JP6057449B2 - Method for producing halogenated formate - Google Patents

Description

  The present invention relates to a method for producing a halogenated carboxylic acid ester, and more particularly to a method for producing a halogenated carboxylic acid ester by an oxidative photoreaction.

  Carbonyl halides are used in various fields as chemical reaction raw materials, and are very useful compounds in organic synthesis. For example, phosgene, which is one of carbonyl halides, is a very useful compound used as a raw material for the synthesis of urea derivatives, carbonate ester derivatives, polycarbonates and the like.

  However, many of the carbonyl halides are very toxic, and some of them produce toxic and corrosive gases upon contact with water, which makes them difficult to store and can be dangerous to handle. . In particular, phosgene has a history of being used as a suffocating toxic gas, and there is a risk of death due to suction during use.

  As a method for performing a chemical reaction involving the carbonyl halide as described above in a safer and simpler manner, Patent Document 1 discloses mixing phosgene and alcohol obtained by irradiating chloroform or the like with light in the presence of oxygen, Disclosed is a method of obtaining a carbonic acid diester by reacting in the presence of a catalyst or adding alcohol and a catalyst to another reactor communicated with a reactor having light irradiation means and blowing phosgene into the reactor. Has been.

JP 2013-181028 A

  However, what is obtained by the method of Patent Document 1 is a carbonic acid diester, not a halogenated carboxylic acid ester.

  Accordingly, an object of the present invention is to provide a method for producing a halogenated carboxylic acid ester, which is a useful compound in organic synthesis, safely and simply from an inexpensive raw material.

  Hereinafter, the present invention will be described.

  [1] Production of a halogenated carboxylic acid ester represented by the following general formula (1), wherein a mixture containing a halocarbon and / or a halogenated hydrocarbon and an alcohol is irradiated with light in the presence of oxygen. Method.

(In the general formula (1), X represents a halogen atom or a halogenated methyl group, and R represents a hydrocarbon group which may have a substituent and / or a hetero atom.)
[2] The method for producing a halogenated carboxylic acid ester according to the above [1], wherein the mixing ratio of the alcohol to the halocarbon and / or the halogenated hydrocarbon is 0.001 to 1 in terms of molar ratio.

  [3] The method for producing a halogenated carboxylic acid ester according to the above [1] or [2], wherein the alcohol is a primary or secondary alcohol.

  [4] The halogenated carboxylic acid ester according to any one of the above [1] to [3], wherein the halogen, that is, the halogen atom substituted for the halocarbon and / or the halogenated hydrocarbon is chlorine or bromine. Production method. For example, when halogen is chlorine, halocarbon is carbon chloride, halogenated hydrocarbon is chlorinated hydrocarbon, halogen atom is chlorine atom, halogenated methyl group is methyl chloride group, halogenated carboxylic acid ester Becomes a chlorocarboxylic acid ester. The same applies when the halogen is bromine.

  [5] The method for producing a halogenated carboxylic acid ester according to any one of the above [1] to [4], wherein the light applied to the mixture includes light having a wavelength of 180 nm to 500 nm.

  According to the production method of the present invention, a halogenated carboxylic acid ester, which is a compound useful in organic synthesis, can be produced safely and simply from a mixture of halocarbon and / or halogenated hydrocarbon and alcohol. In addition, according to the present invention, halocarbons and halogenated hydrocarbons used as a solvent or the like can be decomposed by light irradiation, and can be effectively reused as a raw material for various chemical reactions.

It is a schematic diagram which shows an example of a structure of the reaction apparatus used for this invention.

  The production method of the present invention is a method for producing a halogenated carboxylic acid ester represented by the following general formula (1), wherein oxygen is present in a mixture containing a halocarbon and / or a halogenated hydrocarbon and an alcohol. It is characterized by light irradiation below.

(In the general formula (1), X represents a halogen atom or a halogenated methyl group, and R represents a hydrocarbon group which may have a substituent and / or a hetero atom.)
In the method of the present invention, one or more halogenated raw material compounds selected from the group consisting of halocarbons and / or halogenated hydrocarbons, that is, halocarbons and halogenated hydrocarbons, are used as raw material compounds.

  Halocarbons and halogenated hydrocarbons (hereinafter, halocarbons and halogenated hydrocarbons may be referred to as “halogenated raw material compounds”) are decomposed relatively easily in the presence of light and oxygen and are harmful gases. Generates carbonyl halide. For this reason, a small amount (for example, about 1%) of alcohol is added as a stabilizer to general commercial products. Accordingly, it has been considered that when an alcohol exceeding the amount used as a stabilizer is present in the reaction system, decomposition of the halogenated raw material compound is suppressed, and the formation reaction of the halogenated carboxylic acid ester does not proceed.

