JP5044788B2 - Method for producing ethylene derivative of trans form - Google Patents

Description

  The present invention relates to a method for producing a trans-form ethylene derivative, an ethylene derivative produced by the method for producing a trans-form ethylene derivative, and an apparatus for producing a trans-form ethylene derivative.

  The cis-trans isomerization reaction of ethylene derivatives is important as a basic organic synthesis reaction, and the price of the trans isomer may be several times the price of the cis isomer depending on the compound of the ethylene derivative. It is also a reaction that creates added value.

Such a cis-trans isomerization reaction of an ethylene derivative, more specifically, a reaction of isomerizing a cis-ethylene derivative into a trans-ethylene derivative is performed in the order of several days to several weeks under light irradiation. There is a method using an expensive catalyst. There is also a method of using halogen or the like as a catalyst. Furthermore, there is a method (Non-patent Document 1) in which a cis-trans isomerization reaction is performed thermally. In Non-Patent Document 1, a cis-trans isomerization reaction of cis-butene-2 is performed at 469 ° C.
B. S. Rabinovitch and K.M. -W. Michel, "The thermal unimolecular cis-trans isomerization of cis-butene-2" J. Am. Chem. Soc. 81, 5065-5071 (1959)

  However, the reaction that isomerizes in the order of several days to several weeks under the above-mentioned light irradiation has problems in simplicity and high speed. In addition, the isomerization reaction using an expensive catalyst has a problem in economical efficiency. And the method performed using halogen etc. for a catalyst has the subject that the load with respect to an environment is large. Further, when the cis-trans isomerization reaction is performed thermally, high temperature conditions are required as reported in Non-Patent Document 1, and there is a problem that it is difficult to use industrially.

  The present invention has been made in order to solve the above-mentioned problems. The first object of the present invention is to provide a transformer body that is simple, high-speed, highly economical, has a low environmental load, and is industrially easy to adopt. It is in providing the manufacturing method of ethylene derivative.

  The present invention has been made in order to solve the above-mentioned problems. The second object of the present invention is to provide a transformer body that is simple, high-speed, highly economical, has a low environmental load, and is industrially easy to adopt. An ethylene derivative produced by the method for producing an ethylene derivative is provided.

  The present invention has been made to solve the above-mentioned problems, and a third object thereof is a transformer body that is simple, high speed, high in economic efficiency, has a small environmental load, and is industrially easy to adopt. It is an object to provide an apparatus for producing an ethylene derivative.

  As a result of intensive studies by the present inventors for the above purpose, when the cis-ethylene derivative was held at a predetermined temperature in an atmosphere in which the reaction with the cis-ethylene derivative was suppressed, The inventors have found that even if the temperature is relatively low, a trans-form ethylene derivative can be produced at a high conversion without using a solvent or a catalyst, and the present invention has been completed.

  In order to solve the above-mentioned problems, a method for producing an ethylene derivative of a trans isomer according to the present invention includes a cis ethylene derivative represented by the following general formula (1) in an inert atmosphere or a supercritical carbon dioxide atmosphere. It has the cis-trans isomerization reaction process hold | maintained at the temperature of 300 degreeC or more.

(In General Formula (1), R ¹ and R ² are each independently a linear or branched alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group having 3 to 18 carbon atoms, or a straight chain having 2 to 18 carbon atoms. Chain or branched alkenyl group, C3-C18 cyclic alkenyl group, C2-C18 linear or branched alkynyl group, heterocyclic group, C6-C18 aryl group, C7-C20 Aralkyl group, linear or branched alkoxy group having 1 to 18 carbon atoms, linear or branched alkenyloxy group having 3 to 18 carbon atoms, linear or branched alkylthio group having 1 to 18 carbon atoms, halogen atom, nitro Group, nitroso group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, mercapto group, hydroxy group, hydroxyamino group, formyl group, sulfonic acid group, carboxyl , Acyl group represented by -COR ^{3, -NR} 3 amino groups represented by ^{R 4,} an acylamino group represented by -NHCOR ^3, carbamate group represented by -NHCOOR ^3, carboxylic acid ester group represented by -COOR ^3, acyloxy group represented by -OCOR ^3, a carbamoyl group represented by -CONR ³ R ^4, a sulfonyl group represented by _-SO 2 ^{R _3,} a sulfamoyl group represented by -SO 2 ^NR 3 ^{R 4,} in _-SO 3 ^{R 3} sulfonic acid ester group represented, a sulfonamide group represented by -NHSO ₂ R ^3, and sulfinyl group represented by -SOR ^3, is ^.R 3, ^{R 4} represent either a represents a hydrocarbon group.)

  According to the present invention, a cis-trans in which the cis-ethylene derivative represented by the general formula (1) is held at a temperature of 50 ° C. or higher and 300 ° C. or lower in an inert atmosphere or a supercritical carbon dioxide atmosphere. Since it has an isomerization reaction step, a cis-trans isomerization reaction can be performed in a state in which the cis-ethylene derivative is difficult to react with the atmosphere and at a relatively low reaction temperature, without using a solvent or a catalyst. Since the cis ethylene derivative can be converted into the trans ethylene derivative, the result is a simple, high speed, high economic efficiency, low environmental impact, and easy industrial adoption. The manufacturing method of can be provided.

  The ethylene derivative of the present invention for solving the above-described problems is characterized by being produced by the above-described method for producing an ethylene derivative of a trans isomer.

