JPS5935912B2 - Method for producing aromatic diester and aryloxy derivative of dinitrile - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing aryloxy derivatives of aromatic diesters and dinitriles.

More specifically, the present invention provides the following method: in the presence of a dipolar solvent,
a) General formula (I) O2NO:O (in the formula, Z represents -CN or -C-OR'' group, R'' represents a monovalent hydrocarbon group having 1 to 12 carbon atoms, and in the case of a) NO2 (b) compounds of the general formula (wherein Z is as described above); and (c) compounds of the general formula Z (wherein Z is (2) (a) - a benzenoid compound selected from the group consisting of compounds of the general formula (as described above, in which case the NO2 group is assumed to be adjacent to the Z group)
A mixture of each component containing a compound of the general formula W (wherein R represents an aromatic group and ALK represents an alkali metal atom) is reacted to form a compound of the general formula W (wherein R and Z are as described above). The present invention relates to a method for producing the compound.

Aryloxy derivatives of aromatic diacids have conventionally been produced by three methods.

The most common method consists of carrying out a copper-catalyzed reaction between an alkali metal phenolate and a haloaromatic compound, followed by oxidation of the alkyl substituent to a carboxylic acid group. For example, Zh, Org, Khim Volume 4, Page 774 (1
In 968), M.M. Codon and F.S. Florinski prepared 2 equivalents of potassium-4,5-dimethylphenolate and 1,4-dibromobenzene at 220-230%
A method for producing 4,4'-dioxyphenylene diphthalic acid is shown by carrying out a copper-catalyzed reaction for 4 to 5 hours at <RTIgt;C,</RTI> followed by oxidation of the methyl group with potassium permanganate to form the carboxylic acid. This method has two major limitations. The first is the difficulty in reproducing copper-catalyzed reactions between alkali metal phenolates and haloaromatic compounds and the high temperatures required to carry out these reactions. The second is that the oxidation-sensitive groups are oxidized together with the desired group to be oxidized. A second method of producing certain aryloxyphthalate esters is described in French Patent No. 1,573,736.

This method involves reacting the sodium salt of dimethyl-4-hydroxyphthalate with 4-chloronitrobenzene to form dimethyl-4-(4-nitrophenoxy)-
I was able to obtain phthalate. It is clear that this method is limited in scope to compounds in which the aromatic halogen is highly activated for nucleophilic displacement. A third method involves reacting between a primary aromatic amine and sodium nitrite to form a diazonium salt, followed by reaction of this intermediate with cuprous cyanide to form an aromatic nitrile; It consists of hydrolysis to form an acid. This reaction rarely proceeds in high yields, requires the handling of highly toxic cyanide, and is too expensive to carry out in large scale production. The present inventors attempted without success to carry out the direct reaction between the nitro derivative of an aromatic diacid and an alkali metal phenolate in a dipolar neutral solvent.

For example, the reaction of sodium carbonate with 4-nitrophthalic acid failed to yield a product corresponding to formula COOH.

Surprisingly, the inventors have discovered that the reaction between sodium calcareous acid and nitro acids does not occur with 3-nitrophthalic acid, nitroterephthalic acid or 2- or 4-nitroisophthalic acids, but that the reaction When carried out between esters such as diethyl 4-nitrophthalate, or metal phenolates such as sodium carbonate and phthalic, isophthalic or terephthalic acids in the form of the corresponding nitrophthalonitrile, the aryloxy of these acids It was discovered that derivatives can be made.

This reaction between metal phenolates and nitroesters or nitriles usually yields phenoxy derivatives in high yields.
A large number of dibasic acids can be prepared from the compounds of the above general formula according to the present invention.

When carrying out the method of the present invention, the general formula (I), (
It is important to use dipolar aprotic solvents in the reaction with either the cyano or ester derivatives of the compounds of (...) or 1.

A particular advantage of the present invention over the prior art is the mildness of the conditions under which the reaction can be carried out (room temperature is often sufficient to carry out the reaction) - generally producing products in high yields. be obtained, be industrially attractive for synthesizing aromatic acids containing oxidizable groups (unachievable to date with known methods), and The advantage is that a wider range of diacids and diacid anhydrides can be made. A monovalent aromatic group (this term is intended to include an organic group containing an aryl group directly bonded to oxygen) which R may represent has, for example, a carbon number of 4
~10 monovalent aromatic hydrocarbon groups, such as aryl groups (e.g., phenyl, naphthyl, biphenyl, etc.), alkaryl groups (e.g., tolyl, xylyl, ethylphenyl, etc.), other organic groups such as organocarbon groups, etc. xyaryl group (e.g. methoxyphenyl group, phenoxyphenyl group,
Ethoxyethoxyphenyl group, ethoxyphenyl group) pyridyl group, etc.

