Process for producing carbonyl halides

Abstract

Provided is a method for efficiently producing a carbonyl halide from a halogenated methane. The method for producing a carbonyl halide according to the present invention is characterized by comprising the steps of: a step of preparing a mixed gas containing a halogenated methane and oxygen, the halogenated methane having one or more halogen groups selected from the group consisting of chlorine, bromine, and iodine; and a step of flowing the mixed gas and irradiating the flowing mixed gas with high-energy light.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for efficiently producing a carbonyl halide with respect to a halogenated methane used. BACKGROUND

[0002] Phosgene and the like carbonyl halides are very important as raw materials of synthetic intermediates, raw materials of various compounds. For example, carbonate compounds are generally produced from phosgene and alcohol compounds.

[0003] However, phosgene is a very toxic substance because it reacts with water to produce hydrogen chloride or has a history of being used as a toxic gas. Phosgene is mainly produced by a high exothermic gas phase reaction of anhydrous chlorine and high-purity carbon monoxide in the presence of an activated carbon catalyst. The carbon monoxide used here is also toxic. The basic production process of phosgene has not changed much since the 1920s. In the production of phosgene using this process, expensive and large equipment is required. However, due to the high toxicity of phosgene, it is indispensable to ensure wide safety in plant design, which leads to an increase in production cost.

[0004] Therefore, the present inventors and the like have developed a technology of generating halogen and / or a carbonyl halide by photoirradiation of a halogenated hydrocarbon in the presence of oxygen (Patent Literature 1). According to the technology, by directly introducing the generated carbonyl halide into a reaction substrate compound such as an amine compound, an alcohol compound, or the like, a reaction can be performed, and thus it can be said to be safe. In addition, the carbonyl halide not used in the reaction can also be recovered by a trap without leaking to the outside. For example, the present inventors and the like have also developed a technology of producing a halogenated carboxylic acid ester by photoirradiation of a mixture containing a halogenated hydrocarbon and an alcohol in the presence of oxygen (Patent Literature 2). In addition, the present inventors and the like have also developed a technology of producing a carbonate derivative by photoirradiation of a halogenated hydrocarbon, a compound containing a nucleophilic functional group, and a composition containing a base in the presence of oxygen (Patent Literature 3 and Patent Literature 4).

[0005] However, in the case of producing a carbonyl halide using the above-described method, a large amount of halogenated hydrocarbon remains compared to the generated carbonyl halide. The halogenated hydrocarbon is not easily disposed because it has a high environmental load, and has to be purified and reused or the like.

[0006] On the other hand, it has been known since ancient times that carbonyl halides are photodecomposed. For example, a method of photoirradiating boron trichloride containing phosgene as an impurity to photodecompose and remove the phosgene is disclosed in Patent Literature 5. It is also described in Non-Patent Literature 1 that phosgene is decomposed by photoirradiation.

[0007] PRIOR ART DOCUMENTS

[0008] PATENT LITERATURE

[0009] Patent Literature 1: Japanese Patent Application Publication No. 2013-181028

[0010] Patent Literature 2: International Publication No. 2015 / 156245

[0011] Patent Literature 3: International Publication No. 2018 / 211952

[0012] Patent Literature 4: International Publication No. 2018 / 211953

[0013] Patent Literature 5: U.S. Patent No. 4,405,423

[0014] Non-Patent Literature

[0015] Non-Patent Literature 1: C. W. Montgomery et al., J. Am. Chem. Soc, 1934, 56, 5, pp. 1089-1092 SUMMARY

[0016] PROBLEMS TO BE SOLVED BY THE INVENTION

[0017] As described above, the present inventors et al. are developing a method of manufacturing a carbonyl halide by photoirradiation of a halogenated hydrocarbon, but the reaction efficiency of the generated carbonyl halide with an alcohol compound or the like is high, on the other hand, since a large amount of halogenated hydrocarbon is used, it is inevitable to say that the yield with respect to the halogenated hydrocarbon is low.

[0018] Therefore, an object of the present application is to provide a method of efficiently manufacturing a carbonyl halide with respect to the halogenated methane used.

[0019] SOLUTION TO THE PROBLEM

[0020] The present inventors et al. have made intensive studies in order to solve the above problem. For example, the present inventors et al. predicted that if high-energy light is irradiated to the vaporized halogenated methane, the halogenated methane can be effectively photolyzed, on the other hand, the generated carbonyl halide also rapidly undergoes photolysis in the gas phase. However, as a result of various studies on the reaction conditions, it was found that if high-energy light is irradiated while the vaporized halogenated methane is flowing, the carbonyl halide can be unexpectedly obtained at a high yield, and thus the present application was completed.

[0021] Hereinafter, the present application will be described.

[0022] [1] A method for manufacturing a carbonyl halide,

[0023] a step of preparing a mixed gas containing a halogenated methane and oxygen, the halogenated methane having one or more halogen groups selected from the group consisting of chlorine, bromine, and iodine; and

[0024] a step of flowing the aforementioned mixed gas, and irradiating high-energy light to the flowing mixed gas.

[0025] [2] The method according to the preceding [1], wherein the shortest distance between the light source of the high-energy light and the flowing mixed gas is 1 m or less.

[0026] [3] The method according to the preceding [1] or [2], wherein the time for irradiating the flowing mixed gas with the high-energy light is 1 second or more and 10,000 seconds or less.

[0027] [4] The method according to any one of the preceding [1] to [3], wherein the temperature at the time of irradiating the flowing mixed gas with the high-energy light is 40°C or more and 200°C or less.

[0028] [5] A method for producing a fluorinated carbonate compound, characterized by comprising the steps of:

[0029] a step of producing a carbonyl halide by the method according to any one of the preceding [1] to [4]; and

[0030] a step of reacting a fluorinated alcohol compound with the carbonyl halide,

[0031] the molar ratio of the fluorinated alcohol compound to the halogenated methane is 1 or more.

[0032] [6] A method for producing a non-fluorinated carbonate compound, characterized by comprising the steps of:

[0033] a step of producing a carbonyl halide by the method according to any one of the preceding [1] to [4]; and

[0034] a step of reacting a non-fluorinated alcohol compound with the carbonyl halide,

[0035] the molar ratio of the non-fluorinated alcohol compound to the halogenated methane is 1 or more.

[0036] [7] A method for producing a fluorinated ester compound of halogenated formic acid, characterized by comprising the steps of:

[0037] a step of producing a carbonyl halide by the method according to any one of the preceding [1] to [4]; and

[0038] a step of reacting a fluorinated alcohol compound with the carbonyl halide,

[0039] the molar ratio of the fluorinated alcohol compound to the halogenated methane is less than 1.

[0040] [8] A method for producing a non-fluorinated ester compound of halogenated formic acid, characterized by comprising the steps of:

[0041] a process of producing a carbonyl halide by the method described in any one of the aforementioned [1] to [4]; and

[0042] a process of reacting a non-fluorinated alcohol compound with the aforementioned carbonyl halide,

[0043] the molar ratio of the aforementioned non-fluorinated alcohol compound to the aforementioned halogenated methane is less than 1.

[0044] [9] A method for producing an isocyanate compound, characterized by comprising the following process:

[0045] a process of producing a carbonyl halide by the method described in any one of the aforementioned [1] to [4]; and

[0046] a process of reacting a primary amine compound with the aforementioned carbonyl halide,

[0047] the molar ratio of the aforementioned primary amine compound to the aforementioned halogenated methane is less than 1.

[0048]

[10] A method for producing an amino acid-N-carboxyanhydride, characterized by,

[0049] the aforementioned amino acid-N-carboxyanhydride is a compound represented by the following formula (VIII),

[0050] the method comprising the following process:

[0051] a process of producing a carbonyl halide by the method described in any one of the aforementioned [1] to [4]; and

[0052] a process of reacting an amino acid compound represented by the following formula (VII) with the aforementioned carbonyl halide.

[0053]

[0054] [In the formula,

[0055] R 4 represents an amino acid side chain group protected by a reactive group,

[0056] R 5 represents H, or P 1 -[-NH-CHR 6 -C(=O)-] l -(In the formula, R 6 represents an amino acid side chain protected by a reactive group, P 1 represents a protecting group of an amino group, and l represents an integer of 1 or more, and when l is an integer of 2 or more, a plurality of R 6 are optionally the same as or different from each other).]

[0057]

[11] A method for producing a Vilsmeier reagent, characterized by

[0058] The aforementioned Vilsmeier reagent is a salt represented by the following formula (X),

[0059]

[0060] [In the formula,

[0061] R 7 represents a hydrogen atom, a C 1-6 alkyl group, or a C 6-12 aromatic hydrocarbon group optionally having a substituent group,

[0062] R 8 and R 9 independently represent a C 1-6 alkyl group, or a C 6-12 aromatic hydrocarbon group optionally having a substituent group, and R 8 and R 9 optionally form a ring structure of 4 or more and 7 or less members together,

[0063] X represents a halogen group selected from the group consisting of chlorine, bromine, and iodine,

[0064] Y - represents a counter anion.

[0065] The method includes the following steps:

[0066] a step of producing a carbonyl halide by the method according to any one of the aforementioned [1] to [4]; and

[0067] a step of reacting the aforementioned carbonyl halide with an amide compound represented by the following formula (IX).

[0068]

[0069] [In the formula, R 7 to R 9 have the same meanings as described above.

[0070] Effects of the Invention

[0071] According to the method of the present application, a carbonyl halide can be effectively produced with respect to the halogenated methane used, and the halogenated methane, which has a high environmental load and is restricted in use or handling, can be effectively utilized. Therefore, the present application is industrially useful as a technology capable of effectively utilizing a halogenated methane and effectively producing a carbonyl halide such as phosgene. BRIEF DESCRIPTION OF DRAWINGS

[0072] [ Figure 1 ] is a schematic diagram showing an example of the configuration of a reaction system used in the present application.

[0073] [ Figure 2 ] is a schematic diagram showing an example of the configuration of a reaction system used in the present application.

[0074] [ Figure 3 ] is a schematic diagram showing an example of the configuration of a reaction system used in the present application.

[0075] [ Figure 4 ] is a schematic diagram showing an example of the configuration of a reaction system used in the present application.

[0076] [ Figure 5 ] is a schematic diagram showing an example of the configuration of a reaction system used in the present application.

[0077] [ Figure 6 ] is a schematic diagram showing an example of the configuration of a reaction system used in the present application. DETAILED DESCRIPTION

[0078] Hereinafter, the method of the present application will be described for each process, but the present application is not limited to the following specific examples.

[0079] 1. Mixed gas preparation process

[0080] In this process, a mixed gas containing a halogenated methane having one or more halogen groups selected from the group consisting of chlorine, bromine and iodine and oxygen is prepared.

[0081] The halogenated methane used in the present application is a methane having one or more halogen groups selected from the group consisting of chlorine, bromine and iodine. This halogenated methane is likely to be decomposed by oxygen and high-energy light to be converted into a carbonyl halide.

[0082] As described above, it is considered that the halogenated methane is decomposed by high-energy light and oxygen in the present application to exert the same action as a carbonyl halide. As the halogenated methane, a polyhalogenated methane having two or more halogen groups is preferable, and further, a perhalogenated methane in which all hydrogen atoms are substituted with halogen groups is preferable.

[0083] As a specific halogenated methane, for example, halogenated methanes such as dichloromethane, chloroform, dibromomethane, bromoform, iodomethane and diiodomethane can be mentioned.

[0084] The halogenated methane can be appropriately selected depending on the target chemical reaction and the desired product, and can be used alone or in combination with two or more. Further, preferably, only one kind of halogenated methane is used depending on the target compound to be produced. Among the halogenated methanes, from the viewpoint of vaporization and cost, a halogenated methane having a chlorine group is preferable.

[0085] ​​​​​Generally, a stabilizer such as an alcohol is contained in a halogenated methane product to inhibit the decomposition of the halogenated methane. In the present application, in order to perform oxidative photodecomposition of the halogenated methane, a halogenated methane from which the stabilizer has been removed can be used. By using a halogenated methane from which the stabilizer has been removed, it is possible to use high-energy light having a lower energy, or to reduce the irradiation time of the high-energy light, or the like, and it is possible to more efficiently decompose the halogenated methane. The method of removing the stabilizer from the halogenated methane is not particularly limited, and, for example, the halogenated methane can be washed with water to remove water-soluble stabilizers, and then dried.

[0086] As the halogenated methane used in the method of the present application, inexpensive chloroform, which can also be used as a general-purpose solvent, can be used. A halogenated methane that has been used temporarily as a solvent, for example, can be recovered and reused. At this time, if a large amount of impurities or water is contained, there is a concern that the reaction will be inhibited, and thus it is preferable to purify to some extent. For example, it is preferable to remove water and water-soluble impurities by water washing, and then to dehydrate using anhydrous sodium sulfate, anhydrous magnesium sulfate, or the like. However, it is considered that the reaction proceeds even if about 1 mass% of water is contained, and thus it is not necessary to perform excessive purification that will reduce the productivity. As the water content, it is more preferable that it be 0.5 mass% or less, further preferable that it be 0.2 mass% or less, and still further preferable that it be 0.1 mass% or less. As the water content, it is preferable that it be the detection limit or 0 mass%. In addition, the halogenated methane that is reused as described above can contain decomposition products of the halogenated methane or the like.

[0087] In particular, in the case where the halogenated methane is not a liquid at normal temperature and pressure, or in the case where it is difficult to vaporize, a solvent can be used in combination with the halogenated methane. In addition, the solvent can also promote the decomposition of the halogenated methane. Furthermore, the solvent can also inhibit the decomposition of the carbonyl halide generated by the oxidative photodecomposition of the halogenated methane. As the solvent, a solvent that can moderately dissolve the halogenated methane and does not inhibit the decomposition of the halogenated methane is preferable. As the solvent, for example, a ketone-based solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, or the like; an ester-based solvent such as ethyl acetate or the like; an aliphatic hydrocarbon solvent such as n-hexane or the like; an aromatic hydrocarbon solvent such as benzene, toluene, xylene, benzonitrile, or the like; an ether-based solvent such as diethyl ether, tetrahydrofuran, dioxane, or the like; and a nitrile-based solvent such as acetonitrile or the like can be mentioned.

[0088] As the oxygen source, a gas containing oxygen is sufficient, and, for example, air, purified oxygen can be used. Purified oxygen can be used in combination with a non-reactive gas such as nitrogen, argon, etc. From the viewpoint of cost and ease, air can also be used. From the viewpoint of improving the decomposition efficiency of the halogenated methane based on the irradiation of high-energy light, the oxygen content in the oxygen-containing gas used as the oxygen source is preferably about 15% by volume or more and 100% by volume or less. In addition, it is also preferable to use only oxygen substantially, except for inevitable impurities. The oxygen content can be appropriately determined depending on the type of the halogenated methane, etc. described above. For example, when dichloromethane, chloroform, or the like is used as the halogenated methane described above, the oxygen content is preferably 15% by volume or more and 100% by volume or less, and when dibromomethane, bromoform, or the like is used, the oxygen content is preferably 90% by volume or more and 100% by volume or less. Note that even when oxygen (oxygen content 100% by volume) is used, the oxygen content can be controlled within the above range by adjusting the flow rate of oxygen introduced into the reaction system.

[0089] As the oxygen source, dry air can be used, but even when air containing water vapor is used, the reaction is not excessively hindered, and thus air without adjusting the water vapor content can be used. Note that the oxygen concentration in air is about 21% by volume, and the oxygen concentration with respect to the oxygen source can also be adjusted to 20 ± 5% by volume. As the ratio, 20 ± 2% by volume is preferable. When air is used as the oxygen source, there is a possibility that the decomposition of the generated carbonyl halide can be suppressed by absorbing the excess high-energy light with the air components other than oxygen, or diluting the generated carbonyl halide.

[0090] In this process, a mixed gas containing gaseous halogenated methane and oxygen is prepared. The preparation conditions of the mixed gas are not particularly limited, and, for example, as shown in Figure 1 , 2 , 4 to 6, a halogenated methane at a prescribed flow rate is sent to a heater 3 with a syringe pump 1, heated to the boiling point or higher to be vaporized, and a gaseous oxygen-containing gas adjusted to a prescribed flow rate with a mass flow controller 2 is mixed with the vaporized halogenated methane, and a mixed gas can be obtained.

[0091] Alternatively, as shown in Figure 3 , the bath temperature of a photoreaction vessel 12 provided with a light source 11 and a bath 13 is set to the boiling point or higher of the halogenated methane in advance, and the halogenated methane is introduced into the photoreaction vessel 12 to be vaporized. In order to promote the vaporization of the halogenated methane, the introduced halogenated methane can be stirred with a stirrer 14. In conjunction with the vaporization of the halogenated methane, a gaseous oxygen-containing gas at a prescribed flow rate can be introduced into the gas phase of the photoreaction vessel 12, and a mixed gas containing the halogenated methane and oxygen can be prepared in the photoreaction vessel 12.

[0092] The ratio of the vaporized halogenated methane to the oxygen in the aforementioned mixed gas is appropriately adjusted within a range in which a carbonyl halide is favorably produced. For example, the ratio of the flow rate of the oxygen contained in the oxygen-containing gas to the flow rate of the halogenated methane in the mixed gas can be set to 0.1 or greater and 10 or less. If this ratio is 0.1 or greater, the halogenated methane can be sufficiently photooxidized. On the other hand, if this ratio is 10 or less, further photooxidation of the produced carbonyl halide can be sufficiently suppressed. As this ratio, 0.2 or greater, more preferably 0.4 or greater, and still more preferably 0.5 or greater, and, in addition, 8 or less, more preferably 6 or less, is preferable. In particular, if this ratio is 0.5 or greater, it is possible to more effectively suppress the generation of by-products and reaction system failures caused by the by-products.

