The name of the invention: 6,6 '- method of manufacturing the (ethylenedioxy) di-2-naphthoic acid diester
Technical field
[0001]
　The present invention, 6,6 '- process for the preparation of (ethylenedioxy) di-2-naphthoic acid diester. 6,6 'obtained by the present invention - (ethylenedioxy) di-2-naphthoic acid diester is a compound useful as a raw material for functional polymers.
Background technique
[0002]
　6,6 '- as the conventional production method of (ethylenedioxy) di-2-naphthoic acid diester, is reacted with an alkali metal salt of 1,2-dihalogenated ethane 6-hydroxy-2-naphthoic acid ester manufacturing methods are known (e.g., see Patent Document 1.). However, in this manufacturing method, the resulting 6,6 '- (ethylenedioxy) the yield of di-2-naphthoic acid diester is extremely low as about 25%. Further, 1,2 as dihalogenated ethane, 1,2 when using the dibromoethane, but the reaction can also be carried out at atmospheric pressure, when using 1,2-dichloroethane, severe high temperature, adoption of the reaction conditions under high pressure is required.
[0003]
　To solve the low yield problems, in the reaction with the alkali metal salt of 1,2-dihalogenated ethane 6-hydroxy-2-naphthoic acid ester, it was added 6-hydroxy-2-naphthoic acid ester a method of reacting on are known (see, for example, Patent Document 2.). However, in this method, in order to yield good reaction requires severe reaction conditions at high temperature and high pressure, 6,6 in about 60% yield '- (ethylenedioxy) di-2-naphthoic acid to obtain diesters are, because of the 6-hydroxy-2-naphthoic acid ester needs to be added in a proportion of about 50 mol% relative to the alkali metal salt of 6-hydroxy-2-naphthoic acid ester, an efficient way I can not say.
[0004]
　Moreover, the presence of potassium carbonate the reaction between 6-hydroxy-2-naphthoic acid ester with 1,2-dihalogenated ethane, a method carried out in alcohol solvents and aprotic polar solvents are known (e.g., see Patent documents 3 and 4.). However, in this method, high temperature, or it is necessary to employ harsh reaction conditions under high pressure, or, alternatively it is necessary to add a reaction accelerator and costly 18-crown-6 . In addition even in the method, the yield of the desired compound as low as about 30 to 50 percent.
[0005]
　Further, 1,2 instead of dihalogenated ethane, 1- and 2-position, but the some manufacturing example using methanesulfonyl on or p- toluenesulfonyl of the ethane, expected that with difficulty in industrial practice is is (for example, see Patent Document 5.). In particular, as 6-hydroxy-2-naphthoic acid ester, 6-hydroxy-2-naphthoic acid if you use the methyl ester, or if you use a low-cost available 1,2-dichloroethane as 1,2-dihalogenated ethane the high temperature, the reaction conditions under high pressure, the yield even when the reaction accelerator added is as low as 30-40%. Therefore, 6,6 '- (ethylenedioxy) manufacturing methods cost and yield to be industrially satisfactory di-2-naphthoic acid diester is not found, 6,6' - (ethylenedioxy ) process for producing di-2-naphthoic acid diester efficiently in high yield is desired.
CITATION
Patent literature
[0006]
Patent Document 1: JP-A-61-001646 JP
Patent Document 2: Kokoku 01-016819 JP
Patent Document 3: Kokoku 05-053782 JP
Patent Document 4: Japanese Unexamined Patent Publication No. 2009-286771
Patent Document 5: JP open 2010-106016 JP
Disclosure of the Invention
Problems that the Invention is to Solve
[0007]
　The present invention has been made in view of the above problems, and an object not satisfied 6,6 'in the prior art - to provide a method for producing a (ethylenedioxy) di-2-naphthoic acid diester is there. That is, an object of the present invention, efficiently in high yield 6,6 '- to provide a process for preparing (ethylenedioxy) di-2-naphthoic acid diester. Yet another object is reacted with 6-hydroxy-2-naphthoic acid ester with 1,2-dihalogenated ethane, 6,6 capable of suppressing the occurrence of vinyl halide '- (ethylenedioxy) di - and to provide a process for producing a 2-naphthoic acid diester.
Means for Solving the Problems
[0008]
　The present inventors have made ​​intensive studies, as a result, a 6-hydroxy-2-naphthoic acid ester is reacted with the presence in 1,2-dihalogenated ethane alkali metal or alkaline earth metal compound in order to solve the above problems on 6,6 '- a method of producing a (ethylenedioxy) di-2-naphthoic acid diester,
6-hydroxy-2-naphthoic acid ester, an alkali metal or alkaline earth metal compounds, and mixtures consisting of a solvent the liquid, while directly continuously added without contacting the gas present 1,2-dihalogenated ethane above the gas-liquid interface of the liquid mixture, which comprises reacting at a temperature of 90 ~ 200 ° C. 6,6 '- by the production method of (ethylenedioxy) di-2-naphthoic acid diester, 6,6 efficiently in high yield' - (ethylenedioxy) di-2-naphthoic acid diester is a manufacturable It found that some, has led to the completion of the present invention.
[0009]
　Also preferably, the present invention employs the following configuration.
2 the mixed liquid, wherein the 6,6 ', characterized by further comprising a portion of the 1,2-dihalogenated ethane used in the reaction - preparation of (ethylenedioxy) di-2-naphthoic acid diester Method.
3 wherein the direct After the continuous addition was terminated also said that comprises reacting maintaining the temperature was continuously added 6,6 '- production method of (ethylenedioxy) di-2-naphthoic acid diester.
4 The amount of the alkali metal or alkaline earth metal compound is of the wherein said is 0.95 to 4.0 moles amount with respect to 6-hydroxy-2-naphthoic acid ester 1 mol of 6, 6 '- the production method of (ethylenedioxy) di-2-naphthoic acid diester.
5 The amount of the 1,2-dihalogenated ethane, said wherein said 0.4 to 5.0 moles amount with respect to 6-hydroxy-2-naphthoic acid ester 1 mol of 6,6 '- the production method of (ethylenedioxy) di-2-naphthoic acid diester.
Said 6,6 6 wherein the alkali metal or alkaline earth metal compound wherein the alkali metal carbonate '- the production method of (ethylenedioxy) di-2-naphthoic acid diester.
Wherein the 6,6 7 wherein the alkali metal carbonate is characterized in that it is a sodium or potassium carbonate '- the production method of (ethylenedioxy) di-2-naphthoic acid diester.
8 wherein the liquid mixture at the beginning of the reaction is above 6, 6 'which is a liquid mixture containing no 1,2-dihalogenated ethane - preparation of (ethylenedioxy) di-2-naphthoic acid diester Method.
Effect of the invention
[0010]
　According to the production method of the present invention, the above 6,6 '- can be produced (ethylenedioxy) di-2-naphthoic acid diester in an efficient and high yield. According to the production method of the present invention, it is possible to suppress the formation of vinyl halide produced in the side reaction. 6,6 obtained in the present invention '- (ethylenedioxy) di-2-naphthoic acid diesters are useful as raw materials for functional polymers, for example 6,6' - (ethylenedioxy) di-2-naphthoic acid as acid component, a polyester containing ethylene glycol and glycol component has a characteristic that has a melting point close to 295 ° C., and a high Young's modulus of the molded article can be produced by melt molding.
Brief description of the drawings
[0011]
[1] without contacting to the gas present in the above the gas-liquid interface of the mixed liquid of the present invention, which is an example of a method for adding corresponding directly to a continuous addition method of.
[Figure 2] without contacting to the gas present in the above the gas-liquid interface of the mixed liquid of the present invention, which is another example of addition method corresponding to a method of directly successive addition.
[3] without contacting to the gas present in the above the gas-liquid interface of the mixed liquid of the present invention is an example of adding method not applicable to a method of directly successive addition.
The sign of the drawings
[0012]
1 reactor
starting compound that is provided to the second reaction, the solvent, the desired compound and liquid mixture (reaction mixture liquid) that contains the reaction intermediate such as
3 gas-liquid interface
added to 4 1,2-dihalogenated ethane reaction mixture in a liquid direction is
5 1,2-dihalogenated ethane addition tube used when added to the reaction mixture in a liquid
stirring blades installed in the 6 reaction vessels
DESCRIPTION OF THE INVENTION
[0013]
　The present invention will be described in detail. That is, the present invention, the 6-hydroxy-2-naphthoic acid ester is reacted with the presence of 1,2-dihalogenated ethane of alkali metal or alkaline earth metal compound 6,6 '- (ethylenedioxy) di a method for producing a 2-naphthoic acid diester, 6-hydroxy-2-naphthoic acid ester, an alkali metal or alkaline earth metal compound, and the mixed liquid composed of a solvent, the mixed liquid of 1,2-dihalogenated ethane while direct continuously added without from the gas-liquid interface of the contacting to the gas present in the upper, 6,6 is characterized by reacting at a temperature of 90 ~ 200 ℃ '- (ethylenedioxy) di-2 the method for producing a naphthoic acid diester.
