Novel compound having naphthalenediamine skeleton and method for producing the same

Abstract

To provide a new compound (general formula (A)) having a naphthalenediamine skeleton and a method for producing the same. (In general formula (A), R1 represents an alkyl group having 6-13 carbon atoms, and R 2 represents a hydrogen atom or an alkyl group having 1-4 carbon atoms.) The two R1s may be the same or different, and the two R2s may be the same or different.

Description

Novel compound having naphthalenediamine skeleton and method for producing same

[0001] The present invention relates to a novel compound having a naphthalenediamine skeleton and a method for producing the same.

[0002] Previously, compounds having a naphthanediamine skeleton were １ -1-naphthalenyl-N １ .N ４ Diphenyl-1,4-naphthalenediamine (CAS Registry Number 111928-42-8) is commercially available.

[0003] An object of the present invention is to provide a novel compound having a naphthalenediamine skeleton and a method for producing the same.

[0004] The compounds and methods for producing the same according to embodiments of the present invention are as follows: [1] A compound represented by the following general formula (A): (In general formula (A), R １ represents an alkyl group having 6 to 13 carbon atoms, and R ２ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. １ may be the same or different, and two R 2 may be the same or different.) [2] R １ [3] The compound according to [1], wherein R is a branched alkyl group having 8 to 13 carbon atoms. ２ [4] The compound according to [1] or [2], wherein R is a hydrogen atom. １ is a 1,1,3,3-tetramethylbutyl group. [5] The compound according to [1] or [2], wherein R is a 1,4-naphthalenediamine,N1-1-naphthalenyl-N1,N4-bis[4-(1,1,3,3-tetramethylbutyl)phenyl]. [6] A production method for producing a compound represented by the following general formula (A) by reacting a compound represented by the following general formula (B) with an oxidizing agent. (In general formula (A), R １ represents an alkyl group having 6 to 13 carbon atoms, and R ２ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. １ may be the same or different, and two R2 may be the same or different. ３ represents an alkyl group having 6 to 13 carbon atoms, and R ４ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. [7] The method according to [6], wherein the oxidizing agent is nitrosodisulfonic acid or butyl hydroperoxide. [8] The method according to [6], wherein the oxidizing agent is potassium nitrosodisulfonate or tert-butyl hydroperoxide. [9] R １ and R ３ is a 1,1,3,3-tetramethylbutyl group, and R ２ and R ４

[10] An antioxidant containing the compound according to [1] as an active ingredient.

[11] R １

[12] The antioxidant according to

[10] , wherein R is a branched alkyl group having 8 to 13 carbon atoms. ２

[13] The antioxidant according to

[10] , wherein R is a hydrogen atom. １ The antioxidant according to

[10] , wherein R is a 1,1,3,3-tetramethylbutyl group. In this specification, the symbol "to" indicates a numerical range including the numerical values ​​before and after it.

[0005] According to the present invention, a novel compound having a naphthalenediamine skeleton can be provided. The compound of the present invention is expected to be useful as an antioxidant, a colorant, or a pigment.

[0006] FIG. 1 is a diagram showing a reaction scheme relating to a method for producing a compound of an embodiment using nitrosodisulfonate as an oxidizing agent. FIG. 2 is a diagram showing another reaction scheme relating to a method for producing a compound of an embodiment using butyl hydroperoxide as an oxidizing agent. FIG. 3 is a diagram showing a chemical reaction scheme estimated as a radical catch reaction of a compound represented by general formula (A). FIG. 4 is a diagram showing a reaction scheme relating to a method for producing a compound of an example (1,4-naphthalenediamine, N1-1-naphthalenyl-N1,N4-bis[4-(1,1,3,3-tetramethylbutyl)phenyl]) using potassium nitrosodisulfonate as an oxidizing agent. １1 is a diagram showing the H-NMR spectrum of the compound prepared in the examples. １３ FIG. 1 is a diagram showing a C-NMR spectrum. FIG. 2 is a diagram showing an INADEQUATE spectrum of a compound produced in an example. FIG. 3 is a diagram showing a reaction scheme relating to a production method of a compound of an example (1,4-naphtharenediamine, N1-1-naphthalenyl-N1,N4-bis[4-(1,1,3,3-tetramethylbutyl)phenyl]) using tert-butyl hydroperoxide as an oxidizing agent. FIG. 4 is a diagram showing a reaction scheme relating to a production method of a compound of an example (1,4-naphtharenediamine, N1-1-naphthalenyl-N1,N4-bis[4-alkylphenyl] (a mixture of alkyl groups having 10 to 13 carbon atoms)) using potassium nitrosodisulfonate as an oxidizing agent. FIG. 5 is a diagram showing a reaction scheme relating to a production method of a compound of an example (1,4-naphtharenediamine, N1-1-naphthalenyl-N1,N4-bis[4-alkylphenyl] (a mixture of alkyl groups having 10 to 13 carbon atoms)) using potassium nitrosodisulfonate as an oxidizing agent. １ 1 is a diagram showing the H-NMR spectrum of the compounds prepared in other examples. １３ FIG. 1 is a diagram showing a C-NMR spectrum.

