JP2001226332A - Aminophenylalkylenebisphenol compounds and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new aminophenylalkylenebisphenol which has high solubility in solvents and is useful as a raw material for polyimide resins having excellent heat resistance, photosensitive resins, epoxy resins, and so on, and further as a curing agent and a developer for heat-sensitive recording materials. SOLUTION: The aminophenylalkylenebisphenol represented by the general formula (1) [R1 is a 1 to 4C alkyl or a 5 to 7C cyckloalkyl; R2 is H, a 1 to 4C alkyl or a 5 to 7C cycloalkyl; (m) is an integer of 1 to 4].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aminophenylalkylenebisphenol having a phenol nucleus substituted with an alkyl group and a method for producing the same. Such polynuclear aromatic amines are also useful as raw materials for polyimide resins, photosensitive resins, epoxy resins, etc., as curing agents, and as color developers for thermosensitive recording materials.

[0002]

2. Description of the Related Art In recent years, in the field of polyimide resins and photosensitive resins, it has been demanded to obtain resins having high solubility in solvents and excellent heat resistance. On the other hand, polynuclear aromatic amines have been used as raw materials for polyimide resins and photosensitive resins, and among such polynuclear aromatic amines, aminophenylmethylenebisphenol is known (J. Chem. Soc., 196.
1, 393-5). However, those in which the phenol nucleus is substituted with an alkyl group have not been known so far. Therefore, when aminophenylalkylenebisphenols in which a phenol nucleus is substituted with an alkyl group are used as a raw material of a polyimide resin or a photosensitive resin, a resin having high solubility in a solvent and excellent heat resistance is used. Is expected to be obtained.

[0003]

Accordingly, the present invention provides a novel phenol nucleus which can be expected to improve the solubility of a resin in a solvent and the heat resistance by using it as a raw material of a polyimide resin or a photosensitive resin. It is an object of the present invention to provide an aminophenylalkylenebisphenol wherein is substituted with an alkyl group and a method for producing the same.

[0004]

According to the present invention, the compound represented by the general formula (I)

[0005]

Embedded image (Wherein, R ₁ represents an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms, and R ₂ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a cycloalkyl having 5 to 7 carbon atoms. Represents an alkyl group, and m represents an integer of 1 to 4.)

There is provided an aminophenylalkylenebisphenol represented by the formula: Furthermore, according to the present invention,
General formula (II)

[0007]

Embedded image (Wherein, R ₁ represents an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms, and R ₂ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a cycloalkyl having 5 to 7 carbon atoms. Represents an alkyl group, and m represents an integer of 1 to 4.)

The method for producing the aminophenylalkylenebisphenols is provided by reducing the nitrophenylalkylenebisphenols represented by the above formula in a solvent in the presence of a transition metal catalyst. The aminophenylalkylenebisphenols of the present invention are represented by the above general formula (I). Here, R ₁ is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group or a butyl group, The group may be linear or branched, and examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. R ₂ is a hydrogen atom, having 1 to 1 carbon atoms.
An alkyl group of 4 or a cycloalkyl group having 5 to 7 carbon atoms, and specific examples of the alkyl group or the cycloalkyl group are the same as those described for R ₁ . m is 1 to 4
Is preferably an integer of 1 or 2.

