JP2005225869A - Method for producing cyclic carbamic acid ester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a cyclic carbamic acid ester efficiently by utilizing harmless and inexpensive carbon dioxide. <P>SOLUTION: This method for producing the cyclic carbamic acid ester is provided by reacting an organic compound having at least two halogen atoms in its molecule with an amine having at least two hydrogen atoms on its nitrogen atom and carbon dioxide. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a cyclic carbamate. More specifically, the cyclic carbamic acid ester is made efficient by performing a reaction using an organic compound containing at least two halogen atoms in the molecule as a raw material, an amine having two or more hydrogen atoms on the nitrogen atom, and carbon dioxide. It relates to a method of manufacturing well.

  Cyclic carbamates are used for batteries, capacitors, capacitor electrolytes, or semiconductor cleaning. It is also used in medicines such as antibiotics.

  Conventionally, Patent Document 1 discloses a method using amino alcohol and phosgene as a method for producing a cyclic carbamate. Patent Documents 2, 3 and 4 describe methods using amino alcohol and carbon monoxide, dimethyl carbonate, or ethylene carbonate as raw materials. Further, as a method considering environmental problems, Patent Document 5 describes a reaction between harmless carbon dioxide and amino alcohol, and Patent Document 6 describes a reaction between harmless carbon dioxide and a cyclic amine.

However, since phosgene is extremely toxic, the use of this phosgene has a drawback of being restricted in terms of the location of the manufacturing apparatus and safety equipment. Further, when amino alcohol is used as a raw material, amino alcohol is disadvantageous in that it is expensive, and a substitution product of cyclic carbamate must be produced from amino alcohol. Also, when carbon dioxide is used, when amino alcohol is used as a raw material, there are similar disadvantages, and an expensive reagent such as a dehydrating agent is required. When a compound having an aziridine structure is used as a raw material, this compound often has high toxicity and has drawbacks such as difficulty in synthesis and high cost.
Japanese Patent Publication No. 7-59570 Japanese Patent Laid-Open No. 49-1116058 JP 59-222481 A JP 2002-105064 A JP 2003-64062 A JP 2003-96058 A

  In the production of cyclic carbamates, there is a demand for effective use of inexpensive and harmless carbon dioxide. In addition, there are few methods for producing carbamic acid esters that do not use expensive amino alcohols, and the development thereof has been desired. The present invention provides a method for producing a cyclic carbamic acid ester safely and inexpensively using harmless and inexpensive carbon dioxide and without using an expensive amino alcohol as a raw material for the cyclic skeleton.

The inventor of the present invention has arrived at the present invention as a result of intensive studies on a method for producing a cyclic carbamic acid ester satisfying the above conditions. That is, the present invention is as follows.
1. A method for producing a cyclic carbamate represented by the general formula (1), wherein the raw material is an organic material containing at least two halogen atoms in the molecule represented by the general formula (2) or (3) The manufacturing method of cyclic carbamate which has the process of reacting using a compound, the amine represented by General formula (4), and a carbon dioxide.

（但し、Ｒ１、Ｒ２、Ｒ３、Ｒ４およびＲ５はそれぞれ同一の基でも異なる基でも繋がった環状の基でも良く、無置換または置換基を有するアリール基、水素、水酸基、１以上のハロゲンまたは１以上の置換基を有する炭素数１〜１２までのアルキル基、アルケニル基、アルキニル基、シクロアルキル基を表す。なお、置換基はアリール基、アルキル基、アルケニル基、アルキニル基、アルコキシ基、カルボニル基、カルボキシル基、水酸基、メルカプト基、ハロゲン、スルホニル基、アミノ基を表す。また、ｎは０≦ｎ≦４を満たす整数である。）

(However, each of R1, R2, R3, R4 and R5 may be the same group or a cyclic group linked by different groups, and is an unsubstituted or substituted aryl group, hydrogen, hydroxyl group, one or more halogens, or one or more. Represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkynyl group, or a cycloalkyl group, wherein the substituent is an aryl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a carbonyl group, Represents a carboxyl group, a hydroxyl group, a mercapto group, a halogen, a sulfonyl group, or an amino group, and n is an integer satisfying 0 ≦ n ≦ 4.)