Typical examples of hydroxy compounds that can be prepared by reacting metal salts of general formula (m) with, for example, alkali metals, alkali metal hydroxides or carbonates include, for example, phenol, o-,
m- and p-chlorophenol, 2,6-dimethylphenol, m- and p-aminophenol, o-, m
- and p-cresol, m- and p-acetamidophenol, 1- and 2-naphthol, m- and p-
-Hydroxybenzoic acid, o- and p-phenylphenol, m- and p-hydroxybenzonitrile, o-
, m- and p-methoxyphenol, 3-hydroxypyridine, o-, m- and p-nitrophenol, 3
-Hydroxyquinoline and 5-hydroxypyrimidine. The R group may also contain inert substituents on the aryl nucleus, such as monovalent hydrocarbon groups such as methyl, ethyl,
Alicyclic groups (e.g. cyclopentyl, cyclohexyl, etc.), aryl groups, e.g. phenyl, biphenyl, etc.
It can also have alkaryl groups, such as tolyl, ethyl phenyl, etc., and aralkyl groups, such as benzyl, phenylethyl, etc. Therefore, the substituent on the aryl group can be any substituent that does not constitute or contain an atom or group reactive with the alkali metal salt of the general formula (M). Since it is ultimately removed by hydrolysis when obtained, R'' is a monovalent hydrocarbon group having 1 to 12 carbon atoms and not strictly limited.

For example, R″ is an alkyl group (e.g. methyl group, ethyl group,
propyl group, isobutyl group, hexyl group, 2-ethylhexyl group, etc.), aryl group (e.g. phenyl group, biphenyl group, etc.), aralkyl group (e.g. benzyl group, phenylethyl group, etc.), alkaryl group (e.g. tolyl group, ethyl phenyl group) etc.). Preferred R″
is an alkyl group having 2 to 4 carbon atoms. The manner in which the process of the invention is carried out and the compounds obtained can vary widely.

Monoalkali metal salts of the general formula (m) are generally monoalkali metal salts of the general formula (I
), () or I), it is advantageous to use 1 mol. It goes without saying that the molar ratio of these two components can vary widely, and 1 to 3 moles or more of the metal salt of the general formula (M) can be widely used per 1 mole of the benzenoid compound of the general formula (I). There is no benefit in using an excess of the metal salt, except to accelerate the reaction towards higher yields and more completeness. It is sometimes advantageous to preform these salts by reacting the corresponding monohydroxy organic compounds with alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and the like.

For example, sodium carbonate, in a well-known manner,
It can be obtained by reacting 1 mol of sodium hydroxide with 1 mol of phenol. Those skilled in the art will understand that general formula (I)
, () or l for use with compounds of the general formula (
There will be no difficulty in determining how to make the alkali metal salt of M. Alternatively, general formula (I),
Adding an alkali metal carbonate at an appropriate molar concentration to a reaction mixture consisting of a compound of () or (□) and a hydroxyaromatic compound as a precursor necessary to form a metal salt of general formula (M). According to the general formula (I)
, () or (), the phenol can be converted into an alkali metal salt.

Metal salt of general formula (I), () or I)
The reaction conditions for reacting with the compound can vary widely.

It is generally advantageous to use temperatures of about 20 DEG to 150 DEG C. However, the reaction components used, the desired reaction products,
Lower or higher temperatures can be used depending on the reaction time and the solvent used. In addition to atmospheric pressure, elevated and reduced pressures can be used depending on the other reaction conditions used, the respective reaction components, and the desired rate at which the reaction is carried out. The reaction time can also vary widely depending on the reaction components used, temperature, desired yield, etc.

