Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B32/00—Carbon; Compounds thereof
  • C01B32/80—Phosgene
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
  • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
  • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D263/44—Two oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C263/00—Preparation of derivatives of isocyanic acid
  • C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C265/00—Derivatives of isocyanic acid
  • C07C265/02—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms
  • C07C265/04—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms of a saturated carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/04—Carbamic acid halides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/58—Preparation of carboxylic acid halides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C68/00—Preparation of esters of carbonic or haloformic acids
  • C07C68/02—Preparation of esters of carbonic or haloformic acids from phosgene or haloformates
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/96—Esters of carbonic or haloformic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
  • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
  • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D317/34—Oxygen atoms
  • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates

Definitions

• the present invention relates to a method for safely and efficiently producing carbonyl halides.
• Carbonyl halides such as phosgene are extremely important as synthetic intermediates for various compounds and as raw materials for materials.
• carbonate compounds are generally produced from phosgene and alcohol compounds.
• phosgene is highly toxic; it easily reacts with water to produce hydrogen chloride and has a history of being used as a poisonous gas.
• Phosgene is primarily produced by the highly exothermic gas-phase reaction of anhydrous chlorine gas and high-purity carbon monoxide in the presence of an activated carbon catalyst. The carbon monoxide used here is also toxic.
• the basic process for producing phosgene has not changed significantly since the 1920s. Producing phosgene using such a process requires expensive, large-scale facilities. However, due to the high toxicity of phosgene, extensive safety measures are essential in plant design, which leads to increased production costs.
• the present inventor's research group has developed a technology for producing halogens and/or carbonyl halides by irradiating halogenated hydrocarbons such as chloroform with light in the presence of oxygen (Patent Document 1). They have also found that carbonyl halides can be efficiently produced by irradiating a mixed gas containing C2-4 halogenated hydrocarbons and oxygen with high-energy light in the gas phase (Patent Document 2). They have further found that carbonyl halides can be efficiently produced by irradiating a composition containing C1-4 halogenated hydrocarbons with light in the presence of oxygen and a substance that generates radicals in response to visible light, such as chlorine (Patent Document 3).
• Non-Patent Document 1 describes that the oxidation reaction of tetrachloroethylene (Cl 2 C ⁇ CCl 2 ) is initiated by chlorine atoms to produce phosgene, etc.
• Non-Patent Document 1 also describes the use of ozone.
• an object of the present invention is to provide a method for safely and efficiently producing a carbonyl halide.
• Non-Patent Document 1 concludes that ozone inhibits the oxidation reaction of tetrachloroethylene initiated by chlorine atoms, they have found that carbonyl halides can be safely and efficiently produced without using halogens such as chlorine by oxidative photolysis of halomethanes using ozone and oxygen in combination, and have completed the present invention.
• halogens such as chlorine by oxidative photolysis of halomethanes using ozone and oxygen in combination
• a method for producing a carbonyl halide comprising the steps of: A method comprising the step of irradiating a halomethane having one or more halogeno groups selected from the group consisting of chloro, bromo and iodo with light in the presence of oxygen and ozone. [2] The method according to [1], wherein a mixed gas containing the halomethane, the oxygen and the ozone is irradiated with light. [3] The method according to [1] or [2], wherein the ratio of the ozone to the total of the oxygen and the ozone is 1 vol % or more and 20 vol % or less.
• [4] The method according to [2], wherein the volume ratio of the halomethane to the ozone is 0.1 to 50 times.
• [5] The method according to [2] or [4], wherein the mixed gas does not contain chlorine.
• [6] The method according to any one of [1] to [5], wherein the time for irradiating the halomethane with the light is 60 seconds or more and 5000 seconds or less.
• [7] The method according to any one of [1] to [6], wherein the temperature when the halomethane is irradiated with the light is 50° C. or higher and 200° C. or lower.
• a method for producing a carbonate compound comprising: A step of producing a carbonyl halide by the method according to any one of the above [1] to [7]; and A method comprising the step of reacting an alcohol compound with the carbonyl halide.
• a method for producing a halogenated formate compound comprising: A step of producing a carbonyl halide by the method according to any one of the above [1] to [7]; and A method comprising the step of reacting an alcohol compound with the carbonyl halide.
• a method for producing an isocyanate compound comprising: A step of producing a carbonyl halide by the method according to any one of the above [1] to [7]; and reacting a primary amine compound with said carbonyl halide.
• a method for producing a carbamoyl halide compound comprising: A step of producing a carbonyl halide by the method according to any one of the above [1] to [7]; and A method comprising the step of reacting a secondary amine compound with the carbonyl halide.
• a method for producing an amino acid N-carboxylic acid anhydride comprising the steps of:
• the amino acid N-carboxylic acid anhydride is represented by the following formula (VIII):
• R4 represents an amino acid side chain group in which a reactive group is protected
• R 6 represents an amino acid side chain in which a reactive group is protected
• P 1 represents a protecting group for an amino group
• l represents an integer of 1 or more, and when l is an integer of 2 or more, multiple R 6s may be the same or different from each other.
• a method for producing a Vilsmeier reagent comprising the steps of:
• the Vilsmeier reagent is a salt represented by the following formula (X):
• R7 represents a hydrogen atom, a C1-6 alkyl group, or a C6-12 aromatic hydrocarbon group which may have a substituent
• R 8 and R 9 are each independently a C 1-6 alkyl group or a C 6-12 aromatic hydrocarbon group which may have a substituent, and R 8 and R 9 may combine together to form a ring structure having 4 to 7 members
• X represents a halogeno group selected from the group consisting of chloro, bromo and iodo
• Y ⁇ represents a counter anion.
• R 7 to R 9 are as defined above.
• the method of the present invention makes it possible to safely and efficiently produce useful carbonyl halides using halomethanes, which have a high environmental impact and are subject to restrictions on their use and disposal, as raw materials.
• Some halomethane products contain stabilizers that can inhibit the oxidative photolysis of halomethanes, but the ozone used in the method of the present invention can break down such stabilizers and promote the oxidative photolysis of halomethanes.
• the method of the present invention does not require the use of halogen gases such as chlorine gas, which are highly corrosive and toxic. Therefore, the present invention is industrially useful as a technology that enables the effective use of halomethanes and the efficient production of carbonyl halides such as carbonyl chloride.
• FIG. 1 is a schematic diagram showing an example of the configuration of a reaction system used in the present invention.
• FIG. 2 is a schematic diagram showing an example of the configuration of a reaction system used in the present invention.
• FIG. 3 is a schematic diagram showing an example of the configuration of a reaction system used in the present invention.
• FIG. 4 is a schematic diagram showing an example of the configuration of a reaction system used in the present invention.
• a halomethane having one or more halogeno groups selected from the group consisting of chloro, bromo, and iodo is irradiated with light in the presence of oxygen and ozone, thereby subjecting the halomethane to oxidative photolysis to obtain a carbonyl halide.
• the halomethane used in the present invention is methane having one or more halogeno groups selected from the group consisting of chloro, bromo, and iodine. Such halomethanes are likely to be decomposed by oxygen, ozone, and light energy and converted to carbonyl halides.
• halomethanes are oxidatively photodecomposed and are considered to function in the same way as carbonyl halides.
• polyhalomethanes having two or more halogeno groups are preferred, and perhalomethanes in which all hydrogen atoms are replaced by halogeno groups are also preferred.
• halomethanes include chloromethane, such as dichloromethane, chloroform, and carbon tetrachloride; bromomethane, such as dibromomethane and bromoform; iodomethane, such as iodomethane and diiodomethane; and halomethanes having two or more halogeno groups, such as bromochloromethane, chloroiodomethane, bromoiodomethane, and bromochloroiodomethane.
