels at the same time. A photoreactor characterized by:

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