  According to the present invention, since the ethylene derivative is produced by the above-described process for producing a trans-ethylene derivative, the cis-ethylene derivative is difficult to react with the atmosphere, and the cis-form under a relatively low reaction temperature. -Trans isomerization reaction is possible, and a cis-ethylene derivative can be converted to a trans-ethylene derivative without using a solvent or a catalyst. As a result, it is simple, fast, economical, and environmentally friendly. It is possible to provide an ethylene derivative produced by a method for producing an ethylene derivative in a trans form, which has a small load and can be easily employed industrially.

  An apparatus for producing an ethylene derivative of a trans isomer according to the present invention for solving the above-mentioned problem is to control a reactor, a supply device for supplying carbon dioxide to the reactor, and the temperature and pressure inside the reactor. And a controller having a controller for controlling the inside of the reactor to a supercritical carbon dioxide atmosphere.

  According to this invention, an apparatus for producing an ethylene derivative in a trans form controls a reactor, a supply device for supplying carbon dioxide to the reactor, and the temperature and pressure inside the reactor to control the inside of the reactor. And a control device having a control unit for controlling the atmosphere to a supercritical carbon dioxide atmosphere, so that the method for producing the trans derivative ethylene derivative can be carried out with a simple device configuration. It is possible to provide an apparatus for producing an ethylene derivative in a trans form, which is highly economical, has a low environmental burden, and is industrially easily adopted.

  In a preferred embodiment of the apparatus for producing a trans-ethylene derivative of the present invention, a stirring device is provided in the reactor.

  According to the present invention, since the stirring device is provided in the reactor, the ethylene derivative of the cis isomer is stirred during the cis-trans isomerization reaction, and the reaction efficiency can be increased. A trans-ethylene derivative production apparatus that is more industrially easy to use.

  According to the method for producing an ethylene derivative of a trans isomer of the present invention, a method for producing an ethylene derivative of a trans isomer that is simple, high speed, economical, has a low environmental burden, and is industrially easy to employ. Can do. More specifically, the trans derivative ethylene derivative production method of the present invention does not require a catalyst or solvent, and is therefore an environmentally friendly clean production method. Since the component is not required, the purity of the obtained ethylene derivative can be easily increased. Furthermore, the separation step of the product after the reaction and the catalyst / solvent can be omitted, which is economically advantageous. The application range of the method for producing a trans-ethylene derivative of the present invention is wide, and can be applied to various cis-trans isomerization reactions.

  According to the ethylene derivative of the present invention, it is possible to provide an ethylene derivative produced by a method for producing a trans form of an ethylene derivative, which is simple, high speed, high in economic efficiency, has a small environmental load, and is industrially easy to employ. Can do. More specifically, since the ethylene derivative of the present invention is obtained by the above-described method for producing an ethylene derivative of a trans isomer that does not require a catalyst or a solvent, it is obtained by an environmentally friendly clean production method, Moreover, since other components, such as a catalyst and a solvent, are not required at the time of reaction, the purity of the ethylene derivative obtained tends to become high. Furthermore, since it is obtained by a production method in which the separation step of the product after the reaction and the catalyst / solvent can be omitted, it is economically advantageous. Since the range of application of the above-described trans derivative ethylene derivative production method is wide, various types of ethylene derivatives can be obtained.

  According to an apparatus for producing an ethylene derivative of a trans isomer of the present invention, an apparatus for producing an ethylene derivative of a trans isomer is provided that is simple, high speed, economical, has a low environmental impact, and is industrially easy to adopt. Can do. More specifically, the trans-ethylene derivative production apparatus of the present invention does not require a catalyst or solvent, and thus becomes an environment-friendly clean production apparatus, and other components such as a catalyst and a solvent during the reaction. This makes it easier to increase the purity of the resulting ethylene derivative. Furthermore, since the separation step of the product after the reaction and the catalyst / solvent can be omitted, it is simple and economically advantageous. The range of application of the production apparatus of the trans derivative ethylene derivative of the present invention is wide, and can be applied to various cis-trans isomerization reactions.

  Next, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

(Production method)
In the method for producing a trans-ethylene derivative of the present invention, a cis-ethylene derivative represented by the following general formula (1) is 50 ° C. or higher and 300 ° C. or lower in an inert atmosphere or a supercritical carbon dioxide atmosphere. It has a cis-trans isomerization reaction step maintained at a temperature.

(In General Formula (1), R ¹ and R ² are each independently a linear or branched alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group having 3 to 18 carbon atoms, or a straight chain having 2 to 18 carbon atoms. Chain or branched alkenyl group, C3-C18 cyclic alkenyl group, C2-C18 linear or branched alkynyl group, heterocyclic group, C6-C18 aryl group, C7-C20 Aralkyl group, linear or branched alkoxy group having 1 to 18 carbon atoms, linear or branched alkenyloxy group having 3 to 18 carbon atoms, linear or branched alkylthio group having 1 to 18 carbon atoms, halogen atom, nitro Group, nitroso group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, mercapto group, hydroxy group, hydroxyamino group, formyl group, sulfonic acid group, carboxyl , Acyl group represented by -COR ^{3, -NR} 3 amino groups represented by ^{R 4,} an acylamino group represented by -NHCOR ^3, carbamate group represented by -NHCOOR ^3, carboxylic acid ester group represented by -COOR ^3, acyloxy group represented by -OCOR ^3, a carbamoyl group represented by -CONR ³ R ^4, a sulfonyl group represented by _-SO 2 ^{R _3,} a sulfamoyl group represented by -SO 2 ^NR 3 ^{R 4,} in _-SO 3 ^{R 3} sulfonic acid ester group represented, a sulfonamide group represented by -NHSO ₂ R ^3, and sulfinyl group represented by -SOR ^3, is ^.R 3, ^{R 4} represent either a represents a hydrocarbon group.)