• chloromethane such as dichloromethane, chloroform, and carbon tetrachloride
• bromomethane such as dibromomethane and bromoform
• iodomethane such as iodomethane and diiodomethane
• halomethanes having two or more halogeno groups such as bromochloromethane, chloroiodomethane, bromoiodomethane,
• the halomethane may be appropriately selected depending on the target chemical reaction and the desired product, and one type may be used alone or two or more types may be used in combination. Preferably, only one type of halomethane is used depending on the compound to be produced. Among halomethanes, halomethanes having a chloro group are preferred from the viewpoint of vaporization and cost, and chloroform is more preferred.
• halomethane from which the stabilizers have been removed may be used in order to decompose halomethane by oxidative photolysis.
• halomethane from which the stabilizers have been removed it is possible to more efficiently decompose halomethane, for example by using visible light with relatively low energy and reducing the light exposure time.
• the method for removing the stabilizers from halomethane but for example, the halomethane may be washed with water to remove the water-soluble stabilizer, and then dried.
• the method of the present invention uses ozone, it is possible that the stabilizer can be decomposed by ozone, and halomethane containing the stabilizer may be used as is.
• halomethane used in the method of the present invention particularly, inexpensive chloroform, which is also used as a general-purpose solvent, can be used. Also, for example, halomethane once used as a solvent may be recovered and reused.
• the reaction since the reaction may be inhibited if a large amount of impurities or water is contained, it is preferable to purify it to a certain extent. For example, it is preferable to remove water and water-soluble impurities by washing with water, and then dehydrate it with anhydrous sodium sulfate or anhydrous magnesium sulfate.
• the reaction since the reaction is considered to proceed even if about 1% by mass of water is contained, excessive purification that reduces productivity is not necessary.
• the water content is more preferably 0.5% by mass or less, even more preferably 0.2% by mass or less, and even more preferably 0.1% by mass or less.
• the water content is preferably below the detection limit or 0% by mass.
• the reused halomethane may contain decomposition products of halomethane, etc.
• a solvent may be used in combination with the halomethane.
• the solvent may also promote the decomposition of the halomethane.
• the solvent may inhibit the decomposition of carbonyl halides produced by oxidative photolysis of the halomethane.
• a solvent capable of dissolving the halomethane to an appropriate degree is preferable.
• solvents examples include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon solvents such as n-hexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and benzonitrile; ether-based solvents such as diethyl ether, tetrahydrofuran, and dioxane; and nitrile-based solvents such as acetonitrile.
• ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone
• aliphatic hydrocarbon solvents such as n-hexane
• aromatic hydrocarbon solvents such as benzene, toluene, xylene, and benzonitrile
• ether-based solvents such as diethyl
• the amount of oxygen supplied may be adjusted as appropriate within a range that allows efficient oxidative photolysis of the halomethane. For example, when oxygen is blown into liquid halomethane, oxygen may be supplied at 10 mL/min or more, 500 mL/min or less, 0.1 mmol/min or more, and 50 mmol/min or less per 100 mL of halomethane.
• the rate is preferably 20 mL/min or more, more preferably 50 mL/min or more, and preferably 300 mL/min or less or 200 mL/min or less, more preferably 100 mL/min or less, preferably 0.5 mmol/min or more, more preferably 1 mmol/min or more, preferably 30 mmol/min or less or 20 mmol/min or less, and more preferably 10 mmol/min or less or 5 mmol/min or less.
• the volume ratio of oxygen to halomethane can be 0.1 or more and 5 or less, and the molar ratio of oxygen to halomethane can also be 0.1 or more and 5 or less.
• the volume ratio and molar ratio are preferably 0.2 or more, more preferably 0.5 or more, and are preferably 3 or less or 2 or less, and more preferably 1.5 or less.
• ozone is not a radical substance, its mechanism of action is unknown, but it can promote the reaction of obtaining carbonyl halides by oxidative photolysis of halomethanes, and it is possible that a polymer with a higher molecular weight can be obtained using the carbonyl halides produced compared to the case where oxygen alone is used.
• stabilizers of halomethanes such as amylene, can be decomposed by ozone.
• coloring of the reaction solution or the target compound can be suppressed by decomposing colored components or suppressing their production by ozone.
• ozone when oxygen is blown into liquid halomethane, ozone can be supplied at a rate of 0.5 mL/min or more, 50 mL/min or less, 0.005 mmol/min or more, and 5 mmol/min or less per 100 mL of halomethane.
• the higher the ratio of ozone to halomethane the better the oxidative photolysis reaction of halomethane can proceed.
• the lower the ratio of ozone to halomethane the more reliably the further photolysis of the carbonyl halides produced can be suppressed.
• the ratio is preferably 1 mL/min or more, more preferably 2 mL/min or more, and is preferably 30 mL/min or less or 20 mL/min or less, more preferably 10 mL/min or less, preferably 0.01 mmol/min or more, more preferably 0.05 mmol/min or more, preferably 3 mmol/min or less or 2 mmol/min or less, and more preferably 1 mmol/min or less or 0.5 mmol/min or less.
• the volume ratio of ozone to halomethane can be 0.005 or more and 0.5 or less, and the molar ratio of ozone to halomethane can also be 0.005 or more and 0.5 or less.
• the volume ratio and molar ratio are preferably 0.01 or more, more preferably 0.05 or more, and are preferably 0.3 or less or 0.2 or less, and more preferably 0.15 or less.
• the volume ratio of halomethane to ozone can be, for example, 0.01 to 100.
• the ratio is preferably 0.05 or more, more preferably 0.1 or more or 1 or more, and is preferably 50 or less or 20 or less.
• the ratio of oxygen to ozone may also be adjusted as appropriate.
• the ratio of ozone to the total of oxygen and ozone may be set to 1 vol% or more and 50 vol% or less.
• the ratio is preferably 30 vol% or less, and more preferably 20 vol% or less.
• an inert gas such as nitrogen or argon may be mixed. Air may also be used as the oxygen source. Air is advantageous from the viewpoint of cost.
• ozone which is safer than chlorine, is used to promote the oxidative photodecomposition reaction of halomethanes.
• the halomethane is irradiated with light in the presence of oxygen and ozone.
• “In the presence of oxygen and ozone” may mean either a state in which oxygen and ozone are dissolved in liquid halomethane, or a state in which gaseous halomethane is mixed with and in contact with oxygen and ozone.
• a mixed gas containing oxygen and ozone may be supplied to the composition containing halomethane by bubbling.
• the composition containing halomethane may consist of only halomethane.
• a mixed gas containing gaseous halomethane, oxygen, and ozone may be prepared, and the mixed gas may be irradiated with light. By irradiating the mixed gas with light, the oxidative photodecomposition of halomethane may proceed more efficiently.
• halomethane may be mixed with oxygen and ozone, delivered to a heater, heated to above the boiling point of halomethane to vaporize it, and delivered to a reactor.
• the upper limit of the heating temperature of halomethane as long as the halomethane is effectively vaporized, but it may be set to, for example, the boiling point + 50°C.
• halomethanes may be subjected to oxidative photolysis in a two-phase system of liquid and gas phases.
• liquid halomethanes may be heated by a heater to a temperature above (boiling point -10°C) and below the boiling point, while the liquid and gas phases are irradiated with light.
• vaporization of the halomethanes is promoted by blowing a mixed gas containing oxygen and ozone into the composition containing the halomethanes by bubbling.
• the mixture containing the halomethanes may be stirred.
• Light containing high energy light including short wavelength light can be used as the light to be irradiated to the halomethanes, for example, light containing ultraviolet light can be used.
• High energy light including short wavelength light may enable efficient oxidative photolysis of the halomethanes.
• light containing light with a wavelength of 180 nm or more and 500 nm or less, and light with a peak wavelength of 180 nm or more and 500 nm or less can be used.
• the wavelength of the irradiated light may be determined appropriately, but light with a wavelength of 400 nm or less, light with a wavelength of 300 nm or less, and light with a peak wavelength within these ranges can also be used.