[0093] In the reaction system shown in, for example, Figure 3 In the case where an oxygen-containing gas is introduced into the gas phase containing the vaporized halogenated methane, it is preferable to use an amount of oxygen that can sufficiently photooxidize the halogenated methane. For example, the flow rate of the oxygen per 1 minute with respect to 1 mole of the halogenated methane can be set to 0.1 L or greater and 100 L or less. As this ratio, 1 L or greater, more preferably 5 L or greater, and still more preferably 10 L or greater, is preferable.

[0094] 2. Oxidative photolysis step

[0095] This step is a step of obtaining a carbonyl halide by photooxidizing a halogenated methane while flowing a mixed gas containing the halogenated methane and oxygen and irradiating high-energy light to the flowing mixed gas in a gas phase.

[0096] As the high-energy light to be irradiated to the flowing mixed gas, light containing short-wavelength light is preferable, and light containing ultraviolet rays is more preferable, and, in more detail, light containing light having a wavelength of 180 nm or greater and 500 nm or less and light having a peak wavelength contained in a range of 180 nm or greater and 500 nm or less is preferable. Note that the wavelength of the high-energy light can be appropriately determined, and 400 nm or less is more preferable, 300 nm or less is still more preferable, and light having a peak wavelength contained in these ranges is also preferable. In the case where the irradiated light contains light in the aforementioned wavelength range, the halogenated methane can be efficiently photooxidized. For example, light containing UV-B having a wavelength of 280 nm or greater and 315 nm or less and / or UV-C having a wavelength of 180 nm or greater and 280 nm or less can be used, and light containing UV-C having a wavelength of 180 nm or greater and 280 nm or less is preferable, and light having a peak wavelength contained in these ranges is also preferable.

[0097] In the present application, since the halogenated methane in the gaseous state is subjected to oxidative photolysis, even high-energy light of relatively low energy is likely to cause oxidative photolysis of the halogenated methane. In particular, when a halogenated methane not containing a stabilizer is used, even high-energy light of relatively low energy is likely to cause oxidative photolysis of the halogenated methane. As high-energy light of relatively low energy, light having a peak wavelength included in the visible light wavelength region can be given. As the visible light wavelength region, 350 nm or more and 830 nm or less, preferably 360 nm or more, more preferably 380 nm or more, and still more preferably 400 nm or more, and, on the other hand, 800 nm or less, more preferably 780 nm or less, and still more preferably 500 nm or more can be given.

[0098] The means for irradiating light is not particularly limited as long as it can irradiate light having the aforementioned wavelength, and, as a light source which emits light having a wavelength region including such a wavelength range, for example, sunlight, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a black light, a metal halide lamp, an LED lamp, and the like can be given. From the aspects of reaction efficiency and cost, it is preferable to use a low-pressure mercury lamp.

[0099] The conditions such as the intensity of the irradiated light can be appropriately set depending on the halogenated methane and the like, and, for example, as the desired light intensity at the position of the shortest distance from the light source to the flowing mixed gas, it depends on the scale of implementation, the wavelength of the irradiated light, and the like, and it is preferable to be 1 mW / cm 2 or more and 200 mW / cm 2 or less. For example, in the case where the wavelength of the irradiated light is relatively short, as the light intensity, it is more preferable to be 100 mW / cm 2 or less or 50 mW / cm 2 or less, and still more preferably 20 mW / cm 2 or less or 10 mW / cm 2 or less. In the case where the wavelength of the irradiated light is relatively long, as the light intensity, it is more preferable to be 10 mW / cm 2 or more or 20 mW / cm 2 or more, it can be 50 mW / cm 2 or more or 100 mW / cm 2 or more. In addition, as the shortest distance from the light source to the flowing mixed gas, it is preferable to be 1 m or less, more preferably 50 cm or less, and still more preferably 10 cm or less or 5 cm or less. The lower limit of the shortest distance is not particularly limited, and it can be 0 cm, that is, the light source is present in the flowing mixed gas.

[0100] The method of irradiating high-energy light to the flowing mixed gas is not particularly limited, and, for example, as Figure 1 , 2As shown in FIGS. 4, 5, and 6, the flow light reaction device 4 can be constructed so that one or more reaction tubes are disposed around the light source, or so that the flow light reaction device 4 has a gas inlet and a gas outlet at both ends and the light source is inserted inside. The mixed gas is circulated in the flow light reaction device 4. In order to effectively irradiate the high-energy light to the mixed gas in the flow light reaction device 4, the reaction tube can be wound in a coil shape around the light source. In order to maintain the gaseous state of the halogenated methane, a heating means can be provided on the flow light reaction device 4. As the heating means, a temperature bath that can immerse a part or all of the flow light reaction device 4, or a heater that can heat a part or all of the outside of the flow light reaction device 4 can be used. Alternatively, as shown in FIGS. 7 and 8, a light reaction vessel 12 having the light source 11 inside can be constructed, the halogenated methane is vaporized in the light reaction vessel 12, and the oxygen-containing gas is introduced into the light reaction vessel 12 while the high-energy light is irradiated from the light source 1. Alternatively, as shown in FIGS. 9 and 10, the vaporized halogenated methane and the oxygen-containing gas can be supplied into the light reaction vessel 12. Figure 3 Figure 5 6

[0101] It is considered that the vaporized halogenated methane is oxidatively photolyzed to a carbonyl halide by the oxygen and the high-energy light. However, it is also known that the carbonyl halide is decomposed by the high-energy light. Therefore, it is important to adjust the irradiation conditions of the high-energy light so that the generated carbonyl halide is not excessively decomposed.

[0102] For example, the time for which the high-energy light is irradiated to the flowing mixed gas depends on the wavelength of the irradiated light and the reaction temperature, but is preferably 1 second or more and 2000 seconds or less. The time for which the high-energy light is irradiated can be the residence time of the flowing mixed gas in the light reaction vessel for which the high-energy light is continuously irradiated to the flowing mixed gas. If the time is 1 second or more, the vaporized halogenated methane can be more reliably oxidatively photolyzed, and if the time is 2000 seconds or less, the excessive decomposition of the generated carbonyl halide can be more reliably suppressed. The time is preferably 5 seconds or more, more preferably 10 seconds or more, and still more preferably 20 seconds or more or 30 seconds or more, and is preferably 1500 seconds or less, 1000 seconds or less, 500 seconds or less, or 300 seconds or less, and more preferably 100 seconds or less, and still more preferably 60 seconds or less or 50 seconds or less. In the case of using the halogenated methane that does not contain a stabilizer, the decomposition of the generated carbonyl halide can be further suppressed by using light of a longer wavelength. In this case, the light irradiation time can be adjusted in the range of 1 second or more and 10000 seconds or less. The light irradiation time is preferably 5000 seconds or less, and more preferably 1000 seconds or less, from the viewpoint of manufacturing efficiency.

[0103] ​​​The longer the irradiation time of the high-energy light, the higher the decomposition efficiency of the halogenated methane, but the generated carbonyl halide has the possibility of further oxidative photodecomposition. However, by adjusting the oxygen concentration in the mixed gas to be low, it is possible to inhibit the oxidative photodecomposition of the carbonyl halide while simultaneously oxidizing and photodecomposing the halogenated methane. For example, in the case where the oxygen concentration in the mixed gas is adjusted to 15 ± 5 vol%, preferably 15 ± 2 vol%, the light irradiation time for the mixed gas can also be adjusted to 50 seconds or more, 100 seconds or more, 150 seconds or more, 200 seconds or more, 500 seconds or more, or 1000 seconds or more.

[0104] The flow rate of the flowing mixed gas in the photoreactor for irradiating the flowing mixed gas with high-energy light is preferably also determined in consideration of the internal volume of the photoreactor. For example, when the internal volume of the photoreactor is large, there is a tendency for the residence time of the mixed gas to be long, and therefore it is preferable to increase the flow rate, and conversely when the internal volume is small, it is preferable to adjust the flow rate of the mixed gas to be slow. Specifically, the internal volume (L) of the photoreactor / the flow rate of the flowing mixed gas (L / sec) corresponds to the residence time (sec) of the flowing mixed gas in the photoreactor, and therefore the flow rate of the flowing mixed gas can be determined in accordance with the desired residence time and the internal volume of the photoreactor. Note that, Figure 3 In the illustrated manner, the flow rate of the flowing mixed gas can be considered to be the same as the flow rate of the oxygen-containing gas.

[0105] In addition, the linear velocity of the flowing mixed gas within the photoreactor can be adjusted to be around 0.001 m / min or more and 100 m / min or less. If the linear velocity is 0.001 m / min or more, the photodecomposition of the carbonyl halide generated from the halogenated methane can be more reliably inhibited by the gas phase reaction, and if it is 100 m / min or less, a sufficient time for the conversion from the halogenated methane to the carbonyl halide can be more reliably obtained. The linear velocity can be calculated by dividing the velocity of the flowing mixed gas within the photoreactor by the cross-sectional area within the photoreactor. In the case where the cross-sectional area within the photoreactor is not fixed, the cross-sectional area can be considered to be the average of the cross-sectional area of the photoreactor in the direction of movement of the flowing mixed gas. The average can be found by dividing the volume within the photoreactor by the length in the direction of movement of the flowing mixed gas within the photoreactor. As the linear velocity, 0.01 m / min or more is preferable, and in addition, 50 m / min or less or 20 m / min or less is preferable, 10 m / min or less or 5 m / min or less is more preferable, and 1 m / min or less or 0.5 m / min or less is further preferable.

[0106] The temperature at the time of irradiation of the vaporized halogenated methane with high-energy light is appropriately adjusted within a range in which the vaporization of the halogenated methane can be maintained and the excessive decomposition of the generated carbonyl halide can be suppressed. For example, the boiling point of dichloromethane is 40°C and the boiling point of chloroform is 61.2°C at normal pressure, but by mixing with oxygen, air or the like, the gaseous state of the halogenated methane can be maintained even at a temperature lower than the boiling point. The temperature can be set to, for example, 35°C or higher and 250°C or lower. As the temperature, 40°C or higher or 50°C or higher is preferable, 70°C or higher or 80°C or higher is more preferable, further 85°C or higher is further preferable, and 200°C or lower is preferable, 150°C or lower is more preferable, and 120°C or lower is further preferable. The temperature can be adjusted according to the temperature of the vaporized halogenated methane and / or the oxygen-containing gas introduced into the reaction vessel. In addition, in order to maintain the temperature of the mixed gas in the reaction vessel, the reaction vessel can be heated with a heating medium.

[0107] The mixed gas containing the halogenated methane and oxygen can not be pressurized at the time of irradiation of the halogenated methane with high-energy light, but is at least pressurized to a degree at which the mixed gas can pass through the reaction vessel. In addition, the productivity is sometimes improved by pressurization of the mixed gas. The gauge pressure of the mixed gas in the reaction vessel can be adjusted to 0 MPaG or higher and 2 MPaG or lower, and 1 MPaG or lower is preferable, and 0.5 MPaG or lower is more preferable.

[0108] It is considered that, by this process, the halogenated methane is photo-decomposed by the oxidation light, and a carbonyl halide [X-C(=0)-X (X represents one or more halogen groups selected from the group consisting of chlorine, bromine and iodine)] is generated. In addition, it is also considered that not only the carbonyl halide but also a carbonyl halide-like compound which exerts the same action as the carbonyl halide is generated. The carbonyl halide described in the present application also includes the carbonyl halide-like compound. Hereinafter, a representative example of a reaction using the carbonyl halide will be described.

[0109] 3. Post-reaction process - production of carbonate compound

[0110] By reacting the carbonyl halide with an alcohol compound, a carbonate compound can be produced.

[0111] The manner of the reaction is not particularly limited, and for example, as shown in Figure 1 , a gas containing the generated carbonyl halide can be blown into a composition containing the alcohol compound in a reaction vessel 6. In addition, as shown in Figure 2 and Figure 4 , the alcohol compound can be introduced into a coil reaction device 9 capable of adjusting the temperature, and the carbonyl halide can be reacted with the alcohol compound in the coil reaction device. At this time, the temperature of the coil reaction device can be adjusted so that the alcohol compound is vaporized and the carbonyl halide is reacted with the alcohol compound in the gas phase. In addition, as shown in Figure 3 , 5As shown in FIG. 6, the carbonyl halide generated in the photoreaction vessel 12 is blown into the composition containing the alcohol compound in the reaction vessel 16 by introducing an oxygen-containing gas to expel the carbonyl halide from the photoreaction vessel 12. As shown in FIG. 7, a cooling pipe 15 can be provided between the photoreaction vessel 12 and the reaction vessel 16. The temperature of the cooling pipe is preferably adjusted so that the generated carbonyl halide can pass through. For example, the boiling point of phosgene, which is a carbonyl halide, is 8.2°C, and therefore, in the case of generating phosgene, the temperature of the cooling pipe 15 is preferably set to 10°C or higher. Figure 3

[0112] The alcohol compound is an organic compound having a hydroxyl group, and examples thereof include monohydric alcohol compounds represented by the following formula (I) and dihydric alcohol compounds represented by the following formula (II). Hereinafter, the compound represented by formula (I) is sometimes referred to as "compound x". For example, the monohydric alcohol compound represented by formula (I) is sometimes referred to as "monohydric alcohol compound (I)".

[0113] R 1 -OH···(I)

[0114] HO-R 2 -OH···(II)

[0115] [In the formula, R 1 represents a monovalent organic group, and R 2 represents a divalent organic group.]

[0116] The organic group is not particularly limited as long as it is an inert group to the reaction in the present process, and examples thereof include C 1-10 aliphatic hydrocarbon groups, optionally substituted C 6-12 aromatic hydrocarbon groups, optionally substituted heteroaromatic groups, 2 to 5 optionally substituted C 1-10 aliphatic hydrocarbon groups, and optionally substituted C 6-12 aromatic hydrocarbon groups, and 2 to 5 optionally substituted C 1-10 aliphatic hydrocarbon groups, and optionally substituted heteroaromatic groups.

[0117] As the C 1-10 aliphatic hydrocarbon group, for example, C 1-10 chain aliphatic hydrocarbon groups, C 3-10 cyclic aliphatic hydrocarbon groups, and 2 to 5 C 1-10 chain aliphatic hydrocarbon groups, and C 3-10 cyclic aliphatic hydrocarbon groups.

[0118] "C 1-10 ​"Chain aliphatic hydrocarbon groups" refer to straight-chain or branched saturated or unsaturated aliphatic hydrocarbon groups with 1 or more but fewer than 10 carbon atoms. For example, as a monovalent carbon... 1-10 Chain-like aliphatic hydrocarbon groups, such as C 1-10 Alkyl, C 2-10 alkenyl and C 2-10 Alkyne group.

[0119] As C 1-10 Alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, 2,2-dimethylethyl, n-pentyl, n-hexyl, 2-hexyl, 3-hexyl, 4-methyl-2-pentyl, n-heptyl, n-octyl, n-decyl, etc., are preferred. 2-8 Alkyl, more preferably C 4-6 alkyl.

[0120] As C 2-10 Alkenyl groups, such as vinyl, 1-propenyl, 2-propenyl (allyl), butenyl, hexenyl, octenyl, decenyl, etc., are preferred. 2-8 alkenyl, more preferably C 4-6 Alkenyl group.

[0121] As C 2-10 Alkynyl groups, such as ethynyl, propynyl, butynyl, hexynyl, octynyl, and pentadecylynyl, are examples. C is preferred. 2-8 Alkyne group, more preferably C 2-6 Alkyne group.

[0122] “C 3-10 "Cyclic aliphatic hydrocarbon group" refers to a cyclic saturated or unsaturated aliphatic hydrocarbon group with 1 or more but fewer than 10 carbon atoms. For example, a monovalent carbon aliphatic hydrocarbon group... 3-10 Cyclic aliphatic hydrocarbon groups, for example, C 3-10 cycloalkyl, C 4-10 Cycloalkenyl and C 4-10 Cycloacetic group.

[0123] C as a value between 2 and 5 1-10 Chain-like aliphatic hydrocarbon groups and C 3-10 Organic groups formed by the bonding of cyclic aliphatic hydrocarbon groups can be exemplified by, for example, C. 3-10 Monovalent cyclic aliphatic hydrocarbon group -C 1-10 Divalent chain aliphatic hydrocarbon group, C 1-10 Monovalent chain aliphatic hydrocarbon group -C 3-10 Divalent cyclic aliphatic hydrocarbon group -C 1-10 Divalent chain aliphatic hydrocarbon group.

[0124] “C 6-12An "aromatic hydrocarbon group" refers to an aromatic hydrocarbon group having a carbon number of 6 or more and 12 or less. For example, a monovalent C 6-12 The aromatic hydrocarbon group is a phenyl group, an indenyl group, a naphthyl group, a biphenyl group, or the like, and is preferably a phenyl group.