（但し、Ｘ_１およびＸ_２はハロゲン原子であり、同一種のハロゲン原子でも異なった種類のハロゲン原子でも良い。また、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７はそれぞれ同一の基でも異なる基でも繋がった環状の基でも良く、無置換または置換基を有するアリール基、水素、水酸基、１以上のハロゲンまたは１以上の置換基を有する炭素数１〜１２までのアルキル基、アルケニル基、アルキニル基、シクロアルキル基を表す。なお、置換基はアリール基、アルキル基、アルケニル基、アルキニル基、アルコキシ基、カルボニル基、カルボキシル基、水酸基、メルカプト基、ハロゲン、スルホニル基、アミノ基を表す。また、ｎは１≦ｎ≦４を満たす整数である。）

(However, X ₁ and X ₂ are halogen atoms, and may be the same type of halogen atom or different types of halogen atoms. R 2, R 3, R 4, R 5, R 6 and R 7 may be the same or different groups. However, it may be a linked cyclic group, an unsubstituted or substituted aryl group, hydrogen, hydroxyl group, one or more halogens or one or more substituted alkyl group, alkenyl group, alkynyl group. In addition, a substituent represents an aryl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a carbonyl group, a carboxyl group, a hydroxyl group, a mercapto group, a halogen, a sulfonyl group, and an amino group. n is an integer satisfying 1 ≦ n ≦ 4.

（但し、Ｘ_１およびＸ_２はハロゲン原子であり、同一種のハロゲン原子でも異なった種類のハロゲン原子でも良い。また、Ｒ４およびＲ５は前記に同じ。）

(However, X ₁ and X ₂ are halogen atoms, and may be the same type of halogen atom or different types of halogen atoms. R 4 and R 5 are the same as above.)

（但し、Ｒ１は前記に同じ。）
２． 環状カルバミン酸エステルが５員環または６員環である第１項記載の環状カルバミン酸エステルの製造方法。
３． 反応を１０〜３５０℃の温度範囲で行なう第１項記載の環状カルバミン酸エステルの製造方法。
４． 環状カルバミン酸エステルが、Ｎ-メチル-２-オキサゾリジノン、３-メチル-１,３-オキサジナン-２-オン、３,４-ジメチル-１,３-オキサゾリジン-２-オン、３,５-ジメチル-１,３-オキサゾリジン-２-オン、２-オキサゾリジノン、４-フェニル-２-オキサゾリジノン、４，５-ジフェニル-２-オキサゾリジノン、５-メチル-２-オキサゾリジノン、またはＮ-フェニル-２-オキサゾリジノンである第１項記載の環状カルバミン酸エステルの製造方法。
５． 環状ウレアと併産される第１項記載の環状カルバミン酸エステルの製造方法。

(However, R1 is the same as above.)
2. The method for producing a cyclic carbamate according to claim 1, wherein the cyclic carbamate is a 5-membered ring or a 6-membered ring.
3. The method for producing a cyclic carbamate according to claim 1, wherein the reaction is carried out in a temperature range of 10 to 350 ° C.
4). The cyclic carbamate is N-methyl-2-oxazolidinone, 3-methyl-1,3-oxazinan-2-one, 3,4-dimethyl-1,3-oxazolidine-2-one, 3,5-dimethyl- 1,3-oxazolidin-2-one, 2-oxazolidinone, 4-phenyl-2-oxazolidinone, 4,5-diphenyl-2-oxazolidinone, 5-methyl-2-oxazolidinone, or N-phenyl-2-oxazolidinone A process for producing the cyclic carbamate according to claim 1.
5). The method for producing a cyclic carbamate according to claim 1, which is produced together with the cyclic urea.