Preferred specific examples of the aminophenylalkylenebisphenols according to the present invention include 2,2 '-(4-aminophenylmethylene) bis (4-methylphenol) and 2,2'-(3-aminophenylmethylene)
Bis (4-methylphenol), 2,2 ′-(2-aminophenylmethylene) bis (4-methylphenol),
4,4 '-(4-aminophenylmethylene) bis (2-
Methylphenol), 4,4 '-(3-aminophenylmethylene) bis (2-methylphenol), 4,4'-(2-aminophenylmethylene) bis (2-methylphenol), 4,4 '-( 4-aminophenylmethylene)
Bis (3-methylphenol), 4,4 ′-(3-aminophenylmethylene) bis (3-methylphenol),
4,4 '-(2-aminophenylmethylene) bis (3-
Methylphenol), 4,4 ′-(4-aminophenylmethylene) bis (2,6-dimethylphenol),
4 '-(3-aminophenylmethylene) bis (2,6-
Dimethylphenol), 4,4 ′-(2-aminophenylmethylene) bis (2,6-dimethylphenol),
4,4 ′-(4-aminophenylmethylene) bis (2,
5-dimethylphenol), 4,4 ′-(3-aminophenylmethylene) bis (2,5-dimethylphenol), 4,4 ′-(2-aminophenylmethylene) bis (2,5-dimethylphenol), 2,2 ′-(4-aminophenylmethylene) bis (4,6-dimethylphenol), 2,2 ′-(3-aminophenylmethylene) bis (4,6-dimethylphenol), 2,2 ′-( 2-
Aminophenylmethylene) bis (4,6-dimethylphenol), 4,4 '-(4-aminophenylmethylene)
Bis (2,3,6-trimethylphenol), 4,4 ′
-(3-aminophenylmethylene) bis (2,3,6-
Trimethylphenol), 4,4 '-(2-aminophenylmethylene) bis (2,3,6-trimethylphenol), 2,2'-(4-aminophenylmethylene) bis (3,5,6-trimethylphenol) ), 2,2 ′-(3-aminophenylmethylene) bis (3,5,6-trimethylphenol), 2,2 ′-(2-aminophenylmethylene) bis (3,5,6-trimethylphenol), 4,4 '-(4-aminophenylmethylene) bis (2-cyclohexylphenol), 4,4'-(3-
Aminophenylmethylene) bis (2-cyclohexylphenol), 4,4 ′-(2-aminophenylmethylene) bis (2-cyclohexylphenol), 4,4 ′
-(4-aminophenylmethylene) bis (2-cyclohexyl-5-methylphenol), 4,4 '-(3-aminophenylmethylene) bis (2-cyclohexyl-5
-Methylphenol), 4,4 '-(2-aminophenylmethylene) bis (2-cyclohexyl-5-methylphenol), 4,4'-(4-aminophenylmethylene) bis (2-t-butylphenol), 4,4 '-(3-aminophenylmethylene) bis (2-t-butylphenol), 4,4'-(2-aminophenylmethylene) bis (2-t-butylphenol), 4,4 '-(4- Aminophenylmethylene) bis (2-isopropylphenol), 4,4 ′-(3-aminophenylmethylene) bis (2-isopropylphenol), 4,4 ′
-(2-aminophenylmethylene) bis (2-isopropylphenol), 4,4 '-(4-aminophenylmethylene) bis (2-t-butyl-5-methylphenol), 4,4'-(3-aminophenol Phenylmethylene) bis (2-t-butyl-5-methylphenol), 4,4 ′
-(2-aminophenylmethylene) bis (2-t-butyl-5-methylphenol), 4,4 '-(4-aminophenylmethylene) bis (2-t-butyl-4-methylphenol), 4,4' -(3-aminophenylmethylene) bis (2-t-butyl-4-methylphenol),
4,4 '-(2-aminophenylmethylene) bis (2-t-butyl-4-methylphenol), 4,4'-(4
-Aminophenylethylidene) bis (2-methylphenol), 4,4 '-(3-aminophenylethylidene)
Bis (2-methylphenol), 4,4 ′-(2-aminophenylethylidene) bis (2-methylphenol), 4,4 ′-(4-aminophenylethylidene) bis (2,6-dimethylphenol), 4,4 '-(3-
Examples thereof include aminophenylethylidene) bis (2,6-dimethylphenol) and 4,4 ′-(2-aminophenylethylidene) bis (2,6-dimethylphenol).

According to the present invention, such an aminophenylalkylenebisphenol according to the present invention is obtained by reducing a nitrophenylalkylenebisphenol represented by the general formula (II) in a solvent in the presence of a transition metal catalyst. Obtainable. In the nitrophenylalkylenebisphenols represented by the general formula (II), R ₁ , R ₂ and m are the same as those in the aminophenylalkylenebisphenols represented by the general formula (I). Such nitrophenylalkylene bisphenols are represented by the general formula (III) in the presence of an acid catalyst.

