JP2007075682A - Continuous flow photochemical reaction apparatus and method for producing photochemical reaction product by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a continuous flow photochemical reaction apparatus which is excellent in reaction efficiency, energy efficiency and maintainability and in which a reaction environment suitable for causing a desired photochemical reaction can be set easily. <P>SOLUTION: The continuous flow photochemical reaction apparatus is provided with: a reaction part to be formed from a light-transmissive flow passage; a liquid supply part for supplying a substance to be reacted to the reaction part; a light source part having at least one light source for emitting light toward the reaction part to cause the photochemical reaction in the substance to be reacted in the light-transmissive flow passage; and a recovery part for recovering a photochemical reaction product produced by the photochemical reaction. The reaction part is unitized as one unit, which is then fit detachably to the light source part and integrated with the light source part. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a flow type photochemical reaction apparatus and a method for producing a photochemical reaction product using the same.

As a prior art related to the present invention, a flask containing a reactant is irradiated with light from a high-intensity high-pressure mercury lamp or xenon lamp having a broad wavelength characteristic in the ultraviolet region, and the reactant in the flask is irradiated. A method of producing a photochemical reaction product by a batch reactor method that generates a photochemical reaction and obtains a desired photochemical reaction product is known.
Also known as a microreactor that can improve the efficiency of the photochemical reaction is to form a groove that repeatedly bends and meanders in a plate-like substrate, and a glass plate is overlaid to cover the groove (for example, Patent Document 1).
In addition, as a device for oxidizing water with ultraviolet light, it has a configuration in which a thin reaction tube is spirally wound around the outer periphery of a straight tube-shaped ultraviolet lamp, and water as a fluid to be treated is a reaction tube. There is also known a photo-oxidizer that passes through water (see, for example, Patent Document 2).
In addition, as a device for generating a photocatalytic reaction by ultraviolet light, a number of transparent glass tubes with a transparent titania film formed on the surface are arranged in a circle around a light source that emits ultraviolet light, and at the beginning of adjacent glass tubes. There is also known a photocatalytic reactor in which a fluid is passed through a glass tube by connecting the end and the end in communication (see, for example, Patent Document 3).
JP 2005-7529 A JP 2003-211159 A Japanese Patent Laid-Open No. 10-15393

Photochemical reaction is one of important reactions in the field of organic synthesis. In general, the batch reactor method as introduced in the above-mentioned background section is the mainstream.
However, in the batch reactor system, light attenuation caused by light absorption by the reaction substrate, the product itself, or the solvent occurs, so that it cannot be said that the reaction efficiency is sufficient, and there is a possibility that product decomposition due to excessive light irradiation may occur. is there.

Then, in order to improve reaction efficiency, it is also attempted to perform a photochemical reaction using a microreactor as described in Patent Document 1.
However, the microreactor cannot be said to have a sufficient flow path length for photochemical reaction, and in order to ensure the reaction, as with the batch reactor method, the microreactor is a high-intensity high-pressure mercury lamp or xenon lamp. Need to be irradiated.

  In other words, several hundred to several tens of kilowatts of high-pressure mercury lamps and xenon lamps are required to produce photochemical reaction products by photochemical reactions, but these large-scale light sources are generally expensive, and various Selecting a required wavelength from the light peak of the wavelength requires many filters, which results in energy loss.

In addition, among the light emitted from the large-scale light source as described above, the light contributing to the photochemical reaction is mainly a small part of the short wavelength light, but the short wavelength high energy photons are the reaction product itself. It may be necessary to suppress the action with a filter or the like.
Furthermore, irradiating light from a large-scale light source as described above to a flask or microreactor that cannot be said to have a large irradiated area is unbalanced in the relationship between the irradiated area and the irradiated area. This is not desirable from the viewpoint of energy efficiency.

  In addition, if a photochemical reaction is performed using a microreactor having a fine flow path, the reaction efficiency is improved over the batch reactor method, but the microreactor is generally expensive and the fine flow path is clogged. And there is no choice but to replace the expensive microreactor itself. In the thing of patent document 1, since the microreactor is comprised so that decomposition | disassembly is possible, when obstruction | occlusion arises in a flow path, it is possible to remove obstruction | occlusion by disassembling and cleaning a microreactor, When the microreactor and the light source unit are combined in a complicated manner, it is not easy to take out only the microreactor.

  In addition, the photochemical reaction has various factors such as preferable conditions for generating a desired photochemical reaction in the reaction substance, that is, the output and wavelength of the light source, or the flow channel configuration and flow channel length when a microreactor is used. Therefore, it is not easy to set an optimal reaction environment to generate a desired photochemical reaction, and it takes time and effort.

  The present invention has been made in view of the above circumstances, and is excellent in reaction efficiency, energy efficiency, maintainability, and can easily set an optimum reaction environment for causing a desired photochemical reaction. A flow-type photochemical reaction device and a method for producing a photochemical reaction product using the same are provided.

  The present invention relates to a reaction part formed by a light-transmitting flow path, a liquid-feeding part for sending a reaction substance to the reaction part, and a photochemical reaction to the reaction substance in the light-transmitting flow path by irradiating the reaction part. A light source unit including at least one light source that generates a photochemical reaction, and a recovery unit that recovers a photochemical reaction product that has undergone a photochemical reaction. The reaction unit is unitized as one unit, and is integrated with the light source unit. The present invention provides a flow type photochemical reaction device that is detachably attached to a light source unit.