[0125] The "heteroaryl group" refers to a 5-membered ring aromatic heterocyclic group, a 6-membered ring aromatic heterocyclic group, or a fused ring aromatic heterocyclic group having at least one heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom. For example, a monovalent 5-membered ring heteroaryl group such as a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a thienyl group, a furanyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, and a thiadiazole group; a monovalent 6-membered ring heteroaryl group such as a pyridyl group, a pyrazinyl group, and a pyrimidinyl group; and a monovalent fused ring aromatic heterocyclic group such as an indolyl group, an isoindolyl group, a quinolyl group, an isoquinolyl group, a benzofuranyl group, an isobenzofuranyl group, and a chromenyl group can be given.

[0126] As the "C 1-10 The aliphatic hydrocarbon group and the C 6-12 An "organic group" in which the aromatic hydrocarbon group is bonded, for example, a C 6-12 An "organic group" in which the aromatic hydrocarbon group is bonded, for example, a C 1-10 An "organic group" in which the aromatic hydrocarbon group is bonded, for example, a C 1-10 An "organic group" in which the aromatic hydrocarbon group is bonded, for example, a C 6-12 An "organic group" in which the aromatic hydrocarbon group is bonded, for example, a C 1-10 An "organic group" in which the aromatic hydrocarbon group is bonded, for example, a C 6-12 An "organic group" in which the aromatic hydrocarbon group is bonded, for example, a C 1-10 An "organic group" in which the aromatic hydrocarbon group is bonded, for example, a C 6-12 An "organic group" in which the aromatic hydrocarbon group is bonded, for example, a C 1-10 An "organic group" in which the aromatic hydrocarbon group is bonded, for example, a C 6-12 As the "C 1-10 An "organic group" in which the aliphatic hydrocarbon group and the heteroaryl group are bonded, for example, a heteroaryl-C 1-10 An "organic group" in which the aliphatic hydrocarbon group and the C 1-10 An "organic group" in which the aliphatic hydrocarbon group and the C 1-10 An "organic group" in which the aliphatic hydrocarbon group and the C 1-10 An "organic group" in which the aliphatic hydrocarbon group and the C 1-10 An "organic group" in which the aliphatic hydrocarbon group and the C

[0127] As the C 1-10 The substituent optionally present on the aliphatic hydrocarbon group, for example, one or more substituents selected from the group consisting of a halogen group, a nitro group, and a cyano group, preferably a halogen group, can be given. As the C 6-12 The substituent optionally present on the aromatic hydrocarbon group and the heteroaryl group, for example, one or more substituents selected from the group consisting of a C 1-6 The substituent optionally present on the alkyl group, the C 1-6one or more substituents selected from the group consisting of an alkoxy group, a halogen group, a nitro group, and a cyano group, preferably a halogen group. As the "halogen group", fluorine, chlorine, bromine, and iodine can be given, and fluorine is preferred.

[0128] Further, the alcohol compound can be classified into a fluoroalcohol compound having a fluoro group as a substituent, and a non-fluoroalcohol not substituted with a fluoro group. The halogen group optionally present as a substituent in the non-fluoroalcohol is one or more halogen groups selected from chlorine, bromine, and iodine. Note that the group "R x " having a fluoro group as a substituent can be denoted as "R F ". x

[0129] "C 1-6 alkyl group" means a linear or branched monovalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms. Examples are a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, and the like. A C 1-4 alkyl group is preferred, a C 1-2 alkyl group is more preferred, and a methyl group is further preferred.

[0130] "C 1-6 alkoxy group" means a linear or branched saturated aliphatic hydrocarbon oxy group having 1 to 6 carbon atoms. Examples are a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a t-butoxy group, an n-pentoxy group, an n-hexyloxy group, and the like, a C 1-4 alkoxy group is preferred, a C 1-2 alkoxy group is more preferred, and a methoxy group is further preferred.

[0131] The monohydric alcohol compound (I) can be a fluoroalcohol compound. As the monovalent fluoroalcohol compound (I), for example, fluorinated ethanol such as difluoroethanol, trifluoroethanol; fluorinated propanol such as monofluoropropanol, difluoropropanol, trifluoropropanol, tetrafluoropropanol, pentafluoropropanol, hexafluoropropanol; and the like can be given.

[0132] As the divalent organic group, a divalent organic group corresponding to the examples of the monovalent organic group can be given. For example, a divalent organic group corresponding to a C 1-10 alkyl group, a C 2-10 alkenyl group, and a C 2-10 alkynyl group as the monovalent organic group is a C 1-10 alkanediyl group, a C 2-10 alkenediyl group, and a C 2-10 alkynediyl group.

[0133] Further, the divalent organic group can be a divalent (poly)alkylene glycol group -[-O-R 2 -] n -[wherein R 2 represents1-8 alkanediyl, n represents an integer of 1 or more and 50 or less.

[0134] Further, as the dihydric alcohol compound (II), for example, the following dihydric alcohol compound (II-1) can be mentioned.

[0135]

[0136] [In the formulae,

[0137] R 11 and R 12 independently represent H, C 1-6 alkyl, C 1-6 fluoroalkyl or C 6-12 aromatic hydrocarbon group, or together form a C 1-6 alkyl group optionally substituted with C 3-6 cycloalkyl group,

[0138] R 13 and R 14 independently represent H, C 1-6 alkyl, or C 6-12 aromatic hydrocarbon group, p1 or p2 is an integer of 2 or more, a plurality of R 13 or R 14 are optionally the same or different from each other,

[0139] p1 and p2 independently represent an integer of 0 or more and 4 or less.

[0140] As the divalent non-fluorinated alcohol compound (II-1), specifically, for example, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxyphenyl)butane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, preferably 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) can be mentioned.

[0141] Diol compounds (II) can be fluorool compounds. Examples of difluorool compounds (II) include fluoroethylene glycol; fluoropropylene glycol such as monofluoropropylene glycol and difluoropropylene glycol; fluorobutanediol such as monofluorobutylene glycol, difluorobutylene glycol, trifluorobutylene glycol, and tetrafluorobutylene glycol; fluoropentanediol such as monofluoropentanediol, difluoropentanediol, trifluoropentanediol, tetrafluoropentanediol, pentafluoropentanediol, and hexafluoropentanediol; and monofluorohexanediol, difluorohexanediol, trifluorohexanediol, and tetrafluorohexanediol. Fluorinated hexanediols include pentafluorohexanediol, hexafluorohexanediol, heptafluorohexanediol, and octafluorohexanediol; fluoroheptanediols include monofluoroheptanediol, difluoroheptanediol, trifluoroheptanediol, tetrafluoroheptanediol, pentafluoroheptanediol, hexafluoroheptanediol, heptafluoroheptanediol, octafluoroheptanediol, nonafluoroheptanediol, and decafluoroheptanediol; and fluorooctanediols include monofluorooctanediol, difluorooctanediol, trifluorooctanediol, tetrafluorooctanediol, pentafluorooctanediol, hexafluorooctanediol, heptafluorooctanediol, and octafluorooctanediol. Fluorooctanediols such as fluorooctanediol, nonafluorooctanediol, decafluorooctanediol, undecanofluorooctanediol, and dodecafluorooctanediol; fluorononanediols such as monofluorononanediol, difluorononanediol, trifluorononanediol, tetrafluorononanediol, pentafluorononanediol, hexafluorononanediol, heptafluorononanediol, octafluorononanediol, nonafluorononanediol, decafluorononanediol, undecanofluorononanediol, dodecafluorononanediol, tridecanofluorononanediol, and tetradecanofluorononanediol; and monofluorodecanediol and difluorodecanediol. Fluorinated decanediols include trifluorodecanediol, tetrafluorodecanediol, pentafluorodecanediol, hexafluorodecanediol, heptafluorodecanediol, octafluorodecanediol, nonafluorodecanediol, decafluorodecanediol, undecanediol, dodecafluorodecanediol, tridecanediol, tetradecanediol, pentafluorodecanediol, hexafluorodecanediol, etc.; and fluorinated polyethylene glycols include diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, etc.

[0142] The amount of alcohol compound used can be adjusted appropriately within the range where the reaction proceeds well. For example, a diol compound with a molar ratio of 1 or more relative to the generated carbonyl halide can be used, and a monool compound with a molar ratio of 2 or more can be used. By using excess alcohol compound, carbonate compounds can be obtained more efficiently. However, since the yield of carbonyl halide relative to the used halomethane is not constant, it is preferable to set the molar ratio of diol compound to halomethane to be 1 or more, and the molar ratio of monool compound to halomethane to be 2 or more. As for the aforementioned molar ratio of diol, it is preferable to be 1.5 or more, more preferably 2 or more, and further preferably 10 or less, more preferably 5 or less. As for the aforementioned molar ratio of monool, it is preferable to be 2 or more, more preferably 4 or more, and further preferably 20 or less, more preferably 10 or less.

[0143] In order to promote the reaction of the carbonyl halide with the alcohol compound, a base can be used. The base is classified into inorganic bases and organic bases. As the inorganic base, for example, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate and the like, carbonates of alkali metals; magnesium carbonate, calcium carbonate, barium carbonate and the like, carbonates of Group 2 metals; lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate and the like, bicarbonates of alkali metals; lithium hydroxide, sodium hydroxide, potassium hydroxide and the like, hydroxides of alkali metals; magnesium hydroxide, calcium hydroxide and the like, hydroxides of Group 2 metals; lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride and the like, fluoride salts of alkali metals can be given, and preferably, carbonates or bicarbonates of alkali metals or Group 2 metals having low hygroscopicity and deliquescence, and more preferably, carbonates of alkali metals. As the organic base, from the viewpoint of low reactivity of the product caused by the photo-reaction with the tetrahaloethene, for example, trimethylamine, triethylamine, diisopropylethylamine and the like, tri(C 1-4 alkyl) amines; sodium tert-butoxide, potassium tert-butoxide and the like, tert-butoxides of alkali metals; diazabicyloundecene, lithium diisopropylamide, lithium tetramethylpiperidine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,1,3,3-tetramethylguanidine (TMG), and N-methylmorpholine and the like, non-nucleophilic organic bases, and pyridine, dimethylpyridine and the like, low-nucleophilic organic bases can also be used.

[0144] In the oxidative photodecomposition reaction of the halogenated methane and the reaction of the carbonyl halide with the alcohol compound, hydrogen halide such as hydrogen chloride is produced as a by-product. The capture of the hydrogen halide by the base is effective, and in the case of using a reaction tube having a small diameter such as the coil reaction apparatus shown in Figure 2 and Figure 4 the salts of the hydrogen halide and the base are precipitated, and sometimes, clogging occurs. In this case, it is preferable to use a base in which the salt of the hydrogen halide and the base becomes an ionic liquid. As the base, for example, imidazole derivatives such as 1-methylimidazole and the like, and the like, organic bases and the like can be given. In addition, a base having a low melting point such as pyridine and the like, hydrochloride salts thereof can also be used.

[0145] The amount of the base is appropriately adjusted within a range in which the reaction proceeds well, and for example, 1 mol or more and 10 mol or less per 1 mol of the halogenated methane can be set.

[0146] The base can be, for example, added to the alcohol compound in advance, and can also be continuously injected together with the alcohol compound.

[0147] In the case of reacting a carbonyl halide with an alcohol compound, a solvent can be used. The solvent can be added, for example, to a composition containing an alcohol compound. As the solvent, there can be mentioned, for example, a ketone-based solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like; an ester-based solvent such as ethyl acetate, and the like; an aliphatic hydrocarbon solvent such as n-hexane, and the like; an aromatic hydrocarbon solvent such as benzene, toluene, xylene, benzonitrile, and the like; an ether-based solvent such as diethyl ether, tetrahydrofuran, dioxane, and the like; a nitrile-based solvent such as acetonitrile, and the like; a halogenated hydrocarbon solvent such as dichloromethane, chloroform, and the like.

[0148] The temperature for reacting a carbonyl halide with an alcohol compound is not particularly limited, and can be appropriately adjusted, and can be set to, for example, 0°C or higher and 250°C or lower. As the temperature, more preferably 10°C or higher, and still more preferably 20°C or higher, and in addition, more preferably 200°C or lower or 150°C or lower, and still more preferably 100°C or lower or 80°C or lower. However, in the case where no base is used, or in the case where a base is used and further promotion of the reaction is intended, the temperature can be adjusted to a relatively high temperature of 50°C or higher, 100°C or higher, or the like.

[0149] The time for reacting a carbonyl halide with an alcohol compound is not particularly limited, and can be appropriately adjusted, and is preferably, for example, 0.5 hours or longer and 50 hours or shorter. As the reaction time, more preferably 1 hour or longer, and still more preferably 5 hours or longer, and in addition, more preferably 30 hours or shorter, and still more preferably 20 hours or shorter. In addition, after the completion of the generation of a carbonyl halide, for example, the reaction liquid can also be continuously stirred until the consumption of an alcohol compound is confirmed.

[0150] By the reaction of a carbonyl halide with an alcohol compound, in the case where a monohydric alcohol compound (I) is used, a chain carbonate compound represented by the following formula (III) is generated, and in the case where a dihydric alcohol compound (II) is used, a polycarbonate compound containing a unit represented by the following formula (IV-1), or a cyclic carbonate compound represented by the following formula (IV-2) is generated. In the case where a dihydric alcohol compound (II) is used, either a polycarbonate compound (IV-1) or a cyclic carbonate compound (IV-2) is generated, and the generation ratio thereof mainly depends on the distance between the 2 hydroxyl groups in the dihydric alcohol compound (II), the Flexibility of the chemical structure. Specifically, this can be confirmed by a preliminary experiment or the like.

[0151] R 1 -O-C(=O)-O-R 1 (III)

[0152] [-A-R 2 -A-C(=O)-](IV-1)

[0153]

[0154] 4. Post-reaction process - production of halogenated formic acid ester

[0155] In the production method of the carbonate compound, by not using a base and setting the molar ratio of the alcohol compound to the halogenated methane to be less than 1, a halogenated formic acid ester can be obtained. As the molar ratio, 0.9 or less, more preferably 0.8 or less is preferable. As the alcohol compound, the aforementioned monohydric alcohol compound (I) can be used. Further, from a fluorinated monohydric alcohol compound (I), a fluorinated halogenated formic acid ester can be obtained, and from a non-fluorinated monohydric alcohol compound (I), a non-fluorinated halogenated formic acid ester can be obtained.

[0156] 5. Post-reaction process - production of isocyanate compound

[0157] By reacting a carbonyl halide with a primary amine compound, an isocyanate compound can be produced. The isocyanate compound is useful as a raw material of a urethane compound, a urea compound, and the like. As the reaction mode, in the production method of the carbonate compound, a primary amine compound can be used instead of an alcohol compound, except for the following points.

[0158] The primary amine compound is not particularly limited as long as it is a compound having one or more amino groups (-NH2 group), and for example, a primary amine compound (V) can be used: R 3 -(NH2) m . In the formula, R 3 represents an m-valent organic group, and m represents an integer of 1 or more and 6 or less, preferably 5 or less, 4 or less, or 3 or less, more preferably 1 or 2, and still more preferably 2.

[0159] The organic group R 3 Among them, as a monovalent organic group, the same groups as exemplified in the production method of the carbonate compound for the monovalent organic group R 1 can be mentioned. As a divalent organic group, the same groups as exemplified in the production method of the carbonate compound for the divalent organic group R 2 can be mentioned. Further, as a trivalent or higher valent organic group, the same groups as exemplified in the production method of the carbonate compound for the monovalent organic group R 1 can be mentioned. For example, the same groups as exemplified in the production method of the carbonate compound for the monovalent organic group C 1-10 alkyl group, C 2-10 alkenyl group, and C 2-10 alkynyl group are C 1-10 alkanetriyl group, C 2-10 alkenetriyl group, and C 2-10 alkynetriyl group.

[0160] By the reaction of the carbonyl halide with the primary amine compound (V), an isocyanate compound (VI) can be obtained: R 3 -(N=C=O) m . However, it is possible that R3 - (N=C=0) m with the primary amine compound (V) to produce a urea compound R 3 - [NH-C(=0)-NH-R 3 ] m To inhibit the reaction, it is preferable to adjust the molar ratio of the primary amine compound (V) to the halogenated methane to be less than 1, or to use a salt as the primary amine compound (V), or to use no base. In addition, by dissolving the produced carbonyl halide in a solvent, adding the primary amine compound (V) or a solution thereof to the solution, and ensuring that the molar ratio of the carbonyl halide to the primary amine compound (V) exceeds 1, it is possible to efficiently produce an isocyanate compound.

[0161] In the case where the target compound is an isocyanate compound, it is preferable to make the molar ratio of the primary amine compound (V) to the produced carbonyl halide be less than 1, but it is sometimes difficult to predict the accurate production amount of the carbonyl halide, and therefore, it is preferable to make the molar ratio of the primary amine compound (V) to the used halogenated methane be less than 1. As the molar ratio, it is preferable to be 0.5 or less, more preferably 0.2 or less, and in addition, it is preferable to be 0.001 or more, more preferably 0.05 or more. On the other hand, in the case where the target compound is a urea compound, as the ratio, it is preferable to be 2 or more, more preferably 4 or more, and in addition, it is preferable to be 20 or less, more preferably 15 or less.