  However, as a result of intensive studies, the present inventor unexpectedly developed an oxidative photolysis reaction of the halogenated raw material compound by irradiating light to the mixture of the halogenated raw material compound and alcohol in the presence of oxygen. Furthermore, the present inventors have found that a halogenated carboxylic acid ester can be obtained in a high yield by reacting a decomposition product carbonyl halide with an alcohol, thereby completing the present invention.

  As described above, in the present invention, the carbonyl halide generated from the halogenated raw material compound by light irradiation is directly reacted with the alcohol in the same reaction system, so that harmful carbonyl halide is released out of the reaction system. Therefore, the halogenated carboxylic acid ester can be produced safely and simply. Moreover, according to this invention, halogenated carboxylic acid ester can be provided on the spot with a simpler photoreaction apparatus.

  Furthermore, the present invention uses halocarbons and / or halogenated hydrocarbons as raw materials that are consumed in large quantities as organic solvents and released into the atmosphere, causing environmental pollution such as air pollution and ozone layer destruction. This is a technology for producing useful compounds by photodegrading, and has a great contribution to industrial and environmental sciences. The present invention will be described below.

  The halocarbon and halogenated hydrocarbon used as the starting material in the production method of the present invention are compounds in which some or all of the hydrogen atoms of the hydrocarbon are substituted with halogen. In the present invention, “halocarbon” means a compound in which all hydrogen atoms of hydrocarbons are substituted with halogen, and “halogenated hydrocarbon” means that some hydrogen atoms of hydrocarbons are halogenated. A substituted compound is meant. Examples of the halogen atom include a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), and an iodine atom (I). In view of reactivity and usefulness of the product, the halogen atom is preferably a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom or a bromine atom.

  The hydrocarbon may have one or more of linear, branched or cyclic structures, and may have an unsaturated bond. Although carbon number which comprises a hydrocarbon is not specifically limited, For example, it is preferable that it is 1-50, More preferably, it is 1-10, 1-8 or 1-6, More preferably, it is 1-5, 1-3. , 1-2 or 1. As a matter of course, the carbon skeleton and the number of carbons of the hydrocarbon correspond to the skeleton and the number of carbons constituting the halocarbon and the halogenated hydrocarbon. The number of substitution with halogen atoms in the halogenated hydrocarbon is preferably 2 or more. Note that the number of substitutions by halogen atoms in the halocarbon is always 2 or more. When the hydrocarbon has 1 to 3 carbon atoms, the number of halogen atoms is preferably 1 to 8, for example. More preferably, it is 2-8, More preferably, it is 3-8. In the halogenated hydrocarbon, it is preferable that two or more halogen atoms are substituted on one carbon atom, or one or more halogen atoms are substituted on two adjacent carbon atoms. . Furthermore, it is preferable that the terminal carbon of the halogenated hydrocarbon is substituted with two or more halogen atoms.

Specific halocarbons include, for example, perhaloalkanes such as tetrafluoromethane, tetrachloromethane, tetrabromomethane, tetraiodomethane, hexafluoroethane, hexachloroethane, hexabromoethane, etc .; 1,1,2,2- And perhaloethene such as tetrafluoroethene, 1,1,2,2-tetrachloroethene, 1,1,2,2-tetrabromoethene, and the like. On the other hand, as the halogenated hydrocarbon, for example, halomethane such as chloromethane, dichloromethane, chloroform, bromomethane, dibromomethane, bromoform; 1,1,2,2-tetrachloroethane, 1,1,1,2-tetrachloroethane, Examples include haloethanes such as 1,1,2-trichloroethane and 1,1,1-trichloroethane; haloalkanes such as halopropane such as 1,1,1,3-tetrachloropropane, and the like. Specific halocarbons and / or halogenated hydrocarbons are selected from the group consisting of perhalo C _1-2 alkanes, perhalo C ₂ alkenes, and C _1-2 alkanes substituted with two or more halogen atoms. One or more of these are preferred.

  Halocarbons and halogenated hydrocarbons may be appropriately selected according to the intended chemical reaction and intended product, and one kind may be used alone, or two or more kinds may be used in combination. May be. For example, halocarbons and halogenated hydrocarbons may be used in combination, or two or more halocarbons or halogenated hydrocarbons may be used in combination. Preferably, only one kind of halocarbon and / or halogenated hydrocarbon is used depending on the production objective compound. Of the halocarbons and halogenated hydrocarbons, compounds having a chlorine atom are preferred.

  The halogenated raw material compound used in the method of the present invention may be, for example, one obtained by recovering the halogenated raw material compound once used as a solvent. At that time, if a large amount of impurities or water is contained, the reaction may be inhibited. Therefore, it is preferable to purify to some extent. For example, it is preferable to dehydrate with anhydrous sodium sulfate or anhydrous magnesium sulfate after removing water and water-soluble impurities by washing with water. However, since the reaction is considered to proceed even if about 1% by volume of water is contained, excessive purification that reduces the productivity is not necessary. The water content is more preferably 0.5% by volume or less, further preferably 0.2% by volume or less, and further preferably 0.1% by volume or less. The reusable halogenated raw material compound may contain a decomposition product of the halogenated raw material compound.