  According to the present invention, an inexpensive and harmless carbon dioxide, an organic compound containing at least two halogen atoms in the molecule, and an amine having two or more hydrogen atoms on the nitrogen atom, without using highly toxic phosgene, are raw materials. By using as, it becomes possible to manufacture a cyclic carbamate ester safely and inexpensively.

  Hereinafter, the manufacturing method of the cyclic carbamate compound by this invention is demonstrated in detail. The present invention relates to a cyclic carbamate having a step of reacting with an organic compound containing at least two halogen atoms in the molecule, an amine having two or more hydrogen atoms on the nitrogen atom, and carbon dioxide as a raw material. It is a manufacturing method. The cyclic carbamic acid ester to be produced is not particularly limited as long as it is cyclic, but a 4- to 8-membered cyclic carbamic acid ester is preferred because it has many uses. In particular, a cyclic carbamate having a 5-membered ring is preferable, and a compound represented by the general formula (5) is preferable.

但し、Ｒ１、Ｒ２、Ｒ３、Ｒ４およびＲ５は前記と同じである。

However, R1, R2, R3, R4 and R5 are the same as described above.

  Specific examples of 5-membered carbamic acid esters include N-methyl-2-oxazolidinone, 3-methyl-1,3-oxazinan-2-one, and 3,4-dimethyl-1,3-oxazolidine-2- ON, 3,5-dimethyl-1,3-oxazolidine-2-one, 2-oxazolidinone, 4-phenyl-2-oxazolidinone, 4,5-diphenyl-2-oxazolidinone, 5-methyl-2-oxazolidinone, N- And phenyl-2-oxazolidinone.

但し、Ｒ１、Ｒ６、Ｒ７、Ｒ８、Ｒ９、Ｒ１０およびＲ１１はそれぞれ同一の基でも異なる基でも繋がった環状の基でも良く、無置換または置換基を有するアリール基、水素、水酸基、ハロゲンまたは置換基を有する炭素数１〜１２までのアルキル基、アルケニル基、アルキニル基、シクロアルキル基、水素を表す。なお、置換基はアリール基、アルキル基、アルケニル基、アルキニル基、アルコキシ基、カルボニル基、カルボキシル基、水酸基、メルカプト基、ハロゲン、スルホニル基、アミノ基を表す。 A 6-membered cyclic carbamate is also preferred, and is a compound represented by the general formula (6).

However, R1, R6, R7, R8, R9, R10 and R11 may be cyclic groups connected to the same group or different groups, and may be unsubstituted or substituted aryl groups, hydrogen, hydroxyl groups, halogens or substituents. Represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkynyl group, a cycloalkyl group, or hydrogen. The substituent represents an aryl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a carbonyl group, a carboxyl group, a hydroxyl group, a mercapto group, a halogen, a sulfonyl group, or an amino group.

  Specific examples of 6-membered carbamic acid esters include [1,3] -2-oxazinanone, alkyl- [1,3] -2-oxazinanone, methyl- [1,3] -2-oxazinanone, N -Methyl- [1,3] -2-oxazinanone, dimethyl- [1,3] -2-oxazinanone, phenyl- [1,3] -2-oxazinanone, N-phenyl- [1,3] -2-oxazinanone , Diphenyl- [1,3] -2-oxazinanone and the like.

  The halogen-containing organic compound that is one of the starting materials used in the present invention is not particularly limited as long as it is an organic compound represented by the general formula (2) or (3) and containing at least two halogen atoms in the molecule. Not. Particularly preferably, the halogen atom is any one of a chlorine atom, a bromine atom and an iodine atom.