  This enables cis-trans isomerization reaction in a state where the cis-ethylene derivative is difficult to react with the atmosphere and at a relatively low reaction temperature, and without using a solvent or a catalyst. Can be converted to a trans-ethylene derivative, resulting in a method for producing a trans-ethylene derivative that is simple, high speed, economical, has a low environmental impact, and is industrially easy to adopt. can do.

  More specifically, the method for producing a trans-ethylene derivative of the present invention does not require a catalyst or solvent, and is therefore an environmentally friendly clean production method. Since the component is not required, the purity of the obtained ethylene derivative can be easily increased. Furthermore, the separation step of the product after the reaction and the catalyst / solvent can be omitted, which is economically advantageous.

(Cis-trans isomerization reaction step)
In the cis-trans isomerization reaction step, the cis ethylene derivative represented by the following general formula (1) is maintained at a temperature of 50 ° C. or higher and 300 ° C. or lower in an inert atmosphere or a supercritical carbon dioxide atmosphere. Is done.

In general formula (1), R ¹ and R ² are each independently a linear or branched alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group having 3 to 18 carbon atoms, or a linear chain having 2 to 18 carbon atoms. Or a branched alkenyl group, a cyclic alkenyl group having 3 to 18 carbon atoms, a linear or branched alkynyl group having 2 to 18 carbon atoms, a heterocyclic group, an aryl group having 6 to 18 carbon atoms, and an aralkyl having 7 to 20 carbon atoms. Group, linear or branched alkoxy group having 1 to 18 carbon atoms, linear or branched alkenyloxy group having 3 to 18 carbon atoms, linear or branched alkylthio group having 1 to 18 carbon atoms, halogen atom, nitro group , Nitroso group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, mercapto group, hydroxy group, hydroxyamino group, formyl group, sulfonic acid group, carboxyl group Acyl group represented by -COR ^{3, -NR} 3 amino groups represented by ^{R 4,} an acylamino group represented by -NHCOR ^3, carbamate group represented by -NHCOOR ^3, carboxylic acid ester group represented by -COOR ^3, - acyloxy group represented by OCOR ^3, a carbamoyl group represented by -CONR ³ R ^4, a sulfonyl group represented by _-SO 2 ^{R _3,} a sulfamoyl group represented by -SO 2 ^NR 3 ^{R 4,} represented by _-SO 3 ^{R 3} sulfonic acid ester group, a sulfonamide group represented by -NHSO ₂ R ^3, and sulfinyl group represented by -SOR ^3, it represents either. R ³ and R ⁴ represent a hydrocarbon group. By using the compound represented by the general formula (1), a cis-trans isomerization reaction of an industrially valuable ethylene derivative is carried out. The manufacturing method becomes. In addition, the property of the cis-form ethylene derivative is usually an individual.

Further, by using the substituents shown above for R ¹ and R ² , the cis-form ethylene derivative is chemically more stable than the trans-form ethylene derivative, and conversion from the cis-form to the trans-form is prevented. In some cases, it is difficult to form a cis ethylene derivative. Even in such a case, in the present invention, the advantage that it is easy to obtain an ethylene derivative of a trans form is easily exhibited.

R ¹ and R ² in the general formula (1) are each independently a linear or branched alkyl group having 1 to 18 carbon atoms, a cyclic alkyl group having 3 to 18 carbon atoms, or a linear chain having 2 to 18 carbon atoms. Or a branched alkenyl group, a cyclic alkenyl group having 3 to 18 carbon atoms, a linear or branched alkynyl group having 2 to 18 carbon atoms, a heterocyclic group, an aryl group having 6 to 18 carbon atoms, and an aralkyl having 7 to 20 carbon atoms. Group, linear or branched alkoxy group having 1 to 18 carbon atoms, linear or branched alkenyloxy group having 3 to 18 carbon atoms, linear or branched alkylthio group having 1 to 18 carbon atoms, halogen atom, nitro group , Nitroso group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, mercapto group, hydroxy group, hydroxyamino group, formyl group, sulfonic acid group, carboxyl group Acyl group represented by -COR ^{3, -NR} 3 amino groups represented by ^{R 4,} an acylamino group represented by -NHCOR ^3, carbamate group represented by -NHCOOR ^3, carboxylic acid ester group represented by -COOR ^3, - acyloxy group represented by OCOR ^3, a carbamoyl group represented by -CONR ³ R ^4, a sulfonyl group represented by _-SO 2 ^{R _3,} a sulfamoyl group represented by -SO 2 ^NR 3 ^{R 4,} represented by _-SO 3 ^{R 3} sulfonic acid ester group, a sulfonamide group represented by -NHSO ₂ R ^3, and sulfinyl group represented by -SOR ^3, it represents either. R ³ and R ⁴ represent a hydrocarbon group. Of the above groups, an alkyl group, a cyclic alkyl group, an alkenyl group, a cyclic alkenyl group, an alkynyl group, a heterocyclic group, an aryl group, an aralkyl group, an alkoxy group, an alkenyloxy group, and an alkylthio group are further substituted. You may have.