[0011]

Embedded image (Wherein R ₂ is the same as that represented by the general formula (II)), and an aromatic nitrocarbonyl compound represented by the general formula (IV)

[0012]

Embedded image (Wherein R ₁ and m are the same as those represented by the above general formula (II)).

Here, R ₂ in the aromatic nitrocarbonyl compound represented by the general formula (III) and R ₁ and m in the alkyl-substituted phenol represented by the above (IV)
Is the same as described above. Therefore, the general formula (I
Specific examples of the aromatic nitrocarbonyl compound represented by II) include, for example, o-, m- or p-nitrobenzaldehyde, o-, m- or p-nitroacetophenone, o
-, M- or p-nitropropiophenone, o-, m- or p-nitrobutyrophenone, n-butylnitrophenyl ketone and the like.

Specific examples of the alkyl-substituted phenol represented by the general formula (IV) include, for example, o-, m- or p-cresol, 2,6- or 2,5-xylenol, 3-methyl-6- t-butylphenol, 4-methyl-2-t-butylphenol, 2,6-t-butylphenol, o-sec-butylphenol, pt-butylphenol, o-cyclohexylphenol, 3-methyl-6-cyclohexylphenol, 4-methyl-2
-Cyclohexylphenol, 2,6-diisopropylphenol, 2,4-di-tert-butylphenol, p
-Isopropylphenol and the like. In the reaction of the aromatic nitrocarbonyl compound with the alkyl-substituted phenol of the present invention, the alkyl-substituted phenol is usually at least 2 moles, preferably 2 to 20 moles, per mole of the aromatic nitrocarbonyl compound. But it is particularly preferably used in the range of 2.5 to 10 times the molar amount.

This reaction is performed in a reaction solvent, if necessary. Examples of the reaction solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic ketones such as MIBK and MEK, aliphatic alcohols such as methanol, and mixtures thereof. Of these, aliphatic alcohols are preferably used. Preferred aliphatic alcohols include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol, isobutyl alcohol in consideration of the reaction raw materials used, the solubility of the obtained product, reaction conditions, and the economics of the reaction. , N
And lower aliphatic alcohols such as -butyl alcohol. Particularly, methanol is preferably used.

Such a reaction solvent is generally used in an amount of 10 parts by weight based on 100 parts by weight of the aromatic nitrocarbonyl compound used.
To 1000 parts by weight, preferably 100 to 500 parts by weight.
Used in parts by weight. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, sulfuric anhydride, p-toluenesulfonic acid,
Examples thereof include methanesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid, and trifluoroacetic acid. Such an acid catalyst is generally used in the range of 1 to 500 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the aromatic nitrocarbonyl compound in the case of, for example, 35% hydrochloric acid.

The above reaction is carried out usually at a temperature of 10 to 80 ° C., preferably 20 to 70 ° C., for about 1 to 48 hours, usually about 2 to 20 hours, while stirring under a nitrogen stream. After completion of the reaction, an alkaline solution such as aqueous ammonia or sodium hydroxide solution is added to the obtained reaction mixture to neutralize the acid catalyst, and then an aromatic hydrocarbon solvent such as toluene is added thereto. After liquid separation, the remaining oil layer was washed with water, and then the above-mentioned aromatic hydrocarbon solvent was distilled off from the oil layer, and then the alkyl-substituted phenol was distilled off under reduced pressure. By precipitation, high-purity nitrophenylbisphenol can be obtained as crystals.