According to the present invention, the reaction unit is unitized as a single unit and is detachably attached to the light source unit so as to be integrated with the light source unit. Therefore, the reaction efficiency is improved, and the reaction efficiency is improved. It is possible to use a light source unit of a scale, and energy efficiency is improved.
That is, when the light-transmitting flow path forming the reaction part is very close to the light source part, the reaction target substance in the light-transmitting flow path is efficiently irradiated with light, and the reaction efficiency is improved. And by improving reaction efficiency, it becomes possible to produce sufficient photochemical reaction even if it is a small-scale light source, and the improvement of energy efficiency is also aimed at.
In addition, since the reaction unit is unitized and is detachably attached to the light source unit, a plurality of types of reaction units with different conditions such as the length of the light transmissive channel and the light transmittance are prepared in advance. Therefore, it is possible to select and install the reaction part that has the optimum conditions for producing the desired photochemical reaction, and to provide the optimum reaction environment for producing the desired photochemical reaction. It becomes possible to set very easily.
Further, since the reaction unit is unitized and can be attached to and detached from the light source unit, the reaction unit can be easily detached from the light source unit even when the light transmissive flow path of the reaction unit is blocked. Can be easily replaced and disassembled.

  The flow-type photochemical reaction device according to the present invention includes a reaction part formed by a light-transmitting channel, a liquid-feeding part that sends a substance to be reacted to the reaction part, and a reaction part that irradiates the reaction part. A light source unit including at least one light source that causes a photochemical reaction to occur in a reaction target, and a recovery unit that recovers a photochemical reaction product that has undergone a photochemical reaction, the reaction unit being unitized as one unit, and a light source unit And is detachably attached to the light source unit so as to be integrated with the light source unit.

In the present invention, the light-transmitting flow path is a flow path through which light irradiated from the outside is transmitted, and any structure capable of flowing a substance to be reacted sent from the liquid sending part can be used. There is no particular limitation.
The reaction unit means a unit that is formed by a light-transmitting flow path, is unitized as one unit so as to be detachable from the light source unit, and functions as a microreactor.
The liquid feeding unit is not particularly limited as long as it has a function of feeding a substance to be reacted to the light transmissive flow path of the reaction unit.

The light source unit is not particularly limited as long as it includes at least one light source and can irradiate the light-transmitting flow path integrally with the unitized reaction unit. Although it does not specifically limit as a light source, For example, a high pressure mercury lamp and a cold cathode fluorescent tube can be used.
Among these, a cold cathode fluorescent tube (black light) that emits fluorescence of a specific wavelength individually from the ultraviolet region to the visible region depending on the composition of the phosphor is preferable from the viewpoint of reaction efficiency and energy efficiency.
The recovery unit is not particularly limited as long as it can accommodate a photochemical reaction product that has undergone a photochemical reaction.

  In the flow type photochemical reaction device according to the present invention, the reaction part and the light source part are integrated. The reaction part and the light source part are substantially integrated in a state where the reaction part is attached to the light source part. This means that the light-transmitting flow path of the reaction part and the light source of the light source part are in close proximity to each other.

  The flow type photochemical reaction apparatus according to the present invention can be used for various photochemical reactions. Specific photochemical reactions include, for example, cis-trans isomerization reaction, photocyclization reaction (eg, cyclization from stilbene to phenanthrene, Norbornadiene intramolecular photocyclization reaction, [2 + 2] cycloaddition reaction, etc.), photo-Fries rearrangement reaction, Puterno-Buchi reaction, cyclobutane photosynthesis reaction, superoxide addition reaction, Norrish Type I / II cleavage reaction, photo pinacol coupling reaction , Photochemical bromination reaction, optical Barton reaction and the like.

  In the flow-type photochemical reaction device according to the present invention, the reaction part is composed of a light-transmitting cylindrical body and a light-transmitting tube wound around the outer peripheral surface of the cylindrical body to form a light-transmitting flow path. The light source unit may be disposed inside the cylindrical body so as to irradiate the tube from the inner peripheral surface of the cylindrical body via the cylindrical body.

  According to such a configuration, since the light transmissive tube wound around the outer peripheral surface of the light transmissive cylindrical body is irradiated by the light source unit disposed inside the cylindrical body, It is possible to irradiate the substance to be reacted with light very efficiently, and it is possible to provide a flow type photochemical reaction apparatus that is very preferable in terms of reaction efficiency and energy efficiency.

As the tube, for example, a flexible Teflon (registered trademark) tube made of a fluororesin or a glass tube made of quartz glass or lime soda glass can be used.
As the cylindrical body, for example, a cylindrical body made of transparent acrylic resin or fluororesin, or a cylindrical body made of quartz glass or lime soda glass can be used.

In the above configuration in which the tube is wound around the outer peripheral surface of the cylindrical body, it is preferable that the cylindrical body has a groove formed on the outer peripheral surface thereof, and the tube is wound along the groove of the cylindrical body.
According to such a configuration, since there is no gap between the tube and the cylindrical body, it becomes easy for light to enter the tube, and light can be irradiated more efficiently by the reactant in the flexible tube. Thus, the reaction efficiency and energy efficiency can be further improved.

  In the flow-type photochemical reaction device according to the present invention, the reaction unit is overlapped on the first substrate so as to cover the groove formed on the first substrate and the first substrate on which the groove corresponding to the light transmissive flow path is formed. The light source part may be provided with the reaction part accommodating part which receives the reaction part so that attachment or detachment is possible.

According to such a configuration, the light-transmitting flow path is formed by the groove formed in the first substrate and the light-transmitting second substrate, and the light source unit includes the reaction unit accommodating unit that detachably receives the reaction unit. Therefore, in a state where the reaction part is received in the reaction part accommodating part of the light source part, the light transmissive flow path is in a state of being very close to the light source part.
As a result, it is possible to irradiate the substance to be reacted in the light-transmitting channel with light very efficiently, and it is possible to provide a flow-type photochemical reaction device that is very preferable in terms of reaction efficiency and energy efficiency.