  Examples of the linear or branched alkyl group having 1 to 18 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and n-heptyl. Groups and the like. Examples of the cyclic alkyl group having 3 to 18 carbon atoms include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. Examples of the straight chain or branched alkenyl group having 2 to 18 carbon atoms include a vinyl group, a propenyl group, and a hexenyl group. As a C3-C18 cyclic alkenyl group, a cyclopentenyl group, a cyclohexenyl group, etc. can be mentioned, for example. Examples of the linear or branched alkynyl group having 2 to 18 carbon atoms include a propynyl group and a hexynyl group. Examples of the heterocyclic group include a 2-thienyl group, a 2-pyridyl group, a 4-piperidyl group, and a morpholino group. Examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a tolyl group, a xylyl group, and a mesityl group. Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenethyl group. Examples of the linear or branched alkoxy group having 1 to 18 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group. Can be mentioned. Examples of the linear or branched alkenyloxy group having 3 to 18 carbon atoms include a propenyloxy group, a butenyloxy group, and a pentenyloxy group. Examples of the linear or branched alkylthio group having 1 to 18 carbon atoms include a methylthio group, an ethylthio group, an n-propylthio group, an n-butylthio group, a sec-butylthio group, and a tert-butylthio group. .

When a heterocyclic group is used for R ¹ and R ² , the heterocyclic group may be a saturated heterocyclic ring such as 4-piperidyl group, morpholino group, 2-morpholinyl group, piperazyl group, 2-furyl group, An aromatic heterocyclic ring such as a 2-pyridyl group, a 2-thiazolyl group, and a 2-quinolyl group may be used. These may contain a plurality of hetero atoms or may further have a substituent, and the bonding position thereof is not particularly limited. Preferred structures for the heterocyclic ring are a 5- or 6-membered saturated heterocyclic ring, a 5- or 6-membered monocyclic ring and an aromatic heterocyclic ring thereof.

R ¹ and R ² may be the above linear or branched alkyl group, cyclic alkyl group, linear or branched alkenyl group, cyclic alkenyl group, linear or branched alkynyl group, linear or branched alkoxy group, and When a linear or branched alkylthio group is used, as described above, these groups may further have a substituent. When R ¹ and R ² are linear or branched alkenyl groups, cyclic alkenyl groups, linear or branched alkynyl groups, linear or branched alkoxy groups, and linear or branched alkylthio groups, When these groups have an alkyl chain, the hydrogen of the alkyl chain may be further substituted with a substituent. Examples of such substituents include the following.

  That is, as such a substituent, for example, an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert-butoxy group; C2-C12 alkoxyalkoxy groups such as methoxymethoxy group, ethoxymethoxy group, propoxymethoxy group, ethoxyethoxy group, propoxyethoxy group, methoxybutoxy group; methoxymethoxymethoxy group, methoxymethoxyethoxy group, methoxyethoxymethoxy group, Alkoxyalkoxyalkoxy groups having 3 to 15 carbon atoms such as methoxymethoxyethoxy group and ethoxyethoxymethoxy group; aryl groups having 6 to 12 carbon atoms such as phenyl group, tolyl group and xylyl group (these are further substituted with an arbitrary substituent) May be)); It can be given an allyloxy group, an alkenyloxy group having 2 to 12 carbon atoms such as vinyloxy group; phenoxy group, tolyloxy group, xylyloxy group, an aryloxy group having 6 to 12 carbon atoms such as naphthyloxy group.

  Furthermore, as other substituents, for example, heterocyclic groups such as 2-thienyl group, 2-pyridyl group, 4-piperidyl group, morpholino group; cyano group; nitro group; hydroxyl group; amino group; N, N-dimethyl An alkylamino group having 1 to 10 carbon atoms such as an amino group and an N, N-diethylamino group; an alkylsulfonylamino group having 1 to 6 carbon atoms such as a methylsulfonylamino group, an ethylsulfonylamino group and an n-propylsulfonylamino group; Halogen atoms such as fluorine atom, chlorine atom and bromine atom; C2-C7 alkoxycarbonyl group such as carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl, etc. ; Methylcarbonyloxy group, ethylcarbonyloxy group, n-propyl cal An alkylcarbonyloxy group having 2 to 7 carbon atoms such as nyloxy group, isopropylcarbonyloxy group, n-butylcarbonyloxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, isopropoxycarbonyloxy group, An alkoxycarbonyloxy group having 2 to 7 carbon atoms such as an n-butoxycarbonyloxy group can also be exemplified.

Furthermore, R ¹ and R ² in the general formula (1) are each independently a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; a nitro group; a nitroso group; a cyano group; an isocyano group; a cyanato group; ; thiocyanato group; isothiocyanato group; a mercapto group; hydroxy group; a hydroxyamino group; a formyl group; a sulfonic group; a carboxyl group; an amino group represented by ^{-NR 3 R 4;;} -NHCOR 3 acyl group represented by -COR ³ acyloxy group represented by -OCOR ^3;; carboxylic acid ester group represented by -COOR ^3; carbamate group represented by -NHCOOR ^3; in acylamino group represented -CONR ³ carbamoyl group represented by R ^4; _-SO 2 R a sulfonyl group represented by _^3; represented by -SO 2 ^NR 3 ^{R 4} It may be any of the sulfinyl group represented by -SOR ^3; sulfamoyl group; _-SO 3 sulfonic acid ester group represented by ^{R 3;} -NHSO ₂ sulfonamide group represented by R ^3.