[0162] In the case where the target compound is an isocyanate compound, the isocyanate compound is difficult to react with an amine salt, and therefore, it is preferable to use a salt as the primary amine compound (V). As the salt, there can be mentioned, for example, inorganic acid salts such as hydrochloride, hydrobromide, hydroiodide, sulfate, nitrate, perchlorate, phosphate, and the like; and organic acid salts such as oxalate, malonate, maleate, fumarate, lactate, malate, citrate, tartrate, benzoate, trifluoroacetate, acetate, methanesulfonate, p-toluenesulfonate, trifluoromethanesulfonate, and the like.

[0163] As for the temperature for maintaining the reaction of the carbonyl halide and the primary amine compound, for example, in order to maintain the liquid state of the carbonyl halide, it is preferable to set it lower than the reaction temperature with the alcohol compound. For example, the reaction temperature can be set to be 15°C or lower, preferably 10°C or lower, more preferably 5°C or lower, and still more preferably 2°C or lower. The lower limit of the temperature is not particularly limited, and for example, as the temperature, it is preferable to be -80°C or higher, more preferably -20°C or higher, or -15°C or higher.

[0164] In the case where the target compound is an isocyanate compound and a base is used, as the base, one or more bases selected from the group consisting of a heterocyclic aromatic amine and a non-nucleophilic strong base are preferred. The heterocyclic aromatic amine refers to a compound containing at least one heterocycle and having at least one amine functional group other than -NH2. As the heterocyclic aromatic amine, for example, pyridine, a-methylpyridine, β-methylpyridine, γ-methylpyridine, 2,3-dimethylpyridine, 2,4-dimethylpyridine, 2,6-dimethylpyridine, 3,5-dimethylpyridine, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine, 2,4,6-trimethylpyridine, 4-dimethylaminopyridine, and the like, and derivatives thereof can be given.

[0165] The "non-nucleophilic strong base" refers to a base in which the nucleophilicity of the lone pair of electrons on the nitrogen atom is weak due to steric hindrance, but the basicity is strong. For example, triethylamine, N,N-diisopropylethylamine, tripropylamine, triisopropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, tridecylamine, tridodecylamine, triphenylamine, tribenzylamine, N,N-diisopropylethylamine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), and 1,1,3,3-tetramethylguanidine (TMG) can be given. In addition, a base having a relatively high basicity can be used. For example, as a base having a basicity (pK BH+ ) of 20 or more in acetonitrile, TBD (pK BH+ : 25.98), MTBD (pK BH+ : 25.44), DBU (pK BH+ : 24.33), DBN (pK BH+ : 23.89), and TMG (pK BH+ : 23.30) can be used.

[0166] Further, as the base, a general organic amine such as trimethylamine, dimethylethylamine, diethylmethylamine, N-ethyl-N-methylbutylamine, 1-methylpyrrolidine, and the like can also be used.

[0167] Note that in the case where the target compound is a urea compound, it is preferred that the molar ratio of the primary amine compound to the halogenated methane, the generated carbonyl halide, exceeds 1. As the molar ratio, 1.5 or more, more preferably 2 or more, is preferred.

[0168] 6. Post-reaction step - production of NCA

[0169] In the above production method of the carbonate compound, the amino acid-N-carboxyanhydride (NCA) (VIII) can also be produced by using the amino acid compound (VII) instead of the alcohol compound.

[0170]

[0171] R 4 represents a protected amino acid side chain group of a reactive group,

[0172] R 5 represents H, or P 1 -[-NH-CHR 6 -C(=O)-]l- (in the formula, R 6 represents a protected amino acid side chain of a reactive group, P 1 represents a protecting group of an amino group, and l represents an integer of 1 or more, and when l is an integer of 2 or more, the plural R 6 are optionally the same as or different from each other).

[0173] 7. Post-reaction process - production of Wess-Meer reagent

[0174] The Wess-Meer reagent (X) can be produced by reacting the carbonyl halide with the amide compound (IX). The production of the Wess-Meer reagent uses the amide compound (IX) instead of the alcohol compound, and does not use a base, and is otherwise performed in the same manner as the above production method of the carbonate compound.

[0175]

[0176] [In the formula,

[0177] R 7 represents a hydrogen atom, C 1-6 alkyl group, or C 6-12 aromatic hydrocarbon group,

[0178] R 8 and R 9 independently represent C 1-6 alkyl group, or C 6-12 aromatic hydrocarbon group, and in addition, R 8 and R 9 optionally form a ring structure of 4 or more and 7 or less members together,

[0179] X represents a halogen group selected from the group consisting of chlorine, bromine, and iodine,

[0180] Y - represents a counter anion.

[0181] C 6-12The substituent group optionally present in the aromatic hydrocarbon group is not particularly limited as long as it does not hinder the reaction of the present application, and for example, one or more substituent groups selected from the group consisting of C 1-6 alkyl group, a C 1-6 alkoxy group, a halogen group, a nitro group, and a cyano group. The number of substituent groups is not particularly limited as long as it can be substituted, and for example, it can be set to 1 or more and 5 or less, preferably 3 or less, more preferably 2 or less, and still more preferably 1. When the number of substituent groups is 2 or more, the substituent groups are optionally the same as or different from each other.

[0182] R 8 and R 9 form a ring structure of 4 to 7 members together with the nitrogen atom, and for example, a pyrrolidinyl group, a piperidinyl group, and a morpholinyl group can be given.

[0183] As the specific amide compound (IX), for example, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-methyl-N-phenylformamide, N-methylpyrrolidone (NMP), 1,3-dimethylimidazolidinone (DMI), tetramethylurea, tetraethylurea, tetrabutylurea, and the like can be given, and from the viewpoints of versatility, cost, and the like, DMF is preferred.

[0184] As Y - in the formula (X), a chloride ion, a bromide ion, and an iodide ion derived from a halomethane can be given, and it is not particularly limited.

[0185] The amount of the amide compound is appropriately adjusted within a range in which the reaction proceeds well, and for example, it can be set to 0.1 mol or more and 100 mol or less per 1 mL of the halomethane.

[0186] When the carbonyl halide is reacted with the amide compound, a solvent can be used. For the solvent, for example, it can be added to a composition containing the amide compound. As the solvent, for example, a ketone-based solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; an ester-based solvent such as ethyl acetate; an aliphatic hydrocarbon solvent such as n-hexane; an aromatic hydrocarbon solvent such as benzene, toluene, xylene, and benzonitrile; an ether-based solvent such as diethyl ether, tetrahydrofuran, and dioxane; and a nitrile-based solvent such as acetonitrile can be given.

[0187] The temperature for reacting the carbonyl halide with the amide compound is not particularly limited, and it is appropriately adjusted, and for example, it can be set to 0°C or higher and 120°C or lower. As the temperature, it is more preferably 10°C or higher, 20°C or higher, and further more preferably 100°C or lower, 80°C or lower, or 50°C or lower.

[0188] The time for reacting the carbonyl halide with the amide compound is not particularly limited, and is appropriately adjusted, for example, preferably 0.5 hours or more and 50 hours or less. As the reaction time, more preferably 1 hour or more, further more preferably 5 hours or more, and additionally, more preferably 30 hours or less, further more preferably 20 hours or less. In addition, after the generation of the carbonyl halide is completed, for example, the reaction solution can also be stirred until the consumption of the amide compound is confirmed.

[0189] By the Vilsmeier-Haack reaction using Vilsmeier reagent, an aromatic compound having an active group can be aldehylated or ketonated. In addition, it is known that Vilsmeier reagent converts a carboxyl group of a carboxylic acid compound into a halogenated formyl group. Furthermore, by reacting Vilsmeier reagent with a hydroxyl group-containing compound, a formic acid ester can be obtained.

[0190] An aromatic compound having an active group (hereinafter, referred to as "active aromatic compound") is an aromatic compound activated by a substituent or the like. For example, an amino group containing an alkyl group-substituted alkylamino group, a hydroxyl group or the like strongly activates an aromatic compound. In addition, an alkylcarbonylamino group (-N(C=0)R), an alkylcarbonyloxy group (-0(C=0)R), an ether group (-OR), an alkyl group (-R) (R represents an alkyl group, preferably a C 1-6 alkyl group), and an aromatic group also activate an aromatic compound. Hereinafter, these substituents are referred to as activating groups. In addition, a compound in which an aromatic ring condenses like anthracene and the like so that a conjugated system expands is also activated to be aldehylated or ketonated by Vilsmeier reagent. It is considered that the aldehylation or ketonation is performed by the electrophilic reaction of the π electron of the activated site with Vilsmeier reagent.

[0191] The active aromatic compound is not particularly limited as long as it is a compound activated to be aldehylated or ketonated by Vilsmeier reagent, and can be exemplified by, for example, benzene, naphthalene or the like C 6-10 aromatic hydrocarbon; condensed aromatic hydrocarbon such as phenanthrene, anthracene or the like optionally substituted by the above-mentioned activating group; 5-membered ring heteroaromatic group such as pyrrole, imidazole, pyrazole, thiophene, furan, oxazole, isoxazole, thiazole, isothiazole, thiadiazole or the like optionally substituted by the above-mentioned activating group; 6-membered ring heteroaromatic group such as pyridine, pyrazine, pyrimidine, pyridazine or the like optionally substituted by the above-mentioned activating group; condensed heteroaromatic group such as indole, isoindole, quinoline, isoquinoline, benzofuran, isobenzofuran, chromene or the like optionally substituted by the above-mentioned activating group. Note that unsubstituted furan, thiophene or the like, although there is no report of aldehylation or ketonation in the Vilsmeier-Haack reaction in the past, can be aldehylated or ketonated at the carbon adjacent to the hetero element according to the method of the present application.

[0192] The active group-containing aromatic compound, the carboxylic acid compound, and the hydroxyl group-containing compound as the substrate compound of the above reaction can be added to the reaction solution after the gas containing the carbonyl halide is blown into the composition containing the amide compound, or can be added to the reaction solution before or during the blowing of the gas containing the carbonyl halide into the composition containing the amide compound.

[0193] The amount of the active group-containing aromatic compound, the carboxylic acid compound, and the hydroxyl group-containing compound can be appropriately adjusted, and for example, can be set to 0.1 times or more and 1.0 times or less of the mole of the amide compound.

[0194] In addition, the Vilsmeier reagent is also useful for obtaining a carboxylic acid halide from a carboxylic acid compound. The Vilsmeier reagent after halogenation of the carboxylic acid compound becomes an amide compound. If an alcohol compound is reacted with the obtained carboxylic acid halide, an ester compound can be obtained, and if a carboxylic acid is reacted, a carboxylic anhydride can be obtained. Note that it is considered that if a carboxylic acid compound and a base are used instead of the amide compound, the carboxylic acid compound anionized by the base is directly converted into a carboxylic acid halide by the carbonyl halide. The carboxylic acid halide can also be used for the production of an ester compound and a carboxylic anhydride.

[0195] 8. Post-treatment step

[0196] Since most of the carbonyl halides are harmful, it is preferable not to allow the generated carbonyl halide to leak out of the system. For example, as shown in Figures 1 to 6 the gas phase discharged from the reaction vessel in which the generated carbonyl halide is reacted is introduced into an alcohol trap, and the gas phase discharged from the alcohol trap is further introduced into a base trap. The alcohol trap can be cooled to a range in which the alcohol used does not freeze, for example, around -80°C or higher and 50°C or lower. In addition, the base trap can use, for example, an aqueous sodium hydroxide solution, an aqueous saturated sodium hydrogen carbonate solution.

[0197] In the case where the compound obtained from the carbonyl halide is relatively unstable such as an isocyanate compound, a further reaction substrate compound can be added to the reaction solution in which the carbonyl halide has been reacted. Alternatively, in the case where the compound obtained from the carbonyl halide is relatively stable such as a carbonate compound, the target compound can be purified from the reaction solution. For example, an organic solvent that is not soluble in water such as chloroform and water can be added to the reaction solution to perform liquid-liquid separation, and the organic phase can be dried with anhydrous sodium sulfate, anhydrous magnesium sulfate, or the like, and then subjected to concentration under reduced pressure, and further purification by chromatography or the like.

[0198] This application claims priority based on Japanese Patent Application No. 2021-21001 filed on February 12, 2021. The specification of Japanese Patent Application No. 2021-21001 filed on February 12, 2021 is incorporated by reference herein in its entirety.

[0199] [Example]

[0200] The present invention will be described in more detail below with examples, but it should be noted that the present invention is not limited to the following examples, and may be implemented by appropriate modifications within the scope of the foregoing / hereafter described, and these modifications are also included within the scope of protection of the present invention.

[0201] Example 1: Synthesis of Phosgene

[0202]

[0203] use Figure 1 The schematically illustrated photoreaction system performs a gas-phase photoreaction. Specifically, a low-pressure mercury lamp ("SUV40D" SEN Light, 40W) is placed inside a quartz glass jacket with a diameter of 30mm and a length of 320mm. A cylindrical flowing photoreaction device 4, consisting of twelve quartz tubes with an inner diameter of 2.1 mm and a length of 320 mm and a capacity of 1.033 mL each, was prepared and arranged around it. The total capacity of this cylindrical flowing photoreaction device 4, including the connector, is 13.3 mL. Furthermore, the illuminance of light with a wavelength of 185 nm at a position 5 mm from the center of the low-pressure mercury lamp is 3.93 mW / cm². 2 The illuminance of light with a wavelength of 254 nm is 11.02 mW / cm². 2 .

[0204] Using syringe pump 1, liquid chloroform is fed into a PTFE tube (inner diameter: 1 mm) at the flow rate shown in Table 1. It is vaporized by a heater heated to the temperature shown in Table 1 and mixed with oxygen whose flow rate is adjusted by mass flow controller 2. This mixture is then fed into the aforementioned flowing photoreactor 4. The pressure inside the flowing photoreactor is adjusted by a back pressure valve 5 installed at the outlet of the flowing photoreactor. At this heater temperature, the injected chloroform vaporizes and mixes with oxygen, flowing as shown in Table 1. The maximum gas flow rates of the vaporized chloroform and oxygen, the linear velocity of the mixed gas, and the residence time can be calculated for each, respectively.

[0205] In a sufficient amount of 1-butanol in the connected reaction vessel 6, the gas generated by the photo-oxidation of a mixture of chloroform and oxygen is blown in at room temperature while stirring for 2–6 hours. Unreacted gas is further captured with 1-butanol in the connected collection vessel 7, and any remaining unreacted gas is introduced into the connected alkali collector for treatment to prevent toxic gas from leaking to the outside.

[0206] In addition, using an air pump ("Nisso air pump silent β-60" manufactured by Marukan Corporation), using air dried with a desiccant ("Dried Silica Gel, Medium Granular (Blue)" manufactured by FUJIFILM Wako Pure Chemical Corporation) instead of oxygen, the same experiment was performed.

[0207] After the reaction, the reaction solution in the reaction vessel 6 and the trap vessel 7 was analyzed by HNMR, and the conversion rate to the generated chloroformate and carbonate was calculated, and the amount of generated phosgene was calculated from the total thereof. The results are summarized in Table 1. Note that the phosgene yield in Table 1 is the yield with respect to the used chloroform. 1

[0208] [Table 1]

[0209]

[0210] *; not determined, ND: not detected

[0211] As shown in the above results, by heating the chloroform to 80°C with the coil heater to gasify it, and mixing it with oxygen to perform the gas phase flow photoreaction, the chloroform could be converted to phosgene at a conversion rate of 78%.

[0212] Further, the temperature of the coil heater was increased to 90°C, and in addition, the oxygen flow rate was increased, and as a result, the chloroform could be converted to phosgene at a conversion rate of 92% (unreacted 5.7%). It is considered that the remaining about 2% is the photodecomposition products of phosgene such as hexachloroethane, CO2, CO, Cl2, etc. produced as by-products in the photodecomposition of chloroform.

[0213] Further, the temperature of the coil heater was increased to 170°C, and as a result, the yield was increased.

[0214] Even if dry air is used instead of oxygen, phosgene is obtained at a high yield, but the yield is reduced compared to the case where oxygen is used. In addition, if the amount of air injection is increased, the unreacted chloroform slightly increases.

[0215] Example 2: Study of gas flow rate

[0216] The gas flow rates of chloroform and oxygen were controlled, the residence time in the flow photoreactor was changed, and in addition, the same as in Example 1, the change in the yield of phosgene due to the exposure time was confirmed. The results are summarized in Table 2.

[0217] [Table 2]

[0218]

[0219] ​As shown in the above results, it was confirmed that the unreacted chloroform decreased and the amount of phosgene generated decreased as the residence time in the flow photoreactor increased. Although it was considered that the generated phosgene was decomposed, it was not a sharp decrease, and as long as the above phosgene yield was sufficient for practical use, it was considered that there was a factor that inhibited the photodecomposition of the generated phosgene in the system. For example, oxygen has an optical absorption band at 100 to 250 nm, and therefore it was considered that excess high-energy light was absorbed by oxygen and the decomposition of the generated phosgene was suppressed.

[0220] Example 3: Synthesis of isocyanate based on a light flow system

[0221]

[0222] Using 11.06 g (92.7 mmol) of chloroform, under the conditions of Example 1 in which the coil heater temperature was set to 90°C, a 1,1,2,2-tetrachloroethane solution (20 mL) of hexylamine hydrochloride (1.38 g, 10 mmol) was used instead of 1-butanol, the solution was heated to 100°C and stirred while blowing the gas generated in the flow photoreactor. After the reaction, dichloromethane was added as an internal standard substance to the reaction liquid, and the reaction liquid was analyzed by 1 HNMR, and it was confirmed that hexyl isocyanate as the target compound was generated at a yield of 83%.