  In the production method of the present invention, an alcohol having the chemical structural formula of R—OH [wherein R represents a hydrocarbon group optionally having a substituent and / or a hetero atom] is used as one of the starting materials. . The alcohol is not particularly limited as long as it has a hydroxy group, and may have one or more of linear, branched, and cyclic structures and has an unsaturated bond. Alternatively, the hydrocarbon group may have a hetero atom (for example, N, O, S, etc.). Further, the carbon number of the alcohol is not particularly limited as long as it is mixed with the halocarbon and the halogenated hydrocarbon. For example, those having 1 to 1000 carbon atoms are preferably used. The number of carbon atoms is more preferably 3 or more, still more preferably 6 or more, and more preferably 800 or less, 600 or less, 500 or less, 200 or less, or 100 or less, and 80 or less, 60 or less, or 50 or less. More preferably, it is 40 or less, 20 or less, or 10 or less. The number of hydroxy groups is not particularly limited, and any of alcohol having one hydroxy group in one molecule, diol, triol or polyol having two or more hydroxy groups in one molecule can be used. The number of hydroxy groups is preferably 1 to 6, for example. In addition, the alcohol may have a substituent. Specific examples of the substituent include an alkyl group having 1 to 100 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen atom, a carboxyl group, a formyl group, Examples thereof include electron withdrawing groups such as nitrile groups, acyloxy groups having 1 to 12 carbon atoms, nitro groups, aryl groups having 6 to 20 carbon atoms, formyl groups, nitrile groups, acyloxy groups having 1 to 12 carbon atoms, and nitro groups. One or more substituents selected from the group consisting of are preferred. The number of substituents is not particularly limited as long as substitution is possible. For example, it is preferably 10 or less, 8 or less or 6 or less, more preferably 4 or less, and even more preferably 1 or 2. Examples of the hetero atom that the hydrocarbon group may have include one or more hetero atoms selected from N, O, and S.

  Specific alcohols include, for example, methanol, ethanol, propanol, isopropanol, propargyl alcohol, ethynyl alcohol, butanol, 2-butanol, tert-butanol, propenol, pentanol, hexanol, cyclohexanol, heptanol, cycloheptanol, octanol Linear, branched or cyclic aliphatic alcohols such as cyclooctanol, or alicyclic alcohols; phenol, 4-tert-butylphenol, 3,5-di-tert-butylphenol, 4-nitrophenol, 4-nitrophenol Fluorophenol, 4-chlorophenol, 4-bromophenol, pentafluorophenol, pentachlorophenol, pentabromophenol, bisphenol A, bisphenol B Bisphenol C, aromatic alcohols such as bisphenol P; polyvinyl alcohol, polyethylene glycol, high molecular weight alcohols such as polypropylene glycol. From the viewpoint of reactivity, primary alcohol or secondary alcohol is preferably used. Moreover, when chain | strand-shaped aliphatic alcohol is used as a raw material, since halogenated carboxylic acid ester is obtained with a sufficient yield, it is preferable. Alcohol may be used individually by 1 type and may be used in combination of 2 or more type.

  The amount of the halocarbon and / or halogenated hydrocarbon used with the alcohol is not particularly limited as long as the reaction proceeds and the desired product is obtained. For example, halocarbon and / or halogenated hydrocarbon The above reaction proceeds even when 1 mole of alcohol is used per mole. From the standpoint of reaction efficiency and reaction time, the mixing ratio of alcohol to halocarbon and / or halogenated hydrocarbon (alcohol / [halocarbon and / or halogenated hydrocarbon], molar ratio) is 0.001 or more. 1 or less is preferable. The mixing ratio is more preferably 0.01 or more, further preferably 0.1 or more, more preferably 0.8 or less, and further preferably 0.5 or less. If the mixing ratio is too large, the amount of alcohol will be relatively large and unreacted alcohol will increase. On the other hand, if the mixing ratio is too small, phosgene may be released outside the reaction system. In addition, unreacted halocarbons and / or halogenated hydrocarbons are increased.

  The mixing mode of the halogenated raw material compound and the alcohol is not particularly limited. The total amount of the halogenated raw material compound and alcohol may be mixed in advance, or the alcohol may be added in several portions to the halogenated raw material compound in the reaction vessel, and continuously at an arbitrary rate. You may add to. In addition, when one or both of the halogenated raw material compound and the alcohol are solid at room temperature, a solvent that can be appropriately dissolved in these raw material compounds and does not inhibit the reaction of the present invention may be used. In the present invention, at least a part of the alcohol is mixed with the halogenated raw material compound before light irradiation.

  Although a catalyst and various additives can be used in the reaction according to the present invention, it is preferable not to use a catalyst or an additive in the present invention from the viewpoint of efficiently obtaining a desired compound.