Here, R ³ and R ⁴ represent a hydrocarbon group. Examples of such hydrocarbon groups include a linear or branched alkyl group; a cyclic alkyl group; a linear or branched alkenyl group; a cyclic alkenyl group; an aralkyl group; and an aryl group. Among them, as R ³ and R ⁴ , straight chain having 1 to 18 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-heptyl group, etc. Or a branched alkyl group; a cyclic alkyl group having 3 to 18 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group and an adamantyl group; a linear or branched chain having 2 to 18 carbon atoms such as a vinyl group, a propenyl group and a hexenyl group An alkenyl group having 3 to 18 carbon atoms such as cyclopentenyl group and cyclohexenyl group; an aralkyl group having 7 to 20 carbon atoms such as benzyl group and phenethyl group; phenyl group, tolyl group, xylyl group and mesityl group It is preferable to use an aryl group having 6 to 18 carbon atoms and the like. In addition, the aryl group part of these groups may be further substituted with the same substituent as R ¹ and R ² described above.

  Examples of the compound represented by the general formula (1) include cis-1,2-di (phenylsulfonyl) ethylene.

In the process for producing a trans-ethylene derivative of the present invention, it is rare that the raw material used for the cis-trans isomerization reaction is a 100% cis-ethylene derivative. A mixture of a cis isomer and a trans isomer is used as the ethylene derivative as a starting material. In this case, from the viewpoint of efficiently obtaining an ethylene derivative of a trans isomer, the trans isomer contained in the raw material is preferably 20% or less. Confirmation of the ratio of the trans isomer to the cis isomer in the raw material can be performed using a conventionally known analysis method, for example, a method of analyzing by nuclear magnetic resonance spectroscopy ( ¹ HNMR).

  The cis ethylene derivative is maintained under an inert atmosphere or a supercritical carbon dioxide atmosphere. Examples of the inert atmosphere include a helium atmosphere, an argon atmosphere, and a nitrogen atmosphere. Among these atmospheres, an argon atmosphere or a supercritical carbon dioxide atmosphere is preferable, and a supercritical carbon dioxide atmosphere is more preferable. By using an argon atmosphere or a supercritical carbon dioxide atmosphere, it is possible to create a state in which the cis ethylene derivative is less likely to react with the atmosphere, and as a result, conversion of the cis ethylene derivative to the trans ethylene derivative is achieved. It becomes easier to promote. Here, supercritical carbon dioxide refers to carbon dioxide that has a critical temperature (31 ° C.) and a critical pressure (7.4 MPa) or higher and has both gas and liquid properties. Since carbon dioxide does not condense even when compressed above the critical temperature, it may be referred to as supercritical carbon dioxide regardless of pressure. In the present invention, since the reaction proceeds in the supercritical fluid, more specifically in the supercritical carbon dioxide, the supercritical fluid has excellent characteristics such as reaction controllability and separation characteristics.

  The atmospheric pressure is usually 0.1 MPa or more and 50 MPa or less. When argon is used, the pressure is preferably 0.1 MPa or more, and preferably 1 MPa or less. If it is the said pressure range, operation of argon will become easy. On the other hand, when supercritical carbon dioxide is used, the pressure is preferably 0.1 MPa or more, and preferably 10 MPa or less. By setting it as the said pressure range, the pressure of a supercritical area | region is also included, and temperature can be raised even at a relatively low pressure, and it can be set as supercritical carbon dioxide.

  The purity of the atmosphere is not particularly limited. For example, when the atmosphere is argon, the purity is usually 99.9% or more. In addition, when the atmosphere is carbon dioxide, the purity is usually 99.995% or more. Higher purity is preferable, but it is not easy to completely eliminate impurities industrially, and thus usually falls within the above range. Note that even though an “inert atmosphere or supercritical carbon dioxide atmosphere” is used, it is usually industrially one that contains a certain amount of impurities as described above. A reaction can occur. Such a reaction is permissible within the scope of the present invention.

  The cis ethylene derivative is held at a temperature of 50 ° C. or higher and 300 ° C. or lower. Although this temperature is the reaction temperature, the method for producing an ethylene derivative of a trans isomer of the present invention has an advantage that the reaction temperature can be greatly reduced as compared with the conventional method. The reaction temperature is preferably 200 ° C. or lower, more preferably 150 ° C. or lower. The reaction temperature is preferably 80 ° C. or higher. This results in a cis-trans isomerization reaction at a lower temperature, and as a result, a method for producing a trans-ethylene derivative that is more easily industrially adopted.

  The time (reaction time) during which the cis-ethylene derivative is maintained at a temperature of 50 ° C. or higher and 300 ° C. or lower in an inert atmosphere or a supercritical carbon dioxide atmosphere is usually 1 minute or longer, preferably 30 minutes or longer. Usually, it is 300 minutes or less, preferably 120 minutes or less. By setting it as the above range, it becomes easy to reliably convert the trans isomer into an ethylene derivative.