[0014]
　In the present invention, 6-Hydroxy-2-functional group constituting the ester group of the naphthoic acid ester, straight-chain alkyl ester group, a branched alkyl ester group, a cyclic alkyl ester group, an aromatic having 6 to 10 carbon atoms it can be exemplified an ester group. Examples of the linear alkyl ester group, a methyl ester group, ethyl ester group, n- propyl ester group, n- butyl ester group, n- pentyl ester group, n- hexyl ester group, n- octyl group, n- decyl It may be exemplified an ester group or n- dodecyl ester groups, (lauryl ester group). Examples of the branched alkyl ester group, iso- propyl ester group, sec- butyl ester group, iso- butyl ester group, tert-butyl ester group, iso- hexyl ester group, iso- octyl ester group or iso- decyl ester group, the like may be exemplified. Examples of the cyclic alkyl ester group, can be exemplified cyclopentyl ester group, a cyclohexyl ester group, cyclooctyl ester group or a cycloalkyl decyl ester groups and the like. In the cyclic alkyl ester group, the ring may be two or more. Examples of the aromatic ester group having 6 to 10 carbon atoms, can be exemplified a phenyl ester group, mono-methylphenyl group, dimethylphenyl group, mono-ethylphenyl group, diethylphenyl group, or naphthyl ester groups and the like. Methyl ester group Among these functional groups or ethyl ester groups, are preferred.
[0015]
　More specific examples of compounds of 6-hydroxy-2-naphthoic acid ester can be used in the present invention include, but are not limited to, 6-hydroxy-2-naphthoic acid methyl ester, 6-hydroxy 2-naphthoic acid ethyl ester, 6-hydroxy-2-naphthoic acid -n- propyl ester, 6-hydroxy-2-naphthoic acid -iso- propyl ester, 6-hydroxy-2-naphthoic acid -n- butyl ester, 6-hydroxy-2-naphthoic acid -iso- butyl ester, 6-hydroxy-2-naphthoic acid -sec- butyl ester, 6-hydroxy-2-naphthoic acid -tert- butyl ester, 6-hydroxy-2-naphthoic acid -n- hexyl ester, 6-hydroxy-2-naphthoic acid -n- octyl ester, 6-hydroxy-2-naphthoic acid -iso- octyl ester, 6-hydroxy-2-naphthoic acid -n- decyl ester, 6- hydroxy-2-naphthoic acid cyclohexyl ester, 6-hydroxy-2-naphthoic acid cyclooctyl ester, 6-hydroxy-2-naphthoic acid cyclo decyl ester, 6-hydroxy-2-naphthoic acid phenyl ester, 6-hydroxy-2- naphthoic acid mono methyl phenyl ester, 6-hydroxy-2-naphthoic acid dimethyl phenyl ester, 6-hydroxy-2-naphthoic acid mono ethyl phenyl ester, 6-hydroxy-2-naphthoic acid diethyl phenyl ester or 6-hydroxy, 2- and the like can be exemplified naphthoic acid naphthyl ester. Among these 6-hydroxy-2-naphthoic acid methyl ester or 6-hydroxy-2-naphthoic acid ethyl ester, to easily obtain the compound with high purity facilitate purification of the compound, the polymer as a raw material for functional polymer, preferable from the viewpoint of that easy to use in the manufacturing process.
[0016]
　In the present invention, the 1,2-dihalogenated ethane, is not particularly limited, 1,2-dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, 1-bromo-2-chloroethane, 1 - and the like can be exemplified iodo-2-chloroethane or 1-iodo-2-bromoethane,. Among these 1,2-dichloroethane is preferred.
　In the present invention, the amount of the 1,2-dihalogenated ethane, for 6-hydroxy-2-naphthoic acid ester 1 mol used in the reaction generally ranges from 0.4 to 5.0 mol amount, preferably is to use 0.5 to 3.5 mol amount. More preferably is the use of 1.0 to 2,8 molar amount, still more preferably is the use of 1.1-2.5 molar amount. When the amount of 1,2-dihalogenated ethane is less than 0.4 molar amounts, tend to feed conversion rate is lowered, whereas, 1,2 usage dihalogenated ethane 5.0 molar amounts when it exceeds is a reaction intermediate 6- (2-halogeno-ethoxy) yield of 2-naphthoic acid ester is increased, the target compound, 6,6 '- (ethylenedioxy) di-2 the yield of naphthoic acid diester tends to decrease. On the other hand, when using 0.4 to 5.0 moles of 1,2-dihalogenated ethane, it may be preferred because it can suppress the yield of and by-products high feedstock conversion.
[0017]
　In the present invention, it may be mentioned as preferred features the use of alkali metal or alkaline earth metal compound. As the alkali metal compound or alkaline earth metal compound is preferably an alkali metal carbonate. Further, as the alkali metal compound or alkaline earth metal compound is not particularly limited, and specifically, carbonates, hydrogen carbonates, phosphates, can be exemplified hydroxides. As the carbonate, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, and the like can be exemplified strontium carbonate or barium carbonate. The bicarbonate can lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, hydrogen carbonate rubidium, cesium hydrogen carbonate, calcium hydrogen carbonate, magnesium hydrogen carbonate, hydrogen carbonate, strontium or be exemplified such as bicarbonate, barium,. The phosphates may be exemplified lithium phosphate, sodium phosphate, potassium phosphate, calcium phosphate or magnesium phosphate, etc.,. Examples of the hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, and the like can be exemplified strontium hydroxide or barium hydroxide. The hydroxide is part of the alkali metal or alkaline earth metal compounds described above, it may be altered by moisture in the air. Viewpoint there is no such a phenomenon occurs, and in view of being readily available in precise weighing that it is possible to form (e.g. powder), carbonates, that bicarbonate is preferably used it can. By precise metering is possible, makes it easy to realize the amount of the alkali metal or alkaline earth metal compound to the 6-hydroxy-2-naphthoic acid ester as described below, the yield of the desired compound there is a case that can be raised. Also, carbonate salts from the viewpoint of solubility in a solvent to be described later, which is one of it is a preferred embodiment to use a bicarbonate. Hereinafter also referred to an alkali metal or alkaline earth metal compound and an alkali metal compound or the like.
[0018]
　In the present invention, the amount of such alkali metal compounds described above, for 6-hydroxy-2-naphthoic acid ester 1 mol used in the reaction is usually 0.95 ~ 4.0 moles amount, preferably 1.0 to 3.5 molar amount, more preferably from 1.7 to 3.2 molar amount, even more preferably using a 2.0-3.0 molar amount. When the amount of such alkali metal compound is less than 0.95 molar amount, tend to feed conversion rate is lowered, whereas, if the amount of the alkali metal weak acid salt exceeds 4.0 mol the amount of , 1,2 for dihalogenated ethane is lost by side reactions such as dehydrohalogenation, or because the stirring efficiency increases the slurry concentration of the reaction solution to decrease the target compound, 6,6 '- (ethylene di oxy) the yield of di-2-naphthoic acid diester tends to decrease. On the other hand, from 0.95 to 4.0 in the case of using a molar amount of the alkali metal compound or the like has a high raw material conversion rate and by-product, a by-product on the basis of the elimination reaction of the particular 1,2-dihalogenated ethane since the yield of the compound can be suppressed it may be preferred.
[0019]
　In the present invention, although the reaction is carried out in a solvent, the solvent used, there can be mentioned alcohol solvents, ether solvents, ketone solvents, aprotic polar solvents or amide group-containing solvent. Examples of the alcohol solvents include methanol, ethanol, n- propanol, isopropanol, butanol, n- hexanol, cyclohexanol or octanol. Examples of the ether solvents include dimethyl ether, ethyl methyl ether, diethyl ether, oxetane, tetrahydrofuran, tetrahydropyran or dioxane. Examples of the ketone solvents include acetone, methyl ethyl ketone (2-butanone), diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone, cyclopentanone, or isophorone. It is not particularly restricted but includes aprotic polar solvents include acetonitrile, propionitrile, butyronitrile, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethyl acetamide , dimethyl sulfoxide, sulfolane, hexamethylphosphoric triamide, N- methyl-2-pyrrolidone, etc. N- ethyl-2-pyrrolidone or 1,3-dimethyl-2-imidazolidinone, and the like. Examples of the amide group-containing solvent, N- monomethyl formamide, N, N- dimethylformamide, N, N- diethylformamide, N- monomethyl acetamide, N, N- dimethylacetamide, N, N- diethyl-acetamide, N- methyl-2 - pyrrolidone, etc. N- ethyl-2-pyrrolidone or 1,3-dimethyl-2-imidazolidinone, and the like. These various solvents may be used in combination or two or more even alone. Additional 1,2-dihalogenated ethane, 6-hydroxy-2-naphthoic acid ester, ether solvents from the standpoint of being able to sufficiently dissolve the alkali metal or the like, a ketone solvent, an aprotic polar solvent or an amide, it may group-containing solvents are preferred.
[0020]
　The amount of the solvent is usually 1 to 20 times by weight relative to the weight of 6-hydroxy-2-naphthoic acid ester used in the reaction, preferably 1 to 10 times. More preferably from 1 to 8 times the amount. If it is less than 1-fold amount, stirring efficiency since the slurry concentration is too high is deteriorated, while when it exceeds 20 times, with the substrate concentration decreased, the reaction rate becomes slow. That By 1 to 20 times by weight, it is possible to achieve an appropriate reaction rate, it may be possible to increase the productivity of the target compound.