  Specific examples of the compound represented by the general formula (2) are 1,2-dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, 1,2-dichloropropane, 1,2-dibromo. Propane, 1,2-diiodopropane, 1,2-dichlorobutane, 1,2-dibromobutane, 1,2-diiodobutane, 1,3-dichloropropane, 1,3-dibromopropane, 1,3-diiodo Examples include propane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, hexachloroethane, 1,4-dichlorobutane, and the like. Specific examples of the compound represented by the general formula (3) include dichloromethane, chloroform, carbon tetrachloride, dibromomethane, bromoform, carbon tetrabromide, diiodomethane, iodoform and the like. In the present invention, not only these examples but also any organic compound having two or more halogen atoms in the molecule is not particularly limited.

  The amine which is one of the starting materials used in the present invention is not particularly limited as long as it is represented by the general formula (4) and has two or more hydrogen atoms on the nitrogen atom. For example, primary amines, ammonia, hydrazine, and hydroxylamines can be used.

  Specific examples of amines are methylamine, ethylamine, n-propylamine, isopropylamine-n-butylamine, sec-butylamine, isobutylamine, t-butylamine, pentylamine, 2-aminopentane, 3-aminopentane. 1-amino-2-methylbutane, 2-amino-2-methylbutane, 3-amino-2-methylbutane, 4-amino-2-methylbutane, hexylamine, 5-amino-2-methylpentane, heptylamine, octyl Amine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, ethanolamine, isopropanolamine, 1-aminopropane-3-ol 1-aminobutane-2- All, 2-aminobutane-1-ol, 3-aminobutane-1-ol, 1-aminobutane-4-ol, 1-amino-2-methylpropan-2-ol, 2-amino-2-methylpropane-1- All, 1-aminopentane-4-ol, 2-amino-4-methylpentane-1-ol, 2-aminohexane-1-ol, 3-aminoheptane-4-ol, 1-aminooctane-2-ol 5-aminooctane-4-ol, 1-aminopropane-2,3-diol, 2-aminopropane-1,3-diol, tris (oxymethyl) aminomethane, 1,2-diaminopropane-3-ol 1,3-Diaminopropan-2-ol, 2- (2-aminoethoxy) ethanol, ethylenediamine, propylenediamine, butylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobuta 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, N-ethylethylenediamine, N, N-diethylethylenediamine, triethylethylenediamine, 1,2,3-triaminopropane, tris (2-aminoethyl) amine, tetra (aminomethyl) methane, diethylenetriamine, triethylenetetramine, tetraethylpentamine, heptaethyleneoctamine, hydroxylamine, O-methylhydroxylamine Can be mentioned.

  Carbon dioxide, which is one of the starting materials used in the present invention, may be supplied in the form of carbonate, bicarbonate, or carbamate. Carbon dioxide exists in the form of carbonate, hydrogen carbonate and carbamate under alkaline conditions, and there is no problem even if it is used in this form in the present invention. Specific examples of the form used for the reaction include carbon dioxide gas, liquefied carbon dioxide, amine carbonate, amine bicarbonate, amine carbamate, alkali metal carbonate, alkali metal bicarbonate, alkali metal carbamate, alkaline earth Alkali carbonates, alkaline earth hydrogen carbonates, alkaline earth carbamates. Carbon dioxide may be supplied in these forms.

  The reaction temperature is appropriately selected because it varies depending on the structure, molar ratio, and solvent type of the raw materials used. The reaction temperature is preferably in the range of 10 to 350 ° C, more preferably in the range of 60 to 250 ° C, and still more preferably in the range of 120 to 160 ° C. The reaction may be any of liquid phase, gas phase, and supercritical, and is not particularly limited.

  The reaction time is not particularly limited, but is preferably in the range of 0.01 to 48 hours, more preferably 0.1 to 12 hours, and further preferably 1 to 4 hours in consideration of industrial production. The reaction pressure may be normal pressure, pressurization, or reduced pressure, and is not particularly limited as long as carbon dioxide is absorbed and reacted with other reactants. In view of industrial production, the reaction pressure is preferably in the range of 0.1 MPa to 30 MPa, more preferably in the range of 0.1 to 5 MPa, and more preferably in the range of 0.1 to 1 MPa. preferable.