In order to obtain the highest yields, it has been found advantageous to use times varying widely between a few minutes and 30-40 hours. The reaction products are then subjected to precipitation of the desired reactive products and/or
Alternatively, it can be treated in any manner necessary to effect the separation. Common solvents such as diethyl ether, water, etc. are generally used for this purpose. For purification, the final product can be redistilled or recrystallized by methods well known to those skilled in the art. It is important that the reaction between the compound of the general formula (I), () or the metal salt of the general formula (()) is carried out in the presence of a dipolar neutral solvent. '' shall mean an organic solvent that does not have active protons that would interfere with the reactions described herein. It is understood by those skilled in the art that the solvent will dissolve each of the reaction components and create intimate contact between the reaction components. Among the preferred dipolar neutral solvents that may be used in carrying out the method of the present invention are non-acidic, oxygen-containing, nitrogen-containing organic solvents. .

These include, for example, N,N-dimethylacetamide, N-
Examples include, but are not limited to, methylpyrrolidone, N,N-dimethylformamide, and dimethylsulfoxide. The amount of solvent used in the reaction mixture can vary widely.

Generally, on a weight basis, each reaction component, i.e., general formula (1), ()
or 0.5 to 50 parts or more of the solvent may be used for a total of 1 part by weight of the metal compound of l and general formula (m).There are no strict regulations on the amount of solvent, but it is generally based on the weight. and a compound of general formula (I), () or l, and -
2 parts of solvent per 1 part by weight of the metal compound of general formula (capital)
It was found that ~20 parts could be used. The present invention will be explained below with reference to Examples.

All parts are by weight unless otherwise specified. Example 1 1.0349 (0.011 mol) of phenol, 0.0349 (0.011 mol) of phenol;
49 (0.01 mol) of sodium hydroxide (0.7
A mixture of 9059 (50.6% aqueous solution), 20 cc of dimethyl sulfoxide (DMSO), and 10 cc of toluene was stirred at reflux temperature on a Dean-Stark trap for 4 hours.

The reaction mixture was cooled to 100 °C and 2.679 (0.0
1 mol) of diethyl-4-nitrophthalate was added,
The solution was stirred for 3 hours at 100-110°C under nitrogen atmosphere. The reaction mixture was poured into 300cc of water and the product was extracted into air. Combine the ether extracts,
Washed with water, washed with 1% aqueous sodium hydroxide solution, dried over sodium sulfate, filtered and the ether removed. 3. Distill the product at 150-160° C. with 0.151 mH9.
09 (95.5% yield) was obtained, which was identified as diethyl 4-phenoxyphthalate by infrared testing and elemental analysis. 11/υ Example 2 Add 0.1199 (0.001
0.173 g (mol) of 2-cyanophenol, 0.173 g (mol)
001 mol) of 4-nitrophthalonitrile and 0.1
389 (0.001 mol) of anhydrous potassium carbonate was added.

After stirring at room temperature for 20 hours, the reaction mixture was poured into water, the product was extracted with ether, the extract was dried over sodium sulfate, the solvent was removed, and recrystallized from ethanol-water, melting point 134-136 °C. 0.168g (69%) of 2,3
',4'-monotricyanodiphenyl ether was obtained. The product was identified by spectroscopic, infrared, and mass spectrometry analyses. Example 3 0.122 g (0.001
mole) of 4-hydroxybenzaldehyde, 0.173
9 (0.001 mol) of 4-nitrophtacanitrile and 0.1389 (0.001 mol) of anhydrous potassium carbonate were added.

After stirring for 20 hours at room temperature, the reaction mixture was poured into water and the product was extracted into ether.

The extract was dried with sodium sulfate and the solvent removed to give an oily residue which crystallized on standing. Recrystallization from ethanol-water gave 0.149 (yield: 60%) of 4-carboxaldehyde-3',-4'-dicyanodiphenyl ether with a melting point of 144-146°C. The product was spectroscopically identified by mass spectrometry. Example 4 1.099 (0.01 mol) of 3-aminophenol
．． 2.679 (0.01 mol) of diethyl-4-nitrophthalate, 1.38 f1 (0.01 mol) of potassium carbonate, and 20 cc (7) of DMSO under nitrogen atmosphere at 100 °C for 24 h. Stir and then allow to cool.

Inject DMSO solution into water to produce . The material was extracted with ether. The ether extract was washed with water, dried over sodium sulfate, and filtered to remove the ether, leaving an oily liquid. 2
Distill this liquid at 20℃ (0.15mmH9) and
2.11 (64% yield) of liquid diethyl 4-(3
-aminophenoxy)butrate was obtained, the identification of which was carried out by infrared spectroscopy and nuclear magnetic resonance analysis.