• light containing UV-B with a wavelength of 280 nm or more and 315 nm or less and/or UV-C with a wavelength of 180 nm or more and 280 nm or less can be used, and light containing UV-C with a wavelength of 180 nm or more and 280 nm or less can be used, and light with a peak wavelength within these ranges can also be used.
• halomethanes are oxidatively photodecomposed in the presence of ozone, so that halomethanes may be oxidatively photodecomposed even with light of relatively low energy.
• relatively low-energy irradiation light include light whose peak wavelength is included in the visible light wavelength range.
• the wavelength range of relatively low-energy light include 250 nm or more and 830 nm or less, preferably 280 nm or more, more preferably 300 nm or more, preferably 800 nm or less or 700 nm or less, more preferably 600 nm or less or 500 nm or less, and even more preferably 400 nm or less, and light whose peak wavelength is included in these ranges is also preferred.
• the means of light irradiation is not particularly limited as long as it can irradiate light of the above wavelengths, but examples of light sources that include light in this wavelength range include sunlight, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, black light lamps, metal halide lamps, LED lamps, etc. From the standpoint of reaction efficiency and cost, low-pressure mercury lamps and LED lamps are preferred, and LED lamps are more preferred.
• the condition such as the intensity of the irradiated light may be appropriately set according to the halomethane, but for example, the desired light intensity at the shortest distance from the light source to the liquid or gaseous halomethane is preferably 1 mW/cm 2 or more and 500 mW/cm 2 or less, depending on the implementation scale and the wavelength of the irradiated light.
• the light intensity is more preferably 100 mW/cm 2 or less or 50 mW/cm 2 or less, and more preferably 20 mW/cm 2 or less or 10 mW/cm 2 or less.
• the wavelength of the irradiated light is relatively long, the light intensity is more preferably 10 mW/cm 2 or more or 20 mW/cm 2 or more, and may be 50 mW/cm 2 or more or 100 mW/cm 2 or more, and more preferably 400 mW/cm 2 or less or
• the shortest distance between the light source and the halomethane is preferably 1 m or less, more preferably 50 cm or less, and even more preferably 10 cm or less or 5 cm or less.
• the lower limit of the shortest distance is not particularly limited, but may be 0 cm, that is, the light source may be present in the liquid or gaseous halomethane.
• a light source may be placed in a reactor in which liquid or gaseous halomethane is present.
• one or more light sources may be placed around a transparent reactor in which liquid or gaseous halomethane is present.
• Halomethanes are thought to be photodecomposed into carbonyl halides through oxidative degradation by oxygen, ozone, and light irradiation.
• carbonyl halides are decomposed, particularly by high-energy light. Therefore, it is important to adjust the light irradiation conditions so that the carbonyl halides produced do not decompose excessively.
• the time for irradiating light to halomethanes is preferably 1 second or more and 5000 seconds or less, depending on the wavelength of the irradiated light and the reaction temperature.
• the time for irradiating light to a flowing mixed gas containing halomethanes, oxygen, and ozone can also be referred to as the residence time of the flowing mixed gas in a light reaction vessel for continuously irradiating the mixed gas with light. If the time is 1 second or more, halomethanes can be more reliably oxidatively decomposed, and if it is 5000 seconds or less, excessive decomposition of the generated carbonyl halide can be more reliably suppressed.
• the time is preferably 5 seconds or more or 10 seconds or more, more preferably 30 seconds or more or 60 seconds or more, even more preferably 120 seconds or more or 600 seconds or more, and preferably 3000 seconds or less, more preferably 2000 seconds or less, and even more preferably 1000 seconds or less.
• a relatively low-energy light with a peak wavelength of 300 nm or more can be used to suppress the decomposition of carbonyl halide.
• the flow rate of the flowing mixed gas in the photoreactor for irradiating the flowing mixed gas with high-energy light is preferably determined taking into consideration the internal volume of the photoreactor. For example, when the internal volume of the photoreactor is large, the residence time of the mixed gas tends to be long, so 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, since the internal volume of the photoreactor (L) / flow rate of the flowing mixed gas (L/sec) corresponds to the residence time (sec) of the flowing mixed gas in the photoreactor, the flow rate of the flowing mixed gas can be determined from the desired residence time and the internal volume of the photoreactor.
• the linear velocity of the flowing mixed gas in the photoreactor can be adjusted to about 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 carbonyl halide generated from halomethane by gas phase reaction can be more reliably suppressed, and if it is 100 m/min or less, sufficient time for conversion of halomethane to carbonyl halide can be more reliably obtained.
• the linear velocity can be calculated by dividing the velocity of the flowing mixed gas passing through the photoreactor by the cross-sectional area of the photoreactor.
• the cross-sectional area of the photoreactor can be considered as the average value of the cross-sectional area of the photoreactor in the moving direction of the flowing mixed gas.
• the average value can be obtained by dividing the volume of the photoreactor by the length of the flowing mixed gas in the moving direction in the photoreactor.
• the linear velocity is preferably 0.01 m/min or more, and more preferably 50 m/min or less or 20 m/min or less, more preferably 10 m/min or less or 5 m/min or less, and even more preferably 1 m/min or less or 0.5 m/min or less.
• the temperature when irradiating the halomethane with light may be adjusted as appropriate within a range that allows the halomethane to be oxidatively photodecomposed and prevents excessive decomposition of the carbonyl halide produced.
• the temperature may be, for example, 35°C or higher and 250°C or lower.
• the temperature is preferably 40°C or higher or 50°C or higher, more preferably 60°C or higher or 70°C or higher, even more preferably 75°C or higher, and preferably 200°C or lower, more preferably 150°C or lower, and even more preferably 120°C or lower.
• the temperature can be adjusted using a heater or heat transfer medium installed in the reactor.
• the mixed gas When irradiating a mixed gas containing halomethane, oxygen, and ozone with light, the mixed gas does not need to be pressurized, but may be pressurized at least to the extent that the mixed gas can pass through the reaction vessel. Pressurizing the mixed gas may also improve productivity.
• the gauge pressure of the mixed gas in the reaction vessel can be adjusted to 0 MPaG or more and 2 MPaG or less, preferably 1 MPaG or less, and more preferably 0.5 MPaG or less.
• a carbonate compound can be produced by reacting a carbonyl halide with an alcohol compound.
• the mode of reaction is not particularly limited, and for example, as shown in Figures 1 to 4, a gas containing the generated carbonyl halide may be blown into a composition containing an alcohol compound.
• a composition containing a halomethane and an alcohol compound may be irradiated with light while oxygen and ozone are blown into it, so that the carbonyl halide generated in the composition can be reacted immediately with the alcohol compound, or the alcohol compound can be continuously supplied to the gas phase together with the halomethane, so that the carbonyl halide generated in the gas phase can be reacted immediately with the alcohol compound.
• a cooler may be provided between the photoreactor and the reactor for the reaction with the reactant such as an alcohol compound.
• the temperature of the cooler is preferably adjusted so that the carbonyl halide produced can pass through it.
• Carbonyl halides are also called carbonyl dihalides, and carbonyl chloride is also called carbonyl dichloride.
• the alcohol compound is an organic compound having a hydroxyl group, and examples thereof include a monohydric alcohol compound represented by the following formula (I) or a dihydric alcohol compound represented by the following formula (II).
• a compound represented by formula x may be abbreviated as "compound x".
• a “monohydric alcohol compound represented by formula (I)” may be abbreviated as "monohydric alcohol compound (I)”.
• R 1 -OH... (I) HO-R 2 -OH... (II) [In the formula, R 1 represents a monovalent organic group, and R 2 represents a divalent organic group.]
• the organic group is not particularly limited so long as it is inert to the reaction in this step, and examples include an optionally substituted C1-10 aliphatic hydrocarbon group, an optionally substituted C6-30 aromatic hydrocarbon group, an optionally substituted heteroaryl group, an organic group to which 2 or more and 5 or less C1-10 optionally substituted aliphatic hydrocarbon groups and C6-12 optionally substituted aromatic hydrocarbon groups are bonded, and an organic group to which 2 or more and 5 or less C1-10 optionally substituted aliphatic hydrocarbon groups and optionally substituted heteroaryl groups are bonded.