[0021]
　In the present invention, the reaction temperature varies depending on the type of 6-hydroxy-2-naphthoic acid ester and 1,2-dihalogenated ethane used in the reaction, usually from 90 ~ 200 ℃. Preferably 100 ~ 190 ℃, more preferably 110 ~ 180 ℃, is even more preferably 115 ~ 175 ℃. When more preferably alkali metal or alkaline earth metal compound is used sodium carbonate is in the range of 140 ~ 175 ℃, when using potassium carbonate as the alkali metal or alkaline earth metal compound is 90 ~ 120. ° C. in the range of. Reaction when the temperature is lower than 90 ℃ tend to whether or reaction time reaction does not proceed is very long. On the other hand, if the reaction temperature is higher than 200 ° C., the decomposition reaction and side reaction products is likely to occur. Further, the reaction temperature range of the 1,2-dihalogenated ethane matters such as, but there is at a temperature below the boiling point will be described later because there is a case in which more than a case or boiling point close to the boiling point, ie the gas-liquid interface of the liquid mixture from the top it should be noted that a direct continuous addition without contacting the gas that is present. The reaction can be carried out at atmospheric pressure or under pressure. It constraints facilities is small, it is preferably carried out at normal pressure because that allows simple in operation. In the present invention, as the reaction time, the aforementioned 6-hydroxy-2-naphthoic acid ester and 1,2-dihalogenated type of ethane used in the reaction varies according to the amount and the reaction temperature but is usually 0.5 to 48 time is preferably 1 to 30 hours.
[0022]
　Additional 6,6 obtainable by the present invention '- Examples (ethylenedioxy) di-2-naphthoic acid diester is not particularly limited, 6,6' - (ethylenedioxy) di-2-naphthoic acid dimethyl ester, 6,6 '- (ethylenedioxy) di-2-naphthoic acid diethyl ester, 6,6' - (ethylenedioxy) di-2-naphthoic di -n- propyl ester, 6,6 ' - (ethylenedioxy) di-2-naphthoic di -iso- propyl ester, 6,6 '- (ethylenedioxy) di-2-naphthoic di -n- butyl ester, 6,6' - (ethylene di oxy) di-2-naphthoic acid di -iso- butyl ester, 6,6 '- (ethylenedioxy) di-2-naphthoic acid di -tert- butyl ester, 6,6' - (ethylenedioxy) di - 2-naphthoic di -n- hexyl ester, 6,6 '- (ethylenedioxy) di-2-naphthoic acid dicyclohexyl ester, 6,6' - (ethylenedioxy) di-2-naphthoic di -n- octyl ester, 6,6 '- (ethylenedioxy) di-2-naphthoic di -iso- octyl ester, 6,6' - (ethylenedioxy) di-2-naphthoic acid dicycloalkyl octyl ester, 6,6 '- (ethylenedioxy) di-2-naphthoic acid didecyl ester, 6,6' - (ethylenedioxy) di-2-naphthoic acid dicycloalkyl decyl ester, 6,6 '- (ethylenedioxy) di - 2-naphthoic acid diphenyl ester, 6,6 '- (ethylenedioxy) di-2-naphthoic acid bis (mono methyl phenyl) ester, 6,6' - (ethylenedioxy) di-2-naphthoic acid bis (dimethylphenyl ) ester, 6,6 '- (ethylenedioxy) di-2-naphthoic acid bis (mono ethyl phenyl) diphenyl ester, 6,6' - (ethylenedioxy) di-2-naphthoic acid bis (diethyl phenyl) diphenyl ester, or 6,6 '- like (ethylenedioxy) di-2-naphthoic acid dinaphthyl esters are exemplified.
[0023]
　In the production method of the present invention, 6-hydroxy-2-naphthoic acid ester, in a mixed liquid consisting of alkali metal compound or the like and a solvent, it is added 1,2-dihalogenated ethane. That is, before initiation of the reaction of 6-hydroxy-2-naphthoic acid ester, it is necessary to prepare a mixed liquid consisting of alkali metal compound or the like and a solvent. However, even if the 1,2-dihalogenated ethane into the mixing liquid contains or may not be included. That may include a portion of the 1,2-dihalogenated ethane used in the reaction according the necessity to the mixed liquid. Preferably 0 to 90 wt% of the total weight of the 1,2-dihalogenated ethane used in the reaction until the end of the reaction, more preferably 0 to 80 wt%, more preferably above 1 to 75 wt% at the start of reaction a case that is included in the mixed liquid. Even more preferably, when the liquid mixture at the beginning of the reaction is a liquid mixture containing no 1,2-dihalogenated ethane, or mixed liquid at the beginning of the reaction is 1,2-dihalogenated ethane is fed to the reaction 30 is the case, including to 75% by weight.
[0024]
　In the production method of the present invention, 6-hydroxy-2-naphthoic acid ester, initiation part of the 1,2-dihalogenated ethane used in the alkali metal compound or the like and react accordingly mixed liquid (required consisting of solvent the same.) may. below also contain before the reaction is carried out while directly continuously added without contacting to the gas present 1,2-dihalogenated ethane above the gas-liquid interface of the mixed liquid. 6-hydroxy-2-naphthoic acid ester, a mixed liquid consisting of alkali metal compound or the like and a solvent, the compound as specifically listed for each of the above, with respect to 6-hydroxy-2-naphthoic acid ester, preferably constructed according to the above times the molar amount or times by weight, can be obtained by ordinary temperature or stirred and heated once to a temperature below the boiling point of the solvent. As described above, even if the 1,2-dihalogenated ethane mixed liquid in at the beginning of the reaction does not contain, it may be included.
[0025]
　In still producing method of the present invention, 1,2-dihalogenated ethane 6-hydroxy-2-naphthoic acid ester, the mixed liquid containing the alkali metal compound or the like, the mixed 1,2-dihalogenated ethane performs direct continuous addition without contacting to the gas present in the above the gas-liquid interface of the liquid, it is necessary to react at a predetermined temperature as described above. From the beginning of reacting at a predetermined temperature, the total amount of 1,2-dihalogenated ethane used in the reaction are present in the mixed liquid, because the alkali metal compound or the like is present in a large amount in a mixed liquid, 1,2-dihalogenated ethane undergoes an elimination reaction, there is that vinyl halide is produced in large quantities. Furthermore, the presence of 6-hydroxy-2-naphthoic acid ester and an alkali metal compound such as a salt of such a large amount of the ester group-containing Nafuchiruokishido metal obtained by reacting (a salt of an alkali metal such as an ester group-containing Nafurato derivative), 1 , may be 2-dihalogenated ethane causes the elimination reaction. Furthermore, in the amount of 1,2-dihalogenated ethane in the reactor is reduced, which is a reaction intermediate 6- (2-halogenoalkyl ethoxy) the amount of 2-naphthoic acid ester is increased. What these factors alone or in combination, the target compound 6,6 '- the idea of ​​the yield of the (ethylenedioxy) di-2-naphthoic acid diester drops would also be possible. Initially I also applicant was thinking like this.
[0026]
　However, as a result of various manufacturing experiment by changing various reaction conditions, we have come to obtain the following findings. That is, the alkali metal compounds present in the mixture in the liquid 1,2-halogenated ethane before taking the elimination reaction, first, 6-hydroxy-2-naphthoic acid ester of dehydrogenation of the hydroxyl group (proton) reaction It is consumed, to produce a salt of alkali metals such as ester group-containing Nafurato derivative. Then, it is present in a small amount of alkali salt is mixed in a liquid such as a metal of the ester group-containing Nafurato derivative, a finding that does not contribute significantly to the remarkable progress of the elimination reaction we have found. In addition to those who 1,2-halogenated ethane a certain amount of the mixed liquid at the beginning of the reaction was present the reaction rate to produce the desired compounds of the initial start of the reaction increases, and said knowledge also we find led was. Therefore, during the liquid mixture at the beginning of the reaction, the optionally raise sufficient yields of some of the objective compound be contained before starting the reaction of 1,2-dihalogenated ethane used in the reaction and I have found that it is. Furthermore, this finding simultaneously, leading to is also a condition required to produce large quantities of the desired compound, finding a condition that can increase the overall reaction rate. By Together these findings, we have completed the present invention. However, the total amount of 1,2-dihalogenated ethane supplied to eventually from the reaction beginning is, when subjected to mixing in the liquid is a reaction intermediate 6- (2-halogeno-ethoxy) -2- you can increase the amount of naphthoic acid ester, by the elimination reaction, it will be the amount of vinyl chloride compound is increased, which is not preferable.
[0027]
　To avoid the situation where the entire amount of 1,2-dihalogenated ethane as described above with continuous addition in the manufacturing method of the present invention are present in a mixed liquid from the start the reaction, is supplied to the mixed liquid after the reaction initiation that 1,2-dihalogenated ethane, over a predetermined time period, indicates that to be supplied to the reaction vessel in small portions. Also, as the concentration of the 1,2-dihalogenated ethane in the mixed liquid containing the 6-hydroxy-2-naphthoic acid ester and an alkali metal compound or the like does not increase more than necessary, the continuous addition rate of 1,2-dihalogenated ethane preferably it is carried out at a constant speed. Since the 1,2-dihalogenated ethane is consumed in the production of a reaction intermediate 6- (2-halogeno-ethoxy) -2-naphthoic acid ester, during the progress of the reaction, in the mixed liquid 1,2-dihalogen concentration of Compound ethane is because reduced. In the present invention from the viewpoints described above, those requiring continuous addition.
　On the other hand those skilled in the art, 1,2-dihalogenated ethane instead of continuous addition, it can be considered a method of continuously adding an alkali metal compound or the like. However, as disclosed in Patent Document 2 above, 6-hydroxy-2-naphthoic acid ester and a salt of an alkali metal such as an ester group-containing Nafurato derivative obtained alkali metal compound or the like is reacted (6- When the alkali metal salts of hydroxy-2-naphthoic acid ester) is present inside the pre-reactor, the reaction is accelerated with the large amount of existing 1,2-dihalogenated ethane in the reaction vessel. As a result leads to a large amount of generation of vinyl halide as. Thus, the reactor in the presence of a pre-6-hydroxy-2-naphthoic acid ester and an alkali metal compound or the like, the condition in which the alkali metal salt is generated is preferably used.