  The process for producing a trans-ethylene derivative according to the present invention comprises maintaining a cis-ethylene derivative at a temperature of 50 ° C. or higher and 300 ° C. or lower in an inert atmosphere or a supercritical carbon dioxide atmosphere. Since the chemical reaction occurs, there is an advantage that it is not necessary to add a solvent or a catalyst during the reaction. As a result, the manufacturing method is simple, high speed, high in economic efficiency, and has a small environmental load. Therefore, in the method for producing a trans-ethylene derivative of the present invention, it is basically not necessary to make components such as additives other than the ethylene derivative exist in the cis-trans isomerization reaction. However, an appropriate amount of components necessary for the cis-trans isomerization reaction may be contained within the scope of the present invention.

(Other processes)
In the method for producing a trans-ethylene derivative of the present invention, necessary pre-processes such as preparing a cis-ethylene derivative can be appropriately performed prior to the cis-trans isomerization reaction process.

  Further, as described above, the method for producing a trans-ethylene derivative of the present invention has an advantage that it is not necessary to add a solvent or a catalyst during the reaction. Thereby, the separation process of the product after the reaction and the catalyst / solvent can be omitted. For this reason, in the manufacturing method of the ethylene derivative of the trans body of this invention, there exists an advantage by which the post process after a cis-trans isomerization reaction process becomes unnecessary. However, if necessary, a predetermined post-process may be performed after the cis-trans isomerization reaction process. Examples of such a post-process include a process of removing the cis-ethylene derivative remaining in the product in order to bring the content of the trans-ethylene derivative close to 100%.

(Ethylene derivative)
The ethylene derivative of the present invention is produced by the above-described method for producing an ethylene derivative in a trans form. This enables cis-trans isomerization reaction in a state where the cis-ethylene derivative is difficult to react with the atmosphere and at a relatively low reaction temperature, and without using a solvent or a catalyst. Can be converted into a trans-form ethylene derivative. As a result, the trans-form ethylene derivative is produced by a method for producing a trans-form ethylene derivative that is simple, high-speed, economical, has a low environmental impact, and is industrially easy to adopt. Ethylene derivatives can be provided. In the present invention, the term “ethylene derivative” refers to an ethylene derivative that is a mixture of a cis isomer and a trans isomer unless otherwise specified.

  More specifically, since the ethylene derivative of the present invention is obtained by the above-described method for producing an ethylene derivative of a trans isomer that does not require a catalyst or a solvent, it is obtained by an environmentally friendly clean production method, Moreover, since other components, such as a catalyst and a solvent, are not required at the time of reaction, the purity of the ethylene derivative obtained tends to become high. Furthermore, since it is obtained by a production method in which the separation step of the product after the reaction and the catalyst / solvent can be omitted, it is economically advantageous. Since the range of application of the above-described trans derivative ethylene derivative production method is wide, various types of ethylene derivatives can be obtained.

  In addition, since the above method for producing a trans-ethylene derivative is used, the conversion rate from a cis-ethylene derivative to a trans-ethylene derivative is increased, and an ethylene derivative having a high content of the trans-ethylene derivative is obtained. Can do. Specifically, the content of the trans derivative ethylene derivative in the ethylene derivative of the present invention is usually 90% or more, preferably 95% or more. When the content of the ethylene derivative in the trans form is within the above range, an ethylene derivative having high utility value and added value is industrially obtained. In addition, the property of the produced | generated ethylene derivative is a solid normally.

(Manufacturing equipment)
The apparatus for producing a trans-ethylene derivative of the present invention comprises a reactor, a supply device for supplying carbon dioxide to the reactor, and a temperature and pressure inside the reactor to control the inside of the reactor supercritically. And a control device having a control unit for controlling the carbon dioxide atmosphere. This makes it possible to carry out the above-described method for producing an ethylene derivative of a trans isomer with a simple apparatus configuration. As a result, it is simple, high speed, high in economic efficiency, has a low environmental impact, and is industrially easy to adopt. An apparatus for producing a trans-ethylene derivative can be provided. More specifically, the production apparatus for the ethylene derivative in the trans form does not require a catalyst or a solvent, and thus becomes an environmentally conscious clean production apparatus, and also requires other components such as a catalyst and a solvent during the reaction. This makes it easier to increase the purity of the ethylene derivative obtained. Furthermore, since the separation step of the product after the reaction and the catalyst / solvent can be omitted, it is simple and economically advantageous. The range of application of such a trans form ethylene derivative production apparatus is wide, and can be applied to various cis-trans isomerization reactions. Hereinafter, an example of such a manufacturing apparatus will be described.

  FIG. 1 is a schematic conceptual diagram showing an example of an apparatus for producing a trans derivative ethylene derivative of the present invention. The trans-ethylene derivative production apparatus 20 includes a reactor 1, a supply device 2 that supplies argon or carbon dioxide to the reactor 1, and a control device 3 that controls the temperature and pressure inside the reactor 1. Have.

  The reactor 1 is used to enclose a raw material ethylene derivative 30 containing a large amount of cis isomer and perform the cis-trans isomerization reaction step described above. For this reason, the reactor 1 is formed of a material that can withstand the temperature and pressure during the reaction. Examples of such materials include stainless steel and glass. From the viewpoint of strength, it is preferable to use stainless steel, but glass may be used if the pressure is about 0.1 MPa. Examples of such glass reactors include general glassware such as ordinary flasks. Thus, as the reactor 1, a conventionally known one can be appropriately used, and the size of the reactor 1 may be appropriately adjusted according to the amount of the ethylene derivative of the trans isomer to be produced.