• C1-10 aliphatic hydrocarbon groups include C1-10 chain aliphatic hydrocarbon groups, C3-10 cyclic aliphatic hydrocarbon groups, and organic groups in which 2 or more and 5 or less C1-10 chain aliphatic hydrocarbon groups and C3-10 cyclic aliphatic hydrocarbon groups are bonded together.
• C1-10 chain aliphatic hydrocarbon group refers to a linear or branched, saturated or unsaturated aliphatic hydrocarbon group having from 1 to 10 carbon atoms.
• examples of the monovalent C1-10 chain aliphatic hydrocarbon group include a C1-10 alkyl group, a C2-10 alkenyl group, and a C2-10 alkynyl group.
• C1-10 alkyl groups include 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.
• C2-10 alkenyl groups examples include ethenyl (vinyl), 1-propenyl, 2-propenyl (allyl), butenyl, hexenyl, octenyl, decenyl, etc. Preferred are C2-8 alkenyl groups, and more preferred are C4-6 alkenyl groups.
• C2-10 alkynyl groups include ethynyl, propynyl, butynyl, hexynyl, octynyl, pentadecynyl, etc. Preferred are C2-8 alkynyl groups, and more preferred are C2-6 alkynyl groups.
• C3-10 cyclic aliphatic hydrocarbon group refers to a cyclic saturated or unsaturated aliphatic hydrocarbon group having from 3 to 10 carbon atoms.
• examples of monovalent C3-10 cyclic aliphatic hydrocarbon groups include a C3-10 cycloalkyl group, a C4-10 cycloalkenyl group, and a C4-10 cycloalkynyl group.
• Examples of the organic group to which 2 or more and 5 or less C1-10 chain aliphatic hydrocarbon groups and C3-10 cyclic aliphatic hydrocarbon groups are bonded include a C3-10 monovalent cyclic aliphatic hydrocarbon group- C1-10 divalent chain aliphatic hydrocarbon group and a C1-10 monovalent chain aliphatic hydrocarbon group- C3-10 divalent cyclic aliphatic hydrocarbon group- C1-10 divalent chain aliphatic hydrocarbon group.
• C6-12 aromatic hydrocarbon group refers to an aromatic hydrocarbon group having at least 6 carbon atoms and no more than 12 carbon atoms.
• monovalent C6-12 aromatic hydrocarbon groups include phenyl, indenyl, naphthyl, biphenyl, etc., and preferably phenyl.
• C6-30 aromatic hydrocarbon group refers to an aromatic hydrocarbon group having a carbon number of 6 or more and 30 or less.
• divalent C6-30 aromatic hydrocarbon groups include divalent C6-12 aromatic hydrocarbon groups such as phenylene, indenylene, naphthylene, biphenylene, and the like, as well as the alcohol compound (II-1) described below.
• heteroaryl group refers to a 5-membered aromatic heterocyclyl group, 6-membered aromatic heterocyclyl group, or fused-ring aromatic heterocyclyl group having at least one heteroatom such as a nitrogen atom, oxygen atom, or sulfur atom.
• Examples include monovalent 5-membered heteroaryl groups such as pyrrolyl, imidazolyl, pyrazolyl, thienyl, furyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, and thiadiazole; monovalent 6-membered heteroaryl groups such as pyridinyl, pyrazinyl, pyrimidinyl, and pyridazinyl; and monovalent fused-ring aromatic heterocyclyl groups such as indolyl, isoindolyl, quinolinyl, isoquinolinyl, benzofuranyl, isobenzofuranyl, and chromenyl.
• monovalent 5-membered heteroaryl groups such as pyrrolyl, imidazolyl, pyrazolyl, thienyl, furyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, and thiadiazol
• Examples of the "organic group having 2 or more and 5 or less C1-10 aliphatic hydrocarbon groups and C6-12 aromatic hydrocarbon groups bonded thereto" include a C6-12 aromatic hydrocarbon group- C1-10 chain aliphatic hydrocarbon group, a C1-10 chain aliphatic hydrocarbon group- C6-12 aromatic hydrocarbon group, a C1-10 chain aliphatic hydrocarbon group- C6-12 aromatic hydrocarbon group- C1-10 chain aliphatic hydrocarbon group, and a C6-12 aromatic hydrocarbon group- C1-10 chain aliphatic hydrocarbon group- C6-12 aromatic hydrocarbon group.
• Examples of the "organic group having 2 or more and 5 or less C1-10 aliphatic hydrocarbon groups and heteroaryl groups bonded thereto" include a heteroaryl group- C1-10 chain aliphatic hydrocarbon group, a C1-10 chain aliphatic hydrocarbon group-heteroaryl group, a C1-10 chain aliphatic hydrocarbon group-heteroaryl group- C1-10 chain aliphatic hydrocarbon group-C6-12 aromatic hydrocarbon group.
• Examples of the alkyl group include a 1-10 chain aliphatic hydrocarbon group, and a heteroaryl group-C 1-10 chain aliphatic hydrocarbon group-heteroaryl group.
• Examples of the substituents that the C1-10 aliphatic hydrocarbon group may have include one or more substituents selected from the group consisting of a halogeno group, a nitro group, and a cyano group, with a halogeno group being preferred.
• Examples of the substituents that the C6-12 aromatic hydrocarbon group and the heteroaryl group may have include one or more substituents selected from the group consisting of a C1-6 alkyl group, a C1-6 alkoxy group, a halogeno group, a nitro group, and a cyano group, with a halogeno group being preferred.
• Examples of the "halogeno group” include fluoro, chloro, bromo, and iodo, with fluoro being preferred.
• alcohol compounds can be divided into fluorinated alcohol compounds that essentially have a fluoro group as a substituent, and non-fluorinated alcohols that are not substituted with a fluoro group.
• the halogeno group that the non-fluorinated alcohol may have as a substituent is one or more halogeno groups selected from chloro, bromo, and iodo.
• the group "R x " having a fluoro group as a substituent may be represented as "R F x ".
• C 1-6 alkyl group refers to a linear or branched monovalent saturated aliphatic hydrocarbon group having from 1 to 6 carbon atoms. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, etc.
• a C 1-4 alkyl group is preferred, a C 1-2 alkyl group is more preferred, and methyl is even more preferred.
• C 1-6 alkoxy group refers to a linear or branched saturated aliphatic hydrocarbon oxy group having from 1 to 6 carbon atoms. Examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, n-pentoxy, n-hexoxy, etc., preferably a C 1-4 alkoxy group, more preferably a C 1-2 alkoxy group, and even more preferably methoxy.
• the monohydric alcohol compound (I) may be a fluorinated alcohol compound.
• the monohydric fluorinated alcohol compound (I) include fluorinated ethanol such as difluoroethanol and trifluoroethanol; and fluorinated propanols such as monofluoropropanol, difluoropropanol, trifluoropropanol, tetrafluoropropanol, pentafluoropropanol, and hexafluoropropanol.
• the divalent organic group may be a divalent organic group corresponding to the examples of the monovalent organic group.
• the divalent organic groups corresponding to the monovalent organic groups, C1-10 alkyl group, C2-10 alkenyl group, and C2-10 alkynyl group are C1-10 alkanediyl, C2-10 alkenediyl, and C2-10 alkynediyl.
• the divalent organic group may also be a divalent (poly)alkylene glycol group --[--O-- R.sub.2 --]. sub.n-- , where R.sub.2 represents a C.sub.1-8 alkanediyl group, and n represents an integer of 1 or more and 50 or less.