  In the present invention, a mixture containing halocarbon and / or halogenated hydrocarbon and alcohol is irradiated with light in the presence of oxygen. The oxygen source may be a gas containing oxygen. For example, air or purified oxygen can be used. The purified oxygen may be used by mixing with an inert gas such as nitrogen or argon. Air is preferably used from the viewpoint of cost and ease. From the viewpoint of increasing the decomposition efficiency of the halogenated raw material compound by light irradiation, the oxygen content in the gas used as the oxygen source is preferably about 15% by volume to 100% by volume. The oxygen content may be appropriately determined depending on the type of halogenated raw material compound. For example, when a chlorinated raw material compound (dichloromethane, chloroform, tetrachloroethane, etc.) is used as the halogenated raw material compound, the oxygen content is 15 volume% to 100 volume. % Is preferable, and when a bromide raw material compound (dibromomethane, bromoform or the like) is used, an oxygen content of about 90% by volume to 100% by volume is preferable. Even when oxygen (oxygen content: 100% by volume) is used, the oxygen content can be controlled within the above range by adjusting the oxygen flow rate into the reaction system. The method for supplying the gas containing oxygen is not particularly limited, and the gas may be supplied from an oxygen cylinder equipped with a flow rate regulator into the reaction system, or may be supplied from the oxygen generator into the reaction system.

  The presence of oxygen may be in a state where a mixture containing a halogenated raw material compound and an alcohol is in contact with oxygen or in a state where oxygen is present in the mixture. Therefore, the reaction according to the present invention may be performed under a gas stream containing oxygen. From the viewpoint of increasing the yield of the product, the gas containing oxygen is a mixture containing a halogenated raw material compound and an alcohol by bubbling. It is preferable to feed in.

  The amount of the gas containing oxygen may be appropriately determined according to the amount of halocarbon and / or halogenated hydrocarbon, the shape of the reaction vessel, and the like. For example, when 20 ml of halocarbon and / or halogenated hydrocarbon is used as the starting material, the flow rate of the gas containing oxygen to the reaction vessel is preferably 100 ml / min or more. More preferably, it is 500 ml / min or more, More preferably, it is 1000 ml / min or more, It is preferable that it is 10,000 ml / min or less, More preferably, it is 5000 ml / min or less, More preferably, it is 3000 ml / min or less. In addition, the amount of oxygen introduced into the reaction system may be smaller, for example, 10 ml / min or more and 500 ml / min or less. If the flow rate is too high, the halocarbon and / or halogenated hydrocarbon may volatilize, while if too low, the reaction may not proceed easily.

  Light that irradiates the mixture is preferably light including short-wavelength light (preferably ultraviolet light), and more specifically light having a wavelength of 180 nm to 500 nm is preferable. The wavelength of light may be appropriately determined according to the type of halocarbon and / or halogenated hydrocarbon, but is more preferably 180 nm to 400 nm, and still more preferably 180 nm to 300 nm. When the irradiation light contains light in the above wavelength range, the halogenated raw material compound can be efficiently oxidatively photodegraded.

  The light irradiation means is not particularly limited as long as it can irradiate light having a wavelength of 180 nm to 500 nm. Examples of the light source including light in such a wavelength range in the wavelength range include sunlight, a low-pressure mercury lamp, Examples thereof include a pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a black light lamp, and a metal halide lamp. From the viewpoint of reaction efficiency and cost, a low pressure mercury lamp or the like is preferably used.

Various conditions such as light intensity and irradiation time may be appropriately set depending on the type and amount of the starting material. For example, the light intensity is preferably 10 μW / cm ² illuminance or more, and 500 μW / cm ² illuminance. in is preferably less, more preferably not more than 100 .mu.W / cm ² illuminance, more preferably not more than 40μW / cm ² illuminance. The light irradiation time is preferably 0.5 hours to 10 hours, more preferably 1 hour to 6 hours, and still more preferably 2 hours to 4 hours. The mode of light irradiation is also not particularly limited, a mode in which light is irradiated continuously from the start to the end of the reaction, a mode in which light irradiation and light non-irradiation are repeated alternately, a mode in which light is irradiated for a predetermined time from the start of the reaction Either embodiment can be adopted, but an embodiment in which light is continuously irradiated from the start to the end of the reaction is preferable.

  Also, the temperature during the reaction is not particularly limited, but it is preferably 0 ° C to 50 ° C, more preferably 10 ° C to 40 ° C, and further preferably 20 ° C to 30 ° C.