[0223] Example 4: Synthesis of isocyanate based on a light flow system

[0224]

[0225] Using Figure 1 the light reaction system schematically shown in

[0226] After the reaction, the reaction liquid was analyzed by 1 HNMR, and it was confirmed that hexyl isocyanate as the target compound was generated at a yield of 83%.

[0227] [Table 3]

[0228]

[0229] Example 5: Synthesis of carbonate based on a light flow system

[0230]

[0231] In reaction vessel 6, the product is stirred at room temperature and then used... Figure 1 The schematically illustrated photoreaction system generates gas in a flowing photoreaction apparatus according to the conditions in Table 4, which is then blown into an alcohol containing pyridine or 1-methylimidazole (NMI) as a base. 1-Butanol is added to the trap container 7 to trap the gas leaking from the reaction container 6.

[0232] After the reaction, 1,1,2,2-tetrachloroethane was added to the reaction solution as an internal standard. 1 HNMR analysis confirmed that the target compound was produced in high yield of the carbonate.

[0233] On the other hand, there are cases where the phosgene yield calculated based on the carbonate generated in reaction vessel 6 and the chloroformate and carbonate generated in trap vessel 7 is relatively low. This is believed to be due to the decomposition of phosgene by pyridine.

[0234] [Table 4]

[0235]

[0236] a: Yield relative to injected CHCl3; b: Yield relative to R-OH

[0237] Example 6: Synthesis of polycarbonate based on photoflow system

[0238] (1) Homogeneous polymerization

[0239]

[0240] use Figure 1 The schematically illustrated photoreaction system, under the conditions shown in Table 5, involves feeding a mixture of vaporized chloroform and oxygen into a flowing photoreaction apparatus and conducting the photoreaction at 90°C. In reaction vessel 6, a solution of bisphenol A, pyridine (4 mL, 50 mmol), and chloroform is stirred while the gas generated in the flowing photoreaction apparatus is blown in. Subsequently, the reaction solution is stirred at 50°C for 1 hour.

[0241] Next, methanol (150 mL) was added to the reaction solution, the precipitate was filtered off, and the precipitate was dried under vacuum to obtain the white target substance.

[0242] [Table 5]

[0243]

[0244] In addition, the obtained polycarbonate was analyzed by gel permeation chromatography (GPC) to determine its molecular weight. The results are shown in Table 6.

[0245] [Table 6]

[0246] Inlet Mw Mn Mw / Mn 1 4,505 2,360 1.91 2 49,000 14,000 3.50

[0247] (2) Homogeneous polymerization

[0248]

[0249] use Figure 1 The schematically illustrated photoreaction system, under the conditions shown in Table 7, involves feeding a mixture of vaporized chloroform and oxygen into a flowing photoreaction apparatus and conducting the photoreaction at 90°C. In reaction vessel 6, a solution obtained by mixing bisphenol AF (BPAF), pyridine, and chloroform is stirred while the gas generated in the flowing photoreaction apparatus is blown in. Subsequently, the reaction solution is further stirred at 50°C for 1 hour.

[0250] Next, methanol (150 mL) was added to the reaction solution, the precipitate was filtered off, and then dried under vacuum to obtain the white target substance.

[0251] [Table 7]

[0252]

[0253] In addition, the obtained polycarbonate was analyzed by gel permeation chromatography (GPC) to determine its molecular weight. The results are shown in Table 8.

[0254] [Table 8]

[0255] Inlet Mw Mn Mw / Mn 3 274,000 174,000 1.57

[0256] (3) Interface aggregation

[0257] use Figure 1 The schematically illustrated photoreaction system, under the conditions shown in Table 9, involves feeding a mixture of vaporized chloroform and oxygen into a flowing photoreaction device to carry out the photoreaction at 90°C. In reaction vessel 6, a solution obtained by mixing bisphenol A, 17wt% sodium hydroxide aqueous solution, and dichloromethane is stirred while the gas generated in the flowing photoreaction device is blown in.

[0258] Next, water and dichloromethane were added to the reaction solution for separation. The lower layer was dried with anhydrous sodium sulfate and then filtered. The filtrate was removed by vacuum distillation. Methanol was added to the residue, and the resulting precipitate was filtered off and dried under vacuum to obtain the yellowish-white target substance (yield relative to chloroform: 19%, yield relative to BPA: 84%).

[0259] [Table 9]

[0260]

[0261] Further, the obtained polycarbonate was analyzed by gel permeation chromatography (GPC) to find the molecular weight. The results are shown in Table 10.

[0262] [Table 10]

[0263] Mw Mn Mw / Mn 16,800 4,400 3.77

[0264] Example 7: Synthesis of polycarbonate based on a light flow system

[0265]

[0266] Using Figure 1 A light reaction system schematically shown, under the conditions shown in Table 11, a mixed gas of vaporized chloroform and oxygen was blown into a flow light reaction device, and a light reaction was performed at 90°C. In a reaction vessel 6, a solution obtained by mixing 1,6-hexanediol (9.45 g, 80 mmol), pyridine (32 mL, 400 mmol), and dichloromethane (40 mL) was stirred while blowing the gas generated in the flow light reaction device.

[0267] Next, 10 wt% hydrochloric acid was added to the reaction solution, and the solution was subjected to liquid separation. The lower layer was dried with anhydrous sodium sulfate, and then filtered. The solvent was removed from the filtrate by distillation under reduced pressure, and further, vacuum drying was performed at 50°C for 2 hours, whereby a white solid of the target product was obtained (yield with respect to chloroform: 58%, yield with respect to the raw material diol: 73%).

[0268] [Table 11]

[0269]

[0270] Further, the obtained polycarbonate was analyzed by gel permeation chromatography (GPC) to find the molecular weight. The results are shown in Table 12.

[0271] [Table 12]

[0272] Mw Mn Mw / Mn 5,740 3,530 1.62

[0273] Example 8: Synthesis of urea compound based on a light flow system

[0274]

[0275] In the conditions of Example 1 in which the coil heater temperature was set to 90°C, 11.46 g (94.3 mmol) of chloroform was used, and in a reaction vessel 6, a solution obtained by mixing aniline (42.3 g, 460 mmol) and dichloromethane (50 mL) instead of 1-butanol was stirred at normal temperature while blowing the gas generated in the flow light reaction device.

[0276] Next, water was added to the reaction solution, the generated precipitate was filtered and washed, and then dried under vacuum at 50°C for 3 hours, thereby obtaining a white target substance solid (yield: 93% with respect to chloroform). It is considered that the isocyanate compound generated by the reaction of phosgene with aniline was further reacted with aniline to obtain the urea compound.

[0277] In this reaction, when the phosgene used in the formation of diphenylurea was combined with the unreacted phosgene captured in the alcohol trap (trap container 7), the conversion rate from chloroform to phosgene was 98%.

[0278] Example 9: Synthesis of amino acid N-carboxyanhydride based on a light flow system

[0279] (1) Synthesis of L-phenylalanine N-carboxyanhydride

[0280]

[0281] Under the conditions of Example 1 in which the coil heater temperature was set to 90°C, 5.7 g (47.7 mmol) of chloroform was used, and in the reaction container 6, a suspension obtained by mixing L-phenylalanine (1.65 g, 10 mmol), chloroform (20 mL), and acetonitrile (15 mL) at 70°C was blown into with the gas generated in the flow light reaction device instead of 1-butanol.

[0282] After that, the unreacted starting material was filtered off, and the filtrate was concentrated under reduced pressure, thereby obtaining the target compound (yield: 61% with respect to the starting material L-phenylalanine).

[0283] (2) Synthesis of amino acid N-carboxyanhydride using air

[0284]

[0285] Using Figure 1 A light reaction system schematically shown was used to perform a gas phase light reaction. Liquid chloroform was fed into a PTFE tube (inner diameter: 1 mm) at a flow rate of 838 μL / min (0.1 mmol / min) and mixed with air whose flow rate was adjusted to 7 mL / min with a gas pump and a mass flow controller, and was fed into the flow light reaction device at 80°C. The injected chloroform was vaporized and flowed mixed with air, and the maximum gas flow rates of the vaporized chloroform and oxygen, the linear velocity of the mixed gas, and the residence time were calculated as shown in Table 13.

[0286] The gas generated by oxidative photolysis of a mixed gas of chloroform gas and air was blown into the THF solution containing the L-amino acid (10 mmol) in the connected reaction vessel 6 at 60°C while stirring for 3 hours. The unreacted gas was further introduced into the connected alkali trap, and treated so that toxic gas would not leak to the outside. After that, the obtained sample solution was washed with water, and extracted with dichloromethane. The organic layer was dried with anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure, and the residue was recrystallized from diethyl ether and hexane, thereby obtaining the target substance as a white solid. The results are shown in Table 13.

[0287] [Table 13]

[0288] *: Separation yield with respect to the raw material amino acid

[0289] Example 10: Synthesis of carbonyl diimidazole based on a light flow system

[0290]

[0291] Under the conditions of Example 1 in which the coil heater temperature was set to 90°C, 2.4 mL (30 mmol) of chloroform was used, and the gas generated in the flow photoreactor was blown into a THF solution of imidazole (5.11 g, 75 mmol) in the reaction vessel 6 while stirring at 0°C.

[0292] After that, the precipitate of imidazole hydrochloride, which was a byproduct accompanying the progress of the reaction, was filtered off, and the filtrate was concentrated under reduced pressure, thereby obtaining the target compound (yield with respect to chloroform: 74%).

[0293] Example 11: Synthesis of polycarbonate based on a light flow system

[0294]

[0295] Under the conditions of Example 1 in which the coil heater temperature was set to 90°C, 3.14 g (26.3 mmol) of chloroform was used, and the gas generated in the flow photoreactor was blown into a solution obtained by mixing 4,4'-cyclo dodecylidene bisphenol (BisP-CDE) (3.52 g, 10 mmol), pyridine (4 mL, 50 mmol), and chloroform (40 mL) in the reaction vessel 6 while stirring at 30°C for 125 minutes.

[0296] Next, methanol (150 mL) was added to the reaction solution, and the generated precipitate was filtered off and vacuum-dried, thereby obtaining a white polycarbonate (yield with respect to BisP-CDE: >99%).

[0297] In addition, the obtained polycarbonate was analyzed by gel permeation chromatography (GPC) to determine its molecular weight. The results are shown in Table 14.

[0298] [Table 14]

[0299] Mw Mn Mw / Mn 269,000 184,000 1.45

[0300] Example 12: Continuous Flow Synthesis Based on Optical Flow Systems

[0301]

[0302] like Figure 2 As shown, except Figure 1 In addition to the flow photoreaction system, it is also connected to a syringe pump 8 for injecting reaction matrix for continuous reaction and a temperature-controlled coil reactor 9 (inner diameter 1.0 mm × length 2830 mm, capacity: 2.22 mL).

[0303] 1-Butanol was further injected into the phosgene gas generated in the flowing photoreaction system under the conditions shown in Table 12 via a syringe pump 8 at a flow rate of 0.052 mL / min, and the reaction was carried out in a coil reactor 9 heated to 0–100 °C. A two-necked flask (recovery container 10) cooled to 0 °C was installed at the outlet of the coil reactor to recover the product. Unreacted decomposition gases were further collected using a connected alcohol trap (trap container 7), and the exhaust gas was treated by an alkali trap to prevent leakage to the outside.

[0304] use 1 The yields of chloroformate and carbonate generated in recovery container 10 and trap container 7 were calculated by comparing the ¹H NMR spectra with an internal standard (1,1,2,2-tetrachloroethane, 50 mmol), and the total amount of phosgene generated was estimated from their sum. The results are shown in Table 15.

[0305] [Table 15]

[0306]

[0307] As shown in Table 15, when 1-butanol, an aliphatic alcohol, is injected from the reaction matrix using syringe pump 8, chloroformate and carbonate can be obtained in approximately 90% yield relative to chloroform injected from syringe pump 1. For the reaction in the coil reactor, the injected alcohol vaporizes due to the high temperature and can react with phosgene in the gas phase, resulting in high reaction efficiency. Consequently, no phosgene is detected at the outlet of the coil reactor, achieving "zero phosgene detection at the system outlet" at a laboratory level.

[0308] As the results above show, by developing a continuous flow reaction system, high-temperature gas-phase reactions can be carried out in the coil reactor section.

[0309] Note that 2-propanol (IPA) which does not normally react with phosgene at room temperature was also injected, and the corresponding chloroformate was obtained at a yield of 74%.

[0310] Example 13: Synthesis of chloroformate based on a light flow system

[0311]

[0312] The coil heater temperature of the light flow system was set to 90°C, and the oxidative photolysis gas synthesized from chloroform gas (7.4 mL / min) and oxygen gas (12.4 mL / min) was mixed with the alcohol injected from the syringe pump at the T-type mixer, introduced into the PTFE tube reactor, and subjected to a flow reaction at 30°C. The product was recovered into a connected two-necked flask cooled to 0°C. The unreacted gas was further introduced into a connected alkali trap, and treated so as not to leak outside. Figure 2

[0313] After the reaction, the reaction solution was analyzed by 1 HNMR, and the corresponding chloroformate was obtained at a yield shown in Table 16.

[0314] [Table 16]

[0315]

[0316] a: Yield relative to chloroform b: Yield relative to alcohol

[0317] Example 14: Synthesis of ethylene carbonate

[0318]

[0319] Ethylene glycol (1.62 mL, 29.0 mmol) was further injected from the syringe pump at a flow rate of 0.014 mL / min for 2 hours in the phosgene gas generated from chloroform (total 2.37 mL, 29.4 mmol) under the same conditions as in Example 12, and the reaction was performed by a coil reactor heated to 200°C. A two-necked flask (recovery container 10) cooled to 0°C was installed at the outlet of the coil reactor, and the product was recovered. The unreacted decomposition gas was further trapped with a connected alcohol trap (trap container 7), and the exhaust gas was treated by an alkali trap, but no phosgene was detected at the stage of the alcohol trap.

[0320] To the obtained reaction solution, 1,1,2,2-tetrachloroethane was added as an internal standard substance, and the amount of the unreacted chloroform was measured by 1 HNMR, and it was confirmed that ethylene carbonate as the target compound was generated at a yield of 54% relative to the used chloroform and ethylene glycol. ​

[0321] Example 15: Continuous flow synthesis based on an optical flow system using NMI

[0322]

[0323] If it is believed that... Figure 2 In a continuous flow reaction system, if an organic base is injected as a catalyst into the coil reactor section, the HCl generated during the reaction will react with the organic base to form a salt, potentially causing blockage of the reactor tubes. The inventors have considered selecting an organic base in this system that does not form a precipitate even when forming a salt with HCl, i.e., becomes a liquid salt, i.e., an ionic liquid.

[0324] (1) Synthesis of bis-1,1,1,3,3,3-hexafluoro-1-propyl carbonate

[0325] The temperature-controlled coil reactor was modified to have an inner diameter of 2.4 mm × a length of 2830 mm and a capacity of 12.8 mL. Otherwise, a mixture of hexafluoroisopropanol (HFIP) (14.8 mL, 188 mmol) and 1-methylimidazole (NMI) (7.9 mL, 75 mmol) was injected at a flow rate of 0.125 mL / min into the phosgene gas generated in the continuous flow photocatalytic reaction system under the same conditions as in Example 12, for a total of 3 hours. The reaction was carried out in a coil reactor 9 heated to 100°C. The products were collected using recovery containers 10-1 and 10-2 connected to the outlet of the coil reactor. The temperature of recovery container 10-1 was adjusted to 100°C to ensure that the salts of NMI and HCl were sufficiently maintained in a liquid state and to recover the target carbonate. However, the target carbonate might also flow out of recovery container 10-1; therefore, the temperature of recovery container 10-2 was adjusted to 0°C. The gas discharged from the recovery container 10-2 is further captured by the connected alcohol trap (trap container 7), and the exhaust gas is treated by the alkali trap, but phosgene is not detected in the alcohol trap stage.

[0326] The recoveries from recovery containers 10-1 and 10-2 were combined. The lower layer of the recovered product, which had been separated into two layers, was washed with 1.4 mol / L hydrochloric acid (20 mL), dried with anhydrous sodium sulfate, and then filtered. The filtrate was concentrated to obtain the target compound as a colorless and transparent liquid (yield relative to the HFIP used: 61%).

[0327] (2) Synthesis of bis-2,2,3,3-tetrafluoropropyl carbonate

[0328] The temperature-controlled coil reactor was changed to an inner diameter of 2.4 mm x length of 2830 mm, a capacity of 12.8 mL, and otherwise, a mixed solution of 2,2,3,3-tetrafluoro-l-propanol (8.86 mL, 100 mmol) and NMI (12 mL, 150 mmol) was injected from the reaction substrate at a flow rate of 0.12 mL / min for a total of 3 hours using a syringe pump 8 into the phosgene gas generated in the continuous flow photoreaction system under the same conditions as in Example 12, and the reaction was performed by the coil reactor 9 heated to 100°C. The product was collected with a recovery container 10-1 heated to 100°C and a recovery container 10-2 cooled to 0°C connected to the outlet of the coil reactor. The unreacted decomposition gas was further captured with an alcohol trap (trap container 7) connected, and the exhaust gas was treated by an alkali trap, but no phosgene was detected at the stage of the alcohol trap.