[0007] Hereinafter, an embodiment of the present invention will be described. The compound of the present embodiment is represented by the following general formula (A).

[0008] In the above general formula (A), R １ is a linear, cyclic or branched alkyl group having 6 to 13 carbon atoms. １ may be the same or different.

[0009] R １ When is a linear alkyl group, examples of the linear alkyl group having 6 to 13 carbon atoms include an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, and an n-tridecyl group.

[0010] R １When is a cyclic alkyl group, examples of the cyclic alkyl group having 6 to 13 carbon atoms include groups consisting only of cyclic alkyl groups such as cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, and cyclotridecyl, as well as groups consisting of a combination of a cyclic alkyl group and at least one of a linear and branched alkyl group, and having 6 to 13 carbon atoms. Examples of the group consisting of a combination of a cyclic alkyl group and at least one of a linear and branched alkyl group include a group in which at least one of a linear and branched alkyl group is bonded to a cyclic alkyl group bonded to the phenyl group of compound A, and a group in which a cyclic alkyl group is bonded to a linear or branched alkyl group bonded to the phenyl group of compound A.

[0011] R １ When is a branched alkyl group, examples of the branched alkyl group having 6 to 13 carbon atoms include the following groups. Examples of branched alkyl groups having 6 carbon atoms include branched alkyl groups whose main chain has 5 carbon atoms and branched alkyl groups whose main chain has 4 carbon atoms. Examples of branched alkyl groups whose main chain has 5 carbon atoms include a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, and a 5-methylpentyl group. Examples of branched alkyl groups whose main chain has 4 carbon atoms include a 1-ethylbutyl group, a 2-ethylbutyl group, a 1,1-dimethylbutyl group, a 1,2-dimethylbutyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 1,3-dimethylbutyl group, and a 3,3-dimethylbutyl group. Examples of branched alkyl groups whose main chain has 3 carbon atoms include a 1-methyl-1-ethylpropyl group, a 2-methyl-1-ethylpropyl group, a 1,1,2-trimethylpropyl group, and a 1,2,2-trimethylpropyl group.

[0012] Examples of branched alkyl groups having 7 carbon atoms include branched alkyl groups whose main chain has 6 carbon atoms, branched alkyl groups whose main chain has 5 carbon atoms, branched alkyl groups whose main chain has 4 carbon atoms, and branched alkyl groups whose main chain has 3 carbon atoms. Examples of branched alkyl groups whose main chain has 6 carbon atoms include a 1-methylhexyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 4-methylhexyl group, and a 5-methylhexyl group. Examples of branched alkyl groups whose main chain has 5 carbon atoms include a 1,1-dimethylpentyl group, a 1,2-dimethylpentyl group, a 1,3-dimethylpentyl group, a 1,4-dimethylpentyl group, a 2,2-dimethylpentyl group, a 2,3-dimethylpentyl group, a 2,4-dimethylpentyl group, a 3,3-dimethylpentyl group, a 3,4-dimethylpentyl group, a 4,4-dimethylpentyl group, a 1-ethylpentyl group, a 2-ethylpentyl group, and a 3-ethylpentyl group. Examples of branched alkyl groups having a main chain of 4 carbon atoms include 1,1,2-trimethylbutyl, 1,2,2-trimethylbutyl, 1,2,3-trimethylbutyl, and 1,3,3-trimethylbutyl. Examples of branched alkyl groups having a main chain of 3 carbon atoms include 1,1-diethylpropyl.