  Examples of the reaction apparatus that can be used in the production method of the present invention include an apparatus equipped with a light irradiation means in a reaction vessel. The reaction apparatus may be provided with a stirring device and a temperature control means. FIG. 1 shows an embodiment of a reaction apparatus that can be used in the production method of the present invention. The reaction apparatus shown in FIG. 1 has a light irradiation means 1 in a cylindrical reaction vessel 6. A mixture containing halocarbon and / or halogenated hydrocarbon and alcohol is added to the cylindrical reaction vessel 6, and a gas containing oxygen is supplied into the reaction vessel 6, or a gas containing oxygen is added to the mixture. While bubbling (not shown), the reaction is performed by irradiating light from the light irradiation means 1. When the light irradiation means 1 is covered with a jacket 2 or the like, the jacket is preferably made of a material that transmits the short wavelength light. Moreover, you may irradiate light from the outer side of reaction container, In this case, it is preferable that a reaction container is a raw material which permeate | transmits the said short wavelength light. The material that transmits the short-wavelength light is not particularly limited as long as the effect of the present invention is not hindered, and preferred examples include quartz glass and Pyrex (registered trademark) glass.

  The product after the reaction may be purified by a conventionally known method. In addition, when the halogenated raw material compound or alcohol used as a starting material is a solvent used as a medium in many reactions, the reaction solution can be used as it is without isolating and purifying the product after completion of the reaction. You may use as a raw material of reaction. Examples of the purification method include distillation, vacuum distillation of starting materials, column chromatography, liquid separation extraction, washing, recrystallization and the like.

  The halogenated carboxylic acid ester obtained by the production method of the present invention is a compound represented by the following general formula (1).

In general formula (1), X represents a halogen atom or a halogenated methyl group. Examples of the halogen atom include a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), and an iodine atom (I). From the viewpoints of reactivity and usefulness of the product, a chlorine atom, a bromine atom or an iodine atom is preferable. When halogenated methane is used as the halogenated raw material compound, X becomes a halogen atom, and when a halogenated raw material compound having 2 or more carbon atoms is used, halogenated acetyl halide is mainly generated, and X is halogenated. It becomes a methyl group. The number of halogen atoms in the methyl halide group depends on the halogenated raw material compound used, the energy of irradiation light, and the like.

  In addition, when a halogenated raw material compound having 3 or more carbon atoms is used, X is a halogen atom or a methyl halide group due to the presence of oxygen and the rearrangement of the halogen atom or the breakage of the carbon chain caused by light irradiation. In addition to the generation of halogenated carboxylic acid esters, it is conceivable that halogenated carboxylic acid esters in which X is an alkyl group having 2 or more carbon atoms or a halogenated alkyl group are generated. For example, when a halogenated raw material compound having 3 or more carbon atoms and a terminal carbon substituted with 2 or more halogen atoms is used, X is an alkyl group having 2 or more carbon atoms or halogenated by the following reaction. There is a possibility that a halogenated carboxylic acid ester which is an alkyl group is formed.

[Wherein, R represents a hydrocarbon group which may have a substituent and a hetero atom, and R ¹ represents a hydrocarbon group having 2 or more carbon atoms which may have a halogen atom and / or a hetero atom. X represents a halogen atom, Y represents a halogen atom or a hydrogen atom]
R represents a hydrocarbon group. The hydrocarbon group corresponds to a portion other than the reactive hydroxy group of the alcohol used. Therefore, examples of the number of carbon atoms of alcohol also apply to hydrocarbon groups as they are. For example, the hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group having 1 to 1000 carbon atoms, or a group in which two or more of these groups are bonded. The hydrocarbon group may have a substituent or may have a heteroatom such as N, O, or S. Furthermore, some or all of the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group may be substituted with a substituent such as a halogen atom. Examples of the substituent include an alkyl group having 1 to 100 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen atom, a carboxyl group, a formyl group, a nitrile group, an acyloxy group having 1 to 12 carbon atoms, and a nitro group. 1 or more substituents selected from the group consisting of an aryl group having 6 to 20 carbon atoms, a formyl group, a nitrile group, an acyloxy group having 1 to 12 carbon atoms and a nitro group are preferable.

  The aliphatic hydrocarbon group preferably has 1 to 1000 carbon atoms, more preferably 3 or more, still more preferably 6 or more, and the carbon number is 800 or less, 600 or less, 500 or less, 200 Or less, 100 or less, more preferably 80 or less, 60 or less, or 50 or less, and even more preferably 40 or less, 20 or less, or 10 or less. Specific examples of the aliphatic hydrocarbon group include, for example, a chain or branched alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, an alkenyl group such as an ethenyl group and a propenyl group, and an alkynyl group such as an ethynyl group. 1 or more substituents selected from the group consisting of an aryl group having 6 to 20 carbon atoms, a formyl group, a nitrile group, an acyloxy group having 1 to 12 carbon atoms and a nitro group are preferable.

  As an alicyclic hydrocarbon group, a C3-C20 thing is preferable, For example, cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc. are mentioned.

  As the aromatic hydrocarbon group, those having 6 to 20 carbon atoms are preferable, for example, phenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, 4-nitrophenyl group, 4 Examples include aryl groups such as -fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, pentafluorophenyl group, pentachlorophenyl group, pentabromophenyl group.