As the first substrate on which the groove is formed, for example, a metal substrate made of copper or Fe—Ni alloy, a resin substrate made of fluororesin, or a glass substrate made of quartz glass or lime soda glass may be used. it can.
As the second substrate, for example, a glass substrate made of quartz glass, lime soda glass, or the like can be used.

  In the flow-type photochemical reaction device according to the present invention, the reaction section covers the first substrate on which the opening pattern corresponding to the light transmissive flow path is formed, and the first substrate so as to close the opening pattern formed on the first substrate. At least one of the sandwiches may be formed of a second and a third substrate having optical transparency, and the light source unit may include a reaction unit housing unit that detachably receives the reaction unit.

According to such a configuration, the light-transmitting flow path is formed by the opening pattern formed in the first substrate and the second and third substrates having at least one light-transmitting property, and the light source unit attaches and detaches the reaction unit. Since the reaction part accommodating part which accepts possible is provided, in the state where the reaction part is received in the reaction part accommodating part of the light source part, the light transmissive flow path is in a state very close to the light source part.
As a result, it is possible to irradiate the substance to be reacted in the light-transmitting channel with light very efficiently, and it is possible to provide a flow-type photochemical reaction device that is very preferable in terms of reaction efficiency and energy efficiency.

As the first substrate on which the opening pattern is formed, for example, a metal substrate made of copper or Fe—Ni alloy, a resin substrate made of fluororesin, or a glass substrate made of quartz glass or lime soda glass is used. Can do.
Moreover, as the second and third substrates, for example, glass substrates made of quartz glass, lime soda glass, or the like can be used.

The reaction unit includes a first substrate having a groove and a light-transmissive second substrate, or a first substrate having an opening, and at least one of the second and third substrates sandwiching the first substrate and having light-transmissive properties. In the above-described configuration, the light source unit may include a plurality of light sources, and the plurality of light sources may be arranged so as to be arranged from the upstream side to the downstream side of the light transmissive flow path.
According to such a configuration, since the plurality of light sources are arranged so as to be aligned along the flow path of the light transmissive flow path, even when the flow path length of the light transmissive flow path is long, the light source is large. It is possible to efficiently irradiate light on the reactants in the light-transmitting flow path by using a plurality of small light sources without using a light source of a scale.

The reaction unit includes a first substrate having a groove and a light-transmissive second substrate, or a first substrate having an opening, and at least one of the second and third substrates sandwiching the first substrate and having light-transmissive properties. In the above-described configuration, the reaction unit may be provided with a plurality of discharge ports partially along the light transmissive flow channel.
According to such a configuration, the progress of the reaction is monitored by sampling the substance to be reacted from the outlet, and the lighting control of the light source unit and the amount of liquid fed from the liquid feeding unit are adjusted according to the progress of the reaction. By doing so, it is possible to suppress decomposition and destruction of the reaction product caused by excessively irradiating the target substance with light.
In particular, when the light source unit includes a plurality of light sources and they are arranged so as to be aligned along the light-transmitting flow path, lighting control is performed for each of the plurality of light sources, and simultaneous lighting or time-series lighting is performed. By performing control or the like, it is possible to perform more preferable light irradiation for causing a desired photochemical reaction.

  The reaction unit includes a first substrate having a groove and a light-transmissive second substrate, or a first substrate having an opening, and at least one of the second and third substrates sandwiching the first substrate and having light-transmissive properties. In the above configuration, the first substrate and the second substrate, or the second substrate and the third substrate are sandwiched between a pair of clamp plates having openings that do not hinder exposure to the grooves or openings of the first substrate. You may be stuck so that decomposition | disassembly is possible.

According to such a configuration, the first and second substrates or the first, second and third substrates can be easily disassembled and cleaned by releasing the engagement state of the pair of clamp plates. Therefore, the same reaction part can be used for various substances to be reacted, and even if the light-transmitting flow path is clogged, the clogged state can be easily removed by disassembly and cleaning, so photochemical reaction The cost for producing the product can be reduced, and the operating rate of the flow type photochemical reaction device can be improved.
As the pair of clamp plates, a metal plate made of aluminum or SUS can be used, and these are screws and bolts with the first and second substrates or the first, second and third substrates sandwiched therebetween. It may be fixed with.

In the above configuration in which the light source unit includes a plurality of light sources, the plurality of light sources may have different peak wavelengths.
According to such a configuration, it becomes possible to irradiate light having different wavelengths in time series to the reactant to be sent from the upstream side to the downstream side of the light-transmitting channel. It is possible to cause a plurality of types of photoreactions in time series in the flow path.

In the flow-type photochemical reaction device according to the present invention, the light source unit may include a temperature adjustment mechanism.
According to such a configuration, it is possible to suppress the heating of the reaction part, which is not preferable for causing a desired photochemical reaction, and to maintain the surface temperature of the light source within an appropriate range, thereby stabilizing the light output. Can be planned.

  From another point of view, the present invention uses the above-described flow-type photochemical reaction device according to the present invention, sends a predetermined target substance to the light-transmitting flow path of the reaction section by the liquid feeding section, and reacts the reaction section by the light source. A method for producing a photochemical reaction product, characterized in that a photochemical reaction is caused to occur in a reaction material in a light-transmitting channel by irradiating light to a desired part, and a desired photochemical reaction product is obtained in a recovery part But there is.

で示される亜硝酸エステルであり、光化学反応としての光バートン反応によって得られる光化学反応生成物質が式（II）：

で示されるオキシイミノアルコールであってもよい。 In the method for producing a photochemical reaction product according to the present invention, the reactant to be fed by the liquid feeding unit is represented by the formula (I):

A photochemical reaction product obtained by the optical Barton reaction as a photochemical reaction is a nitrite represented by the formula (II):

The oxyimino alcohol shown by these may be sufficient.