  The method for producing the cyclic carbamic acid ester of the present invention can be carried out in any of batch, semi-batch and continuous flow methods. Further, a solvent can be used during the reaction. As this solvent, water, an amine compound, an alcohol compound, an ether compound, an amide compound, or the like is easily used. Particularly preferred are water, alcohol compounds and ether compounds.

  The reaction mechanism in the method for producing a cyclic carbamate of the present invention is a desalting reaction from a halogen-containing organic compound, and a cyclic carbamate is produced by the progress of this reaction. The hydrohalide produced by the reaction is free and can be taken out as a salt with the used amine or a salt of an alkali compound. Even if an alkaline compound is added to the reaction in order to take out as a salt of the alkali compound, there is no problem. For example, there is no problem even if alkaline hydroxide, carbonate, bicarbonate or the like is added to the reaction. The reaction proceeds even without catalyst, but a catalyst can be added as necessary. Either homogeneous or heterogeneous catalysts can be used. There is no problem even if a transition metal catalyst, a complex catalyst, a metal ion, a metal oxide, an enzyme, or the like is used. After the reaction, the cyclic carbamate can be purified by a method such as extraction, distillation, recrystallization, or chromatography. In the present invention, the purification method can be used without any particular limitation.

  Furthermore, in the present invention, cyclic urea can be produced together by changing the reaction temperature, reaction time, pressure, and molar ratio. Cyclic urea can be produced by further reaction between a cyclic carbamate and an amine.

  When the cyclic urea is co-produced, the reaction is preferably carried out at a temperature higher by 10 ° C. or more, preferably 20 ° C. or more than that in the case of producing the cyclic carbamate ester alone. Specifically, the reaction is preferably performed in the range of 30 ° C to 400 ° C, more preferably in the range of 80 ° C to 290 ° C, and further preferably in the range of 140 ° C to 180 ° C.

  At the time of co-production, the production ratio of cyclic urea to cyclic carbamate can be increased by carrying out for a longer time than when cyclic carbamate is produced alone. Therefore, the reaction time may be appropriately selected according to the necessary co-production amount of the product. In this case, the extended reaction time is 10 minutes to 48 hours.

  In order to produce a large amount of cyclic urea, the molar ratio of the raw material amine to the halogen-containing compound (amine / halogen-containing compound) may be increased. Preferably, the molar ratio of amine / halogen-containing compound is 2 to 100, more preferably 3 to 50, still more preferably 4 to 10.

  The reaction pressure is secondarily determined depending on the composition ratio of the raw materials and the reaction temperature.

  Cyclic urea is important as a solvent for pharmaceutical production, a reaction intermediate, a battery, a capacitor, a capacitor electrolyte, and a semiconductor cleaning. In the present invention, there is an advantage that the production ratio of the cyclic carbamate ester and the cyclic urea can be changed by changing the conditions as described above.

  Examples of the present invention are shown below. The present examples are specific descriptions of the present invention, and are not limited to these examples without departing from the spirit of the present invention.

Example 1
1,2-dichloroethane (1 g) and 40% methylamine aqueous solution (5.5 g) were placed in a 20 ml pressure vessel made of SUS316, and carbon dioxide gas was pressurized to 0.5 MPa to absorb 1.9 g. This was heated at 120 ° C. for 2 hours. After cooling the pressure vessel, the contents were taken out and analyzed by gas chromatography. As a result, N-methyl-2-oxazolidinone was obtained with a yield of 94% based on 1,2-dichloroethane. Hydrogen chloride produced as a by-product during the reaction was neutralized with an excess of amine.