  Examples of the halogenated carboxylic acid ester represented by the general formula (1) include, for example, ethyl fluoroformate, propyl fluoroformate, butyl fluoroformate, hexyl fluoroformate, cyclohexyl fluoroformate, ethyl trifluoroacetate, propyl trifluoroacetate, Butyl trifluoroacetate, hexyl trifluoroacetate, cyclohexyl trifluoroacetate, fluoroformate-tert-butylphenyl, fluoroformate-3,5-di-tert-butylphenyl, fluoroformate-4-nitrophenyl, fluoroformate-4- Fluorophenyl, fluoroformate-4-chlorophenyl, fluoroformate-4-bromophenyl, fluoroformate-pentafluorophenyl, fluoroformate-pentachlorophenyl, fluoroformate-pentabromophenyl, fluoroant -(2-methoxyethoxy) ethyl, ethyl chloroformate, propyl chloroformate, butyl chloroformate, hexyl chloroformate, cyclohexyl chloroformate, ethyl trichloroacetate, propyl trichloroacetate, butyl trichloroacetate, hexyl trichloroacetate, cyclohexyl trichloroacetate, chloro Formate-tert-butylphenyl, chloroformate-3,5-di-tert-butylphenyl, chloroformate-4-nitrophenyl, chloroformate-4-fluorophenyl, chloroformate-4-chlorophenyl, chloroformate-4-bromo Phenyl, chloroformate-pentafluorophenyl, chloroformate-pentachlorophenyl, chloroformate-pentabromophenyl, chloroformate- (2-methoxyethoxy) ethyl, trichloroacetate-tert-butylphenyl Trichloroacetic acid-3,5-di-tert-butylphenyl, trichloroacetic acid-4-nitrophenyl, trichloroacetic acid-4-fluorophenyl, trichloroacetic acid-4-chlorophenyl, trichloroacetic acid-4-bromophenyl, trichloroacetic acid-pentafluoro Phenyl, trichloroacetic acid-pentachlorophenyl, trichloroacetic acid-pentabromophenyl, trichloroformate- (2-methoxyethoxy) ethyl, ethyl bromoformate, propyl bromoformate, butyl bromoformate, hexyl bromoformate, cyclohexyl bromoformate, ethyl tribromoacetate, Propyl tribromoacetate, butyl tribromoacetate, hexyl tribromoacetate, cyclohexyl tribromoacetate, bromo-formate-tert-butylphenyl, bromoformate-3,5-di-tert-butyl Phenyl, bromo formic acid-4-nitrophenyl, bromo formic acid-4-fluorophenyl, bromo formic acid-4-chlorophenyl, bromo formic acid-4-bromophenyl, bromo formic acid-pentafluorophenyl, bromo formic acid-pentachlorophenyl, bromo formic acid-penta Examples thereof include bromophenyl and bromoformate- (2-methoxyethoxy) ethyl, but the halogenated carboxylic acid ester produced by the method of the present invention is not limited to the compounds exemplified above.

  The halogenated carboxylic acid ester can be used as a raw material when synthesizing urethane, asymmetric carbonic acid ester, carbamic acid ester and the like.

  This application claims the benefit of priority based on Japanese Patent Application No. 2014-80559 filed on Apr. 9, 2014. The entire contents of the specification of Japanese Patent Application No. 2014-80559 filed on April 9, 2014 are incorporated herein by reference.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, and may be appropriately modified within a range that can be adapted to the purpose described below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.

[NMR measurement]
Identification of the product was performed using an AVANCE 500 spectrometer (500 MHz) manufactured by Bruker. 2 mg of the product obtained in each experimental example was dissolved in 0.5 ml of deuterated chloroform (internal standard substance: tetramethylsilane), and a ¹ H-NMR spectrum was measured under the conditions of a temperature of 20 ° C. and a total of 16 times.

  Experimental Example 1 Production of butyl chloroformate

A cylindrical reaction vessel (diameter 42 mm) equipped with a quartz glass jacket with a diameter of 30 mm in the center is prepared, and a low-pressure mercury lamp (SEN Light, UVL20PH-6, 20 W, φ24 × 120 mm) is placed in the quartz glass jacket for reaction. Chloroform 20 ml (250 mmol, manufactured by Kishida Chemical Co., Ltd.) and n-butanol 0.46 ml (5 mmol, reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.) purified by washing with water and distillation were added to the container. While stirring the mixed solution, the reaction was carried out for 3 hours while bubbling air at 500 ml / min and at a temperature of 20 ° C. while irradiating light with the low-pressure mercury lamp. The progress of the reaction was confirmed by NMR, and the reaction was terminated when no peak derived from butanol as a starting material was confirmed. Then, chloroform was distilled off under reduced pressure to obtain a colorless oily crude product. It was confirmed by NMR measurement that the product was butyl chloroformate, and the yield was confirmed to be 62% from the comparison of the integrated value with the internal standard substance.
¹ H-NMR (solvent: deuterated chloroform) δ 4.30 (t, 2H, J = 6.6 Hz), 1.72 (quin, 2H, J = 7.1 Hz), 1.41 (m, 2H), 0.96 (t, 3H, J = 7.2 Hz)
Experimental Example 2 Production of hexyl chloroformate 1