Example 5 0.419 (0.00375 mol) of 4-aminophenol, 19 (0.00375 mol) of diethyl ι4
- nitrophthalate, 0.525y (0.00375 mol) potassium carbonate and IOCC dry DMSO stirred at about 110'C under nitrogen atmosphere for 48 hours,
Allowed to cool.

The reaction mixture was poured into water and the product was extracted into ethyl ether. Ether? The extract was washed with water, dried over sodium sulfate, filtered, and the ether removed, leaving an oily liquid, which was distilled at 200-210 °C (0.1 mm H9) to yield 1.18 f1 (96% yield). ) liquid was obtained. This was allowed to stand at room temperature and gradually crystallized. The distilled product 5 was recrystallized from ethanol-water to give long needle-like white crystals, with a melting point of 74-76°C. This material has been shown to be diethyl 4-(
It was identified as 4-aminophenoxy) phthalate. Four-element analysis Actual value Theoretical value C% 66.365.6H% 5.935.78N% 4.604.26 Example 6 0.949 (0.01 mol) of phenol, 0.40
9 sodium hydroxide (50.5% aqueous solution 0.79
29, 0.01 mol), anhydrous DMSO purged with nitrogen
A mixture of 2OCC) and 10 cc of benzene was refluxed and stirred for 4 hours using a Dean-Stark trap under a nitrogen atmosphere, and the benzene was distilled off.

The DMSO solution was cooled to 50°C and the
mol) of 4-nitrophthalonitrile was added. The mixture was stirred at room temperature for 15 minutes under nitrogen atmosphere, then water
Injected into cc. The product was extracted from the aqueous solution into ether, the ether extract was washed with water, dried over sodium sulfate,
Filtered. Removal of ether gave a white solid. This is distilled at 155-165℃ (0.15mmH9) to obtain 2
．． 109 (95.50●) was obtained as a pale green solid. Recrystallization from absolute ethanol gave white needle-like crystals, which were filtered and dried under reduced pressure. The melting point was 100-101°C.
The product was identified as 4-huenoxyphthalonitrile by infrared and elemental analysis. Example 7 2.789 (0.02 mol) 3-nitrophenol, 3.46y (0.02 mol) 4-nitrophthalonitrile, 2.769 (0.02 mol) anhydrous potassium carbonate, and nitrogen 20 cc dry DMSO purged with
The mixture was stirred at room temperature under nitrogen atmosphere for 4 hours, then the reaction mixture was poured into 10() CC of water.

The product was poured into methylene chloride, washed with water, sodium sulfate and filtered. The solvent was distilled off, leaving a white solid, which was heated at 180-230°C (0.1-0.05 m
mH9) to obtain a fixed 5.23f1, which was recrystallized from acetonitrile to obtain 3.651 (69%)
Pale blue-green needle-like crystals were obtained. The melting point was 167-168°C. This product was identified by infrared and elemental analysis as 4-(3
-nitrophenoxy)phthalonitrile. Example 8 A solution of sodium carbonate in dimethyl sulfoxide (DMSO) is 20cc (7) of 0.5f1 in DMSO
Add 0.94 g (0.01 mol) of phenol to a 50% aqueous solution of sodium hydroxide (0.01 mol),
It was made by heating it to 70℃.

20 cc of toluene was added and water was removed by azeotropic distillation.
The apparatus was kept under nitrogen atmosphere. When the solution became dry, the toluene was distilled off and 2.679 (0.01 mol) of diethyl nitroterephthalate was added. 6 at 100℃
After heating for an hour, the solution was poured into water and the product was extracted with ether.

The extract was dried over sodium sulfate, concentrated and distilled in a Kugelrohr. 150~160℃ (0.1m?RH9
2.6 g (86%) of distilled fraction was obtained.

The product was identified as diethyl phenoxy terephthalate by nuclear magnetic resonance and mass spectrometry analysis. Example 9 A solution of sodium carbonate in dimethyl sulfoxide prepared as in Example 8 was mixed with 20 cc of toluene and the water was removed by azeotropic distillation, while the apparatus was kept under a nitrogen atmosphere.