[0028]
　Further, in the present invention, the liquid mixture, 1,2-dihalogenated ethane must be added without contacting to the gas present in the above the gas-liquid interface of the mixed liquid. Specifically, FIG. 1, may be mentioned a mode of addition as reported in Figure 2. On the other hand, mode of addition as reported in Figure 3 does not apply to the addition method described above of the present invention.
　The addition method is not applicable with the addition of the appropriate method in the present invention will be described with reference to FIGS. 1-3 below. From the viewpoint of accelerating the reaction required, the reaction temperature in the present invention is to 90 ~ 200 ° C. As mentioned above, preferably 100 ~ 190 ℃. However, in this temperature range, 1,2-dihalogenated ethane, though varies depending on the kind of the specific compounds, some cases at a temperature below the boiling point of the 1,2-dihalogenated ethane is close to the boiling point , or it may exceed the boiling point of the compound.
[0029]
　First, the 1,2-case dihalogenated close to the boiling point albeit at a temperature below the boiling point of ethane or even when exceeding the boiling point, the top of the gas-liquid interface of the liquid mixture of 1,2-dihalogenated ethane, the case was added so as to be in contact with the gas present in the description. That is, if the requirement of the manufacturing method of the present invention are not met. As a mode of specific additives include cases such as those listed in Figure 3. If the reaction vessel 1 before the reaction, 6-hydroxy-2-naphthoic acid ester, one of the 1,2-dihalogenated ethane used in the alkali metal compound or the like and the reaction depending mixture liquid 2 (required consisting of solvent parts may a comprise before starting the reaction. filled with the same hereinafter.), the upper part of the mixed liquid has a gas-liquid interface 3. Also mixed liquid 2 is stirred by stirring blades 6 which is installed in the reaction vessel. When production of the present invention is started, the liquid mixture 2 according to the manufacturing progresses, from the direction of the arrow 1,2-dihalogenated ethane shown by 4 via the addition tube 5 into the reaction vessel mixture is added to the liquid 2, reaction is initiated. Reaction intermediates as the reaction progresses, the target compound, and by-products and the like are produced during the mixing liquid 2. When the tip of the addition tube 5 is present above the gas-liquid interface 3, and the addition of 1,2-dihalogenated ethane in a state of contacting to the gas present in the above the gas-liquid interface 3, 1,2-dihalogen before the ethane reduction is mixed with the liquid mixture 2, 1,2-dihalogenated ethane is to be in contact with the gas present in the gas-liquid interface 3 top that has been heated to the reaction temperature or reaction temperature close to 90 ~ 200 ℃. This phenomenon, at least a portion of the 1,2-dihalogenated ethane to be added to the mixed liquid is vaporized, it will not be added to the mixed liquid. Then, not finally reacting an alkali metal salt and 6-hydroxy-2-naphthoic acid ester in the mixed liquid 2 or 6-hydroxy-2-naphthoic acid ester, vaporized 1,2-dihalogenated ethane, liquid mixture it may be present on top of the gas-liquid interface. As a result, the target compound 6,6 '- will be the yield of the (ethylenedioxy) di-2-naphthoic acid diester to decrease, which is undesirable.
[0030]
　On the other hand, the 1,2-case dihalogenated close to the boiling point albeit at a temperature lower than the boiling point of ethane or even when exceeding the boiling point, the top of the gas-liquid interface of the liquid mixture of 1,2-dihalogenated ethane the case was added so as not to come into contact with the gas present in the description. That is, if the requirement of the manufacturing method of the present invention are satisfied. As a mode of body additives include cases such as those listed in Figure 1 and Figure 2. In embodiments of the additives shown in FIG. 1, the tip of the addition tube 5 is located in a liquid mixture 2, 1,2-dihalogenated ethane from the direction of the arrow inside the reaction vessel expressed in 4 similarly to FIG. 3 is added to the mixed liquid 2, reaction is initiated. Thus 1,2-so-dihalogenated ethane is added along surrounded by addition tube 5 the space into a mixed liquid 2, without contacting the gas present above the gas-liquid interface 3 1,2 dihalogenated ethane is fed to the liquid mixture 2 in the interior of the reaction vessel 1. Even if part of the internal with 1,2-dihalogenated ethane addition tube 5 is vaporized, the reaction vessel 1 from the addition pipe 5 is caused by the liquid 1,2-dihalogenated ethane that are not yet vaporized the flow in the direction of the mixing liquid in the inside, a part of the 1,2-dihalogenated ethane vaporized along with the addition pipe 5 is also added to the mixed liquid 2 in the interior of the reaction vessel 1. In other words, it never vaporized 1,2-dihalogenated ethane is spread from the gas-liquid interface 3 to the top of the space. Therefore alkali metal salt of 6-hydroxy-2-naphthoic acid ester of all 1,2-dihalogenated ethane provided in addition to the interior of the reaction tank 1 is mixed in a liquid or 6-hydroxy-2-naphthoic acid ester react promptly with, and thus to contribute to the generation of reactive intermediates and target compound. Further, in the embodiment of the additives shown in FIG. 2, the addition pipe 5 is installed on the side wall of the reaction vessel 1, and the addition pipe 5 in the downward direction of the reaction vessel 1 from the gas-liquid interface 3. Thus, the addition pipe 5 in a mixed liquid 2 that is inside the reactor 1 along the direction of the fourth arrow, so that the 1,2-dihalogenated ethane are added. Then, 1,2-dihalogenated ethane is clear that to be supplied to the liquid mixture 2 in the interior of the reaction vessel 1 without contacting to the gas present in the upper part of the gas-liquid interface 3. Thus, 1,2 and a dihalogenated ethane directly continuously added without contacting to the gas present in the above the gas-liquid interface 3 of the mixed liquid of 1,2-dihalogenated ethane 6- hydroxy-2 - without contacting the gas present from the gas-liquid interface 3 of the mixed liquid at the top prior to the naphthoic acid ester (or its alkali metal salt) is charged into the mixed liquid containing the alkali metal compound or the like, directly above it is intended to refer to when added to the mixed liquid. The gases from the mixture gas-liquid interface 3 of the liquid present in the upper part, shows a gas in particular there from the gas-liquid interface 3 of the mixed liquid at the top, it contains vapor of the solvent constituting the liquid mixture .
[0031]
　In terms aspects of added equipment, as an additive method corresponding to the present invention is a case of supplying e.g. 1,2-dihalogenated ethane from the dropping funnel into the reaction vessel 1, the addition of the dropping funnel portion corresponding to the distal end of the tube 5 can be cited as may be immersed in the mixed liquid as shown in FIG. On the other hand, if not corresponding to the addition method of the present invention, there may be mentioned a case where the total amount of the 1,2-dihalogenated ethane to be supplied to the reaction from the very beginning of the reaction is in the mixed liquid inside of the reaction vessel 1 it can. Furthermore, in a case of supplying a liquid 1,2-dichloroethane from the dropping funnel into the reaction vessel 1, so that a portion corresponding to the tip of the addition tube 5 of the dropping funnel is shown in FIG. 3, the reaction it can be given if there from the gas-liquid interface 3 in the mixed liquid in the tank at the top. In such a case, since the leading end of the addition port is from the gas-liquid interface 3 to the upper, 1,2-dihalogenated ethane supplied from the tip of the addition port is contacted with the gas present above the gas-liquid interface It will be added while. This latter embodiment include when added to the mixed liquid with the interior of the reaction vessel by a process commonly referred to as "dropping".
[0032]
　6,6 obtained by reaction of the present invention '- (ethylenedioxy) di-2-naphthoic acid diester can be isolated from the solution containing the reaction product by various methods, distillation, column chromatography, crystallization, recrystallization, can be easily purified by performing the impurities removing operations such as cleaning.
　The details of the purification and isolation process operation, it is possible to preferably employ a method given below. The mixed liquid after completion of the reaction, used for the reaction, 1,2-dihalogenated ethane, the types of the like, or a solvent an alkali metal compound, the amount of solvent and the like based on the starting material compounds, nor dissolved in the reaction solvent at a reaction temperature there is a case in which inorganic salts and the like are present. Removing them quickly are preferred operation in order to purify the target compound. Specifically, the state temperature was maintained during the reaction, or a state of being cooled from the reaction at a temperature to a temperature above about room temperature, specifically, solid-liquid separation operation in the range of 100 ~ 180 ℃ (hereinafter, the solid is referred to as a liquid separation operation a.) carried out, it is preferable to get rid of them in the inorganic salt. Specifically as solid-liquid separation operation A, mention may be made ​​of filtration or centrifugal separation.
[0033]
　The after its solid-liquid separation operation A, it is preferable to carry out purification treatment by utilizing the difference in solubility in a solvent. The purpose is the compound 6,6 '- (ethylenedioxy) di-2-naphthoic acid diester whereas if solubility in solvents is small can be assumed, which is one of the raw material 6-hydroxy-2-naphthoic and esters is a reaction intermediate 6- (2-halogeno-ethoxy) -2-naphthoic acid esters is that the solubility in the solvent it is expected that relatively large. Also as another raw material, 1,2-dihalogenated ethane boiling decided 1,2-dihalogenated ethane compound that halogen species, depending on the value of the melting point or the like, to the reactor outside at the reaction temperature atmosphere evaporation or believed to hardly remain in the mixing liquid in the reactor after completion of the reaction in the auxiliary reaction raw material as it states. Specifically, the solid-liquid separating operation A liquid component after that cooled down to 10 ~ 50 ° C., it is that the above raw material, is separation and purification of reaction intermediates and the desired compounds is facilitated. Preferably by cooling to 20 ~ 40 ℃. To further utilize the difference in the solubility effectively, after the above solid-liquid separation operation A, at least a portion of the solvent was removed by vacuum distillation, the raw material in the mixed liquid after completion of the reaction, the reaction intermediate can be preferably employed to perform an operation of increasing the concentration of such desired compounds. Therefore, only the target compound by cooling the liquid component after solid-liquid separation operation A as described above in 10 ~ 50 ℃ is produced as a precipitate, which again the solid-liquid separation operation (or less, and the solid-liquid separation operation B referred.) sometimes the objective compound can be efficiently purified and isolation by performing.