The reaction was carried out for 3 hours while irradiating with light in the same manner as in Experimental Example 1 except that 0.62 ml (5 mmol, reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.) was used as the starting alcohol. . Chloroform was distilled off under reduced pressure to obtain a colorless oily crude product. It was confirmed by NMR measurement that the product was hexyl chloroformate, and the yield was confirmed to be 70% from comparison of the integrated value with the internal standard substance.
¹ H-NMR (solvent: deuterated chloroform) δ 4.32 (t, 2H, J = 6.8 Hz), 1.73 (quin, 2H, J = 7.1 Hz), 1.36 (m, 6H), 0.90 (t, 3H, J = 7.0 Hz)
Experimental Example 3 Production of cyclohexyl chloroformate

The reaction was carried out for 3 hours while irradiating light in the same manner as in Experimental Example 1 except that 0.52 ml of cyclohexanol (5 mmol, reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.) was used as the starting material alcohol. . From the NMR measurement by sampling the reaction solution, it was confirmed that the product was cyclohexyl chloroformate, and the yield was confirmed to be 30% by comparing the integral value with the internal standard substance.
¹ H-NMR (solvent: deuterated chloroform) δ 4.87 (m, 1H), 1.99 -1.31 (m, 10H)
Experimental Example 4 Production of 4-nitrophenyl chloroformate

The reaction was carried out for 3 hours while irradiating with light in the same manner as in Experimental Example 1 except that 696 mg of 4-nitrophenol (5 mmol, reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.) was used as the starting material alcohol. From the NMR measurement by sampling the reaction solution, it was confirmed that the product was 4-nitrophenyl chloroformate, and the yield was confirmed to be about 10% from the comparison of the integrated value with the internal standard substance.
¹ H-NMR (solvent: deuterated chloroform) δ 8.35 (d, 2H, J = 9.2 Hz), 8.29 (d, 2H, J = 9.2 Hz)
Experimental Example 5 Production of hexyl chloroformate 2
The reaction was carried out for 3 hours while irradiating light in the same manner as in Experimental Example 2 except that the amount of n-hexanol used was changed to 1.23 ml (10 mmol, reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.). Chloroform was distilled off under reduced pressure to obtain a colorless oily crude product. It was confirmed by NMR measurement that the product was hexyl chloroformate, and the yield was confirmed to be 70%.
¹ H-NMR (solvent: deuterated chloroform) δ 4.32 (t, 2H, J = 6.8 Hz), 1.73 (quin, 2H, J = 7.1 Hz), 1.36 (m, 6H), 0.90 (t, 3H, J = 7.0 Hz)
Experimental Example 6 Production of hexyl chloroformate 3

Instead of chloroform, 20 ml of tetrachloromethane (206 mmol, reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.) and 0.62 ml of n-hexanol (5 mmol, reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.) instead of n-butanol were used. The reaction was carried out for 3 hours while irradiating light in the same manner as in Experimental Example 1 except that it was used. Tetrachloromethane was distilled off under reduced pressure to obtain a colorless oily crude product. It was confirmed by NMR measurement that the product was hexyl chloroformate, and the yield was 13%.
¹ H-NMR (solvent: deuterated chloroform) δ 4.32 (t, 2H, J = 6.8 Hz), 1.73 (quin, 2H, J = 7.1 Hz), 1.36 (m, 6H), 0.90 (t, 3H, J = 7.0 Hz)
Experimental Example 7 Production of hexyl trichloroacetate

As in Experimental Example 1, 20 ml of 1,1,2,2-tetrachloroethene (196 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) and hexanol 0 were added as halogenated hydrocarbons in a cylindrical reaction vessel equipped with a low-pressure mercury lamp. .62 ml (5 mmol, reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.) was added. While stirring the mixed solution, the reaction was carried out for 3 hours while bubbling air at 500 ml / min and at a temperature of 20 ° C. while irradiating light with the low-pressure mercury lamp. From NMR measurement by sampling of the reaction solution, it was confirmed that the product was hexyl trichloroacetate, and the yield was confirmed to be 65%.
¹ H-NMR (solvent: deuterated chloroform) δ 4.36 (t, 2H, J = 8.0 Hz), 1.78 -1.28 (m, 8H), 0.90 (t, 3H, J = 8.0 Hz)
Experimental Example 8 Production of hexyl chloroformate 4
The reaction was carried out for 3 hours while irradiating light in the same manner as in Experimental Example 2 except that the amount of n-hexanol used was changed to 6.15 ml (50 mmol, reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.). From NMR measurement by sampling the reaction solution, it was confirmed that the product was hexyl chloroformate, and the yield was confirmed to be about 10%. When the reaction was continued for 2 hours while irradiating with light, the yield of the product was 15% (NMR measurement).
¹ H-NMR (solvent: deuterated chloroform) δ 4.32 (t, 2H, J = 6.8 Hz), 1.73 (quin, 2H, J = 7.1 Hz), 1.36 (m, 6H), 0.90 (t, 3H, J = 7.0 Hz)
Experimental Example 9 Preparation of chloroformic acid 2- (2-methoxyethoxy) ethyl ester