• examples of the dihydric alcohol compound (II) include the following dihydric alcohol compound (II-1):
• R 11 and R 12 independently represent H, a C 1-6 alkyl group, a C 1-6 fluoroalkyl group, or a C 6-12 aromatic hydrocarbon group, or together form a C 3-6 cycloalkyl group optionally substituted with a C 1-6 alkyl group;
• R 13 and R 14 each independently represent H, a C 1-6 alkyl group, or a C 6-12 aromatic hydrocarbon group; when p1 or p2 is an integer of 2 or greater, a plurality of R 13s or R 14s may be the same or different from each other; p1 and p2 independently represent an integer of 0 or more and 4 or less.
• dihydric alcohol compound (II-1) examples include 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, and 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, with 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) being preferred.
• the dihydric alcohol compound (II) may be a fluorinated alcohol compound.
• the dihydric fluorinated alcohol compound (II) include fluorinated ethylene glycol; fluorinated propylene glycols such as monofluoropropylene glycol and difluoropropylene glycol; fluorinated butanediols such as monofluorobutanediol, difluorobutanediol, trifluorobutanediol, and tetrafluorobutanediol; fluorinated pentanediols such as monofluoropentanediol, difluoropentanediol, trifluoropentanediol, tetrafluoropentanediol, pentafluoropentanediol, and hexafluoropentanediol; monofluorohexanediol,
• fluorinated hexanediols such as monofluoroheptanediol, difluoroheptanediol, trifluoroheptanediol, tetrafluoroheptanediol, pentafluoroheptanediol, hexafluoroheptanediol, heptafluoroheptanediol, octafluoroheptanediol, nonafluoroheptanediol, decafluoroheptanediol, and the like; fluorinated heptanediols such as monofluorooctanediol, difluorooctanediol, trifluorooctanediol, tetrafluorooctanediol, pentafluorooctaned
• the amount of the alcohol compound used may be adjusted as appropriate within the range in which the reaction proceeds well, but it is preferable that the molar ratio of the alcohol compound to the carbonyl halide produced is (2/valence of the alcohol compound) or more and (20/valence of the alcohol compound) or less.
• the molar ratio of the alcohol compound to the carbonyl halide produced is (2/valence of the alcohol compound) or more and (20/valence of the alcohol compound) or less.
• a dihydric alcohol compound having a molar ratio of 1 or more to the carbonyl halide produced can be used, and a monohydric alcohol compound having a molar ratio of 2 or more can be used.
• a carbonate compound can be obtained more efficiently.
• the molar ratio of the alcohol compound to the halomethane is (2/valence of the alcohol compound) or more and (20/valence of the alcohol compound) or less.
• the molar ratio of the dihydric alcohol compound to the halomethane is 1 or more, and the molar ratio of the monohydric alcohol compound to the halomethane is 2 or more.
• the molar ratio of the dihydric alcohol is preferably 1.5 or more, more preferably 2 or more, and also preferably 10 or less, and preferably 5 or less.
• the molar ratio of monohydric alcohol is preferably 2 or more, more preferably 4 or more, and is preferably 20 or less, more preferably 10 or less.
• a base may be used to promote the reaction between the carbonyl halide and the alcohol compound.
• the base is classified into an inorganic base and an organic base.
• inorganic bases include carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; carbonates of Group 2 metals such as magnesium carbonate, calcium carbonate, and barium carbonate; hydrogen carbonates of alkali metals such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and cesium hydrogen carbonate; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; hydroxides of Group 2 metals such as magnesium hydroxide and calcium hydroxide; and fluoride salts of alkali metals such as lithium fluoride, sodium fluoride, potassium fluoride, and cesium fluoride.
• carbonates or hydrogen carbonates of alkali metals or Group 2 metals having relatively low hygroscopicity and deliquescence are preferred, and carbonates of alkali metals are more preferred.
• fine ones such as powders may be used, or an aqueous solution may be used.
• organic base from the viewpoint of low reactivity with the product of the photoreaction of tetrahaloethylene, for example, tri(C 1-4 alkyl)amines such as trimethylamine, triethylamine, and diisopropylethylamine; sodium tert-butoxide, potassium tert-butoxide of an alkali metal; diazabicycloundecene, 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
• Hydrogen halides such as hydrogen chloride are produced as by-products during the oxidative photolysis of halomethanes and the reaction of carbonyl halides with alcohol compounds.
• Bases are effective in capturing such hydrogen halides, but when using a reaction tube with a small diameter, such as a coil reactor, a salt of the hydrogen halide and the base may precipitate and cause clogging. In such cases, it is preferable to use a base that forms an ionic liquid as a salt of the hydrogen halide and the base.
• bases include organic bases such as imidazole derivatives such as 1-methylimidazole.
• Bases such as pyridine, whose hydrochloride salts have a relatively low melting point, can also be used.
• the amount of base used may be adjusted as appropriate within the range in which the reaction proceeds well, but for example, it can be 1 mol or more and 10 mol or less per 1 mol of halomethane.
• the base may, for example, be added to the alcohol compound or may be continuously injected together with the alcohol compound.
• a solvent When reacting a carbonyl halide with an alcohol compound, a solvent may be used.
• the solvent may be added, for example, to a composition containing an alcohol compound.
• the solvent include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic hydrocarbon solvents such as n-hexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and benzonitrile; ether-based solvents such as diethyl ether, tetrahydrofuran, and dioxane; nitrile-based solvents such as acetonitrile; and halogenated hydrocarbon solvents such as dichloromethane and chloroform.
• the temperature for reacting the carbonyl halide with the alcohol compound is not particularly limited and may be adjusted as appropriate, but may be, for example, 0°C or higher and 250°C or lower.
• the temperature is preferably 10°C or higher, more preferably 20°C or higher, more preferably 200°C or lower or 150°C or lower, and even more preferably 100°C or lower or 80°C or lower.
• the temperature may be adjusted to a relatively high temperature, such as 50°C or higher or 100°C or higher.
• the time for reacting the carbonyl halide with the alcohol compound is not particularly limited and may be adjusted as appropriate, but is preferably, for example, 0.5 hours or more and 50 hours or less.
• the reaction time is more preferably 1 hour or more, even more preferably 5 hours or more, more preferably 30 hours or less, and even more preferably 20 hours or less.
• stirring of the reaction solution may be continued, for example, until consumption of the alcohol compound is confirmed.
• a linear carbonate compound represented by the following formula (III) is produced by the reaction of a carbonyl halide with an alcohol compound, and when 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 produced.
• a dihydric alcohol compound (II) is used, whether a polycarbonate compound (IV-1) or a cyclic carbonate compound (IV-2) is produced, and the production ratio thereof, mainly depend on the distance between the two hydroxyl groups in the dihydric alcohol compound (II) and the flexibility of the chemical structure. Specifically, this can be confirmed by a preliminary experiment or the like.
• the polymerization reaction proceeds very efficiently, and it is possible to obtain a polycarbonate compound with a large molecular weight.
• the polystyrene-equivalent weight average molecular weight of the polycarbonate compound obtained by the method of the present invention is preferably 10,000 or more and 1,000,000 or less, and the number average molecular weight is preferably 5,000 or more and 500,000 or less.
• a halogenated formate fluorinated ester can be obtained from the fluorinated monohydric alcohol compound (I), and a halogenated formate non-fluorinated ester can be obtained from the non-fluorinated monohydric alcohol compound (I).
• Post-reaction step - production of isocyanate compound 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 for carbamate compounds, urethane compounds, etc.
• a primary amine compound may be used instead of an alcohol compound, except for the following points.
• the primary amine compound is not particularly limited as long as it is a compound having one or more amino groups ( -NH2 groups), and for example, primary amine compound (V): R3- ( NH2 ) m can be used.
• R3 represents an organic group having a valence of m
• m represents an integer of 1 to 6, preferably 5 or less, 4 or less, or 3 or less, more preferably 1 or 2, and even more preferably 2.
• the monovalent organic groups can be exemplified by the same groups as the monovalent organic group R1 in the above-mentioned method for producing a carbonate compound
• the divalent organic groups can be exemplified by the same groups as the divalent organic group R2
• the trivalent or higher organic groups can be exemplified by the trivalent or higher organic groups corresponding to the examples of the monovalent organic group R1 .