[0034]
　Then for solid-liquid separation operations solid component after B if necessary, recrystallization, it is preferred to carry out the washing operation with a solvent. The solvent for the recrystallization or washing, highly soluble, ketone solvents, may be mentioned aprotic polar solvents. Among these types of solvents, the ketone solvent, methyl ethyl ketone (2-butanone), diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone or isophorone. As the aprotic polar solvent include acetonitrile, N, N- dimethylformamide, N, N- dimethylacetamide, dimethyl sulfoxide, sulfolane, or N- methyl-2-pyrrolidone. Moreover, the solvent used for the recrystallization and washing with the reaction solvent is preferably used another type of solvent.
Industrial applicability
[0035]
　According to the production method of the present invention, the above-mentioned 6,6 '- it can be produced (ethylenedioxy) di-2-naphthoic acid diester in an efficient and high yield. 6,6 obtained in the present invention '- (ethylenedioxy) di-2-naphthoic acid diesters are useful as raw materials for functional polymers, for example 6,6' - (ethylenedioxy) di-2-naphthoic acid as acid component, a polyester containing ethylene glycol and glycol component has a characteristic that has a melting point close to 295 ° C., and a high Young's modulus of the molded article can be produced by melt molding.
[0036]
EXAMPLES
　Hereinafter is a description of the present invention embodiment, the present invention is not limited only to these examples. Note that the analysis of the compound was carried out by comparing the separate standard chromatogram obtained using HPLC. The amount of generated as a gas containing vinyl halide compound was measured by a mass flow meter (manufactured by Horiba, Ltd. SEF-51 Co., Ltd.), 0 ℃, was converted to under 1 atm. The gas component 5μL obtained from the reaction were quantified by gas chromatography (manufactured by Shimadzu Corporation GC-14B).
[0037]

　Example 1 6-hydroxy-2-naphthoic acid methyl ester 26.0g (0.13mol), sodium carbonate 21.1g (0.20mol), N- methyl-2-pyrrolidone (NMP) 200g (2. 0 mol) was added and the solution. 3 hours from the dropping funnel 1,2-dichloroethane at a constant rate of 12.4g / over (total 37.2g (0.38mol)), continuously added while 170 ℃ to the NMP solution, atmospheric pressure conditions lower, to obtain a reaction product was reacted for 3 hours. While performing the continuous addition, the distal end of the drip opening in the dropping funnel was a condition in which there to the NMP solution (state shown in FIG. 1).
　After completion of the reaction, the temperature of the liquid containing the reaction product and 170. ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (257 g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 60 g (0.61 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Was this solid component (c) dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 24.4g the (ethylenedioxy) di-2-naphthoic acid dimethyl ester (yield: 88.2%) was obtained.
[0038]
[Example
　2] to 6-hydroxy-2-naphthoic acid ethyl ester 27.8g (0.13mol), sodium carbonate 21.1g (0.20mol), N- methyl-2-pyrrolidone 180g the (1.8mol) In addition, to obtain a solution. 3 hours from the dropping funnel 1,2-dichloroethane at a constant rate of 12.4g / over (total 37.2g (0.38mol)), continuously added while 170 ℃ to the NMP solution, atmospheric pressure conditions lower, to obtain a reaction product was reacted for 3 hours. While performing the continuous addition, the distal end of the drip opening in the dropping funnel was a condition in which there to the NMP solution (state shown in FIG. 1).
　After completion of the reaction, the temperature of the liquid containing the reaction product and 0.89 ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) a was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 20 g (0.20 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Where this solid component (c) was dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 25.5g the (ethylenedioxy) di-2-naphthoic acid diethyl ester (yield: 86.5%) was obtained.
[0039]
[Example
　3] to 6-hydroxy-2-naphthoic acid ethyl ester 27.8g (0.13mol), sodium carbonate 21.1g (0.20mol), N- methyl-2-pyrrolidone 180g the (1.8mol) In addition, to obtain a solution. 6 hours from the dropping funnel of 1,2-dichloroethane at a constant rate of 6.2g / over (total 37.2g (0.38mol)), continuously added while 150 ℃ to the NMP solution, atmospheric pressure conditions lower, to obtain a reaction product was reacted for 6 hours. While performing the continuous addition, the distal end of the drip opening in the dropping funnel was a condition in which there to the NMP solution (state shown in FIG. 1).
　After completion of the reaction, the temperature of the liquid containing the reaction product and 0.89 ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) a was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 20 g (0.20 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively.
Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Where this solid component (c) was dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 24.7g the (ethylenedioxy) di-2-naphthoic acid diethyl ester (yield: 83.9%) was obtained.
[0040]
[Example
　4] to 6-hydroxy-2-naphthoic acid methyl ester 26.0g (0.13mol), sodium carbonate 21.1g (0.20mol), 1,2- dichloroethane 22.2g (0.22mol) , N- methyl-2-pyrrolidone (NMP) 200g (2.0mol) was added to obtain a solution. 1,2-dichloroethane 5.0g / 3 hours from the dropping funnel at a constant rate of time (total 15.0g (0.15mol)) over, continuously added while 170 ℃ to the NMP solution, atmospheric pressure conditions lower, to obtain a reaction product was reacted for 3 hours. While performing the continuous addition, the distal end of the drip opening in the dropping funnel was a condition in which there to the NMP solution (state shown in FIG. 1).
　After completion of the reaction, the temperature of the liquid containing the reaction product and 170. ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (255.5 g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 60 g (0.61 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Was this solid component (c) dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 23.5g the (ethylenedioxy) di-2-naphthoic acid dimethyl ester (yield: 84.9%) was obtained.
[0041]
[Example
　5] to 6-hydroxy-2-naphthoic acid ethyl ester 27.8g (0.13mol), sodium carbonate 21.1g (0.20mol), 1,2- dichloroethane 22.2g (0.22mol) , N- methyl-2-pyrrolidone 180g the (1.8mol) was added and the solution. 1,2-dichloroethane 5.0g / 3 hours from the dropping funnel at a constant rate of time (total 15.0g (0.15mol)) over, continuously added while 170 ℃ to the NMP solution, atmospheric pressure conditions lower, to obtain a reaction product was reacted for 3 hours. While performing the continuous addition, the distal end of the drip opening in the dropping funnel was a condition in which there to the NMP solution (state shown in FIG. 1).
　After completion of the reaction, the temperature of the liquid containing the reaction product and 0.89 ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) a was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 20 g (0.20 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Where this solid component (c) was dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 23.6g the (ethylenedioxy) di-2-naphthoic acid diethyl ester (yield: 80.1%) was obtained.
[0042]
[Example
　6] to 6-hydroxy-2-naphthoic acid methyl ester 26.0g (0.13mol), sodium carbonate 21.1g (0.20mol), 1,2- dichloroethane 16.4g (0.17mol) , N- methyl-2-pyrrolidone (NMP) 200g (2.0mol) was added to obtain a solution. 1,2-dichloroethane 3.5g / 6 hours from the dropping funnel at a constant rate of time (total 21.0g (0.21mol)) over, continuously added while 150 ℃ to the NMP solution, atmospheric pressure conditions lower, to obtain a reaction product was reacted for 6 hours. While performing the continuous addition, the distal end of the drip opening in the dropping funnel was a condition in which there to the NMP solution (state shown in FIG. 1).
　After completion of the reaction, the temperature of the liquid containing the reaction product and 170. ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (253.0g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 60 g (0.61 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) and washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Was this solid component (c) dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 22.9g the (ethylenedioxy) di-2-naphthoic acid dimethyl ester (yield: 82.8%) was obtained.
[0043]
[Comparative Example
　1] to 6-hydroxy-2-naphthoic acid ethyl ester 27.8g (0.13mol), sodium carbonate 21.1g (0.20mol), N- methyl-2-pyrrolidone 180g the (1.8mol) In addition, to obtain a solution. 3 hours from the dropping funnel 1,2-dichloroethane at a constant rate of 12.4g / over (total 37.2g (0.38mol)), continuously added while 170 ℃ to the NMP solution, atmospheric pressure conditions lower, to obtain a reaction product was reacted for 3 hours. While performing the continuous addition, the distal end of the drip opening in the dropping funnel was state in 3cm above the gas-liquid interface of the NMP solution (state shown in FIG. 3).
　After completion of the reaction, the temperature of the liquid containing the reaction product and 0.89 ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (254.5g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 20 g (0.20 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Where this solid component (c) was dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 20.4g the (ethylenedioxy) di-2-naphthoic acid diethyl ester (yield: 69.2%) was obtained.
[0044]
[Comparative Example
　2] 6-hydroxy-2-naphthoic acid ethyl ester 27.8g (0.13mol), potassium carbonate 21.1g (0.20mol), 1,2- dichloroethane 37.2g (0.38mol), N- methyl-2-pyrrolidone 180g of (1.8 mol) were then added to in one reactor, 170. ° C., under atmospheric conditions to obtain a reaction product was reacted for 3 hours. After completion of the reaction, the temperature of the liquid containing the reaction product and 0.89 ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (252.6 g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 20 g (0.20 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Where this solid component (c) was dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 15.6g the (ethylenedioxy) di-2-naphthoic acid diethyl ester (yield: 52.9%) was obtained.