[0013] Examples of branched alkyl groups having 8 carbon atoms include branched alkyl groups whose main chain has 7 carbon atoms, branched alkyl groups whose main chain has 6 carbon atoms, branched alkyl groups whose main chain has 5 carbon atoms, branched alkyl groups whose main chain has 4 carbon atoms, and branched alkyl groups whose main chain has 3 carbon atoms. Examples of branched alkyl groups whose main chain has 7 carbon atoms include 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, and 6-methylheptyl groups. Examples of branched alkyl groups having a main chain of 6 carbon atoms include a 1,1-dimethylhexyl group, a 1,2-dimethylhexyl group, a 1,3-dimethylhexyl group, a 1,4-dimethylhexyl group, a 1,5-dimethylhexyl group, a 2,2-dimethylhexyl group, a 2,3-dimethylhexyl group, a 2,4-dimethylhexyl group, a 2,5-dimethylhexyl group, a 3,3-dimethylhexyl group, a 3,4-dimethylhexyl group, a 3,5-dimethylhexyl group, a 4,4-dimethylhexyl group, a 4,5-dimethylhexyl group, a 5,5-dimethylhexyl group, a 1-ethylhexyl group, a 2-ethylhexyl group, a 3-ethylhexyl group, and a 4-ethylhexyl group. Examples of branched alkyl groups having a main chain of 5 carbon atoms include a 1,1,2-trimethylpentyl group, a 1,1,3-trimethylpentyl group, a 1,2,3-trimethylpentyl group, a 2,2,3-trimethylpentyl group, and a 2,2,4-trimethylpentyl group. Examples of branched alkyl groups having a main chain of 4 carbon atoms include a 1,1,2,2-tetramethylbutyl group, a 1,2,2,3-tetramethylbutyl group, a 1,1,2,3-tetramethylbutyl group, a 1,1,3,3-tetramethylbutyl group, a 1,1-diethylbutyl group, a 1,2-diethylbutyl group, a 2,2-diethylbutyl group, a 1-methyl-1-propylbutyl group, a 2-methyl-1-propylbutyl group, and a 3-methyl-1-propylbutyl group. Examples of branched alkyl groups having a main chain of 4 carbon atoms include a 2-methyl-1,1-diethylpropyl group.

[0014] Examples of branched alkyl groups having 9 carbon atoms include branched alkyl groups whose main chain has 8 carbon atoms, branched alkyl groups whose main chain has 7 carbon atoms, branched alkyl groups whose main chain has 6 carbon atoms, branched alkyl groups whose main chain has 5 carbon atoms, branched alkyl groups whose main chain has 4 carbon atoms, and branched alkyl groups whose main chain has 3 carbon atoms. Examples of branched alkyl groups whose main chain has 8 carbon atoms include 1-methyloctyl, 2-methyloctyl, 3-methyloctyl, 4-methyloctyl, 5-methyloctyl, 6-methyloctyl, and 7-methyloctyl. Examples of branched alkyl groups whose main chain has 7 carbon atoms include dimethylheptyl, 1-ethylheptyl, 2-ethylheptyl, 3-ethylheptyl, 4-ethylheptyl, 5-ethylheptyl, and 6-ethylheptyl. Examples of branched alkyl groups having a main chain of 6 carbon atoms include a 1-methyl-1-ethylhexyl group, a 1-methyl-2-ethylhexyl group, a 1-methyl-3-ethylhexyl group, a 1-methyl-4-ethylhexyl group, a 2-methyl-3-ethylhexyl group, a 3-methyl-3-ethylhexyl group, a 2-methyl-4-ethylhexyl group, a 3-methyl-4-ethylhexyl group, a 4-methyl-4-ethylhexyl group, a 5-methyl-4-ethylhexyl group, a 1-propylhexyl group, a 2-propylhexyl group, and a 3-propylhexyl group. Examples of branched alkyl groups having a main chain of 5 carbon atoms include a 1,1,3,3-tetramethylpentyl group, a 2,2,4,4-tetramethylpentyl group, a 1-butylpentyl group, a 1,1-diethylpentyl group, a 1,2-diethylpentyl group, a 1,3-diethylpentyl group, a 2,2-diethylpentyl group, a 2,3-diethylpentyl group, a 3,3-diethylpentyl group, etc. Examples of branched alkyl groups having a main chain of 4 or less carbon atoms include a 1,1,2,2,3-pentamethylbutyl group and a 1,1,2,2,3,3-hexamethylpropyl group.