When the solution becomes anhydrous, the toluene is distilled off and 2.67
1 (0.01 mol) of diethyl 2-nitroisophthalate was added. After heating at 100° C. for 3 hours, the solution was poured into water and the product was extracted with ether.

The extract was dried with sodium sulfate and concentrated to a small volume.
Distilled in a Kugelrohr. The fraction distilled at 150-160°C was 2.751 (91%) and identified as diethyl 2-phenoxyisophthalate by nuclear magnetic resonance and mass spectrometry analysis.

Example 10 1.229 (0.01 mol) of 3,4-dimethylphenol, 0.4y of sodium hydroxide (0.07929 of a 50.5% aqueous solution, 0.01 mol), 15 CC of nitrogen-purged DMSO) and 15 CC of benzene was stirred under reflux for 4 hours under a nitrogen atmosphere using a Dean-Stark trap, and the benzene was distilled off.

The reaction mixture was cooled to 40 °C and DM was purged with dry nitrogen.
2.679 (0.01 mol) diethyl 4-nitrophthalate in SO5CC was added and the mixture was stirred at room temperature under nitrogen atmosphere for 64 hours. The reaction mixture was poured into water and the product, which separated as an oil, was extracted into diethyl ether. The ether extract was washed with water, washed with an aqueous solution of sodium bicarbonate, dried with sodium sulfate, separated in a furnace, and the ether was removed.
A yellow oil remained. This oil was heated to 165-175℃ (0.02
Distilled at 5 mm H9) to obtain 3.0 g (88% yield) of liquid, which was determined by infrared and nuclear magnetic resonance analysis to be 4-(
It was identified as 3,4-dimethylphenoxy)-diethyl phthalate.

Example 11 Using the same conditions as shown in Examples 1 and 6 and substituting other reactants of general formula (I), () or 1 for the corresponding reactants of these examples, the general formula Other products could also be prepared by substituting the corresponding metal salts used in these examples with other reaction components.

Table I below lists some of the reaction components that can be used to form these products. The "reaction component A" in the header corresponds to the compound of general formula (I), () or (2), and the "reaction component B" in the header corresponds to the precursor hydroxy compound of general formula (2). The products derived from the reaction of Reaction Component A and Reaction Component B are shown under the heading "Products".
In all tables, the symbol EN shall mean the group -C2H5.The reference examples below are given by the direct reaction of nitrodiacids with metal phenolates instead of nitroesters or nitronitrile as intended in the present invention. An example is shown in which a plan to create an aryloxy derivative of an aromatic diacid was not successful.

Reference example A lOCC (7) Sodium carbonate in DMSO 1.16
y (0.010 mol), add 0.70y (0.0
03 mol) of 4-nitrophthalic acid was added and the resulting solution was heated at 100° C. for 24 hours.

A portion of the solution was removed, neutralized with hydrochloric acid, and bistrimethylsilylacetamide was added. Gas-liquid chromatography of the solution showed only bistrimethylsilyl ester of 4-nitrophthalic acid. Not even a trace of bistrimethylsilyl ester of 4-phenoxyphthalic acid was obtained.

Heating was continued for an additional 24 hours at 100° C. and showed no evidence of 4-phenoxyphthalic acid formation.

Reference example B lOcc(7) 1.169 (0.010 in DMSO)
A solution of mono 0 sodium carbonate was added with 0.70θ (0.
003 mol) of nitroterephthalic acid was added and the formed solution was heated at 100° C. for 24 hours.

A portion of the solution was removed, neutralized with hydrochloric acid, bistrimethylsilylacetamide was added, and gas-liquid chromatography of the solution showed only bistrimethylsilyl ester of nitroterephthalic acid, which indicates that phenoxyterephthalic acid was formed. It shows that it has disappeared. Further at 100℃ 24
No phenoxyterephthalic acid could be formed even after continued heating for hours. Reference example C l. To a solution of l6y (0.010 mol) of sodium carbonate in IOCC(7) DMSO, 0.709(0
．． 003 mol) of 2-nitroisophthalic acid was added and the formed solution was heated at 100° C. for 24 hours.

A portion of the solution was removed, neutralized with hydrochloric acid, and bistrimethylsilylacetamide was added. Gas-liquid chromatography of the solution showed only bistrimethylsilyl ester of 2-nitroisophthalic acid, indicating that no 2-phenoxyisophthalic acid was obtained. 2 more at 10℃
Continuing heating for 4 hours did not show any substitution by phenoxy groups.