In the method for producing a photochemical reaction product, the nitrite represented by the above formula (I) is allowed to undergo a photobarton reaction to produce the oxyimino alcohol represented by the above formula (II). Examples of hydroxy protecting groups include aralkyl (methoxybenzyl, nitrobenzyl, 2,4-dimethoxybenzyl, trityl, etc.), alkylcarbonyl (acetyl, acetyl halide, pivaloyl, formyl, cyclohexylacetyl, etc.), arylcarbonyl (benzoyl), and the like. , Toluoyl, xylyl, indanyl, etc.), alkoxycarbonyl (methoxycarbonyl, t-butoxycarbonyl, cyclopropoxycarbonyl, etc.), alkenyloxycarbonyl (propenyloxycarbonyl, etc.), aryloxycarbonyl (phenoxy) Sulfonyl), aralkyloxycarbonyl (nitrobenzyloxycarbonyl, etc.), silyl type (trimethylsilyl, t-butyldimethylsilyl, dimethylphenylsilyl, t-butoxydiphenylsilyl, etc.) and ether type (alkyl ether, aryl ether, aralkyl ether, Methoxymethyl, tetrahydrofuranyl and the like). Preferable is alkanoyl such as acetyl.
Examples of the oxo protecting group that may be protected together include, for example, dialkyl acetal type (dimethyl acetal, diethyl acetal, etc.), alkylene dithio, propylene dioxy, etc. and alkylene dithio type (ethylene dithio, propylene dithio). Etc.), and an alkylenedioxy type such as ethylenedioxy is particularly preferable.

  Hereinafter, the present invention will be described in detail based on embodiments shown in the drawings.

Example 1
A flow-type photochemical reaction device according to Embodiment 1 of the present invention will be described with reference to FIGS. 1 is a schematic diagram showing the overall configuration of a flow-type photochemical reaction device according to Embodiment 1 of the present invention, FIG. 2 is a perspective view of a reaction section, FIG. 3 is a cross-sectional view taken along line AA of the reaction section shown in FIG. 4 is a perspective view showing a state in which the light source unit is disposed inside the reaction unit shown in FIG. 2, FIG. 5 is a cross-sectional view of the reaction unit according to the modification, and FIG. 6 is a schematic diagram of the reaction unit according to the modification. FIG.

  In general, as shown in FIG. 1, a flow-type photochemical reaction device 1 according to Example 1 includes a reaction unit 3 formed by a Teflon (registered trademark) tube (light-transmitting flow path) 2, and a reaction unit 3 covered with the reaction unit 3. A light source comprising a liquid feed pump (liquid feed part) 4 comprising a microsyringe for delivering a reactive substance, and a black light (light source) 5 for irradiating the reaction part 3 to cause a photochemical reaction to occur in the reactant in the silicon tube 2a. Unit 6 and a recovery unit 7 that recovers a photochemical reaction product that has undergone a photochemical reaction, and the reaction unit 3 is unitized as a single unit with respect to the light source unit 6 so as to be integrated with the light source unit 6. It is detachably attached.

As shown in FIG. 2 and FIG. 3, the reaction unit 3 includes a Teflon tube (inner diameter 1.2 mm, length 2.85 m) 2 spirally wound around the outer periphery of a transparent quartz glass tubular body 8. It has the structure which was made.
The Teflon tube 2 spirally wound around the outer periphery of the cylindrical body 8 is held by the clamp 9 so that the spiral start and end positions are fixed by the clamp 9 so that the spirally wound shape does not collapse. ing.

Connecting adapters 10 are respectively attached to both ends of the Teflon tube 2 in order to connect tubes extending from the liquid feed pump 4 and the recovery unit 7.
The connecting adapters 10 attached to both ends of the Teflon tube 2 are screwed into the through holes of the upper and lower collars 11 and 12 that are respectively fitted to both ends of the cylindrical body 8 and serve also as the lid of the reaction unit 3. A cylindrical aluminum body body 13 covering the cylindrical body 8 and the Teflon tube 2 is sandwiched between the collars 11 and 12 to constitute a single reaction unit 3.

As shown in FIGS. 2 to 4, the upper collar 11 and the lower collar 12 are from an outer diameter of 50 mm of a black light (manufactured by Toshiba Lighting & Technology Co., Ltd., Neoball 5 (registered trademark), power consumption 15 W, peak wavelength 352 nm) 5. The black light 5 is inserted from the opening 11a of the upper collar 11 until it hits the U-shaped stopper 14 attached to the lower collar 12 and has a slightly larger opening of 51 mm. .
That is, in a state where the black light 5 is inserted into the reaction portion 3, the inner peripheral surface of the cylindrical body 8 and the outer peripheral surface of the black light 5 are substantially in contact with each other.

Thereby, it becomes possible to irradiate light efficiently to the to-be-reacted substance in the Teflon tube 2, and the reaction efficiency and energy efficiency are improved. Moreover, even if the cylindrical body 8 and the Teflon tube 2 deteriorate due to the near-ultraviolet light emitted from the black light 5, the reaction unit 3 can be removed from the light source unit 6 and easily replaced with a new cylindrical body 8 or Teflon tube 2.
Of course, the reaction unit 3 itself may be replaced with a new one. Even when the reaction unit 3 is replaced with a new one, as described above, the reaction unit 3 is made of an inexpensive material and has a simple configuration. In view of this, the cost required to replace the reaction unit 3 is negligible.

  In the flow-type photochemical reaction device of Example 1 having the above-described configuration, when a reaction substance is sent from the liquid feed pump 4, the reaction substance flows into the Teflon tube 2 of the reaction unit 3 and is spirally wound. When flowing through the rotated Teflon tube 2, a photochemical reaction is caused by irradiation with near-ultraviolet light having a peak wavelength of 352 nm emitted from the black light 5 and flows into the recovery unit 7. At this time, it is preferable to appropriately adjust the flow rate of the reactant to be sent out from the liquid feed pump 4 according to the progress of the photochemical reaction.