[0045]
[Comparative Example
　3] 6-hydroxy-2-naphthoic acid ethyl ester 27.8g to (0.13mol), sodium carbonate 21.1g (0.20mol), 1,2- dichloroethane 22.2g (0.22mol) , N- methyl-2-pyrrolidone 180g the (1.8mol) was added and the solution. 1,2-dichloroethane 5.0g / 3 hours from the dropping funnel at a constant rate of time (total 15.0g (0.15mol)) over, continuously added while 170 ℃ to the NMP solution, under atmospheric conditions to obtain a reaction product was reacted for 3 hours. While performing the continuous addition, the distal end of the drip opening in the dropping funnel was state in 3cm above the gas-liquid interface of the NMP solution (state shown in FIG. 3).
　After completion of the reaction, the temperature of the liquid containing the reaction product and 0.89 ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (254.5g) was obtained, respectively.
After removing the filtrate from (a) N- methyl-2-pyrrolidone 20 g (0.20 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Where this solid component (c) was dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 20.3g the (ethylenedioxy) di-2-naphthoic acid diethyl ester (yield: 68.9%) was obtained.
　Above Examples 1-6, it shows the results of Comparative Examples 1 to 3 in Table 1 and Table 2.
[0046]
[Table 1]

[0047]
[Table 2]

[0048]

　Example 7 6-hydroxy-2-naphthoic acid methyl 26.0g (0.13mol), sodium carbonate 21.1g (0.20mol), N- methyl-2-pyrrolidone (NMP) 200g (2.0mol ) was added and the solution. 1,2-dichloroethane 9.9g / 3 hours from the dropping funnel at a constant rate of time (total 29.7g (0.30mol)) over, continuously added while 150 ℃ to the NMP solution, atmospheric pressure conditions lower, and including the continuous addition time and reacted for 6 hours to obtain a reaction product. While performing the continuous addition, the distal end of the drip opening in the dropping funnel was a condition in which there to the NMP solution (state shown in FIG. 1).
　After completion of the reaction, the temperature of the liquid containing the reaction product and 170. ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (261 g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 60 g (0.61 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Was this solid component (c) dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- (ethylenedioxy) di-2-naphthoic acid dimethyl 24.8g (yield: 89 .6%) was obtained.
[0049]
[Example
　8] to 6-hydroxy-2-naphthoic acid methyl 26.0g (0.13mol), sodium carbonate 21.1g (0.20mol), N- methyl-2-pyrrolidone 200g (2.0mol) added , was the solution. 1,2-dichloroethane 13.6g / 2 hours from the dropping funnel at a constant rate of time (total 27.2g (0.27mol)) over, continuously added while 150 ℃ to the NMP solution, atmospheric pressure conditions lower, and including the continuous addition time and reacted for 6 hours to obtain a reaction product. While performing the continuous addition, the distal end of the drip opening in the dropping funnel was a condition in which there to the NMP solution (state shown in FIG. 1).
　After completion of the reaction, the temperature of the liquid containing the reaction product and 170. ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (259 g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 60 g (0.61 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Was this solid component (c) dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- (ethylenedioxy) di-2-naphthoic acid dimethyl 23.9g (yield: 86 .4%) was obtained.
[0050]
[Example
　9] to 6-hydroxy-2-naphthoic acid methyl 26.0g (0.13mol), sodium carbonate 21.1g (0.20mol), N- methyl-2-pyrrolidone 200g (2.0mol) added , was the solution. 1,2-dichloroethane 16.1g / 2 hours from the dropping funnel at a constant rate of time (total 32.2g (0.33mol)) over, continuously added while 170 ℃ to the NMP solution, atmospheric pressure conditions lower, and including the continuous addition time and reacted for 3 hours to obtain a reaction product. While performing the continuous addition, the distal end of the drip opening in the dropping funnel was a condition in which there to the NMP solution (state shown in FIG. 1).
　After completion of the reaction, the temperature of the liquid containing the reaction product and 170. ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (249 g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 60 g (0.61 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Was this solid component (c) dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- (ethylenedioxy) di-2-naphthoic acid dimethyl 25.0g (yield: 90 .3%) was obtained.
[0051]
[Example
　10] to 6-hydroxy-2-naphthoic acid methyl 26.0g (0.13mol), sodium carbonate 21.1g (0.20mol), 1,2- dichloroethane 22.2g (0.22mol), N - methyl-2-pyrrolidone 200g of (2.0 mol) was added and the solution. 1,2-dichloroethane 2.5g / 3 hours from the dropping funnel at a constant rate of time (for a total of 7.5g (0.076mol)) over, continuously added while 150 ℃ to the NMP solution, atmospheric pressure conditions lower, and including the continuous addition time and reacted for 6 hours to obtain a reaction product. While performing the continuous addition, the distal end of the drip opening in the dropping funnel was a condition in which there to the NMP solution (state shown in FIG. 1).
　After completion of the reaction, the temperature of the liquid containing the reaction product and 170. ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (261 g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 60 g (0.61 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Was this solid component (c) dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- (ethylenedioxy) di-2-naphthoic acid dimethyl 24.9g (yield: 90 .0%) was obtained.
[0052]
[Example
　11] to 6-hydroxy-2-naphthoic acid methyl 26.0g (0.13mol), sodium carbonate 21.1g (0.20mol), 1,2-dichloroethane 16.4g (0.17mol), N- methyl-2-pyrrolidone 200g of (2.0 mol) was added and the solution. 1,2-dichloroethane 4.5g / 3 hours from the dropping funnel at a constant rate of time (total 13.5g (0.14mol)) over, continuously added while 150 ℃ to the NMP solution, atmospheric pressure conditions lower, and including the continuous addition time and reacted for 6 hours to obtain a reaction product. While performing the continuous addition, the distal end of the drip opening in the dropping funnel was a condition in which there to the NMP solution (state shown in FIG. 1).
　After completion of the reaction, the temperature of the liquid containing the reaction product and 170. ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (259 g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 60 g (0.61 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Was this solid component (c) dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- (ethylenedioxy) di-2-naphthoic acid dimethyl 24.1g (yield: 87 .1%) was obtained.
[0053]
[Example
　12] to 6-hydroxy-2-naphthoic acid ethyl 27.8g (0.13mol), sodium carbonate 21.1g (0.20mol), 1,2-dichloroethane 22.2g (0.22mol), N- methyl-2-pyrrolidone 200g of (2.0 mol) was added, 3 hours from the dropping funnel 1,2-dichloroethane at a constant rate of 2.5 g / (total 7.5g (0.076mol)) over a period, the above NMP solution continuously added while 170. ° C. to normal pressure conditions, to give the reaction product is 6 hours, including the time of continuous addition. While performing the continuous addition, the distal end of the drip opening in the dropping funnel was a condition in which there to the NMP solution (state shown in FIG. 1).
　After completion of the reaction, the temperature of the liquid containing the reaction product and 170. ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (249 g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 60 g (0.61 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Was this solid component (c) dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- (ethylenedioxy) di-2-naphthoic acid dimethyl 25.1g (yield: 85 .2%) was obtained.
　The results of the above Examples 7-12 are shown in Table 3.
[0054]
[table 3]

[0055]
[Example
　13] to 6-hydroxy-2-naphthoic acid methyl ester 26.0g (0.13mol), sodium carbonate 21.1g (0.20mol), N- methyl-2-pyrrolidone 200g the (2.0mol) In addition, to obtain a solution. 3 hours of 1,2-dichloroethane at a constant speed when 9.9g / (total 29.7g (0.30mol)) continuously added while 150 ℃ to the liquid phase, atmospheric pressure conditions, the production reaction reacted for 6 hours I got things. At the same time a gas component generated during the reaction was collected in the gas collection bottle (the amount of the resulting gaseous component was 4.7L.). Continuous addition operation to the liquid phase, using a dropping funnel, the tip of the dropping funnel were performed in a state (state shown in FIG. 1) as in the above NMP solution.
　After completion of the reaction, the temperature of the liquid containing the reaction product and 170. ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (260.5g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 60 g (0.61 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Was this solid component (c) dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 24.5g the (ethylenedioxy) di-2-naphthoic acid dimethyl ester (yield: 88.5%) was obtained. Also from the recovered gas component, the chloride Binirugasu 1.2L (0.054mol, 17.9mol% of the charged 1,2-dichloroethane has been converted.) Was obtained.
[0056]
[Example
　14] to 6-hydroxy-2-naphthoic acid methyl ester 26.0g (0.13mol), sodium carbonate 21.1g (0.20mol), N- methyl-2-pyrrolidone 200g the (2.0mol) In addition, to obtain a solution. 3 hours of 1,2-dichloroethane at a constant speed when 12.4g / (total 37.2g (0.38mol)) continuously added while 170 ℃ to the liquid phase, under atmospheric conditions, the reaction product and reacted for 3 hours I got things. At the same time a gas component generated during the reaction was collected in the gas collection bottle (the amount of the resulting gaseous component was 8.3L.). Continuous addition operation to the liquid phase, using a dropping funnel, the tip of the dropping funnel were performed in a state (state shown in FIG. 1) as in the above NMP solution.
　After completion of the reaction, the temperature of the liquid containing the reaction product and 170. ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (274 g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 60 g (0.61 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Was this solid component (c) dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 24.7g the (ethylenedioxy) di-2-naphthoic acid dimethyl ester (yield: 89.3%) was obtained. Also from the recovered gas component, the chloride Binirugasu 2.3L (0.103mol, 27.3mol% of the charged 1,2-dichloroethane has been converted.) Was obtained.