Products made according to the invention have many uses.

One important use is as an intermediate for the production of other products. Furthermore, many of the products of the invention, which are liquids, particularly at room temperature, have themselves uses as solvents in the production of other organic compounds. Furthermore, Examples 1 to 9
Regarding the simple aryloxy diesters contained by the products obtained in These dicarboxy-substituted compounds can be reacted with long chain monohydric alcohols, such as 2-ethylhexanol, to form ester compounds, which are plasticizers for halogenated vinyl resins, such as polyvinyl chloride resins. It is useful as As a specific example, the compound 4-phenoxyphthalonitrile of Example 6 was dissolved in anhydrous H
Simultaneous treatment with CI and about 2 moles of 2-ethylhexanol can give the corresponding diester having the formula:

This can be used as a plasticizer for halogenated vinyl resins. The diethyl 4-phenoxyphthalate of Example 1 can also be hydrolyzed to 4-phenoxyphthalic acid and then esterified with a long chain monohydric alcohol such as 2-ethylhexanol as described above to form the same diester.
It can be used to plasticize various polymers, especially polyvinyl chloride resins. Additionally, these compounds can also be used as UV stabilizers for polyolefins, cellulose esters, and polyvinyl chloride resins. One of the important applications in which dicarboxy compounds can be used is in the production of polyester polymers. As a specific example, the diethyl 2-phenoxyisophthalate of Example 9 can be reacted with 1,4-butanediol in a well-known manner to make the corresponding polyester, which can be used for packaging. It can be applied to a useful film. When there is an ester group in place of the nitrile group on the aryl nucleus, the ester group is hydrolyzed to form the corresponding carboxy group in a well-known manner and then treated for esterification as described above. can.

One of the important uses of the products made according to the present invention is
It finds use as an intermediate in the production of heat-resistant polyimides, the uses of which are well known.

In particular, diethyl 4-(3-aminophenoxy)-phthalate of Example 4 is hydrolyzed to a diacid, followed by self-polymerization to a polyimide by heating in a suitable solvent such as N-methylpyrrolidone. I can do it. Polymers with mixed functionality, particularly polyesterimides and polyamideimides, can be made from products that fall within the scope of this invention.

These materials have many uses as insulating materials.
The 2,3',4' monotricyanodiphenyl ether of Example 2 is hydrolyzed to the corresponding tricarboxyether, which can be converted to polyesterimide or polyamideimide by methods well known to those skilled in the art. In addition to the above-mentioned uses for the polymeric compounds derived from difunctional aryloxy compounds in the process of the invention, these polymeric products may also have other uses. These polymer products can be used to form fibers, films, or molded articles. Formation of fibers derived from these polymeric compositions, for example by extrusion from the melt or precipitation from solution, to produce various textile materials designed for coating and similar uses. Can be used for Furthermore, solutions of polymers can be used to coat electrical conductors for insulation purposes. Various fillers may be incorporated into the polymer composition prior to its shaping.

Among such fillers can be mentioned glass fibers, carbon black, titanium dioxide, silica, mica, bentonite, and the like. Moldings derived from mixtures of such components can be used as gears, cooking utensil hands. The blending of abrasive particles such as carborundum, diamond powder, etc. makes shaped articles derived from polymeric compositions useful as abrasive wheels. carbon in the polymer composition,
Additions of silicon carbide, powdered metals, conductive oxides, etc. result in so-called resistive or semiconductive paints that have many useful applications. The polymer compositions shown herein can also be incorporated into other materials to modify their properties.

Claims (1)

[Claims] 1 In the presence of a dipolar neutral solvent, (1) (a) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, Z is -CN or -C-OR'' group) (where R'' represents a monovalent hydrocarbon group having 1 to 12 carbon atoms), (b) General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, Z is as described above. (c) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, Z is as described above, and in the case of c) NO
_2 group is adjacent to the Z group); and (2)
(a) A general method characterized by carrying out a reaction of a mixture of components containing a compound of the general formula R-O-ALK (wherein R represents a monovalent aromatic group and ALK represents an alkali metal atom). A method for producing a compound having the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, R and Z are as described above).