In addition, this Example 1 is not restricted to said structure, The light source intensity | strength, luminescent color, and wavelength of the black light 5, the light transmittance of the Teflon tube 2, etc. are preferable when producing a desired photochemical reaction. What is necessary is just to select suitably.
Further, a glass tube made of quartz glass or lime soda glass may be used instead of the Teflon tube 2, or a fluororesin, an acrylic resin, or a lime soda glass may be used instead of the cylindrical body 8 made of quartz glass. A cylindrical body made of may be used.

  In order to generate a desired photochemical reaction, a plurality of types of reaction sections 3 having a preferable flow path length and diameter are prepared in advance, and the reaction section 3 having the most suitable conditions for generating a desired photochemical reaction is prepared. If it is appropriately selected and used, it becomes possible to quickly set an optimal reaction environment for the photochemical reaction of many substances, and the reaction unit 3 is detachably attached to the light source unit 6 as one unit. The advantage of the

Reaction example 1
A 2 + 2 cycloaddition reaction of benzophenone and prenyl alcohol as shown in the following formula (III) was performed using the flow type photochemical reaction apparatus 1 according to Example 1 shown in FIGS. In Reaction Example 1 shown below, as Comparative Example 1, the apparatus configuration is substantially the same as in Example 1. However, a flow-type photochemical reaction apparatus using a 300 W high-pressure mercury lamp as a light source is separately prepared. The reaction efficiencies of were compared by yield per power consumption.

  As shown in Table 1, the run 1 of Comparative Example 1 using a 300 W high-pressure mercury lamp as the light source has a yield per power consumption of 0.18, whereas the example using 15 W black light as the light source. In run 2 of 1, the yield per power consumption is 1.63, and it can be seen that the flow-type photochemical reaction apparatus 1 according to Example 1 is improved by about 9 times in the reaction efficiency (yield / Wh). Thereby, it was confirmed that the flow type photochemical reaction device 1 according to Example 1 is excellent in both reaction efficiency and energy efficiency.

Modified Example of Reaction Unit A modified example of the reaction unit in the flow type photochemical reaction apparatus according to Example 1 is shown in FIGS. FIG. 5 is a cross-sectional view of a reaction part according to a modification, and FIG. 6 is an enlarged view of a main part.
As shown in FIG. 5, the tubular body 108 of the reaction unit 103 according to the modification has a groove 108a formed on the outer peripheral surface thereof, and the Teflon tube 2 is wound along the groove 108a so as to be fitted in the groove 108a. ing.

  As a result, as shown in FIG. 6, there is no gap between the Teflon tube 2 and the outer peripheral surface of the cylindrical body 108, and the outer peripheral surface of the Teflon tube 2 and the cylindrical body 108 is in close contact with each other. Of the light components emitted from the black light 5, the light components emitted and reflected on the surface of the Teflon tube 2 are reduced, and the light emitted from the black light 5 is likely to enter the Teflon tube 2. For this reason, in the reaction part 103 by a modification, it becomes possible to aim at the further improvement of reaction efficiency and energy efficiency.

Example 2
A flow-type photochemical reaction device according to Embodiment 2 of the present invention will be described with reference to FIGS. 7 is a schematic diagram showing the overall configuration of a flow-type photochemical reaction device according to Example 2, FIG. 8 is an exploded perspective view of the reaction unit, FIG. 9 is a perspective view of the reaction unit, FIG. 10 is a perspective view of the light source unit, and FIG. 9 is a perspective view showing how the reaction part shown in FIG. 9 is inserted into the light source part shown in FIG. 10, FIG. 12 is an exploded perspective view of the reaction part according to the modification, and FIG. 13 is a view of the reaction part according to the modification. FIG. 14 is a perspective view of a light source unit according to a modification.

  In general, as shown in FIG. 7, the flow-type photochemical reaction device 21 according to the second embodiment includes a reaction part 23 formed by a light-transmitting flow path 22 (see FIG. 9), and a substance to be reacted to the reaction part 23. A liquid-feeding pump (liquid-feeding part) 24 for feeding liquid; a light-source part 26 including a black light (light source) 25 that irradiates the reaction part 23 and causes a reaction substance in the light-transmissive channel 22 to cause a photochemical reaction; And a recovery unit 27 that recovers a photochemical reaction product that has undergone a photochemical reaction. The reaction unit 23 is unitized as a single unit and is detachably attached to the light source unit 26 so as to be integrated with the light source unit 26. Has been.

The flow type photochemical reaction device 21 further includes a power source 28, a control unit 29 including a CPU, a ROM, a RAM, a timer, an I / O port, an input / output driver, and the like, and a temperature adjustment mechanism connected to the control unit 29 30. The temperature adjusting mechanism 30 adjusts the temperature of the reaction unit 23 to an optimum temperature for stabilizing and promoting the photochemical reaction under the control of the control unit 29, and keeps the surface temperature of the black light 25 in an appropriate range. Stabilize the light output.
The control unit 29 is also connected to the light source unit 26 and controls the lighting of the black light 25 according to the progress of the reaction. As will be described later, when the light source unit 26 includes a plurality of black lights 25, lighting control of the plurality of black lights 25, that is, simultaneous lighting, time-series lighting control, and the like according to the progress of the reaction. I do.