[0329] To the obtained product sample solution, 1,1,2,2-tetrachloroethane was added as an internal standard substance, and the analysis was performed by GC-MS. 1 The HNMR analysis confirmed that the target compound was produced at a yield of 70% with respect to the used alcohol.

[0330] The raw material was removed from the obtained sample solution by distillation, and after washing with 1.4 mol / L HC1 (20 mL) and drying with anhydrous sodium sulfate, filtration was performed, and the filtrate was concentrated to obtain the target substance as a colorless transparent liquid (yield with respect to the used 2,2,3,3-tetrafluoro-l-propanol: 44%).

[0331] (3) Synthesis of Bis-2,2,2-trifluoroethyl carbonate

[0332] The temperature-controlled coil reactor was changed to an inner diameter of 2.4 mm x length of 2830 mm, a capacity of 12.8 mL, and otherwise, a mixed solution of 2,2,2-trifluoroethanol (10 g, 100 mmol) and NMI (12 mL, 150 mmol) was injected from the reaction substrate at a flow rate of 0.11 mL / min for a total of 3 hours using a syringe pump 8 into the phosgene gas generated in the continuous flow photoreaction system under the same conditions as in Example 12, and the reaction was performed by the coil reactor 9 heated to 110°C. The product was collected with a recovery container 10-1 heated to 100°C and a recovery container 10-2 cooled to 0°C connected to the outlet of the coil reactor. The unreacted decomposition gas was further captured with an alcohol trap (trap container 7) connected, and the exhaust gas was treated by an alkali trap, but no phosgene was detected at the stage of the alcohol trap.

[0333] To the obtained reaction solution, 1,1,2,2-tetrachloroethane was added as an internal standard substance, and the analysis was performed by GC-MS. 1 The HNMR analysis confirmed that the target compound was produced at a yield of 60% with respect to the used alcohol.

[0334] The starting material compound was removed from the obtained product sample solution by distillation. The obtained residue was washed with 3M hydrochloric acid (20 mL), dried with anhydrous sodium sulfate, filtered, and the filtrate was concentrated to obtain the target substance as a colorless transparent liquid (yield: 6.43 g, yield relative to the used 2,2,2-trifluoroethanol: 44%).

[0335] (4) Synthesis of diphenyl carbonate

[0336] The temperature-controlled coil reactor was changed to an inner diameter of 2.4 mm x length of 2830 mm, capacity: 12.8 mL, and otherwise, a mixed solution of phenol (18.8 mL, 200 mmol) and NMI (24 mL, 300 mmol) was injected from the reaction substrate into the phosgene gas generated in the continuous flow light reaction system under the same conditions as in Example 12 with a syringe pump 8 at a flow rate of 0.23 mL / min for a total of 3 hours, and the reaction was performed by the coil reactor 9 heated to 115°C. The product was collected with a recovery container 10 connected to the outlet of the coil reactor, which was heated to 100°C. The unreacted decomposition gas was further trapped with an alcohol trap (trap container 7) connected, and the exhaust gas was treated with an alkali trap, but no phosgene was detected at the stage of the alcohol trap.

[0337] To the obtained reaction solution, 1,1,2,2-tetrachloroethane was added as an internal standard substance, and the solution was analyzed by GC-MS. 1 HNMR, and as a result, it was confirmed that the target compound was produced at a yield of 72% relative to the used phenol.

[0338] The obtained sample solution was subjected to liquid-liquid separation with dichloromethane and HCl (1.4 mol / L), the lower layer was extracted, dried with anhydrous sodium sulfate, filtered, and the solvent was removed from the filtrate by distillation under reduced pressure. The residue was vacuum-dried under heating conditions using a glass tube oven, and thus the target substance was obtained as a white solid (separation yield relative to the used chloroform: 56%).

[0339] [Table 17]

[0340]

[0341] a: Yield relative to the injected CHCl3

[0342] As shown in the above results, it was found that even if the base is delivered to the coil reactor, if the base is a base such as 1-methylimidazole that forms an ionic liquid with the by-produced hydrogen chloride, the coil does not clog and the continuous reaction can be continued favorably.

[0343] Example 16: Continuous flow synthesis based on a flow system using pyridine

[0344] As shown in the above results, it was found that even if the base is delivered to the coil reactor, if the base is a base such as 1-methylimidazole that forms an ionic liquid with the by-produced hydrogen chloride, the coil does not clog and the continuous reaction can be continued favorably.

[0345] To the phosgene gas generated in the continuous flow light reaction system under the same conditions as in Example 15, a mixture of phenol (9.41 g, 100 mmol) and pyridine (12 mL, 150 mmol) was injected from the reaction substrate with a syringe pump 8 at a flow rate of 0.11 mL / min for a total of 3 hours, and the reaction was performed by a coil reactor 9 heated to 160°C. The product was collected with a recovery vessel 10-1 and a recovery vessel 10-2 connected to the outlet of the coil reactor. The temperature of the recovery vessel 10-1 was adjusted to 155°C, so that the salt of pyridine and HCl could be maintained in a liquid state sufficiently, and the target carbonate could be recovered. However, it was also possible that the target carbonate flowed out from the recovery vessel 10-1, and therefore, the temperature of the recovery vessel 10-2 was adjusted to -5°C. The gas discharged from the recovery vessel 10-2 was further captured with an alcohol trap (trap container 7) connected thereto, and the exhaust gas was treated by an alkali trap, but no phosgene was detected at the stage of the alcohol trap.

[0346] As a result, no precipitation of pyridine hydrochloride was confirmed in the coil reactor, and it was considered that the generated pyridine hydrochloride was dissolved or melted and flowed out.

[0347] To the obtained reaction solution, 1,1,2,2-tetrachloroethane was added as an internal standard substance, and the amount of the generated phosgene was measured by gas chromatography. 1 HNMR analysis was performed, and as a result, diphenyl carbonate as the target compound was confirmed to be generated (yield with respect to the used phenol: 65%, yield with respect to the used chloroform: 72%).

[0348] Example 17: Continuous flow synthesis based on a flow system using a solvent

[0349]

[0350] It was considered that if an organic base as a catalyst was injected to the coil reactor part of the continuous flow reaction system, Figure 2 HCl generated by the progress of the reaction reacts with the organic base to form a salt, and it is possible to cause clogging of the reactor tube. The present inventors and others considered that a solvent that can dissolve even if an HCl salt is formed should be used in this system.

[0351] To the phosgene gas generated in the continuous flow photoreaction system under the same conditions as in Example 15, a mixture of phenol (1.88 g, 20 mmol) and pyridine (6.4 mL, 80 mmol) dissolved in chloroform (16 mL) was injected from the reaction substrate at a flow rate of 0.2 mL / min for a total of 2 hours using a syringe pump 8, and the reaction was carried out at room temperature by the coil reactor 9. The product was collected in a two-necked flask (recovery container 10) connected to the outlet of the coil reactor. The exhaust gas was treated by an alkali trap (trap container 7).

[0352] As a result, no precipitation of pyridine hydrochloride was confirmed in the coil reactor, and it was considered that the generated pyridine hydrochloride was dissolved in chloroform and flowed out.

[0353] To the obtained reaction solution, 1,1,2,2-tetrachloroethane was added as an internal standard substance, and the analysis was performed by GC-MS. 1 The analysis by HNMR confirmed that diphenyl carbonate as the target compound was generated (yield: 90% with respect to the used phenol).

[0354] After that, the obtained sample solution was washed with 1M hydrochloric acid and water, and extracted with dichloromethane. The organic layer was dried with anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The residue was subjected to distillation under reduced pressure in a glass tube oven, and diphenyl carbonate was obtained as a white solid from the components at 100 to 155°C (yield: 1.79 g, yield: 84%).

[0355] Example 18: Continuous flow synthesis based on a flow system using a solvent

[0356]

[0357] To the phosgene gas generated in the continuous flow photoreaction system under the same conditions as in Example 15, a mixture of phenol (1.88 g, 20 mmol) and pyridine (6.4 mL, 80 mmol) dissolved in chloroform (16 mL) was injected from the reaction substrate at a flow rate of 0.2 mL / min for a total of 2 hours using a syringe pump 8, and the reaction was carried out at room temperature by the coil reactor 9. The product was collected in a two-necked flask (recovery container 10) connected to the outlet of the coil reactor. The exhaust gas was treated by an alkali trap (trap container 7). To the obtained reaction solution, 1,1,2,2-tetrachloroethane was added as an internal standard substance, and the analysis was performed by GC-MS. 1 The analysis by HNMR confirmed that diphenyl carbonate as the target compound was generated (yield: 90% with respect to the used phenol).

[0358] After that, the obtained sample solution was washed with 1M hydrochloric acid and water, and extracted with dichloromethane. The organic layer was dried with anhydrous sodium sulfate, and the target substance was obtained as a colorless liquid from a fraction of 60 to 70°C by distillation under reduced pressure using a diaphragm pump (yield: 2.09 g, yield: 72%).

[0359] Example 19: Continuous flow synthesis based on a solvent- using flow system

[0360]

[0361] To the phosgene gas generated in the continuous flow photo- reaction system under the same conditions as in Example 15, a mixture solution in which HFIP (2.31 mL, 20 mmol) and pyridine (6.4 mL, 80 mmol) were dissolved in chloroform (16 mL) was injected from the reaction matrix with a syringe pump 8 at a flow rate of 0.2 mL / min for a total of 2 hours, and the reaction was carried out at room temperature by a coil reactor 9. The product was collected with a two-necked flask (recovery container 10) connected to the outlet of the coil reactor. The exhaust gas was treated by an alkali trap (trap container 7). To the obtained reaction solution, 1,1,2,2-tetrachloroethane was added as an internal standard substance, and the amount of the target substance was analyzed by GC-MS. 1 HNMR, and as a result, it was confirmed that bis(l,l,l,3,3,3-hexafluoropropan-2-yl) carbonate (yield with respect to the used alcohol: 61%) was generated as the target compound.

[0362] After that, the obtained sample solution was washed with 1M hydrochloric acid and water, and extracted with dichloromethane. The organic layer was dried with anhydrous sodium sulfate, and the target substance was obtained as a colorless liquid from a fraction of 65 to 75°C by distillation (yield: 1.45 g, yield: 40%).

[0363] Example 20: Synthesis of carbonate using a gas feeding method

[0364]

[0365] As Figure 3 shown schematically, a photo-reaction system was constructed in which a quartz glass jacket of 30 mm in diameter was loaded into a cylindrical reaction container of 42 mm in diameter and 100 mL in capacity, and further a low-pressure mercury lamp ("UVL20PH-6" manufactured by SEN Light Co., 20 W, 254 nm, 185 nm) was loaded into the quartz glass jacket. Note that the irradiation light from this low-pressure mercury lamp contains UV-C of 185 nm and 254 nm, and the irradiance of the light of 185 nm at a position of 5 mm from the central part of the lamp, which is the shortest position from the reaction solution, is 2.00 to 2.81 mW / cm , and the irradiance of the light of 254 nm is 5.60 to 8.09 mW / cm 2 .2 In the cylindrical photoreactor 12, a cooling tube 15 for selectively transporting the generated low-boiling gas component was installed, which was cooled to 10°C, and was connected to a two-necked flask (reaction vessel 16) having a cooling tube 15 cooled to -10°C. The cooling tube 15 was further connected to a two-necked flask filled with an alcohol and a trap vessel filled with an aqueous alkali solution.

[0366] After adjusting the bath temperature of the photoreactor 12 to the temperature of Table 18, liquid chloroform was fed from a PTFE tube (inner diameter: 1 mm) to the photoreactor at the flow rate of Table 18 using a syringe pump, and vaporization was promoted while stirring. Subsequently, oxygen was fed at a rate of 0.1 mL / min to the gas phase in the photoreactor from the other side, and a mixed gas of chloroform and oxygen was prepared in the photoreactor 12, and light irradiation was performed using a low-pressure mercury lamp. The gas generated by oxidative photolysis of the mixed gas was blown into 1-hexanol (30 mL, 239 mmol) filled in the connected two-necked flask (reaction vessel 16) at room temperature while stirring. The unreacted gas was further trapped by the connected 1-hexanol trap (trap vessel), and the exhaust gas from the trap vessel was introduced into the alkali trap, and was treated so that no toxic gas leaked to the outside.

[0367] By 1 The yield of the chloroformate and carbonate generated in the reaction vessel 16 and the trap vessel was estimated from HNMR spectra, and the amount of phosgene generated was quantified from the total, and the results of Table 18 were obtained.

[0368] [Table 18]

[0369]

[0370] a: Yield relative to the injected halocarbon

[0371] As shown in the results of Table 18, when the gas-phase photoreaction of chloroform vapor and oxygen was performed by continuously injecting chloroform from the outside to the photoreactor heated to a temperature above the boiling point of chloroform using a syringe pump, it was considered that chloroform was rapidly decomposed to obtain phosgene.

[0372] The phosgene gas generated at a high conversion rate of 97% or more did not contain a significant amount of by-products, and reacted with an alcohol to obtain a chloroformate or carbonate with high purity. Note that a small amount of by-products were carbon monoxide and carbon dioxide.

[0373] Example 21: Synthesis of thionyl chloride based on gas-phase photoreaction

[0374]

[0375] While stirring, blow the solution into the connected two-necked flask containing N,N-dimethylformamide (DMF) (5.5 mL, 70 mmol) at room temperature. Figure 1 The schematically illustrated photoreaction system, similar to that in Example 1, produced an oxidative photodecomposition gas from a total of 6.83 g (57.2 mmol) of chloroform for 4 hours. Unreacted gas was further processed by connected alcohol and alkali traps to prevent leakage to the outside.

[0376] After the reaction, use 1 ¹H NMR analysis of the reaction solution confirmed that Wilsmer's reagent was obtained in a yield of over 51% relative to the chloroform used. It should be noted that Wilsmer's reagent reacts with moisture in the air and decomposes into the starting amide; therefore, the actual yield is considered to be higher than the above value. The results are summarized in Table 19.

[0377] [Table 19]

[0378]

[0379] As shown in the results above, chloroform was heated to 90°C using a coil heater to vaporize it, and then mixed with oxygen to carry out a gas-phase photoreaction. As a result, Wilsmer reagent was obtained from DMF in a yield of over 51% through phosgene generated from chloroform in the gas phase.

[0380] Example 22: Synthesis of Wilsmayer's reagent and acyl chloride based on gas-phase photoreaction

[0381]

[0382] While stirring, an oxidation photodecomposition gas, synthesized from chloroform gas (7.4 mL / min) and oxygen (12.4 mL / min), was blown into a connected two-necked flask at 30°C into a chloroform solution (100 mL) prepared by dissolving benzoic acid or propionic acid and DMF. This gas was produced using the same flowing photoreaction system as in Example 21. The gas remained unreacted and was further treated by introducing connected alcohol and alkali traps to prevent leakage.

[0383] After the reaction, use 1 The HNMR analysis of the reaction solution yielded the results shown in Table 20, indicating the presence of a considerable amount of carboxyl chloride.

[0384] [Table 20]

[0385]

[0386] *: Yield relative to the carboxylic acid used

[0387] As shown in Table 20, the higher the amount of chloroform and the proportion of DMF relative to carboxylic acid, the higher the conversion rate from carboxylic acid to carboxyl chloride.

[0388] Example 23: Synthesis of Wilsmer's reagent and formate ester based on gas-phase photoreaction

[0389]

[0390] While stirring, the oxidative photodecomposition gas obtained from 5.82 g (48.8 mmol) of chloroform was blown into the DMF (8.0 mL, 100 mmol) in a connected two-necked flask at room temperature. This gas was prepared by mixing chloroform gas (7.4 mL / min) and oxygen (12.4 mL / min) using the same flowing photoreaction system as in Example 21. The reaction was carried out for 3 hours. Unreacted gas was further introduced into connected alcohol and alkali traps to prevent leakage to the outside.

[0391] 1-Butanol (4.57 mL, 50 mmol) was added to the reaction solution, and the mixture was stirred at room temperature for 1.5 hours. Then, saturated sodium carbonate aqueous solution (50 mL) was added for hydrolysis. Dichloromethane was added for separation, and the organic phase was dried with anhydrous sodium sulfate and then filtered.

[0392] use 1 ¹H NMR analysis of the resulting solution confirmed the formation of a formate ester in 60% yield relative to the chloroform used. The results are summarized in Table 21.

[0393] [Table 21]

[0394]

[0395] Example 24: Synthesis and formylation of Wilsmer's reagent based on gas-phase photoreaction

[0396]

[0397] While stirring, the oxidative photodecomposition gas obtained from 5.37 g (45.0 mmol) of chloroform was blown into a connected two-necked flask at room temperature using a flow photoreaction system identical to that used in Example 21, consisting of 3.9 mL (50 mmol) of DMF mixed with chloroform gas (7.4 mL / min) and oxygen (12.4 mL / min) at a flow rate of 3000 mL / min. Unreacted gas was further treated by introducing connected alcohol and alkali traps to prevent leakage.

[0398] An aromatic compound, 1-methylpyrrole or 2-methylfuran (50 mmol), was added to the reaction solution, and the mixture was stirred at 70 °C for 2 hours. Hydrolysis was then initiated by adding 100 mL of saturated sodium carbonate aqueous solution. Water and dichloromethane were added for separation, and the organic phase was dried with anhydrous sodium sulfate and filtered. The solvent was removed from the filtrate by distillation using an evaporator. The resulting dark green oil was purified by column chromatography to obtain the target analyte in 98% or 74% yield. The results are summarized in Table 22.

