KR-102962139-B1 - Method for preparing carbonyl halides

KR102962139B1KR 102962139 B1KR102962139 B1KR 102962139B1KR-102962139-B1

Abstract

The present invention aims to provide a method for safely manufacturing halogenated carbonyls at low cost and with low environmental impact. The method for manufacturing halogenated carbonyls according to the present invention is characterized by comprising a process of irradiating light onto a mixed gas comprising methane, a halogen element gas, and oxygen.

Inventors

츠다, 아키히코

Assignees

고쿠리츠다이가쿠호진 고베다이가쿠

Dates

Publication Date: 20260507
Application Date: 20241011
Priority Date: 20231012

Claims (14)

As a method for preparing a carbonyl halide, A method characterized by including a process of irradiating a mixed gas containing methane, a halogen gas, and oxygen with light having a peak wavelength of 180 nm or more and 500 nm or less.
In Article 1, A method in which the above-mentioned halogenated carbonyl is carbonyl chloride and the above-mentioned halogenated gas is chlorine gas.
In Article 1, A method in which the above light has a peak wavelength of 360 nm or more and 500 nm or less.
In Article 1, A method of irradiating the above mixed gas with the above light at room temperature.
In Article 1, A method in which the shortest distance between the light source for the above light irradiation and the above mixed gas is 1m or less.
In Article 1, Additionally, a method comprising a process for obtaining an aqueous sodium halide solution by neutralizing the hydrogen halide produced by irradiating the mixed gas with light into a basic sodium salt.
In Article 1, Additionally, a method comprising a process for obtaining the halogen element gas and sodium hydroxide by electrolysis of an aqueous sodium halide solution.
As a method for manufacturing a carbonate compound, A process for producing a halogenated carbonyl by a method described in any one of claims 1 to 7, and, A method characterized by including a process of reacting an alcohol compound with the carbonyl halide.
As a method for preparing a halogenated formic acid ester compound, A process for producing a halogenated carbonyl by a method described in any one of claims 1 to 7, and, A method characterized by including a process of reacting an alcohol compound with the carbonyl halide.
As a method for preparing an isocyanate compound, A process for producing a halogenated carbonyl by a method described in any one of claims 1 to 7, and, A method characterized by including a process of reacting a primary amine compound with the carbonyl halide.
As a method for preparing a carbamoyl halide compound, A process for producing a halogenated carbonyl by a method described in any one of claims 1 to 7, and, A method characterized by including a process of reacting a secondary amine compound with the carbonyl halide.
A method for preparing amino acid-N-carboxylic acid anhydride, The above amino acid-N-carboxylic acid anhydride is represented by the following formula (VIII), and A process for producing a halogenated carbonyl by a method described in any one of claims 1 to 7, and, A method characterized by including a process of reacting an amino acid compound represented by the following formula (VII) with the carbonyl halide: In the above formula, R 4 represents an amino acid side chain in which the reactive group is protected, and R5 represents H, or P1 -[-NH- CHR6 -C(=O)-] l (wherein R6 represents an amino acid side chain in which the reactive group is protected, P1 represents a protecting group of the amino group, l represents an integer greater than or equal to 1, and if l is an integer greater than or equal to 2, multiple R6s may be the same or different from each other).
As a method for preparing a Bilsmeyer reagent, The above Bilsmayr reagent is a salt represented by the following formula (X), and A process for producing a halogenated carbonyl by a method described in any one of claims 1 to 7, and, A method characterized by including a process of reacting the above-mentioned halogenated carbonyl with an amide compound represented by the following formula (IX): In the above formula, R7 represents a hydrogen atom, a C1-6 alkyl group, or a C6-12 aromatic hydrocarbon group that may have a substituent, and R8 and R9 independently represent a C1-6 alkyl group or a C6-12 aromatic hydrocarbon group that may have a substituent, and R8 and R9 can combine to form a ring structure of 4 to 7 members, and X represents a halogen group selected from the group consisting of chloro, bromo, and iodine, and Y - indicates a counter no.
As a method for manufacturing a urea compound, A process for producing a halogenated carbonyl by a method described in any one of claims 1 to 7, and, A method characterized by including a process of reacting a primary amine compound or a secondary amine compound with the halogenated carbonyl.