  As shown in FIG. 8 and FIG. 9, the reaction part 23 has a thickness of 200 μm of Fe— in which a groove 22 a having a width of 1 mm, a depth of 107 μm, and a length of 2.2 m corresponding to the light transmitting channel 22 is formed. A thin metal plate (first substrate) 31 made of Ni alloy, a quartz glass plate (second substrate) 32 overlaid on the thin metal plate 31 so as to cover the groove 22a formed in the thin metal plate 31, and the thin metal plate 31 and quartz It is mainly composed of a pair of an upper clamp plate 33 and a lower clamp plate 34 for fixing the glass plate 32 therebetween. The groove 22a corresponding to the light transmissive flow path 22 is formed by photoetching, cutting, pressing, or the like.

  Of the pair of clamp plates 33, 34, the upper clamp plate 33 is formed with an opening 33 a so as not to impede light irradiation on the groove 22 a of the thin metal plate 31, that is, the light transmissive channel 22. The pair of clamp plates 33 and 34 are bolted at the eight positions on the periphery with allen bolts 35, and the metal thin plate 31 and the quartz glass plate 32 are brought into close contact with each other. That is, the reaction portion 23 has a highly convenient structure that can be easily disassembled and cleaned by releasing the bolting of the pair of clamp plates 33 and 34 and can easily cope with the blockage of the flow path 22 and the like. ing. Of course, the same reaction part 23 can also be utilized with respect to various to-be-reacted substances by performing decomposition | disassembly and cleaning.

Grooves 22a formed in the thin metal plate 31 have a first inflow portion 36 and a second inflow portion 37 at two locations of the light transmissive flow path 22, and a first discharge portion 38, a second discharge portion 39 at three locations, and The third discharge part 40 is designed to be formed, and corresponds to the first and second inflow parts 36 and 37 and the first, second and third discharge parts 38, 39 and 40 of the quartz glass plate 32. Through holes are respectively formed at positions, and a septum made of an elastic material is fitted into each through hole, so that the first inlet 41 and the second inlet 42 of the reaction unit, the first outlet 43, the second A discharge port 44 and a third discharge port 45 are formed.
Instead of the metal thin plate 31 in which the groove 22a corresponding to the light transmissive channel 22 is formed, a quartz glass plate, a lime soda glass plate, or a fluororesin plate in which similar grooves are formed may be used. .
A lime soda glass plate may be used instead of the quartz glass plate 32 covering the metal thin plate 31.

  According to the reaction unit 23 having the above-described configuration, for example, the A reactant and the B reactant are supplied from the first inlet 41 and the second inlet 42, respectively, The first and second outlets 43 and 44 existing between the first and second outlets 45 and 44, which are joined to each other to generate a photochemical reaction and end up at the end of the light-transmitting flow path 22, are in the course of the reaction. By collecting the product substance and analyzing it using a gas chromatograph device or the like, it is possible to monitor the progress of the reaction as needed.

  Specifically, cyclohexenone is supplied from the first inlet 41, vinyl acetate (vinyl acetate) is supplied from the second inlet 42, and a photochemical reaction is generated, so that the cycloaddition cyclobutane is supplied from the third outlet 45. When the derivative is to be obtained, the photochemical reaction product in the course of the reaction is sampled from the first outlet 43 and the second outlet 44, and each component is analyzed by a gas chromatograph device to obtain the first. It is possible to monitor the progress of the photochemical reaction at any time, as if the reaction has progressed 40% at the position of the discharge port 43 and 80% at the position of the second discharge port 44.

When a long channel length is not required for generating a photochemical reaction, the first discharge port 43 is used as an inflow port, and the photochemical reaction product is supplied from the second discharge port 44 or the third discharge port 45. A utilization method such as recovery is also possible, and the reaction unit 23 of the second embodiment has a highly convenient flow path configuration that allows various utilization methods.
Of course, in the same manner as in Example 1, a plurality of types of reaction units 23 having preferable conditions are prepared in advance for generating a desired photochemical reaction, and the most preferable reaction unit for generating a desired photochemical reaction. If 23 is appropriately selected and attached to the light source unit, an optimum reaction environment can be quickly set for the photochemical reaction of many substances, and the reaction unit 23 is connected to the light source unit 26 as one unit. The advantage of being detachably mounted can be further utilized.

On the other hand, as shown in FIG. 10, the light source unit 26 includes an aluminum case 46 having a reaction part accommodating part 47 that removably receives the reaction part 23, and a clamp plate attached to the upper inner wall of the case 46. 48 mainly supported by a black light 25 (manufactured by Toshiba Lighting & Technology Co., Ltd., Neoball 5, power consumption 15 W, peak wavelength 352 nm).
The casing 46 is mirror-finished on the inner surface so that the light emitted from the black light 25 is reflected and the irradiation efficiency to the reaction unit 23 is increased, and a lid 49 that can be opened and closed at two positions on the upper surface. It has.

As shown in FIG. 11, when the reaction part 23 is accommodated in the reaction part accommodation part 47, the needle (not shown) attached to the tip of the flow path extending from the liquid feed pump 24 and the recovery part 27 are connected. A needle (not shown) attached to the tip of the flow path is connected to the first inlet 41 and / or the second inlet 42 and the third outlet 45 of the reaction section via the lid 49, respectively. When monitoring the reaction state, the needle at the tip of the syringe is connected to the first outlet 43 and / or the second outlet 44 via a lid 49 as necessary, and sampling is performed.
The reaction part accommodating part 47 includes a pair of movable regulation plates 50 that restrict the width of the reaction part accommodating part 47 according to the width of the reaction part 23 to be received. It is configured so that it can be used.

Reaction example 2
A 2 + 2 cycloaddition reaction of benzophenone and prenyl alcohol as shown in the following formula (IV) was performed using the flow-type photochemical reaction device 21 according to Example 2 shown in FIGS. In Reaction Example 2 shown below, as Comparative Example 2, the apparatus configuration is substantially the same as in Example 2. However, a flow-type photochemical reaction apparatus using a 300 W high-pressure mercury lamp as a light source is separately prepared. The reaction efficiencies were compared in terms of yield per power consumption.