[0399] [Table 22]

[0400]

[0401] *: Separation yield

[0402] Example 25: Synthesis of esters or carboxylic anhydrides

[0403]

[0404] Will Figure 2 The schematically illustrated photodynamic system has its coil heater set to 90°C. An oxidizing photodecomposition gas, synthesized from chloroform (0.02 mL / min) and oxygen (10 mL / min), is mixed with a solution containing carboxylic acid and 5 molar amounts of pyridine or 1 molar amount of DMF, injected from a syringe pump, in a T-mixer. This mixture is then fed into a PTFE tube reactor (inner diameter 2.4 mm, length: 2830 mm, volume: 12.8 mL) for a flow reaction. The product is blown into a stirred chloroform solution of alcohol or carboxylic acid in a two-necked flask. Unreacted gas is further introduced into a connected alkali trap to prevent leakage to the outside.

[0405] After the reaction, use 1 The reaction solution was analyzed by HNMR, and the results showed that esters or carboxylic anhydrides were obtained in the yields shown in Table 23.

[0406] In addition, the reaction solution was washed with water and extracted with dichloromethane. The extract was dried with anhydrous sodium sulfate, and the solvent was removed by vacuum distillation. The target analyte was then purified by vacuum distillation or silica gel column chromatography. It should be noted that in the table, "BA" represents benzoic acid, "4-FBA" represents 4-fluorobenzoic acid, "PA" represents propionic acid, and "Py" represents pyridine.

[0407] [Table 23]

[0408]

[0409] a: Yield determined by NMR b: Separation yield

[0410] As the results above suggest, it is possible that in the coil reactor, the decomposition products of chloroform react directly with carboxylic acids, or that the decomposition products of chloroform and DMF generate Wilsmer reagent, which reacts with carboxylic acids to generate carboxyl chloride, which further reacts with alcohols or carboxylic acids to generate esters or carboxylic anhydrides.

[0411] Example 26: Synthesis of Amides

[0412]

[0413] Will Figure 2 The schematically illustrated photodynamic system has its coil heater set to 90°C. An oxidative photodecomposition gas, synthesized from chloroform (2.4 mL, 30 mmol, 0.02 mL / min) and oxygen (10 mL / min), is mixed with a solution containing carboxylic acid and either 5 molar amounts of pyridine or 1 molar amount of DMF, injected from a syringe pump, in a T-mixer. This mixture is then fed into a PTFE tube reactor (inner diameter 2.4 mm, length: 2830 mm, volume: 12.8 mL) for a flow reaction. The product is blown into a stirred amine solution in a two-necked flask. Unreacted gas is further introduced into a connected alkali trap to prevent leakage to the outside.

[0414] After the reaction, use 1 The reaction solution was analyzed by HNMR, and the amide was obtained in the yields shown in Table 24.

[0415] The reaction solution was washed with water and extracted with dichloromethane. The extract was dried with anhydrous sodium sulfate, and the solvent was removed by vacuum distillation. Further purification was performed by recrystallization as needed to obtain the target compound. It should be noted that in the table, "cHex-NH2" represents cyclohexylamine.

[0416] [Table 24]

[0417]

[0418] a: Yield determined by NMR b: Separation yield

[0419] As the results above suggest, it is possible that in the coil reactor, the decomposition products of chloroform react directly with carboxylic acid, or that the decomposition products of chloroform and DMF generate Wilsmer reagent, which reacts with carboxylic acid to generate carboxyl chloride, which further reacts with amine to generate amide.

[0420] Example 27: Formylation of aromatic compounds based on Wilsmayer's reagent

[0421]

[0422] (1) Formylation of 1-methylpyrrole

[0423] As shown in Figure 4 addition to the flow photoreaction system of Figure 1 the reaction substrate injection syringe pump 8-1 was connected to the tube reactor 17 (inner diameter 2.4 mm x length 182 mm, capacity: 0.8 mL) for performing a continuous reaction, and further the reaction substrate injection syringe pump 8-2 was connected to the temperature-controlled coil reactor 9 (inner diameter 2.4 mm x length 994 mm, capacity: 4.5 mL) for performing a subsequent continuous reaction.

[0424] To the phosgene gas generated in the continuous flow photoreaction system under the same conditions as in Example 1, a mixed solution of DMF (2.32 mL, 30 mmol) and chloroform (7.8 mL) was injected from the reaction substrate injection syringe pump 8-1 at a flow rate of 3.26 mL / h, and reacted at room temperature through the tube reactor 17. Further, a mixed solution of 1-methylpyrrole (2.66 mL, 30 mmol) and dichloromethane (7.0 mL) was injected from the other reaction substrate injection syringe pump 8-2 at a flow rate of 3.2 mL / h for a total of 3 hours, and reacted at room temperature through the coil reactor 9.

[0425] The product was injected into a saturated aqueous sodium carbonate solution (50 mL) in a two-necked flask (recovery container 10) connected to the outlet of the coil reactor, and stirred at a bath temperature of 0°C. Dichloromethane and water were added to the reaction solution to separate the layers, and the organic phase was dried over anhydrous sodium sulfate and then filtered. To the resulting dried organic phase, acetone (0.74 mL, 10 mmol) was added as an internal standard substance, and the mixture was analyzed by1H NMR, and as a result, it was confirmed that 1-methyl-lH-pyrrolecarboxaldehyde (yield: 53% relative to the used 2-methylpyrrole and DMF) was produced as the target compound. 1 HNMR, and as a result, it was confirmed that 1-methyl-lH-pyrrolecarboxaldehyde (yield: 53% relative to the used 2-methylpyrrole and DMF) was produced as the target compound.

[0426] (2) Formylation of 2-methylfuran

[0427] To the phosgene gas generated in the continuous flow photoreaction system under the same conditions as in Example 27 (1), a mixed solution of DMF (2.32 mL, 30 mmol) and chloroform (7.8 mL) was injected from the reaction substrate injection syringe pump 8-1 at a flow rate of 3.26 mL / h, and reacted at room temperature through the tube reactor 17. Further, a mixed solution of 2-methylfuran (2.32 mL, 30 mmol) and dichloromethane (7.0 mL) was injected from the other reaction substrate injection syringe pump 8-2 at a flow rate of 3.2 mL / h for a total of 3 hours, and reacted at room temperature through the coil reactor 9.

[0428] The product was injected into a saturated sodium carbonate solution (50 mL) in a two-necked flask (recovery container 10) connected to the outlet of the coil reactor, and stirred at a bath temperature of 0°C. Dichloromethane and water were added to the reaction solution for separation. The organic phase was dried with anhydrous sodium sulfate and then filtered. 1 HNMR analysis of the obtained dry organic phase confirmed the formation of 5-methyl-2-furfural as the target compound (conversion relative to the 2-methylfuran and DMF used: 95%).

[0429] The solvent was removed by distillation from the aforementioned dried organic phase, and the resulting residue was fed to silica gel column chromatography (elution: dichloromethane) to separate the target compound (yield relative to the 2-methylfuran and DMF used: 80%).

[0430] Example 28: Study of a gas-phase photoreactor

[0431]

[0432] use Figure 5 The schematically illustrated photoreaction system performs a gas-phase photoreaction. Specifically, it is a reaction system constructed by placing a quartz glass jacket inside a cylindrical reaction vessel, and then placing a low-pressure mercury lamp (“SUL-20P”, manufactured by SEN Light, 20W, emitting part length: 130mm, wavelength: 185–600nm, peak wavelength: 184.9nm and 253.7nm) inside the quartz glass jacket. The dimensions of the cylindrical reaction vessel (outer tube) and the quartz glass jacket (inner tube) are shown in Table 25.

[0433] Liquid chloroform and dry air at 20°C are introduced into the coil heater 3, which is heated to 90°C, at the flow rates shown in Table 25. The mixture is heated and supplied to the photoreactor 12 for 2 hours. The temperature of the heater 13 used for heating the photoreactor is set to 100°C.

[0434] The gas that has passed through reaction vessel 12 is blown into 1-butanol in reaction vessel 16-1, and then the gas that has passed through reaction vessel 16-1 is blown into 1-butanol in reaction vessel 16-2. 1-Butanol is added to reaction vessels 16-1 and 16-2 at a molar ratio relative to the amount of chloroform used. The gas that has passed through reaction vessel 16-2 is further introduced into an alkali trap for treatment to prevent the toxic gas from leaking to the outside.

[0435] After the reaction, 1,2-dichloroethane, used as an internal standard, was added to the reaction solution in reaction vessels 16-1 and 16-2. 1HNMR analysis was performed to determine the amounts and yields of the generated chloroformate and carboxylic anhydride, and the amount of phosgene generated was calculated from the total of these. The results are summarized in Table 25. Note that the phosgene yield in Table 25 is the yield relative to the chloroform used.

[0436] [Table 25]

[0437]

[0438] As shown by the results in Table 25, when the volume of the photoreaction vessel is small, the residence time of the mixed gas becomes short, and therefore, in order to maintain a high phosgene yield and reduce unreacted chloroform, it is necessary to reduce the amount of chloroform injected.

[0439] Therefore, when the volume of the photoreaction vessel is increased, the residence time of the mixed gas becomes long, and therefore, the amount that can be injected is increased, and the phosgene yield can be increased. However, there is a possibility that regions that are not sufficiently irradiated with high-energy light are generated, and therefore, the amount of unreacted chloroform is slightly increased.

[0440] Example 29: Study of a gas-phase photoreaction vessel

[0441]

[0442] Using Figure 5 A photoreaction system schematically shown was used to perform a gas-phase photoreaction. Specifically, a cylindrical reaction vessel 10 having a length of 550 mm was installed in a quartz glass jacket 11 having a length of 550 mm, and further, a low-pressure mercury lamp ("SUV-400" manufactured by SEN Light Co., 40 W, length of light-emitting portion: 380 mm, wavelength: 185 to 600 nm, peak wavelengths: 184.9 nm and 253.7 nm) was installed in the quartz glass jacket 11. The effective volume in the photoreaction vessel was 976 mL. A syringe pump 1 and a mass flow controller 2 ("MODEL 8500 MC" manufactured by KOFLOC Co.) were used to supply liquid chloroform and oxygen at 20°C to a coil heater 3 heated to 150°C at the flow rates shown in Table 26, to perform mixed heating, and to supply the photoreaction vessel 12 for 2 hours. The temperature of the heater 13 for heating the reaction vessel was set to 100°C.

[0443] A syringe pump 1 and a mass flow controller 2 ("MODEL 8500 MC" manufactured by KOFLOC Co.) were used to supply liquid chloroform and oxygen at 20°C to a coil heater 3 heated to 150°C at the flow rates shown in Table 26, to perform mixed heating, and to supply the photoreaction vessel 12 for 2 hours. The temperature of the heater 13 for heating the reaction vessel was set to 100°C.

[0444] ​The gas that passed through the photo-reaction vessel 12 was blown into 1-butanol in the reaction vessel 16-1, and the gas that passed through the reaction vessel 16-1 was further blown into 1-butanol in the reaction vessel 16-2. 1-Butanol was added to the reaction vessel 16-1 and the reaction vessel 16-2 at 1.5 to 2.0 times the molar amount relative to the chloroform used. The gas that passed through the reaction vessel 16-2 was further introduced into the alkali trap, and was treated so that no toxic gas leaked to the outside.

[0445] After the reaction, 1,2-dichloroethane was added to the reaction liquid in the reaction vessel 16-1 and the reaction vessel 16-2 as an internal standard, and the reaction liquid was analyzed by1H NMR, and the yield and the yield of the generated chloroformic acid ester and the carboxylic anhydride were calculated, and the amount of the generated phosgene was calculated from the total thereof. The results are summarized in Table 26. Note that the phosgene yield in Table 26 is the yield relative to the chloroform used. 1 HNMR, and the yield and the yield of the generated chloroformic acid ester and the carboxylic anhydride were calculated, and the amount of the generated phosgene was calculated from the total thereof. The results are summarized in Table 26. Note that the phosgene yield in Table 26 is the yield relative to the chloroform used.

[0446] [Table 26]

[0447]

[0448] As shown in the results shown in Table 26, by using a long light source to irradiate a chloroform-oxygen mixed gas with strong high-energy light for a long time, it was possible to further improve the decomposition efficiency of chloroform.

[0449] Example 30: Investigation of the oxygen source

[0450] The reaction conditions were changed as shown in Table 27, and otherwise, the phosgene production efficiency was tested in the same manner as in Example 29. Note that air was used as the oxygen source, and for inlet 1, inlet 4, and inlet 5, the air was dried using a desiccant ("Drying Silica Gel, Medium Granular (Blue)" manufactured by FUJIFILM Wako Pure Chemical Corporation), for inlet 2, the air was not dried when the humidity was 60 to 80% in rainy weather and was used directly, and for inlet 3, the air was used from a dry air tank. The results are shown in Table 27.

[0451] [Table 27]

[0452]

[0453] As shown in the results shown in Table 27, even in the case where air that was not dried was used (inlet 2), the decomposition efficiency of chloroform and the phosgene yield did not decrease, and it was found that a slight amount of moisture was not a problem.

[0454] In addition, in the case where the flow rate of oxygen was less than the flow rate of chloroform (inlet 1 and inlet 4), the unreacted chloroform was also small, and the phosgene yield relative to chloroform was also high.

[0455] It should be noted that when the oxygen flow rate is lower than the chloroform flow rate at inlet 5, but the proportion of unreacted chloroform is relatively high, this is considered to be due to the higher flow rates of chloroform and air. However, the phosgene generation at inlet 5 is very high, and the phosgene yield is also relatively high; therefore, it can be said that inlet 5 is highly efficient.

[0456] Example 31: Study of a gas-phase photoreactor

[0457] like Figure 6 As illustrated, a photoreaction system is used, consisting of two gas-phase photoreactors connected in series, to perform a gas-phase photoreaction. Specifically, it is constructed on... or The cylindrical reaction vessel is filled with A quartz glass jacket is used to house a photoreaction container 12-1 containing a low-pressure mercury lamp ("SUL-20P" manufactured by SEN Light, 20W, emitting part length: 130mm, wavelength: 185-600nm, peak wavelength: 184.9nm and 253.7nm). The cylindrical reaction vessel is filled with The reaction system is formed by connecting a quartz glass jacket and a photoreaction container 12-2 containing the same low-pressure mercury lamp inside the quartz glass jacket.

[0458] Liquid chloroform and dry air at 20°C are fed into the coil heater 3, which is heated to 90°C, at the flow rates shown in Table 28, and mixed for heating. This process is continued for 2 hours in the photoreaction vessel 12-1. The temperature of the heater 13 used to heat the photoreaction vessel 12 is set to 100°C.

[0459] The gas that has passed through reaction vessel 12-2 is blown into 1-butanol in reaction vessel 16-1, and then the gas that has passed through reaction vessel 16-1 is blown into 1-butanol in reaction vessel 16-2. 1-Butanol is added to reaction vessels 16-1 and 16-2 at a molar ratio relative to the amount of chloroform used. The gas that has passed through reaction vessel 16-2 is further introduced into an alkali trap for treatment to prevent the toxic gas from leaking to the outside.

[0460] After the reaction, 1,2-dichloroethane, used as an internal standard, was added to the reaction solution in reaction vessels 16-1 and 16-2. 1 ¹H NMR analysis was performed to determine the yields and quantities of the generated chloroformate and carboxylic anhydride, and the amount of phosgene produced was calculated from their total. The results are summarized in Table 28. It should be noted that the phosgene yields in Table 28 are relative to the yield of chloroform used.

[0461] [Table 28]

[0462]

[0463] For example, when comparing inlet 1 of Example 30 with inlet 2 of Example 31, it can be said that by connecting two photo reactors, the conversion of chloroform, and the production and yield of phosgene are improved. In addition, it is considered that when the mixed gas flows in the fine tube connecting the first photo reactor 12-1 and the second photo reactor 12-2, the unreacted gas chloroform and oxygen are more uniformly mixed, and the oxidative photodecomposition of chloroform is effectively performed in the second photo reactor 12-2.

[0464] Example 32: Study of a gas phase photo reactor

[0465] Using Figure 6 A photo reactor system schematically shown was used to perform a gas phase photo reaction. Specifically, a cylindrical reactor vessel 12-1 was constructed in which a quartz glass jacket 12-2 was housed, and further in the quartz glass jacket, a low-pressure mercury lamp ("SUL-20P" manufactured by SEN Light, 20 W, light-emitting portion length: 130 mm, wavelength: 185 to 600 nm, peak wavelength: 184.9 nm and 253.7 nm) was housed. A photo reactor system schematically shown was used to perform a gas phase photo reaction. Specifically, a cylindrical reactor vessel 12-1 was constructed in which a quartz glass jacket 12-2 was housed, and further in the quartz glass jacket, a low-pressure mercury lamp ("SUL-20P" manufactured by SEN Light, 20 W, light-emitting portion length: 130 mm, wavelength: 185 to 600 nm, peak wavelength: 184.9 nm and 253.7 nm) was housed. A photo reactor system schematically shown was used to perform a gas phase photo reaction. Specifically, a cylindrical reactor vessel 12-1 was constructed in which a quartz glass jacket 12-2 was housed, and further in the quartz glass jacket, a low-pressure mercury lamp ("SUL-20P" manufactured by SEN Light, 20 W, light-emitting portion length: 130 mm, wavelength: 185 to 600 nm, peak wavelength: 184.9 nm and 253.7 nm) was housed.