[0057]
[Example
　15] to 6-hydroxy-2-naphthoic acid ethyl ester 27.8g (0.13mol), sodium carbonate 21.1g (0.20mol), N- methyl-2-pyrrolidone 180g the (1.8mol) In addition, to obtain a solution. 6 hours of 1,2-dichloroethane at a constant speed when 6.2g / (total 37.2g (0.38mol)) continuously added while 150 ℃ to the liquid phase, atmospheric pressure conditions, the production reaction reacted for 6 hours I got things. At the same time a gas component generated during the reaction was collected in the gas collection bottle (the amount of the resulting gaseous component was 5.7L.). Continuous addition operation to the liquid phase, using a dropping funnel, the tip of the dropping funnel were performed in a state (state shown in FIG. 1) as in the above NMP solution.
　After completion of the reaction, the temperature of the liquid containing the reaction product and 0.89 ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (257.5 g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 20 g (0.20 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Where this solid component (c) was dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 25.7g the (ethylenedioxy) di-2-naphthoic acid diethyl ester (yield: 87.2%) was obtained. Also from the recovered gas component, the chloride Binirugasu 1.7L (0.076mol, 20.2mol% of the charged 1,2-dichloroethane has been converted.) Was obtained.
[0058]
[Example
　16] to 6-hydroxy-2-naphthoic acid ethyl ester 27.8g (0.13mol), sodium carbonate 21.1g (0.20mol), N- methyl-2-pyrrolidone 200g the (2.0mol) In addition, to obtain a solution. 3 hours of 1,2-dichloroethane at a constant speed when 12.4g / (total 37.2g (0.38mol)) continuously added while 170 ℃ to the liquid phase, under atmospheric conditions, the reaction product and reacted for 3 hours I got things. At the same time a gas component generated during the reaction was collected in the gas collection bottle (the amount of the resulting gaseous component was 8.6L.). Continuous addition operation to the liquid phase, using a dropping funnel, the tip of the dropping funnel were performed in a state (state shown in FIG. 1) as in the above NMP solution.
　After completion of the reaction, the temperature of the liquid containing the reaction product and 0.89 ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (260 g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 20 g (0.20 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Where this solid component (c) was dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 26.6g the (ethylenedioxy) di-2-naphthoic acid diethyl ester (yield: 90.3%) was obtained. Also from the recovered gas component, the chloride Binirugasu 2.6L (0.116mol, 30.9mol% of the charged 1,2-dichloroethane has been converted.) Was obtained.
[0059]
[Example
　17] to 6-hydroxy-2-naphthoic acid methyl ester 26.0g (0.13mol), sodium carbonate 21.1g (0.20mol), 1,2- dichloroethane 22.2g (0.22mol) , N- methyl-2-pyrrolidone 200g of (2.0 mol) was added and the solution. 3 hours of 1,2-dichloroethane at a constant speed when 2.5g / (total 7.5g (0.076mol)) continuously added while 150 ℃ to the liquid phase, atmospheric pressure conditions, the production reaction reacted for 6 hours I got things. At the same time a gas component generated during the reaction was collected in the gas collection bottle (the amount of the resulting gaseous component was 4.7L.). Continuous addition operation to the liquid phase, using a dropping funnel, the tip of the dropping funnel were performed in a state (state shown in FIG. 1) as in the above NMP solution.
　After completion of the reaction, the temperature of the liquid containing the reaction product and 170. ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (260.5g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 60 g (0.61 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Was this solid component (c) dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 25.2g the (ethylenedioxy) di-2-naphthoic acid dimethyl ester (yield: 91.1%) was obtained. Also from the recovered gas component, the chloride Binirugasu 1.2L (0.054mol, 17.9mol% of the charged 1,2-dichloroethane has been converted.) Was obtained.
[0060]
[Example
　18] to 6-hydroxy-2-naphthoic acid methyl ester 26.0g (0.13mol), sodium carbonate 21.1g (0.20mol), 1,2- dichloroethane 22.2g (0.22mol) , N- methyl-2-pyrrolidone 200g of (2.0 mol) was added and the solution. 3 hours of 1,2-dichloroethane at a constant speed when 5.0g / (total 15.0g (0.15mol)) continuously added while 170 ℃ to the liquid phase, under atmospheric conditions, the reaction product and reacted for 3 hours I got things. At the same time a gas component generated during the reaction was collected in the gas collection bottle (the amount of the resulting gaseous component was 8.3L.). Continuous addition operation to the liquid phase, using a dropping funnel, the tip of the dropping funnel were performed in a state (state shown in FIG. 1) as in the above NMP solution.
　After completion of the reaction, the temperature of the liquid containing the reaction product and 170. ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (274 g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 60 g (0.61 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Was this solid component (c) dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 25.0g the (ethylenedioxy) di-2-naphthoic acid dimethyl ester (yield: 90.3%) was obtained. Also from the recovered gas component, the chloride Binirugasu 2.3L (0.103mol, 27.3mol% of the charged 1,2-dichloroethane has been converted.) Was obtained.
[0061]
[Example
　19] to 6-hydroxy-2-naphthoic acid methyl ester 26.0g (0.13mol), sodium carbonate 21.1g (0.20mol), 1,2- dichloroethane 9.9g (0.10mol) , N- methyl-2-pyrrolidone 200g of (2.0 mol) was added and the solution. 3 hours of 1,2-dichloroethane at a constant speed when 6.6g / (total 19.8g (0.20mol)) continuously added while 170 ℃ to the liquid phase, under atmospheric conditions, the reaction product and reacted for 3 hours I got things. At the same time a gas component generated during the reaction was collected in the gas collection bottle (the amount of the resulting gaseous component was 8.3L.). Continuous addition operation to the liquid phase, using a dropping funnel, the tip of the dropping funnel were performed in a state (state shown in FIG. 1) as in the above NMP solution.
　After completion of the reaction, the temperature of the liquid containing the reaction product and 170. ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (274 g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 60 g (0.61 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Was this solid component (c) dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 24.8g the (ethylenedioxy) di-2-naphthoic acid dimethyl ester (yield: 89.6%) was obtained. Also from the recovered gas component, the chloride Binirugasu 1.4L (0.063mol, 20.8mol% of the charged 1,2-dichloroethane has been converted.) Was obtained.
[0062]
[Example
　20] to 6-hydroxy-2-naphthoic acid ethyl ester 27.8g (0.13mol), sodium carbonate 21.1g (0.20mol), 1,2- dichloroethane 22.2g (0.22mol) , N- methyl-2-pyrrolidone 180g the (1.8mol) was added and the solution. 3 hours of 1,2-dichloroethane at a constant speed when 2.5g / (total 7.5g (0.076mol)) continuously added while 150 ℃ to the liquid phase, atmospheric pressure conditions, the production reaction reacted for 6 hours I got things. At the same time a gas component generated during the reaction was collected in the gas collection bottle (the amount of the resulting gaseous component was 5.7L.). Continuous addition operation to the liquid phase, using a dropping funnel, the tip of the dropping funnel were performed in a state (state shown in FIG. 1) as in the above NMP solution.
　After completion of the reaction, the temperature of the liquid containing the reaction product and 0.89 ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (257.5 g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 20 g (0.20 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Where this solid component (c) was dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 26.1g the (ethylenedioxy) di-2-naphthoic acid diethyl ester (yield: 88.6%) was obtained. Also from the recovered gas component, the chloride Binirugasu 1.7L (0.076mol, 25.3mol% of the charged 1,2-dichloroethane has been converted.) Was obtained.
[0063]
[Example
　21] to 6-hydroxy-2-naphthoic acid ethyl ester 27.8g (0.13mol), sodium carbonate 21.1g (0.20mol), 1,2- dichloroethane 22.2g (0.22mol) , N- methyl-2-pyrrolidone 200g of (2.0 mol) was added and the solution. 3 hours of 1,2-dichloroethane at a constant speed when 5.0g / (total 15.0g (0.15mol)) continuously added while 170 ℃ to the liquid phase, under atmospheric conditions, the reaction product and reacted for 3 hours I got things. At the same time a gas component generated during the reaction was collected in the gas collection bottle (the amount of the resulting gaseous component was 8.6L.). Continuous addition operation to the liquid phase, using a dropping funnel, the tip of the dropping funnel were performed in a state (state shown in FIG. 1) as in the above NMP solution.
　After completion of the reaction, the temperature of the liquid containing the reaction product and 0.89 ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (260 g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 20 g (0.20 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Where this solid component (c) was dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 26.4g the (ethylenedioxy) di-2-naphthoic acid diethyl ester (yield: 89.6%) was obtained. Also from the recovered gaseous component to give the chloride Binirugasu 2.6L (0.116mol, 30.9mol% of the charged 1,2-dichloroethane is converted.) A.
　The results of Examples 13-21 are shown in Table 4 and Table 5.
[0064]
[Table 4]

[0065]
[table 5]

[0066]

　Example 22 6-hydroxy-2-naphthoic acid methyl ester 26.0g (0.13mol), potassium carbonate 36.8g (0.27mol), N- methyl-2-pyrrolidone 200g of (2.0 mol) In addition, to obtain a solution. 6 hours of 1,2-dichloroethane at a constant speed when 6.2g / (total 37.2g (0.38mol)) continuously added while 120 ℃ to the liquid phase, atmospheric pressure conditions, the production reaction reacted 9 hours I got things. At the same time a gas component generated during the reaction was collected in the gas collection bottle (the amount of the resulting gaseous component was 6.2L.). Continuous addition operation to the liquid phase, using a dropping funnel, the tip of the dropping funnel were performed in a state (state shown in FIG. 1) as in the above NMP solution.