As shown in Table 2, the run 1 of Comparative Example 2 using a 300 W high pressure mercury lamp as the light source has a yield per power consumption of 0.25, whereas the example using 15 W black light as the light source. In run 2 of 2, the yield per power consumption is 2.3, and it is understood that the flow-type photochemical reaction apparatus according to Example 2 is improved by about 9.2 times in the reaction efficiency (yield / Wh). .
Thereby, it was confirmed that the flow type photochemical reaction device 21 according to Example 2 is excellent in both reaction efficiency and energy efficiency.

Reaction example 3
In Reaction Example 3, as in Reaction Example 2, the flow-type photochemical reaction device 21 according to Example 2 and the flow-type photochemical reaction device of Comparative Example 2 were used, and cyclohexenone and vinyl acetate represented by the following formula (V) were used. 2 + 2 cycloaddition reactions were performed and their reaction efficiencies were compared in yield per power consumption.

As shown in Table 3, the run 1 of Comparative Example 2 using a 300 W high pressure mercury lamp as the light source has a yield per power consumption of 0.11, whereas the example using 15 W black light as the light source. In run 2 of 2, the yield per power consumption is 2.6, and the reaction efficiency (yield / Wh) of the flow-type photochemical reaction device 21 according to Example 2 is improved by about 23.6 times. I understand. Thereby, it was confirmed that the flow type photochemical reaction device 21 according to Example 2 is excellent in both the reaction efficiency and the energy efficiency in another photochemical reaction, that is, in the 2 + 2-cycloaddition reaction of cyclohexenone and vinyl acetate. It was.
Note that the flow rate and residence time are slightly different between run 1 and run 2, but considering that the yield per power consumption has improved by about 23.6 times as described above, the flow rate and residence time are The difference is considered negligible.

Reaction example 4
In Reaction Example 4, the flow type photochemical reaction device 21 of Example 2 and the flow type photochemical reaction device of Comparative Example 2 were used in the same manner as Reaction Example 2 and Reaction Example 3, and the polycyclic ring represented by the following formula (VI) was used. The optical barton reaction from nitrite (nitrite ester) type to oxime (oximino alcohol) was performed, and their reaction efficiencies were compared in terms of yield per power consumption. In Reaction Example 4, the raw material nitrite was diluted to 9 mmol / L with acetone, and 0.2 mol equivalent of pyridine was added to the raw material as the material to be reacted.

As shown in Table 4, the run 1 of Comparative Example 2 using a 300 W high-pressure mercury lamp as the light source has a yield per power consumption of 1.89, whereas the example using 15 W black light as the light source. In run 2 of No. 2, the yield per power consumption is 23.7, and the flow-type photochemical reaction device 21 according to Example 2 is improved by about 12.5 times in reaction efficiency (yield / Wh). I understand.
As a result, the flow type photochemical reaction device 21 according to Example 2 is effective in both the reaction efficiency and the energy efficiency in the optical Barton reaction from the polycyclic nitrite body (nitrite ester) to the oxime body (oxyimino alcohol). It was confirmed to be excellent.

Modification of Reaction Unit A modification of the reaction unit in the flow type photochemical reaction device according to Example 2 is shown in FIGS. FIG. 12 is an exploded perspective view of the reaction unit according to the modification, and FIG. 13 is a perspective view of the reaction unit according to the modification.

  As shown in FIG. 12 and FIG. 13, the reaction unit 123 according to the modification forms an opening pattern 122 a corresponding to the light transmissive flow path 22 in the thin metal plate 131, and the front and back surfaces of the thin metal plate 131 are made of quartz glass. Between the plates 132 and 133, openings 134a and 135a are formed in both the upper clamp plate 134 and the lower clamp plate 135 so as not to impede light irradiation on the light transmissive flow path 22. The opening pattern 122a of the metal thin plate 131 is formed by photoetching, cutting, or punching.

In the reaction unit 123 according to the modified example, since light enters from both the front surface side and the back surface side of the reaction unit 123, it is possible to further improve the reaction efficiency and the energy efficiency.
In the reaction part 123 according to the modified example, a quartz glass plate, a lime soda glass plate, or a fluororesin plate having a similar opening pattern is used instead of the metal thin plate 131 having the opening pattern 122a. Can do.
A lime soda glass plate may be used instead of the quartz glass plates 132 and 133 sandwiching the metal thin plate 131.

Modification of Light Source Unit FIG. 14 shows a modification of the light source unit in the flow type photochemical reaction device according to the second embodiment. FIG. 14 is a perspective view of a light source unit according to a modification.
As shown in FIG. 14, the light source unit 126 according to the modification includes two black lights (Toshiba Lighttech Co., Ltd., Neoball 5, power consumption 15 W, peak wavelength 352 nm) 25 on the upstream side of the light transmitting channel 22. Are arranged so as to be lined up from a position corresponding to 1 to a position corresponding to the downstream side.

When the light source unit 126 according to such a modification is used, even if the light transmission channel 22 has a long channel length, the reactant is uniformly distributed along the light transmission channel 22. It becomes possible to irradiate light efficiently, and it becomes possible to deal with a reaction section having a long flow path length.
In addition, as described above, the reactants in the course of the reaction are sampled from the first outlet 43 and the second outlet 44 to check the progress of the reaction, and two black lights are controlled by the control according to the progress of the reaction. By performing lighting control of 25, that is, simultaneous lighting, time-series lighting control, etc., it is possible to perform light irradiation under more desirable conditions for causing a photochemical reaction. Of course, by the lighting control as described above, it is possible to suppress decomposition and destruction of the reaction product caused by excessively irradiating the photoreactive substance with light.