• the trivalent organic groups corresponding to the monovalent organic groups C1-10 alkyl group, C2-10 alkenyl group, and C2-10 alkynyl group are C1-10 alkanetriyl, C2-10 alkenetriyl, and C2-10 alkyntriyl groups.
• the produced carbonyl halide is dissolved in a solvent to prepare a carbonyl halide solution, and the primary amine compound (V) or a solution thereof is added to the solution to maintain the molar ratio of the carbonyl halide to the primary amine compound (V) at more than 1, thereby efficiently producing an isocyanate compound.
• the target compound is an isocyanate compound
• the molar ratio is preferably 0.5 or less, more preferably 0.2 or less, and also preferably 0.001 or more, more preferably 0.05 or more.
• the ratio is preferably 2 or more, more preferably 4 or more, and also preferably 20 or less, more preferably 15 or less.
• a salt as the primary amine compound (V) since isocyanate compounds are unlikely to react with amine salts.
• examples of such salts include inorganic acid salts such as hydrochloride, hydrobromide, hydroiodide, sulfate, nitrate, perchlorate, and phosphate; and organic acid salts such as oxalate, malonate, maleate, fumarate, lactate, malate, citrate, tartrate, benzoate, trifluoroacetate, acetate, methanesulfonate, p-toluenesulfonate, and trifluoromethanesulfonate.
• the temperature for the reaction between the carbonyl halide and the primary amine compound is preferably set lower than the reaction temperature with the alcohol compound, for example, in order to maintain the carbonyl halide in a liquid state.
• the reaction temperature can be 15°C or lower, preferably 10°C or lower, more preferably 5°C or lower, and even more preferably 2°C or lower.
• the temperature is preferably -80°C or higher, and more preferably -20°C or higher or -15°C or higher.
• the base is preferably one or more bases selected from heterocyclic aromatic amines and non-nucleophilic strong bases.
• Heterocyclic aromatic amines refer to compounds that contain at least one heterocycle and have at least one amine functional group other than -NH2 .
• heterocyclic aromatic amines include pyridine and its derivatives, such as pyridine, ⁇ -picoline, ⁇ -picoline, ⁇ -picoline, 2,3-lutidine, 2,4-lutidine, 2,6-lutidine, 3,5-lutidine, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine, 2,4,6-trimethylpyridine, and 4-dimethylaminopyridine.
• non-nucleophilic strong base refers to a base in which the nucleophilicity of the lone pair on the nitrogen atom is weak due to steric hindrance, but which is a strong base.
• the base include 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-d
• a base with a relatively high basicity may also be used.
• bases 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.
• bases that can be used include general-purpose organic amines such as trimethylamine, dimethylethylamine, diethylmethylamine, N-ethyl-N-methylbutylamine, and 1-methylpyrrolidine.
• the target compound is a urea compound
• the molar ratio of the primary amine compound to the halomethane or the carbonyl halide produced is greater than 1.
• the molar ratio is preferably 1.5 or more, and more preferably 2 or more.
• a carbamoyl halide compound can be produced by reacting a carbonyl halide with a secondary amine compound.
• the carbamoyl halide compound is useful as a synthetic intermediate for carbamate esters, such as carbamate compounds having insecticidal properties, and physiologically active substances such as medicines and agricultural chemicals.
• a secondary amine compound may be used instead of a primary amine compound in the above-mentioned method for producing an isocyanate compound.
• the secondary amine compound is not particularly limited as long as it is a compound having one or more secondary amino groups (-NHR groups), and for example, secondary amine compound (XI): R 21 -NH-R 22 can be used.
• R 21 and R 22 each independently represent a monovalent organic group, and examples thereof include the same groups as the monovalent organic group R 1 in the above-mentioned method for producing a carbonate compound, with a C 1-10 alkyl group being preferred.
• the amount of the secondary amine compound (XI) used to a relatively low level for example, to adjust the molar ratio of the secondary amine compound (XI) to methane to 1 or less, or not to use a base.
• the generated carbonyl halide is dissolved in a solvent to prepare a carbonyl halide solution, and a secondary amine compound (XI) or a solution thereof is added to the solution to maintain the molar ratio of the carbonyl halide to the secondary amine compound (XI) at more than 1, thereby enabling efficient production of a carbamoyl halide compound.
• the target compound is a carbamoyl halide compound
• the molar ratio of secondary amine compound (XI) to the methane used is preferably 0.5 or less, more preferably 0.2 or less, and also preferably 0.001 or more, more preferably 0.05 or more.
• the ratio is preferably 2 or more, more preferably 4 or more, and also preferably 20 or less, more preferably 15 or less.
• the temperature for the reaction of the carbonyl halide with the secondary amine compound (XI) is preferably set lower than the reaction temperature with the alcohol compound, for example, in order to maintain the carbonyl halide in a liquid state.
• the reaction temperature can be 15°C or lower, preferably 10°C or lower, more preferably 5°C or lower, and even more preferably 2°C or lower.
• the temperature is preferably -80°C or higher, and more preferably -20°C or higher or -15°C or higher.
• the target compound is a carbamoyl halide compound and a base is used, it is preferable to use one or more bases selected from the heterocyclic aromatic amines and non-nucleophilic strong bases exemplified in the production conditions for the isocyanate compound.
• the target compound is a urea compound, it is preferable to set the molar ratio of the secondary amine compound to methane or the generated carbonyl halide to more than 1. The molar ratio is preferably 1.5 or more, and more preferably 2 or more.
• NCA amino acid N-carboxylic anhydride
• R4 represents an amino acid side chain group in which a reactive group is protected
• R6 represents an amino acid side chain in which a reactive group is protected
• P1 represents a protecting group for an amino group
• l represents an integer of 1 or more, and when l is an integer of 2 or more, multiple R6s may be the same or different.
• Vilsmeier reagent (X) can be prepared by reacting carbonyl halide with amide compound (IX).
• the Vilsmeier reagent can be prepared in the same manner as in the above-mentioned method for preparing a carbonate compound, except that amide compound (IX) is used instead of an alcohol compound and no base is used.
• R7 represents a hydrogen atom, a C1-6 alkyl group, or a C6-12 aromatic hydrocarbon group which may have a substituent
• R 8 and R 9 are each independently a C 1-6 alkyl group or a C 6-12 aromatic hydrocarbon group which may have a substituent, and R 8 and R 9 may combine together to form a ring structure having 4 to 7 members
• X represents a halogeno group selected from the group consisting of chloro, bromo and iodo
• Y ⁇ represents a counter anion.
• the substituents that the C6-12 aromatic hydrocarbon group may have are not particularly limited as long as they do not inhibit the reaction according to the present invention, and examples thereof include one or more substituents selected from the group consisting of a C1-6 alkyl group, a C1-6 alkoxy group, a halogeno group, a nitro group, and a cyano group.
• the number of substituents is not particularly limited as long as it is substitutable, and can be, for example, 1 to 5, preferably 3 or less, more preferably 2 or less, and even more preferably 1. When the number of substituents is 2 or more, the substituents may be the same or different from each other.
• Examples of the 4- to 7-membered ring structure formed by R 8 and R 9 together with the nitrogen atom include a pyrrolidyl group, a piperidyl group, and a morpholino group.
• amide compound (IX) examples include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-methyl-N-phenylformamide, N-methylpyrrolidone (NMP), 1,3-dimethylimidazolidinone (DMI), tetramethylurea, tetraethylurea, and tetrabutylurea, with DMF being preferred from the standpoint of versatility, cost, and the like.
• DMF N,N-dimethylformamide
• DMA N,N-dimethylacetamide
• NMP N-methylpyrrolidone
• DI 1,3-dimethylimidazolidinone
• tetramethylurea tetraethylurea
• tetrabutylurea examples include tetrabutylurea, with DMF being preferred from the standpoint of versatility, cost, and the like.