A cylindrical reaction vessel (diameter 42 mm) equipped with a quartz glass jacket with a diameter of 30 mm in the center is prepared. 20 ml of chloroform (250 mmol, manufactured by Kishida Chemical Co., Ltd.) and 1.18 ml of diethylene glycol monomethyl ether (10 mmol, reagent special grade, manufactured by Tokyo Chemical Industry Co., Ltd.) purified by washing with water and distillation were added to the container. While stirring the mixed solution, oxygen was bubbled at 50 ml / min, and the reaction was carried out for 2 hours at 20 ° C. while irradiating light with the low-pressure mercury lamp. The progress of the reaction was confirmed by NMR, and the reaction was terminated when no peak derived from diethylene glycol monomethyl ether as a starting material was confirmed. From the NMR measurement by sampling the reaction solution, it was confirmed that the product was chloroformic acid 2- (2-methoxyethoxy) ethyl ester, and the yield was 80% from the comparison of the integrated value with the internal standard substance. It was confirmed.
¹ H-NMR (solvent: deuterated chloroform) δ 4.47 (m, 2H), 3.78 (m, 2H), 3.67 (m, 2H), 3.57 (m, 2H), 3.39 (s, 3H)
Experimental Example 10 Production of Halogenated Carboxylic Acid Ester Using Recovered Halogenated Hydrocarbon Chloroform used in another experiment was recovered and washed with water, and then dehydrated using anhydrous sodium sulfate. When the obtained recovered chloroform was analyzed, it contained several percent hexane, several percent methylene chloride, and a decomposition product of chloroform. Chloroformic acid 2- (2-methoxyethoxy) ethyl ester was produced in the same manner as in Example 9 except that 20 ml of the recovered chloroform was used. When the yield was determined in the same manner as in Example 9, the yield was 65%.

  As described above, it was proved that the halogenated carboxylic acid ester can be produced in a good yield according to the method of the present invention even when the halogenated hydrocarbon is recovered and reused.

  According to the production method of the present invention, a halogenated carboxylic acid ester that is a useful compound in organic synthesis can be produced safely and simply from a mixture of a halogenated raw material compound and an alcohol. Further, although many halogenated carboxylic acid esters are unstable, according to the present invention, a halogenated carboxylic acid ester can be produced in situ with a relatively simple reaction apparatus. Furthermore, according to the present invention, the halogenated hydrocarbon used as a solvent or the like can be decomposed by light irradiation, and can be effectively reused as a raw material for various chemical reactions.

  The halogenated carboxylic acid ester obtained by the production method of the present invention can be used as a raw material for synthesizing urethane, asymmetric carbonic acid ester, carbamic acid ester and the like.

DESCRIPTION OF SYMBOLS 1 Light irradiation means 2 Jacket 3 Water bath 4 Stir bar 5 Refrigerant 6 Cylindrical reaction container

Claims (4)

Halocarbon and / or halogenated hydrocarbon (wherein halocarbon refers to a hydrocarbon having 1 carbon atom in which all hydrogen atoms have been replaced by chlorine, bromine or iodine atoms, A hydrocarbon having 1 part of carbon atoms in which some hydrogen atoms are substituted by chlorine, bromine or iodine atoms), and the mixing ratio with respect to the halocarbon and / or halogenated hydrocarbon is 0.001 to 0.001 in molar ratio. 1, the mixture comprising the alcohol represented by the general formula ROH, without using a catalyst, halogenated ant acid represented by the following general formula, which comprises light irradiation (1) in the presence of oxygen Ester production method.
(In general formula ROH and general formula (1), X represents a chlorine atom, a bromine atom or an iodine atom, and R represents a hydrocarbon group which may have a substituent and / or a hetero atom.) The alcohol production method of the halogenated ant ester according to claim 1 is a primary or secondary alcohol. The halocarbon and / or halogenated hydrocarbons substituted to have a halogen atom, and the X method of producing a halogenated ant ester according to claim 1 or 2 is a chlorine atom or a bromine atom. Light irradiated on the mixture, halogenated manufacturing method of ants ester according to claim 1 comprising a light having a wavelength 180Nm～500nm.