  The supply device 2 supplies argon or carbon dioxide to the reactor 1. The supply device in the apparatus for producing an ethylene derivative of a trans isomer according to the present invention is configured to supply at least carbon dioxide to the reactor, but the supply device 2 can selectively supply argon in addition to carbon dioxide. It is configured.

  The supply device 2 includes an argon cylinder 7 and a supply line 9 a connected from the argon cylinder 7 to the reactor 1, a supply line 9 b and 9 c connected from the carbon dioxide cylinder 8 and the carbon dioxide cylinder 8 to the reactor 1, The pump 10 is arranged between the lines 9b and 9c, and valves 12a, 12b and 12c for starting and stopping the supply of argon or carbon dioxide to the reactor 1 are constituted. The pump 10 is used to send liquid carbon dioxide into the reactor 1. That is, in order to increase the pressure of carbon dioxide, although not shown in FIG. 1, the carbon dioxide flowing out from the carbon dioxide cylinder 8 is cooled and liquefied by a cooling device. Then, this liquid carbon dioxide is fed into the reactor 1 by the pump 10. As the argon cylinder 7, the carbon dioxide cylinder 8, the supply lines 9a, 9b, 9c, the pump 10, and the valves 12a, 12b, 12c, conventionally known ones may be appropriately used.

  The control device 3 is for controlling the temperature and pressure inside the reactor 1. The control device 3 includes a thermometer 4, a pressure gauge 5, an oven 6, a pressure adjustment line 13, pressure adjustment valves 14a and 14b, and a control unit not shown in FIG. . The controller controls the on / off of the oven 6, the opening and closing of the valves 12a, 12b and 12c, and the opening and closing of the pressure adjusting valves 14a and 14b while monitoring the data of the thermometer 4 and the pressure gauge 5, and at least the reactor 1 has the function of controlling the inside to a supercritical carbon dioxide atmosphere.

  The operation of the control device 3 will be described. The temperature is measured by the thermometer 4, the pressure is measured by the pressure gauge 5, and the measured temperature data and pressure data are input to the control unit, and the control unit receives the input temperature data, pressure data, and temperature. The difference between the data set value (reaction temperature) and the pressure data set value (reaction pressure) is detected, and if necessary, the oven 6 is turned on / off, the valves 12a, 12b, 12c are opened and closed, and the pressure adjustment valve. 14a and 14b are opened and closed, and the temperature and pressure in the cis-trans isomerization reaction step are controlled. Here, if the set value of temperature data (reaction temperature) and the set value of pressure data (reaction pressure) are set to a temperature and pressure at which a supercritical carbon dioxide atmosphere is established, the inside of the reactor 1 is supercritical carbon dioxide atmosphere. Can be controlled.

  As the thermometer 4, pressure gauge 5, oven 6, pressure adjustment line 13, pressure adjustment valves 14 a and 14 b, and controller used in the control device 3, conventionally known ones may be appropriately used.

  The trans-ethylene derivative production apparatus 20 further includes a stirring device. The stirrer is used to stir the raw ethylene derivative 30 in the cis-trans isomerization reaction step to promote the conversion of the cis-form ethylene derivative to the trans-form ethylene derivative. By using a stirrer, the ethylene derivative of the cis isomer is stirred during the cis-trans isomerization reaction and the reaction efficiency can be increased. A derivative manufacturing apparatus 20 is obtained.

  The stirrer includes a stirrer 11, and the trans-ethylene derivative manufacturing apparatus 20 further includes a rotating unit 15 for rotating the stirrer 11. In the apparatus 20 for producing an ethylene derivative in a trans form, the stirrer 11 is a Teflon (registered trademark) stirrer, and the rotating unit 15 is a magnet stirrer. As the stirrer 11 and the rotating unit 15, conventionally known ones may be used as appropriate. In addition, as a rotating apparatus, you may use the type using a stirring blade.

  Next, a specific operation of the cis-trans isomerization reaction step using the trans-ethylene derivative production apparatus 20 will be described. First, the raw material ethylene derivative 30 is sealed in the reactor 1. Thereafter, when the atmosphere to be used is argon, the valve 12a is opened and the inside of the reaction vessel 1 is replaced with argon. Here, when the atmosphere to be used is critical carbon dioxide, the valves 12b and 12c are opened to allow carbon dioxide to flow out from the carbon dioxide cylinder 8, and this is cooled and liquefied into the reactor 1 by the pump 10. Send it in. Here, the liquid carbon dioxide sent out by the pump 10 is heated again in the supply line 9c and the reactor 1 to become a gaseous state, whereby the inside of the reactor 1 is replaced with the compressed carbon dioxide. Next, the oven 6 and the stirring device are operated to raise the temperature of the reactor 1 to the reaction temperature while stirring the raw ethylene derivative 30. Then, while monitoring the temperature in the reactor 1 with the thermometer 4 and the pressure in the reactor 1 with the pressure gauge 5, the reactor 1 is held at the reaction temperature for a predetermined time (reaction time). After the desired reaction time has elapsed, the oven 6 and the stirring device are stopped and the reactor 1 is cooled. Here, you may perform operation which shortens cooling time by immersing the reactor 1 in a cold water bath. Then, after the reactor 1 is cooled, the gas in the reactor is discharged from, for example, a back pressure valve, and the reacted product may be taken out from the reactor 1. Through the above, the cis-trans isomerization reaction step is completed.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to description of a following example, unless the summary is exceeded.