[0466] Liquid chloroform and dry air at 20°C were fed to the coil heater 3 heated to 150°C at the flow rates shown in Table 29, and the mixture was heated to supply to the photo reactor 12-1 for 2 hours. The temperature of the heater for heating the photo reactor 12 was set to 100°C.

[0467] The gas that had passed through the photo reactor 12 was blown into 1-butanol in the reactor vessel 16-1, and further the gas that had passed through the reactor vessel 16-1 was blown into 1-butanol in the reactor vessel 16-2. In the reactor vessel 16-1 and the reactor vessel 16-2, 1.5 to 2.0 times the mole of 1-butanol relative to the chloroform used was added. The gas that had passed through the reactor vessel 16-2 was further introduced into a caustic trap, and was treated so that noxious gas did not leak to the outside.

[0468] After the reaction, 1,2-dichloroethane was added as an internal standard to the reaction liquid in the reactor vessel 16-1 and the reactor vessel 16-2, and the amount of chloroform was measured by gas chromatography. 1 ​​¹H NMR analysis was performed to determine the yields and quantities of the generated chloroformate and carboxylic anhydride, and the amount of phosgene produced was calculated from their total. The results are summarized in Table 29. It should be noted that the phosgene yields in Table 29 are relative to the yield of chloroform used.

[0469] [Table 29]

[0470]

[0471] As shown in Table 29, the results demonstrate that photocatalytic reaction of a gas containing air with an oxygen molar ratio of approximately 0.55 relative to chloroform significantly improves the conversion rate of chloroform, as well as the yield and production of phosgene. Furthermore, excessive absorption of high-energy light, particularly ultraviolet light, by the air may inhibit further decomposition of the generated phosgene.

[0472] Example 33

[0473]

[0474] Use and Figure 5 The schematically illustrated photoreaction system is similar to a gas-phase photoreaction. Specifically, a cylindrical reaction vessel with a diameter of 60 mm and a capacity of 1360 mL is constructed, containing a 30 mm diameter quartz glass jacket. A low-pressure mercury lamp (“SUV40D”, manufactured by SEN Light, 40W) is then placed inside the quartz glass jacket. A reaction system with wavelengths of 185–600 nm, peak wavelengths of 184.9 nm and 253.7 nm. It should be noted that the irradiation light includes UV-C with wavelengths of 185 nm and 254 nm. The illuminance of the 185 nm light at a distance of 5 mm from the center of the lamp (the shortest distance from the reaction liquid) is 2.00–2.81 mW / cm². 2 The illuminance of light with a wavelength of 254 nm is 5.60–8.09 mW / cm². 2 The total capacity of the cylindrical flowing photoreaction device 12 is 976 mL.

[0475] Using syringe pump 1, liquid chloroform (450 mmol) is fed into a PTFE tube (inner diameter: 1 mm) at a flow rate of 0.2 mL / min (2.5 mmol / min). This mixture is then mixed with air, the flow rate of which is adjusted to 200 mL / min using a gas pump and mass flow controller 2. The mixture is vaporized in heater 3, which is heated to 60°C, and then fed into the aforementioned flowing photoreactor 4. The mixed gas inside the flowing photoreactor is reheated by heater 13, which is installed at the bottom of the device. The heater temperature is set to 100°C. The linear velocity of the mixed gas inside the photoreactor can be estimated to be 0.18 m / min, and the residence time to be 188 seconds.

[0476] To the reaction vessel 16 was added phenol (900 mmol) and pyridine was added at a flow rate of 0.52 mL / min (6.5 mmol / min) using a syringe pump while stirring, and in addition, the gas generated by oxidative photolysis of a mixed gas of chloroform gas and air was blown in for 3 hours at 0°C. The unreacted gas was further introduced into a connected alkali trap and treated so that no toxic gas leaked outside.

[0477] After that, the reaction solution in the reaction vessel 16 was washed with 1 M hydrochloric acid and water and extracted with dichloromethane. The resulting extract was dried with anhydrous sodium sulfate and the solvent was removed by distillation under reduced pressure to obtain diphenyl carbonate as a white solid (yield: 70.9 g, 74%).

[0478] Example 34

[0479]

[0480] A gas phase photoreaction was performed using the photoreaction system used in Example 33. Liquid chloroform (450 mmol) was sent into a PTFE tube (inner diameter: 1 mm) at a flow rate of 0.2 mL / min (2.5 mmol / min) using a syringe pump 1, mixed with air adjusted to a flow rate of 200 mL / min using a gas pump and a mass flow controller 2, and vaporized in a heater 3 heated to 60°C, and sent into a flow photoreactor 4. The mixed gas sent into the inside of the flow photoreactor 4 was heated again by a heater 13 installed at the bottom of the flow photoreactor. The heater temperature was set to 100°C. The linear velocity of the mixed gas was estimated to be 0.18 m / min and the residence time was 188 seconds.

[0481] To the reaction vessel 16 was added a chloroform solution of HFIP (900 mmol) and pyridine was added at a flow rate of 0.52 mL / min (6.5 mmol / min) using a syringe pump while stirring, and in addition, the gas generated by oxidative photolysis of a mixed gas of chloroform gas and air was blown in for 3 hours at 0°C. The unreacted gas was further introduced into a connected alkali trap and treated so that no toxic gas leaked outside.

[0482] After that, the reaction solution in the reaction vessel 16 was washed with 1 M hydrochloric acid and water and extracted with dichloromethane. 1 The reaction solution was analyzed by HNMR and it was confirmed that bis (hexafluoroisopropyl) carbonate (BHFC) was produced at a yield of 85%.

[0483] In addition, the washed reaction solution was dried with anhydrous sodium sulfate and separated by distillation into BHFC as a colorless liquid (separation yield: 88.0 g, 384 mmol, yield with respect to HFIP: 54%).

[0484] Example 35

[0485]

[0486] Similar to Example 34, high-energy light was used to oxidize and decompose gaseous chloroform.

[0487] A chloroform solution containing bisphenol A (BPA) (405 mmol) and pyridine (2025 mmol) was added to reaction vessel 16. While stirring, the mixture of chloroform and air was blown in at 0°C to allow the gas produced by the photo-oxidation of the chloroform gas to pass through, for 3 hours. Unreacted gas was further introduced into a connected alkali trap for treatment to prevent the toxic gas from leaking to the outside.

[0488] The reaction solution in reaction vessel 16 was then washed with 1M hydrochloric acid and water, and extracted with dichloromethane. The resulting extract was dried with anhydrous sodium sulfate, and the solvent was removed by vacuum distillation, thereby yielding a white solid of polycarbonate (yield: 102 g, yield: 95%).

[0489] The obtained polycarbonate was analyzed by gel permeation chromatography (GPC) to determine its molecular weight. The results are shown in Table 30.

[0490] [Table 30]

[0491] Mw Mn Mw / Mn 21,900 10,100 2.16

[0492] Example 36

[0493]

[0494] Use and Figure 5 The schematically illustrated photoreaction system is similar to a gas-phase photoreaction. Specifically, it is a reaction system constructed within a cylindrical reaction vessel with a diameter of 140 mm and a capacity of 2575 mL, containing a 30 mm diameter quartz glass jacket. Within the quartz glass jacket, a low-pressure mercury lamp (“UVL20PH-6”, manufactured by SEN Light, 20W, Φ24 mm × 120 mm, wavelength: 185–600 nm, peak wavelengths: 184.9 nm and 253.7 nm) is placed. It should be noted that the illumination light from this low-pressure mercury lamp includes UV-C wavelengths of 185 nm and 254 nm. The illuminance of the 185 nm wavelength light at a distance of 5 mm from the center of the lamp, where it is closest to the reaction liquid, is 2.00–2.81 mW / cm². 2 The illuminance of light with a wavelength of 254 nm is 5.60–8.09 mW / cm². 2 The total capacity of the cylindrical flowing photoreaction device 12 is 2450 mL.

[0495] Using syringe pump 1, liquid chloroform (900 mmol) was fed into a PTFE tube (inner diameter: 1 mm) at a flow rate of 0.4 mL / min (5.0 mmol / min), and mixed with air at a flow rate of 200 mL / min adjusted by a gas pump and mass flow controller 2. The mixture was then vaporized in heater 3, which was heated to 60°C, and fed into the aforementioned flowing photoreactor 12. The mixed gas inside the flowing photoreactor was reheated by heater 13, which was installed at the bottom of the device. The heater temperature was set to 100°C. The linear velocity of the mixed gas inside the photoreactor was estimated to be 0.046 m / min, and the residence time to be 235 seconds.

[0496] A chloroform solution containing HFIP (1200 mmol) and pyridine (1800 mmol) was placed in reaction vessel 16. While stirring, the mixture was blown into the vessel at 0°C with gas generated from the photochemical oxidation of a chloroform-air mixture for 3 hours. Unreacted gas was further introduced into a connected alkali trap for treatment to prevent toxic gas leakage to the outside.

[0497] Afterwards, the reaction solution in reaction vessel 16 was rinsed with 1M hydrochloric acid and water, and then... 1 HNMR analysis confirmed the formation of bis(hexafluoroisopropyl) carbonate (yield: 588 mmol, yield: 98%).

[0498] Example 37: Chloroform decomposition based on visible light

[0499]

[0500] The chloroform product containing ethanol as a stabilizer was washed with distilled water (500 mL), followed by separation. This process was repeated three times. The chloroform layer was dried with anhydrous sodium sulfate, and after filtration to separate the anhydrous sodium sulfate, calcium hydride (1 g) was added, and the mixture was stirred overnight at 30°C. Then, chloroform without the stabilizer was obtained by distillation.

[0501] Use and Figure 5 The schematically illustrated photoreaction system is similar to a gas-phase photoreaction system. Specifically, it is constructed on... The cylindrical reaction vessel is filled with The reaction system consists of a quartz glass jacket, within which a low-pressure mercury lamp (“UVL20PH-6”, manufactured by SEN Light, 20W, Φ24mm×120mm, wavelength: 185~600nm, peak wavelength: 184.9nm and 253.7nm) is installed. Furthermore, a 365nm LED lamp (“LKI-152”, manufactured by Polarstar, 30W, emitting part: 250×150mm, peak wavelength: 365nm) is positioned approximately 1cm from the outer side of the cylindrical reaction vessel. The effective volume of the photoreaction device 12 is 2.5L. Additionally, the illuminance at a distance of 5mm from the LED lamp is 34~38mW / cm². 2 .

[0502] Using syringe pump 1 and mass flow controller 2 ("MODEL 8500MC", manufactured by KOFLOC), liquid chloroform (with stabilizer removed as described above) and oxygen at 20°C were fed into coil heater 3, which was heated to 110°C, at the flow rates shown in Table 31. The mixture was heated and supplied to photoreactor 12 for 2 hours. The temperature of heater 13 for heating the reaction apparatus was set to 100°C.

[0503] The mixed gas in the photoreaction device 12 is irradiated with visible light only from an LED lamp, or after being irradiated with visible light from an LED lamp for 5 minutes, UV-C light is added from a low-pressure mercury lamp for 1 minute, and then it is irradiated with visible light only again.

[0504] The gas passing through the photoreactor is blown into 1-butanol in reaction vessel 16-1, and then the gas passing through reaction vessel 16-1 is blown into 1-butanol in reaction vessel 16-2. 1-Butanol is added to reaction vessels 16-1 and 16-2 at a molar ratio relative to the amount of chloroform used. The gas passing through reaction vessel 16-2 is further introduced into an alkali trap for treatment to prevent the toxic gas from leaking to the outside.

[0505] After the reaction, 1,2-dichloroethane as an internal standard was added to the reaction solution in reaction vessels 16-1 and 16-2. 1 ¹H NMR analysis was performed to determine the yields and quantities of the generated chloroformate and carboxylic anhydride, and the amount of phosgene produced was calculated from their total. The results are summarized in Table 31. It should be noted that the phosgene yields in Table 31 are relative to the yield of chloroform used.

[0506] [Table 31]

[0507]

[0508] As shown in the results of Table 31, by using chloroform containing no stabilizer, although the amount of unreacted chloroform increased slightly, chloroform was decomposed even by visible light to generate phosgene. It is considered that by using chloroform containing no stabilizer and performing the oxidative photodecomposition reaction in the gas phase, chloroform is decomposed to generate phosgene even by light of a relatively low energy.

[0509] In addition, by irradiating ultraviolet light for a short time in addition to visible light at the initial stage of the oxidative photodecomposition reaction, the yield and the yield of phosgene increased and the amount of unreacted chloroform decreased. As a reason therefor, it is considered that because the C-Cl bond is cleaved by the ultraviolet light of a higher energy, the oxidative photodecomposition reaction of chloroform proceeds by the radical chain mechanism even by using only visible light thereafter.

[0510] Explanation of Reference Numerals

[0511] 1: syringe pump 2: mass flow controller 3: heater

[0512] 4: flow photoreactor 5: back pressure valve 6: reaction vessel

[0513] 7: trap vessel 8: syringe pump for injection of reaction substrate 9: coil reactor

[0514] 10: recovery vessel 11: light source 12: photoreactor

[0515] 13: bath 14: stirrer 15: cooling tube

[0516] 16: reaction vessel 17: tube reactor

Claims

1. A process for the manufacture of phosgene, characterized in that The process includes the following steps: a step of preparing a mixed gas containing a halogenated methane and oxygen, the halogenated methane having a chlorine group; and a step of flowing the aforementioned mixed gas and irradiating the flowing mixed gas with light whose peak wavelength is included in a range of 180 nm or more and 500 nm or less.

2. The method of claim 1, wherein, The shortest distance between a light source of the light and the flowing mixed gas is 1 m or less.

3. The method of claim 1, wherein, The time for irradiating the flowing mixed gas with the light is 1 second or more and 10,000 seconds or less.

4. The method of claim 1, wherein, The temperature at the time of irradiating the flowing mixed gas with the light is 40°C or more and 200°C or less.

5. The method of claim 1, wherein, The halogenated methane is dichloromethane or chloroform.

6. A method for producing a fluoro carbonate compound, characterized by, The process includes the following steps: a step of preparing a mixed gas containing a halogenated methane and oxygen, the halogenated methane having a chlorine group; and a step of reacting a fluorinated alcohol compound with the phosgene, The molar ratio of the fluorinated alcohol compound to the halogenated methane is 1 or more.

7. A method for producing a non-fluorinated carbonate compound, characterized by, The process includes the following steps: a step of preparing a mixed gas containing a halogenated methane and oxygen, the halogenated methane having a chlorine group; and a step of reacting a non-fluorinated alcohol compound with the phosgene, The molar ratio of the non-fluorinated alcohol compound to the halogenated methane is 1 or more.

8. A process for producing a haloformic acid fluorinated ester compound, characterized by, The process includes the following steps: a step of preparing a mixed gas containing a halogenated methane and oxygen, the halogenated methane having a chlorine group; and a step of reacting a fluorinated alcohol compound with the phosgene, The molar ratio of the fluorinated alcohol compound to the halogenated methane is less than 1.

9. A process for the manufacture of a non-fluorinated ester compound of a haloformic acid characterized in that, The process includes the following steps: a step of preparing a mixed gas containing a halogenated methane and oxygen, the halogenated methane having a chlorine group; and a step of reacting a non-fluorinated alcohol compound with the phosgene, The molar ratio of the non-fluorinated alcohol compound to the halogenated methane is less than 1.

10. A method for producing an isocyanate compound, characterized by, The process includes the following steps: a step of preparing a mixed gas containing a halogenated methane and oxygen, the halogenated methane having a chlorine group; and a step of reacting a primary amine compound with the phosgene, The molar ratio of the primary amine compound to the halogenated methane is less than 1.

11. A method for producing an amino acid-N-carboxyanhydride, characterized in that, the amino acid-N-carboxyanhydride is a compound represented by the following formula (VIII), the method includes the following steps: a step of preparing a mixed gas containing a halogenated methane and oxygen, the halogenated methane having a chlorine group; and a step of reacting an amino acid compound represented by the following formula (VII) with the phosgene, in the formula, R 4 represents an amino acid side chain group whose reactive group is protected, R 5 represents H, or P 1 -[-NH-CHR 6 -C(=O)-] l -, formula P 1 -[-NH-CHR 6 -C(=O)-] l -wherein R 6 represents a reactive group-protected amino acid side chain, P 1 represents a protecting group for an amino group, and l represents an integer of 1 or more, and when l is an integer of 2 or more, the multiple R 6 may optionally be the same or different from each other.

12. A method for producing a Wieselman reagent, characterized in that, the Wieselman reagent is a salt represented by the following formula (X), in the formula (X), R 7 represents a hydrogen atom, a C 1-6 alkyl group, or a C 6-12 aromatic hydrocarbon group optionally having a substituent, R 8 and R 9 independently represent C 1-6 alkyl, or C 6-12 aromatic hydrocarbon group, and R 8 and R 9 optionally form a ring structure of 4 or more and 7 or less members, X represents chlorine, Y - represents a counter anion, the method includes the following steps: a step of preparing a mixed gas containing a halogenated methane and oxygen, the halogenated methane having a chlorine group; and a step of reacting the phosgene with an amide compound represented by the following formula (IX). In the formula (IX), R 7 ~R 9 have the same meanings as described above.

Images