　After completion of the reaction, the temperature of the liquid containing the reaction product and 120. ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (258.2g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 60 g (0.61 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) and washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Was this solid component (c) dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 25.1g the (ethylenedioxy) di-2-naphthoic acid dimethyl ester (yield: 90.7%) was obtained. Also from the recovered gas component, the chloride Binirugasu 1.0L (0.045mol, 11.9mol% of the charged 1,2-dichloroethane has been converted.) Was obtained.
[0067]

　Example 23 6-hydroxy-2-naphthoic acid methyl ester 26.0g (0.13mol), potassium carbonate 36.8g (0.27mol), N- methyl-2-pyrrolidone 200g of (2.0 mol) In addition, to obtain a solution. 3 hours of 1,2-dichloroethane at a constant speed when 9.3g / (total 27.9g (0.28mol)) continuously added while 120 ℃ to the liquid phase, atmospheric pressure conditions, the production reaction reacted for 8 hours I got things. At the same time a gas component generated during the reaction was collected in the gas collection bottle (the amount of the resulting gaseous component was 7.7L.). Continuous addition operation to the liquid phase, using a dropping funnel, the tip of the dropping funnel were performed in a state (state shown in FIG. 1) as in the above NMP solution.
　After completion of the reaction, the temperature of the liquid containing the reaction product and 120. ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (249.6g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 60 g (0.61 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, mixing the solid component (b) and cyclohexanone 150g and (1.5 mol), solid-liquid separation by filtration, the solid component (c) to obtain a filtrate, respectively. Was this solid component (c) dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 24.8g the (ethylenedioxy) di-2-naphthoic acid dimethyl ester (yield: 89.6%) was obtained. Also from the recovered gas component, the chloride Binirugasu 1.1L (0.049mol, 17.4mol% of the charged 1,2-dichloroethane has been converted.) Was obtained.
[0068]

　Example 24 6-hydroxy-2-naphthoic acid ethyl ester 27.8g (0.13mol), potassium carbonate 36.8g (0.27mol), N- methyl-2-pyrrolidone 130g of (1.8 mol) In addition, to obtain a solution. 3 hours of 1,2-dichloroethane at a constant speed when 9.3g / (total 27.9g (0.28mol)) continuously added while 120 ℃ to the liquid phase, atmospheric pressure conditions, the production reaction allowed to react for 11 hours I got things. At the same time a gas component generated during the reaction was collected in the gas collection bottle (the amount of the resulting gaseous component was 4.7L.). Continuous addition operation to the liquid phase, using a dropping funnel, the tip of the dropping funnel were performed in a state (state shown in FIG. 1) as in the above NMP solution.
　After completion of the reaction, the temperature of the liquid containing the reaction product and 120. ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (247.5g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 30 g (0.30 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) was mixed with cyclohexanone 150 g (1.5 mol), solid-liquid separation by filtration, the solid component (c) and the filtrate was obtained, respectively. Where this solid component (c) was dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 26.1g the (ethylenedioxy) di-2-naphthoic acid diethyl ester (yield: 88.6%) was obtained. Also from the recovered gaseous component, a chloride Binirugasu 0.6L (0.027mol, 9.5mol% of the charged 1,2-dichloroethane is converted.) Was obtained.
[0069]

　Example 25 6-hydroxy-2-naphthoic acid ethyl ester 27.8g (0.13mol), potassium carbonate 36.8g (0.27mol), N- methyl-2-pyrrolidone 130g of (2.0 mol) In addition, to obtain a solution. 2 hours 1,2-dichloroethane at 14.0g / constant speed at the time (for a total of 28.0g (0.28mol)) continuously added while 120 ℃ to the liquid phase, atmospheric pressure conditions, the response generated by reacting 9 hours I got things. At the same time a gas component generated during the reaction was collected in the gas collection bottle (the amount of the resulting gaseous component was 6.6L.). Continuous addition operation to the liquid phase, using a dropping funnel, the tip of the dropping funnel were performed in a state (state shown in FIG. 1) as in the above NMP solution.
　After completion of the reaction, the temperature of the liquid containing the reaction product and 120. ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (247.9g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 30 g (0.30 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) was mixed with cyclohexanone 150 g (1.5 mol), solid-liquid separation by filtration, the solid component (c) and the filtrate was obtained, respectively. Where this solid component (c) was dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 26.2g the (ethylenedioxy) di-2-naphthoic acid diethyl ester (yield: 88.9%) was obtained. Also from the recovered gas component, the chloride Binirugasu 1.3L (0.058mol, 20.5mol% of the charged 1,2-dichloroethane has been converted.) Was obtained.
[0070]
[Comparative Example
　4] 6-hydroxy-2-naphthoic acid methyl ester 26.0g (0.13mol), potassium carbonate 27.6g (0.20mol), 1,2- dichloroethane 37.2g (0.38mol), N- methyl-2-pyrrolidone 180g the (1.8mol) was added and the solution. 120. ° C. In this state, under atmospheric conditions to obtain a reaction product reacted for 10 hours. At the same time a gas component generated during the reaction was collected in the gas collection bottle (the amount of the resulting gaseous component was 14.3L.).
　After completion of the reaction, the temperature of the liquid containing the reaction product and 170. ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (275.5g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 60 g (0.61 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Was this solid component (c) dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 21.1g the (ethylenedioxy) di-2-naphthoic acid dimethyl ester (yield: 76.3%) was obtained. Also from the recovered gas component, the chloride Binirugasu 4.0L (0.179mol, 47.5mol% of the charged 1,2-dichloroethane has been converted.) Was obtained.
[0071]
[Comparative Example
　5] 6-hydroxy-2-naphthoic acid ethyl ester 27.8g (0.13mol), potassium carbonate 27.6g (0.20mol), 1,2- dichloroethane 37.2g (0.38mol), N- methyl-2-pyrrolidone 180g the (1.8mol) was added and the solution. 120. ° C. In this state, under atmospheric conditions to obtain a reaction product reacted for 10 hours. At the same time a gas component generated during the reaction was collected in the gas collection bottle (the amount of the resulting gaseous component was 13.1L.).
　After completion of the reaction, the temperature of the liquid containing the reaction product and 0.89 ° C., solid-liquid separation by filtration, the solid component and the filtrate (a) and (260.5g) was obtained, respectively. After removing the filtrate from (a) N- methyl-2-pyrrolidone 20 g (0.20 mol) by vacuum distillation, after the cooling to 35 ℃ the distillation residue, the solid-liquid separation by filtration, the solid component (b) and the filtrate was obtained, respectively. Thereafter, the solid component (b) is washed with cyclohexanone 150 g (1.5 mol), was obtained solid component (c). Where this solid component (c) was dried for 12 hours at 90 ~ 100 ℃ of steam dryer, 6,6 '- 22.7g the (ethylenedioxy) di-2-naphthoic acid diethyl ester (yield: 77.0%) was obtained. Also from the recovered gas component, the chloride Binirugasu 3.7L (0.165mol, 43.9mol% of the charged 1,2-dichloroethane has been converted.) Was obtained.
　Above Examples 22-25, the results of Comparative Examples 4-5 are shown in Table 6.
[0072]
[Table 6]

The scope of the claims
[Claim 1]
6-hydroxy-2-naphthoic acid ester is reacted with the presence in 1,2-dihalogenated ethane alkali metal or alkaline earth metal compound 6,6 '- (ethylenedioxy) di-2-naphthoic acid diester a method for producing a,
6-hydroxy-2-naphthoic acid ester, an alkali metal or alkaline earth metal compound, and the mixed liquid composed of a solvent, above the gas-liquid interface of the mixed liquid of 1,2-dihalogenated ethane while direct continuously added without contacting the gas present, 6,6, characterized by reacting at a temperature of 90 ~ 200 ℃ '- the production method of (ethylenedioxy) di-2-naphthoic acid diester .
[Claim 2]
　The the mixing liquid, 6,6 according to claim 1, characterized in that it comprises further a part of the 1,2-dihalogenated ethane used in the reaction '- (ethylenedioxy) di-2-naphthoic acid method of manufacturing a diester.
[Claim 3]
　Preparation of (ethylenedioxy) di-2-naphthoic acid diesters - 6,6 'according to claim 1, also comprising reacting maintaining the temperature was continuously added After terminating the direct continuous addition Method.
[Claim 4]
　According to claim 1 amount of the alkali metal or alkaline earth metal compound, wherein said is 0.95 to 4.0 moles amount with respect to 6-hydroxy-2-naphthoic acid ester 1 mol method of manufacturing the (ethylenedioxy) di-2-naphthoic acid diester - 6, 6 'of.
[Claim 5]
　The 1,2 The amount of dihalogenated ethane, according to claim 1, wherein 0.4 to 5.0 mol amounts with respect to 6-hydroxy-2-naphthoic acid ester 1 mol 6,6 '- production method of (ethylenedioxy) di-2-naphthoic acid diester.
[6.]
　6,6 according to claim 1, wherein the alkali metal or alkaline earth metal compound wherein the alkali metal carbonate '- the production method of (ethylenedioxy) di-2-naphthoic acid diester.
[7.]
　6,6 according to claim 6, wherein the alkali metal carbonate is sodium carbonate or potassium carbonate '- the production method of (ethylenedioxy) di-2-naphthoic acid diester.
[8.]
　The liquid mixture at the beginning of the reaction is, 1,2-6,6 according to claim 1, wherein the dihalogenated a liquid mixture containing no reduction ethane '- (ethylenedioxy) di-2-naphthoic acid method of manufacturing a diester.