• Y ⁇ in formula (X) includes, but is not particularly limited to, chloride ions, bromide ions, and iodide ions derived from halomethanes.
• the amount of amide compound used may be adjusted as appropriate within the range in which the reaction proceeds well, but for example, it can be set to 0.1 mol or more and 100 mol or less per 1 mL of halomethane.
• a solvent When reacting a carbonyl halide with an amide compound, a solvent may be used.
• the solvent may be added, for example, to a composition containing an amide compound.
• the solvent include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as ethyl acetate; aliphatic hydrocarbon solvents such as n-hexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, and benzonitrile; ether-based solvents such as diethyl ether, tetrahydrofuran, and dioxane; and nitrile-based solvents such as acetonitrile.
• ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohe
• the temperature for reacting the carbonyl halide with the amide compound is not particularly limited and may be adjusted as appropriate, but may be, for example, 0°C or higher and 120°C or lower.
• the temperature is preferably 10°C or higher, more preferably 20°C or higher, more preferably 100°C or lower, and even more preferably 80°C or lower or 50°C or lower.
• the time for reacting the carbonyl halide with the amide compound is not particularly limited and may be adjusted as appropriate, but is preferably, for example, 0.5 hours or more and 50 hours or less.
• the reaction time is more preferably 1 hour or more, even more preferably 5 hours or more, more preferably 30 hours or less, and even more preferably 20 hours or less.
• stirring of the reaction solution may be continued, for example, until consumption of the amide compound is confirmed.
• Aromatic compounds with active groups can be converted to aldehydes or ketones by the Vilsmeier-Haack reaction using the Vilsmeier reagent.
• the Vilsmeier reagent is also known to convert the carboxy group of a carboxylic acid compound to a haloformyl group.
• formic esters can be obtained by reacting the Vilsmeier reagent with a hydroxyl group-containing compound.
• Aromatic compounds having an active group are aromatic compounds activated by a substituent or the like.
• amino groups including alkylamino groups substituted with alkyl groups and hydroxyl groups strongly activate aromatic compounds.
• these substituents are referred to as activated groups.
• the activated aromatic compound is not particularly limited as long as it is a compound that is activated and can be converted into an aldehyde or keton by a Vilsmeier reagent, and examples thereof include C6-12 aromatic hydrocarbons such as benzene and naphthalene substituted with the above-mentioned activating group; condensed aromatic hydrocarbons such as phenanthrene and anthracene which may be substituted with the above-mentioned activating group; 5-membered ring heteroaryl groups such as pyrrole, imidazole, pyrazole, thiophene, furan, oxazole, isoxazole, thiazole, isothiazole, thiadiazole, etc.
• 6-membered ring heteroaryls such as pyridine, pyrazine, pyrimidine, pyridazine, etc. which may be substituted with the above-mentioned activating group
• condensed heteroaryls such as indole, isoindole, quinoline, isoquinoline, benzofuran, isobenzofuran, chromene, etc. which may be substituted with the above-mentioned activating group.
• the substrate compounds for the above reaction may be added to the reaction liquid after the carbonyl halide-containing gas is blown into the composition containing the amide compound, or may be added to the reaction liquid before or during the blowing of the carbonyl halide-containing gas into the composition containing the amide compound.
• the amounts of the active group-containing aromatic compound, carboxylic acid compound, and hydroxyl group-containing compound used may be adjusted as appropriate, but may be, for example, 0.1 to 1.0 times the molar amount of the amide compound.
• the Vilsmeier reagent is also useful for obtaining carboxylic acid halides from carboxylic acid compounds.
• a carboxylic acid compound is halogenated, the Vilsmeier reagent returns to an amide compound. If the obtained carboxylic acid halide is reacted with an alcohol compound, an ester compound is obtained, and if a carboxylic acid is reacted with it, a carboxylic acid anhydride is obtained. It is considered that if a carboxylic acid compound and a base are used instead of an amide compound, the carboxylic acid compound anionized by the base can be directly converted to a carboxylic acid halide by a carbonyl halide. Such carboxylic acid halides can also be used to produce ester compounds and carboxylic acid anhydrides.
• Post-treatment process Since many carbonyl halides are harmful, it is preferable not to allow the generated carbonyl halide to leak out of the system.
• the alcohol trap may be cooled to a temperature within a range in which the alcohol used does not solidify, for example, between -80°C and 50°C.
• an aqueous sodium hydroxide solution or a saturated aqueous sodium hydrogen carbonate solution can be used for the alkali trap.
• an additional reaction substrate compound may be added to the reaction solution obtained by reacting the carbonyl halide.
• the target compound may be purified from the reaction solution.
• a water-insoluble organic solvent such as chloroform and water may be added to the reaction solution to separate the liquids, and the organic phase may be dried over anhydrous sodium sulfate or anhydrous magnesium sulfate, concentrated under reduced pressure, and further purified by chromatography, etc.
• Example 1 Preparation of carbonyl chloride Using the flow photoreaction system shown in FIG. 1, ozone photooxidation of chloroform containing 10 ppm of amylene as a stabilizer was carried out. Chloroform was pumped from a syringe pump, and was mixed with a mixed gas of ozone and oxygen generated by an ozone gas generator ("PZH-05N" manufactured by Kofloc Co., Ltd.), mixed in an arbitrary ratio in a PTFE tube, and a mixed gas of chloroform, ozone, and oxygen was prepared through a coil heater heated to 120°C, and sent to the flow photoreactor.
• PZH-05N ozone gas generator
• the flow photoreactor (volume: 700 mL, length: 180 mm) is composed of a cylindrical borosilicate glass container ( ⁇ 80 mm) with an inner tube ( ⁇ 30 mm) made of quartz glass, a 20 W low-pressure mercury lamp ("SUL-20P” manufactured by Sen Special Light Sources Co., Ltd., light-emitting part length: 130 mm) inserted in the inner tube, and a hot plate ("HTP452AB” manufactured by ADVANTEC Co., Ltd.) with the bottom heated to 100°C.
• the wavelength range of the lamp light was 185-600 nm, with peak wavelengths of 184.9 nm and 253.7 nm.
• the illuminance of the 185 nm light at a position 5 mm from the lamp was 2.00-2.81 mW/cm 2 , and the illuminance of the 254 nm light at the same position was 5.60-8.09 mW/cm 2.
• the flow rates of chloroform and ozone gas were adjusted as shown in Table 1, and the residence time of the reaction gas in the flow photoreaction reactor was controlled to 3.4 minutes to study the ozone photooxidation reaction of chloroform.
• the gaseous product generated in the system was blown into 1-butanol placed in the first reaction vessel to obtain a mixed product of chloroformate and carbonate.
• the gas from the first reaction vessel was similarly supplied to a second reaction vessel containing 1-butanol.
• reaction liquids in the first reaction vessel and the second reaction vessel were analyzed to determine the amounts of ethyl chloroformate, dibutyl carbonate, and carbonyl chloride produced.
• the results are shown in Table 1.
• the amount of carbonyl chloride produced was calculated on the assumption that all of the produced carbonyl chloride reacted with 1-butanol.
• Example 2 Production of carbonyl chloride Using a flow photoreaction system as shown in FIG. 2, ozone photooxidation of chloroform containing 10 ppm of amylene as a stabilizer was carried out. Chloroform was pumped from a syringe pump, and was mixed with a mixed gas of ozone and oxygen generated by an ozone gas generator ("PZH-05N" manufactured by Kofloc Co., Ltd.), mixed in a PTFE tube, and passed through a coil heater heated to 120°C to prepare a mixed gas of chloroform, ozone, and oxygen, which was then sent to the flow photoreactor.
• PZH-05N ozone gas generator
• the flow photoreactor was composed of a borosilicate glass container (outer dimensions: 250 mm x 400 mm x 50 mm, plate thickness: 3.3 mm, internal volume: 4157 cm 3 ), an LED lamp (manufactured by Polarstar Co., Ltd., peak wavelength: 365 nm, 30 W, LED (14 cm x 18 cm) x 2), and a hot plate ("HTP452AB" manufactured by ADVANTEC Co., Ltd.) heated to 100°C.