The black light 25 does not necessarily have the same peak wavelength, and black lights having different peak wavelengths may be used.
In this case, it becomes possible to irradiate light having different wavelengths in time series to the reactant to be sent from the upstream side to the downstream side of the light transmissive flow path 22. Thus, it is possible to cause multiple types of photoreactions in time series.

In Example 1 and Example 2 described above, black light is used as the light source. However, the light source is of course not limited to black light, and a high-power high-pressure mercury lamp as used in Comparative Example 1 and Comparative Example 2 is used. May be used.
That is, the flow-type photochemical reaction device according to the present invention is advantageous in that it has excellent reaction efficiency, energy efficiency, and maintainability, and can easily set an optimum reaction environment for causing a desired photochemical reaction. Even when a high-power high-pressure mercury lamp is used as the light source, these advantages are similarly exhibited.

It is the schematic which shows the whole structure of the flow type photochemical reaction apparatus by Example 1 of this invention. It is a perspective view of a reaction part. It is AA sectional drawing of the reaction part shown by FIG. It is a perspective view which shows the state by which the light source part was arrange | positioned inside the reaction part shown by FIG. It is sectional drawing of the reaction part which concerns on a modification. It is a principal part enlarged view of the reaction part which concerns on a modification. FIG. 3 is a schematic diagram showing the overall configuration of a flow-type photochemical reaction device according to Example 2. It is a disassembled perspective view of a reaction part. It is a perspective view of a reaction part. It is a perspective view of a light source part. It is a perspective view which shows a mode that the reaction part shown by FIG. 9 is inserted in the light source part shown by FIG. It is a disassembled perspective view of the reaction part which concerns on a modification. It is a perspective view of the reaction part concerning a modification. It is a perspective view of the light source part which concerns on a modification.

Explanation of symbols

1, 21 ... Flow-type photochemical reaction device 2 ... Teflon tube (light-transmissive channel)
3, 23, 103, 123 ... reaction part 4, 24 ... liquid feed pump 5, 25 ... black light 6, 26, 126 ... light source part 7, 27 ... collection part 8, 108 ... Cylindrical body 9 ... Clamp 10 ... Connecting adapter 11 ... Upper collar 11a, 12a, 33a, 134a, 135a ... Open 12 ... Lower collar 13 ... Body body 14 ... Stopper 22 ... Light transmissive flow path 22a ... Groove 28 ... Power supply 29 ... Control unit 30 ... Temperature adjustment mechanism 31 ... Metal thin plate 32,132,133 ... Quartz glass plate 33, 134 ... Upper clamp plate 34, 135 ... Lower clamp plate 35 ... Allen bolt 36 ... First inflow portion 37 ... Second inflow portion 38 ... First Discharge part 39 ... 2nd discharge 40 ... 3rd discharge part 41 ... 1st inlet 42 ... 2nd inlet 43 ... 1st discharge port 44 ... 2nd discharge port 45 ... 3rd discharge port 46. ..Case 47 ... Reaction part accommodating part 48 ... Clamp plate 49 ... Lid 50 ... Regulation plate

Claims (9)

  A reaction part formed by the light-transmitting flow path, a liquid-feeding part for sending the reaction substance to the reaction part, and at least causing the reaction part to irradiate the reaction part and cause a photochemical reaction in the light-transmitting flow path A light source unit having one light source and a recovery unit for recovering a photochemical reaction product that has undergone a photochemical reaction are provided, and the reaction unit is unitized as a single unit so as to be integrated with the light source unit. A flow-type photochemical reaction device that is detachably mounted.   The reaction part is composed of a light-transmitting cylindrical body and a light-transmitting tube wound around the outer peripheral surface of the cylindrical body to form a light-transmitting flow path, and the light source part is an inner peripheral surface of the cylindrical body. The flow type photochemical reaction device according to claim 1, wherein the flow type photochemical reaction device is disposed inside the cylindrical body so as to irradiate the tube through the cylindrical body.   The flow type photochemical reaction device according to claim 2, wherein a groove is formed on an outer peripheral surface of the cylindrical body, and the tube is wound along the groove of the cylindrical body.   The reaction unit includes a first substrate in which a groove corresponding to the light transmissive channel is formed, and a light transmissive second substrate that is stacked on the first substrate so as to cover the groove formed in the first substrate. The flow type photochemical reaction device according to claim 1, wherein the light source unit includes a reaction unit accommodating unit that detachably receives the reaction unit.   The reaction unit includes a first substrate on which an opening pattern corresponding to the light transmitting channel is formed, and a first substrate sandwiching the first substrate so as to close the opening pattern formed on the first substrate. 2. The flow type photochemical reaction device according to claim 1, comprising a reaction part accommodating part that includes two substrates and a third substrate, and wherein the light source part detachably receives the reaction part.   The flow type photochemistry according to claim 4 or 5, wherein the light source section includes a plurality of light sources, and the plurality of light sources are arranged so as to be arranged from the upstream side to the downstream side of the light transmitting channel. Reactor.   The flow type photochemical reaction device according to claim 1, wherein the light source unit includes a temperature adjustment mechanism.   A flow-type photochemical reaction device according to any one of claims 1 to 7, wherein a predetermined substance to be reacted is fed to the light-transmitting flow path of the reaction unit by the liquid feeding unit, and the reaction unit is fed by the light source unit. A method for producing a photochemical reaction product, which comprises irradiating light to cause a photochemical reaction in a material to be reacted in a light-transmitting flow path and obtaining a desired photochemical reaction product in a recovery part. The reactant to be fed by the liquid feeding unit is represented by the formula (I):

A photochemical reaction product obtained by the optical Barton reaction as a photochemical reaction is a nitrite represented by the formula (II):

The method for producing a photochemical reaction product according to claim 8, wherein the photochemical reaction product is an oxyimino alcohol represented by the formula:

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