Example 2
The following experiment was also performed in the same manner as in Example 1. 1 g of 1,2-dichloroethane and 5.3 g of a 40% methylamine methanol solution were put into a 20 ml pressure vessel made of SUS316, and carbon dioxide gas was pressurized to about 0.5 MPa to absorb 2.7 g. This was heated at 160 ° C. for 3 hours. N-methyl-2-oxazolidinone was obtained in a yield of 6%, and N, N′-dimethylimidazolidinone was obtained in a yield of 23%.

Example 3
1.24 g of 1,3-dichloropropane and 5.15 g of a 40% methylamine aqueous solution were placed in a 20 ml pressure vessel made of SUS316, and carbon dioxide gas was pressurized to ca. 0.5 MPa to absorb 1.95 g. This was heated at 120 ° C. for 2 hours. 3-methyl-1,3-oxazinan-2-one was obtained in a yield of 15%, and 1,3-dimethyltetrahydropyridimin-2 (1H) -one was obtained in a yield of 64%.

Example 4
1.10 g of 1,2-dichloropropane and 7.18 g of a 40% methylamine aqueous solution were placed in a 20 ml pressure vessel made of SUS316, and carbon dioxide gas was pressurized to about 0.5 MPa to absorb 2.11 g. This was heated at 160 ° C. for 4 hours. The total yield of 3,4-dimethyl-1,3-oxazolidine-2-one and 3,5-dimethyl-1,3-oxazolidine-2-one was 64% and 1,3,4-trimethylimidazolidin-2-one. ON was obtained in a yield of 23%.

Claims (5)

A method for producing a cyclic carbamate represented by the general formula (1), wherein the organic material contains at least two halogen atoms in the molecule represented by the general formula (2) or (3) as a raw material. The manufacturing method of cyclic carbamate which has the process of reacting using a compound, the amine represented by General formula (4), and a carbon dioxide.

(However, R 1, R 2, R 3, R 4 and R 5 may be the same or different cyclic groups connected to each other, and are unsubstituted or substituted aryl groups, hydrogen, hydroxyl groups, one or more halogens, or one or more. Represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkynyl group, or a cycloalkyl group, wherein the substituent is an aryl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a carbonyl group, Represents a carboxyl group, a hydroxyl group, a mercapto group, a halogen, a sulfonyl group, or an amino group, and n is an integer satisfying 0 ≦ n ≦ 4.)

(However, X ₁ and X ₂ are halogen atoms, and may be the same type of halogen atom or different types of halogen atoms. R 2, R 3, R 4, R 5, R 6 and R 7 may be the same or different groups. However, it may be a linked cyclic group, an unsubstituted or substituted aryl group, hydrogen, hydroxyl group, one or more halogens or one or more substituted alkyl group having 1 to 12 carbon atoms, alkenyl group, alkynyl group The substituent represents an aryl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a carbonyl group, a carboxyl group, a hydroxyl group, a mercapto group, a halogen, a sulfonyl group, or an amino group. n is an integer satisfying 1 ≦ n ≦ 4.

(However, X ₁ and X ₂ are halogen atoms, and may be the same type of halogen atom or different types of halogen atoms. R 4 and R 5 are the same as above.)

(However, R1 is the same as above.)   The method for producing a cyclic carbamate according to claim 1, wherein the cyclic carbamate is a 5-membered ring or a 6-membered ring.   The method for producing a cyclic carbamate according to claim 1, wherein the reaction is carried out in a temperature range of 10 to 350 ° C.   The cyclic carbamate is N-methyl-2-oxazolidinone, 3-methyl-1,3-oxazinan-2-one, 3,4-dimethyl-1,3-oxazolidine-2-one, 3,5-dimethyl- 1,3-oxazolidin-2-one, 2-oxazolidinone, 4-phenyl-2-oxazolidinone, 4,5-diphenyl-2-oxazolidinone, 5-methyl-2-oxazolidinone, or N-phenyl-2-oxazolidinone A method for producing the cyclic carbamate according to claim 1.   The method for producing a cyclic carbamate according to claim 1, which is produced together with the cyclic urea.