Accordingly, various nitrophenylalkylenebisphenols can be obtained corresponding to the aromatic nitrocarbonyl compound and the alkyl-substituted phenol used. Specifically, for example, 2,2 ′-(4-nitrophenylmethylene) bis (4-methylphenol),
4 '-(3-nitrophenylmethylene) bis (2-methylphenol), 4,4'-(2-nitrophenylmethylene) bis (3-methylphenol), 4,4 '-(4
-Nitrophenylmethylene) bis (2,6-dimethylphenol), 2,2 ′-(4-nitrophenylmethylene) bis (4,6-dimethylphenol), 4,4 ′-(4-nitrophenylmethylene) bis (2,3,6-trimethylphenol), 4,4 ′-(4-nitrophenylmethylene) bis (4-cyclohexylphenol),
4,4 '-(4-nitrophenylmethylene) bis (2-
Cyclohexyl-5-methylphenol), 4,4 '-(4-nitrophenylmethylene) bis (2-t-butylphenol), 4,4'-(4-nitrophenylmethylene) bis (2-t-butyl-5- Methylphenol),
4,4 '-(4-nitrophenylethylidene) bis (2
-Methylphenol), 4,4 '-(4-nitrophenylethylidene) bis (2,6-dimethylphenol) and the like.

According to the present invention, the desired aminophenylalkylenebisphenol can be obtained by reducing the nitrophenylalkylenebisphenol thus obtained in a solvent in the presence of a transition metal catalyst. . The transition metal catalyst used in the present invention is a supported transition metal catalyst in which a transition metal catalyst component such as palladium, nickel, rhodium, ruthenium, and vanadium is supported on a carrier, preferably 1 to 20% by weight. As the catalyst metal component, palladium and nickel are preferable, and palladium is particularly preferable. As the palladium component, in addition to palladium metal, an oxide or hydroxide of palladium is used, and preferably, palladium metal is used. Further, as the carrier, for example,
Examples thereof include carbon, alumina, titanium oxide, and activated clay. Among them, carbon is preferably used. The supported amount of the metal component in the supported catalyst is usually 1 to 20% by weight, preferably 1 to 10% by weight, more preferably 3 to 10% by weight.
It is in the range of 6% by weight.

The transition metal catalyst used in the present invention is not particularly limited in its form, and any suitable form such as powder, granules, pellets and the like can be used. According to the present invention, the transition metal catalyst is a nitrophenylalkylenebisphenol 100 as a raw material.
It is used in an amount of usually 0.5 to 10 parts by weight, preferably 1.0 to 5.0 parts by weight based on parts by weight. In the present invention, a known co-catalyst such as an alkali metal can be used together with the transition metal catalyst.
When a co-catalyst is used, it is usually used with respect to 100 parts by weight of the starting material, nitrophenylalkylenebisphenol.
0.01 to 0.5 part by weight, preferably 0.05 to 0.2
Used in parts by weight.

In the present invention, the reduction reaction of nitrophenylalkylenebisphenols is carried out in the presence of the above transition metal catalyst by replacing the system with an inert gas such as nitrogen gas or argon gas and then again with hydrogen gas. . The amount of hydrogen supplied into the reaction system is preferably a stoichiometric amount. The reaction temperature is generally in the range of 10 to 80C, preferably in the range of 30 to 60C. Hydrogen pressure is usually in the range of atmospheric pressure to 10 kg / cm ² . Such a temperature,
In the range of pressure, the reaction is usually completed in about 0.5 to 10 hours, preferably about 1 to 6 hours.

The reduction reaction of the nitrophenylalkylenebisphenol in the present invention is preferably carried out in an organic solvent. As the organic solvent, for example, an alcohol or an ether is used. However, since the starting material and the target substance are easily dissolved and the reaction operation is convenient, particularly, the compound having 3 carbon atoms is preferable.
The above monohydric saturated aliphatic alcohols are preferred, and among them, monovalent saturated aliphatic alcohols having 3 to 12 carbon atoms are preferred. As such a monovalent saturated aliphatic alcohol,
For example, linear or branched propyl alcohol,
Examples thereof include butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, and dodecyl alcohol. Among them, isopropyl alcohol, s-butyl alcohol,
S-octyl alcohol (capryl alcohol) is preferably used. Further, the organic solvents can be used alone or in combination of two or more.