[Example 1]
A solid mixture of Compound 1 (cis-1,2-di (phenylsulfonyl) ethylene) and Compound 2 (trans-1,2-di (phenylsulfonyl) ethylene) shown below was prepared. This mixture was analyzed by nuclear magnetic resonance spectroscopy ( ¹ HNMR), and the conversion rate (% calculated by {trans isomer amount (mol) / (cis isomer amount (mol) + trans isomer amount (mol))} × 100] ) Was calculated. As a result, the ratio of compound 1 (cis isomer) to compound 2 (trans isomer) in this mixture was compound 1 (cis isomer): compound 2 (trans isomer) = 84 (%): 16 (%). It was. By nuclear magnetic resonance spectroscopy, using VNMR500 of BRUKER Corp., measurement conditions were medium CDCl _3.

(Cis-trans isomerization reaction step)
Next, 0.05 g of the above mixture was introduced into a stainless steel reactor having an internal volume of 50 ml, and the inside of the reactor was replaced with argon. The amount of argon introduced was adjusted so that the pressure inside the reactor was atmospheric pressure (0.1 MPa). While raising the temperature of the reactor to a predetermined reaction temperature, the stirrer was rotated for reaction. After 60 minutes, the reaction was stopped by immersing the reactor in a cold water bath. After releasing the gas from the back pressure valve, the reactor was opened and the product was recovered. The product was also solid. Analysis by thin layer chromatography (TLC) revealed that the product was a mixture of Compound 1 (cis isomer) and Compound 2 (trans isomer). Here a thin layer chromatography analysis apparatus, using Merck _{Silica gel60 F 254, TLC Aluminium Sheets} , was measured with CHCl ₃ as a developing solvent.

Thereafter, the cis-trans ratio of the product was analyzed by nuclear magnetic resonance spectroscopy ( ¹ HNMR), and the conversion rate (%) was calculated again. The measurement apparatus and measurement conditions for NMR analysis were the same as those described above.

  The above experiment was performed several times while changing the reaction temperature, and the conversion rate (%) at each reaction temperature was obtained. The results are shown in Table 1 and FIG. FIG. 2 is a graph showing the relationship between the reaction temperature and the conversion rate. In the figure, “Temperature [° C.]” on the horizontal axis represents the reaction temperature, and “Conversion [%]” on the vertical axis represents the conversion rate.

  From the results shown in Table 1 and the figure, in the argon gas phase, the conversion rate was almost constant up to a temperature of 80 ° C., and the reaction hardly proceeded, but the conversion rate increased from a temperature of 90 ° C. And the conversion rate became 90% or more at the temperature of 100 degreeC.

[Example 2]
In the cis-trans isomerization reaction step, the inside of the reactor was replaced with carbon dioxide, and the amount of carbon dioxide introduced was adjusted so that the pressure inside the reactor was 20 MPa, and the reaction was performed in supercritical carbon dioxide. Except that, the relationship between the reaction temperature and the conversion rate was examined in the same manner as in Example 1. The results are shown in Table-2 and FIG. “Sc-CO ₂ ” in the figure indicates that the reaction is in a supercritical carbon dioxide atmosphere. As shown in Table 2 and the same figure, the same results as in Example 1 (in the case of argon) were obtained.

[Example 3]
In the cis-trans isomerization reaction step, the conversion rate was measured in the same manner as in Example 1 except that the reactor was a glass container and the reaction temperature was only 120 ° C., and it was 91%. From this result, it was found that the cis-trans isomerization reaction in Examples 1 and 2 was not due to the catalytic action of stainless steel.

[Comparative Example 1]
In the cis-trans isomerization reaction step, the cis-trans isomerization reaction was attempted in the same manner as in Example 1 except that the inside of the reactor was replaced with air (atmosphere) and the reaction temperature was only 120 ° C. However, unlike the cases of Examples 1 to 3, the color of the product suggested the progress of the oxidation reaction.

It is a typical conceptual diagram which shows an example of the manufacturing apparatus of the ethylene derivative of the trans body of this invention. It is a graph which shows the relationship between reaction temperature and conversion rate.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Reactor 2 Supply apparatus 3 Control apparatus 4 Thermometer 5 Pressure gauge 6 Oven 7 Argon cylinder 8 Carbon dioxide cylinder 9 (9a, 9b, 9c) Supply line 10 Pump 11 Stirrer 12 (12a, 12b, 12c) Valve 13 Pressure Adjustment line 14 (14a, 14b) Pressure adjustment valve 15 Rotating unit 20 Transformer ethylene derivative production apparatus 30 Raw material ethylene derivative

Claims (1)

A cis ethylene derivative represented by the following general formula (1) is maintained at a temperature of 50 ° C. or higher and 300 ° C. or lower in an inert atmosphere or a supercritical carbon dioxide atmosphere, without solvent and without catalyst. A process for producing an ethylene derivative of a trans isomer, comprising a trans isomerization reaction step;

(In the general formula (1), ^{R 1} and ^{R 2} each independently, - .R ³ to a sulfonyl group represented by _SO 2 ^{R 3} represents a phenyl group.)

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