• the illuminance of the light at a position 5 mm from the lamp was 54.7 to 54.4 mW/cm 2 .
• the flow rates of chloroform and ozone gas were adjusted to control the residence time of the reaction gas in the flow photoreactor to 35 minutes, and the ozone photooxidation reaction of chloroform was investigated.
• the gaseous product generated in the system was blown into 1-butanol placed in a first reaction vessel to obtain a mixed product of chloroformate and carbonate.
• the gas from the first reaction vessel was supplied to a second reaction vessel, which also contained 1-butanol.
• the reaction solutions in the first and second reaction vessels were analyzed to determine the amounts of ethyl chloroformate, dibutyl carbonate, and carbonyl chloride produced. For comparison, an experiment was also carried out in the same manner except that no ozone was supplied. The results are shown in Table 2.
• chloroform containing amylene (2-pentene) as a stabilizer was hardly photo-oxidized when irradiated with visible light (365 nm).
• chloroform containing amylene as a stabilizer was photooxidized to produce carbonyl chloride in a high yield of 95%. It was experimentally confirmed by 1 H NMR that amylene (2-pentene) was decomposed by reaction with ozone to give acetaldehyde and propionaldehyde.
• Example 3 Production of carbonyl chloride Ozone photooxidation of chloroform was carried out using a flow photoreaction system as shown in Fig. 3.
• the chloroform used included one containing amylene as a stabilizer, one from which the stabilizer had been removed, and one pretreated with ozone to decompose amylene.
• Chloroform was pumped from a syringe pump, and was mixed with a mixed gas of ozone and oxygen generated by an ozone gas generator ("PZH-05N" manufactured by Kofloc Co., Ltd.), mixed in a PTFE tube, and passed through a coil heater heated to 120°C to prepare a mixed gas of chloroform, ozone, and oxygen, which was then sent to the flow photoreactor.
• PZH-05N ozone gas generator
• the flow photoreactor was composed of a PFA tube (inner diameter: 0.2 cm, outer diameter: 0.3 cm, length: 1940 cm, volume: 61.0 cm 3 ), an LED lamp (manufactured by Polarstar Co., Ltd., peak wavelength: 365 nm, 30 W, LED (14 cm x 18 cm) x 2), and a hot plate ("HTP452AB" manufactured by ADVANTEC Co., Ltd.) heated to 100°C.
• the illuminance of the light at a position 5 mm from the lamp was 54.7 to 54.4 mW/cm 2 .
• the flow rates of chloroform and ozone gas were adjusted to control the residence time of the reaction gas in the flow photoreactor to 1.5 minutes, and the ozone photooxidation reaction of chloroform was investigated.
• the gaseous product generated in the system was blown into 1-butanol placed in a first reaction vessel to obtain a mixed product of chloroformate and carbonate.
• the gas from the first reaction vessel was supplied to a second reaction vessel, which also contained 1-butanol.
• the reaction solutions in the first and second reaction vessels were analyzed to determine the amounts of ethyl chloroformate, dibutyl carbonate, and carbonyl chloride produced.
• chloroform containing amylene (2-pentene) as a stabilizer was not photo-oxidized by irradiation with oxygen and visible light (365 nm) alone, without the use of ozone.
• Chloroform without stabilizers or chloroform from which the stabilizers had been decomposed by pretreatment with ozone was photooxidized to some extent by irradiation with visible light alone, but the conversion efficiency was not sufficient.
• chloroform containing a stabilizer was hardly decomposed by oxidation without light irradiation.
• the addition of ozone to oxygen significantly improved the yield, and the yield increased further as the proportion of ozone increased.
• Carbonyl chloride could also be successfully produced from chloroform containing a stabilizer by using ozone in combination.
• the yield was somewhat reduced.
• the relatively low conversion efficiency compared to other examples is likely due to the short residence time of the gas in the reactor of 1.5 minutes.
• Example 4 Production of carbonyl chloride Using a flow photoreaction system as shown in FIG. 4, ozone photooxidation of chloroform containing about 10 ppm of amylene as a stabilizer was carried out. Liquid chloroform was placed in a 1L two-necked eggplant flask and heated and stirred at 60°C. A mixed gas of ozone and oxygen generated by an ozone gas generator ("PZH-05N" manufactured by Kofloc) was blown into the liquid chloroform through a PTFE tube (inner diameter: 0.2 cm, outer diameter: 0.3 cm), and the flask was irradiated with light.
• PZH-05N ozone gas generator
• the flow photoreaction reactor was composed of the eggplant flask equipped with a cooling condenser (0°C), a magnetic stirrer, an LED lamp (manufactured by Polarstar, 365 nm, 30 W, LED (14 cm x 18 cm) x 1), and an aluminum block bath.
• the flow rate of the ozone gas was adjusted to control the residence time of the gas in the reactor as shown in Table 4, and the ozone photooxidation reaction of chloroform was examined.
• the gaseous product generated by the system was blown into 1-butanol placed in a two-necked eggplant flask to obtain a mixed product of chloroformate and carbonate.
• the mixed product was analyzed to determine the amounts of ethyl chloroformate, dibutyl carbonate, and carbonyl chloride produced.
• the results are shown in Table 4.
• the results in Table 4 are average values calculated from a 2-hour reaction.
• the isolated yield based on the raw material phenol was 89%. Ozone may oxidize phenol and cause it to turn brown, but no such coloring was observed in this reaction, and visual observation showed that the diphenyl carbonate produced using ozone was less colored than the diphenyl carbonate produced in the same manner except that only oxygen was used. The mechanism is unknown, but it may be due to the decolorizing effect of ozone.
• the solvent was removed from the organic phase under reduced pressure using an evaporator, n-hexane was added, and the resulting precipitate was collected by filtration and dried in vacuum at 80°C for 2 hours to obtain the target compound as a white solid (9.18 g, 36.1 mmol).
• the isolation yield based on the raw material bisphenol A was 72%.
• the method of the present invention may be able to produce polycarbonate with higher transparency.
• most of the polycarbonate obtained by the method of the present invention was insoluble in organic solvents, and even the molecular weight of the soluble portion was much larger than that of the polycarbonate produced in the same manner except that only oxygen was used. Therefore, it is possible that the use of ozone in addition to oxygen accelerated not only the oxidative photodecomposition reaction of chloroform but also the polymerization reaction.
• dichloromethane 100mL was placed in a two-neck flask, and the gas obtained from the flow photoreactor was blown in for 1 or 2 hours while stirring at 0°C.
• the LED lamp was turned off, the injection of chloroform was stopped, and under normal room lighting, a dichloromethane solution of an amine or diamine shown in Table 6 was injected into the above dichloromethane solution.
• pyridine was added in an amount 5 times the molar amount of the amino group of the added amine or diamine, and the mixture was stirred at 0° C. for 1 hour.
• dichloromethane 200 mL was placed in a two-neck flask, and the gas obtained from the flow photoreactor was blown into it over a period of 1 hour while stirring at 0° C.
• the LED lamp was turned off, the injection of chloroform was stopped, and a secondary amine or its hydrochloride (15 mmol) shown in Table 7 was injected into the dichloromethane solution under normal room lighting.
• triethylamine (TEA) 60 mmol was added in an amount four times the molar amount of the added amine, and the mixture was stirred at 0° C. for 1 hour.
• Example 9 Preparation of phenylalanine-N-carboxylic anhydride
• chloroform containing amylene as a stabilizer was injected at a flow rate of 50.3 ⁇ L/min, vaporized by a heater, and mixed with the ozone-oxygen mixed gas to prepare an ozone-oxygen-chloroform mixed gas.
• the ozone-oxygen-chloroform mixed gas was continuously fed into the flow photoreactor, and light with a peak wavelength of 365 nm was irradiated at 100° C.

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