Such an organic solvent is usually 100 to 500 parts by weight, preferably 100 to 500 parts by weight, based on 100 parts by weight of the nitrophenylalkylenebisphenol, although it depends on the kind of the nitrophenylalkylenebisphenol and the organic solvent used. Used in the range of 300 parts by weight. After completion of the reaction, the catalyst is separated and removed from the obtained reaction mixture to obtain the desired aminophenylalkylenebisphenols. For example, the reaction is carried out using isopropyl alcohol as a reaction solvent, the catalyst is separated by filtration from the obtained reaction mixture, the reaction solvent is distilled off by distillation or the like, and water or a crystallization solvent is added thereto, and crystallization is performed. Is carried out to obtain a crude crystal of the object. The crude crystals can be further purified as necessary by recrystallization or the like.

[0024]

EXAMPLES Reference Example 1 (Synthesis of 4,4 ′-(4-nitrophenylmethylene) bis (2-methylphenol)) A 1-L four-necked flask equipped with a thermometer, a dropping funnel, a backflow condenser, and a stirrer 270 g of O-cresol
And 27 g of 35% sulfuric acid, and the temperature was raised to 40 ° C., and at this temperature, 62.9 g of P-nitrobenzaldehyde was added in 3 g.
It was dropped over time. After completion of the dropwise addition, the mixture was stirred at the same temperature for 15 hours to complete the reaction. 16 to the resulting reaction mixture.
68.8 g of a 10% aqueous sodium hydroxide solution was added to neutralize the mixture, 275 g of toluene was added, the aqueous layer containing sodium chloride was extracted, and the obtained oil layer was washed twice with 100 g of water. next,
After distilling the oil layer under normal pressure to recover toluene, O-cresol was recovered by vacuum distillation. The obtained crystals were collected by filtration and dried, and 123.4 g of 4,4 ′-(4-nitrophenylmethylene) bis (2-methylphenol) was obtained.
(Purity 99.3%).

Example 1 (Synthesis of 4,4 '-(4-aminophenylmethylene) bis (2-methylphenol)) A 1 L four-necked flask equipped with a thermometer, a dropping funnel, a backflow condenser, and a stirrer was used. 4, obtained in Reference Example 1
7 ′ g of 4 ′-(4-nitrophenylmethylene) bis (2-methylphenol) and isopropyl alcohol 2
80 g was charged and dissolved by heating to 50 ° C. To the resulting solution was added 3.5 g of a palladium on carbon catalyst,
After purging with nitrogen for 20 minutes, while maintaining the temperature at 50 ° C., hydrogen was blown in for 8 hours to complete the reaction (selectivity of target substance 9).
7.1%). After completion of the reaction, the inside of the flask was replaced with nitrogen for 20 minutes, and then the reaction mixture was filtered to remove the palladium-on-carbon catalyst, and the obtained filtrate was subjected to normal pressure distillation to remove about half of the isopropyl alcohol used. . Water was added to the obtained concentrated solution, followed by cooling and crystallization. The obtained crystals were collected by filtration, dried and dried to obtain 4,4 ′-(4-aminophenylmethylene) bis (2-methylphenol). 55 g were obtained (purity 98.2%). ¹ H-NMR (DMSO solvent,
400MHz)

[0026]

[Table 1] Chemical shift δ (ppm) Signal Proton number Attribution ─────────────────────────────────── 2.0 s6-CH3 4.8 s2-NH2 5.1 s1-CH 6.5-6.8 m10 Aromatic proton 9.0 s2-OH ─────────────────────────

[0027]