Description

Method for preparing carbonyl halides The present invention relates to a method for producing carbonyl halogenates safely and at a lower cost. Carbonyl halides, such as carbonyl chloride, are very important as synthetic intermediates for various compounds. For example, carbonate derivatives are generally prepared from carbonyl chloride and compounds containing nucleophilic functional groups. However, carbonyl chloride is highly toxic, as it readily reacts with water to produce hydrogen chloride and has a history of being used as a poisonous gas. Carbonyl chloride is primarily produced by a highly exothermic gas-phase reaction of anhydrous chlorine gas and high-purity carbon monoxide in the presence of an activated carbon catalyst (Patent Document 1, etc.). The carbon monoxide used here is also toxic. The basic manufacturing process of carbonyl chloride has not changed significantly since the 1920s. The production of carbonyl chloride by such a process is expensive and requires massive facilities. However, due to the high toxicity of carbonyl chloride, ensuring broad safety is indispensable in plant design, which leads to increased manufacturing costs. Furthermore, the large-scale manufacturing process of carbonyl chloride raises concerns about causing many environmental problems. In addition, carbonyl chloride is produced by decomposing triphosgene [bis(trichloromethyl) carbonate] or diphosgene (trichloromethyl chloroformate) with bases such as triethylamine. However, it is known that triphosgene and diphosgene are expensive reagents, carry a potential risk of decomposing into carbonyl chloride upon physical or chemical stimulation, and are themselves highly toxic. Accordingly, the inventors have developed a technique for generating halogens and/or halogenated carbonyls by irradiating halogenated hydrocarbons with light in the presence of oxygen (Patent Document 2). According to this technique, the generated halogenated carbonyls can be reacted immediately by coexisting with reaction substrate compounds such as amine compounds or alcohol compounds, so it can be said to be safe. In addition, it is possible to recover halogenated carbonyls not used in the reaction by trapping them so that they do not leak out. For example, the inventors have also developed a technique for producing halogenated carboxylic acid esters by light irradiating a mixture containing a halogenated hydrocarbon and an alcohol in the presence of oxygen (Patent Document 3). The inventors have also developed a technique for producing carbonate derivatives by light irradiating a composition containing a halogenated hydrocarbon, a compound containing a nucleophilic functional group, and a base in the presence of oxygen (Patent Documents 4 and 5). FIG. 1 is a schematic diagram showing an example of the configuration of a reaction device used in the present invention. Figure 2 is the result of analyzing the reaction gas according to the present invention using 13C NMR. The method of the present invention is described below in order of process, but the present invention is not limited to the following specific examples. · Light irradiation process In this process, halogenated carbonyls are produced by irradiating a mixed gas containing methane, a halogen gas, and oxygen with light. Also, halogenated carbonyls are also called dihalogenated carbonyls, and for example, carbonyl chloride is also called dichlorinated carbonyl. Since methane has a boiling point of -161.6°C and is a gas at room temperature and pressure, it can be used directly, for example, from a methane gas cylinder. Alternatively, it is possible to use low-environmental-impact methane gas obtained by fermenting organic matter such as food waste, paper waste, and livestock manure using methane bacteria, or to use methane derived from methane hydrate. Also, since most city gas is methane gas, it is possible to use city gas directly or to use methane gas purified from city gas. Furthermore, methods for producing methane from carbon dioxide and hydrogen have been developed, and methane gas synthesized by such methods can be used. Biogas can be used as a raw material gas containing methane. Biogas is a gas generated by the methane fermentation of excrement from animals such as livestock, household waste, sludge derived from sewage, paper waste, vegetation waste, energy crops, etc., and consists mainly of methane and carbon dioxide. For example, biogas contains 50 to 75 vol% methane and 25 to 50 vol% carbon dioxide, and may also contain nitrogen, hydrogen, hydrogen sulfide, oxygen, siloxane, etc. Biogas is obtained by methane fermentation of biological resources, and since carbon can be fixed according to the present invention, it can be called carbon negative. Among biogas, that which is generated by the anaerobic fermentation of sewage sludge is called digestion gas, and digestion gas can also be used in the present invention. City gas may be used as a raw material gas containing methan