Embedded image

Example 2 (Synthesis of 4,4 '-(4-aminophenylmethylene) bis (2,6-dimethylphenol)) A 1-L four-necked port equipped with a thermometer, a dropping funnel, a backflow condenser, and a stirrer A flask was charged with 80 g of 4,4 ′-(4-nitrophenylmethylene) bis (2,6-dimethylphenol) and 480 g of isopropyl alcohol, and dissolved by heating to 50 ° C. 4.0 g of a palladium-on-carbon catalyst was added to the resulting solution, and after purging with nitrogen for 30 minutes, hydrogen was blown in for 5 hours while maintaining the temperature at 50 ° C. After completion of the reaction, the inside of the flask was replaced with nitrogen for 20 minutes, and then the reaction mixture was filtered to remove the palladium-on-carbon catalyst, and the obtained filtrate was subjected to normal pressure distillation to remove about half of the isopropyl alcohol used. . The obtained concentrated solution was cooled and crystallized, and the obtained crystals were collected by filtration, dried and dried to obtain 4,4 ′-(4-aminophenylmethylene).
51 g of bis (2,6-dimethylphenol) was obtained (purity: 98.6%, yield: 68.6%). ¹ H-NMR (DMSO solvent, 400 MHz)

[0029]

[Table 2] Chemical shift δ (ppm) Signal Proton number Attribution ─────────────────────────────────── 2.0 s12-CH3 4.8 s2-NH2 5.0 s1-CH 6.4-6.9 m8 aromatic nucleus proton 7.9 s2-OH ─────────────────────────

[0030]

Embedded image

Example 3 (Synthesis of 4,4 '-(2-aminophenylmethylene) bis (2-methylphenol)) A 1 L four-necked flask equipped with a thermometer, a dropping funnel, a backflow condenser, and a stirrer was used. , 4,4 '-(2-nitrophenylmethylene) bis (2-methylphenol) 10
0g and isopropyl alcohol 500g, 50
The temperature was raised to ° C. to dissolve. 5.0 g of a palladium-on-carbon catalyst was added to the obtained solution, and after purging with nitrogen for 40 minutes, hydrogen was blown in for 43 hours while maintaining the temperature at 70 ° C. After completion of the reaction, the inside of the flask was replaced with nitrogen for 20 minutes, and then the reaction mixture was filtered to remove the palladium-on-carbon catalyst, and the obtained filtrate was subjected to atmospheric distillation to remove almost all of the used isopropyl alcohol. . The obtained concentrated solution was cooled and crystallized, and the obtained crystals were collected by filtration and dried to obtain 65 g of 4,4 ′-(2-aminophenylmethylene) bis (2-methylphenol). (Purity 98.5
%, Yield 71.7%). ¹ H-NMR (DMSO solvent, 400 MHz)

[0032]

[Table 3] Chemical shift δ (ppm) Signal Proton number Attribution ─────────────────────────────────── 2.0 s6-CH3 4.4 s2-NH2 5.2 s1-CH 6.4-6.9 m10 Aromatic nuclear proton 9.1 s2-OH ─────────────────────────

[0033]

Embedded image

[0034]

The aminophenylalkylenebisphenols according to the present invention have an alkyl substituent on the phenol nucleus and, by using this as a raw material, have high solubility in solvents and excellent heat resistance. Resin can be obtained. According to the present invention, aminophenylalkylenebisphenols can be obtained by reducing the corresponding nitrophenylalkylenebisphenols in a solvent in the presence of a transition metal catalyst.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Nishiki Morita 2-115, Kozaiga, Wakayama-shi, Wakayama F-term in the Research Institute, Honshu Chemical Industry Co., Ltd. (Reference) 4H006 AA01 AA02 AC52 BA12 BA21 BA23 BA24 BA25 BB14 BB15 BE20 BJ20 BJ50 BN30 BU46 4H039 CA71 CB40

Claims (2)

[Claims] An aminophenylalkylenebisphenol represented by the general formula (I): (Wherein, R ₁ represents an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms, and R ₂ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a cycloalkyl having 5 to 7 carbon atoms. Represents an alkyl group, and m represents an integer of 1 to 4.) 2. The production of an aminophenylalkylenebisphenol according to claim 1, wherein the nitrophenylalkylenebisphenol represented by the general formula (II) is reduced in a solvent in the presence of a transition metal catalyst. Method (Wherein, R ₁ represents an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms, and R ₂ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a cycloalkyl having 5 to 7 carbon atoms. Represents an alkyl group, and m represents an integer of 1 to 4.)