[0015] Examples of branched alkyl groups having 10 carbon atoms include branched alkyl groups whose main chain has 9 carbon atoms, branched alkyl groups whose main chain has 8 carbon atoms, branched alkyl groups whose main chain has 7 carbon atoms, branched alkyl groups whose main chain has 6 carbon atoms, branched alkyl groups whose main chain has 5 carbon atoms, and branched alkyl groups whose main chain has 4 carbon atoms. Examples of branched alkyl groups whose main chain has 9 carbon atoms include 1-methylnonyl group, 2-methylnonyl group, 3-methylnonyl group, 4-methylnonyl group, 5-methylnonyl group, 6-methylnonyl group, 7-methylnonyl group, and 8-methylnonyl group. Examples of branched alkyl groups having a main chain of 8 carbon atoms include a 1,1-dimethyloctyl group, a 1,2-dimethyloctyl group, a 1,3-dimethyloctyl group, a 1,4-dimethyloctyl group, a 1,5-dimethyloctyl group, a 1,6-dimethyloctyl group, a 1,7-dimethyloctyl group, a 2,2-dimethyloctyl group, a 2,3-dimethyloctyl group, a 2,4-dimethyloctyl group, a 2,5-dimethyloctyl group, a 2,6-dimethyloctyl group, and a 2,7-dimethyloctyl group. Examples include a 3,3-dimethyloctyl group, a 3,4-dimethyloctyl group, a 3,5-dimethyloctyl group, a 3,6-dimethyloctyl group, a 3,7-dimethyloctyl group, a 4,4-dimethyloctyl group, a 4,5-dimethyloctyl group, a 4,6-dimethyloctyl group, a 4,7-dimethyloctyl group, a 5,5-dimethyloctyl group, a 5,6-dimethyloctyl group, a 5,7-dimethyloctyl group, a 6,6-dimethyloctyl group, and a 6,7-dimethyloctyl group. Examples of branched alkyl groups having a main chain of 7 carbon atoms include a 1,1,2-trimethylheptyl group, a 3,3,4-trimethylheptyl group, a 5,5,6-trimethylheptyl group, a 1,3,3-trimethylheptyl group, a 2,4,4-trimethylheptyl group, a 3,5,5-trimethylheptyl group, a 1,2,2-trimethylheptyl group, a 3,4,4-trimethylheptyl group, a 5,6,6-trimethylheptyl group, a 3,3,4-trimethylheptyl group, a 3,3,5-trimethylheptyl group, a 1-methyl-3-ethylheptyl group, a 2-methyl-4-ethylheptyl group, a 3-methyl-5-ethylheptyl group, a 4-methyl-2-ethylheptyl group, a 5-methyl-3-ethylheptyl group, and a 6-methyl-4-ethylheptyl group.Examples of branched alkyl groups having a main chain of 6 carbon atoms include a 1-methyl-1-butylhexyl group, a 1-methyl-2-butylhexyl group, a 1-methyl-3-butylhexyl group, a 1,1-diethylhexyl group, a 3,3-diethylhexyl group, a 1,5-diethylhexyl group, a 1,1,3,3-tetramethylhexyl group, a 2,2,4,4-tetramethylhexyl group, and a 3,3,5,5-tetramethylhexyl group. Examples of branched alkyl groups having a main chain of 5 carbon atoms include methyl-1-butylpentyl group, dimethyl-2-propylpentyl group, 1-methyl-1,2-diethylpentyl group, 1-methyl-1,3-diethylpentyl group, 2-methyl-1,1-diethylpentyl group, 2-methyl-1,2-diethylpentyl group, 1-methyl-1,3-diethylpentyl group, 1,2,2,3,3-heptamethylpentyl group, etc. Examples of branched alkyl groups having a main chain of 4 carbon atoms include 1,1,2,2,3,3-hexamethylbutyl group, etc.

[0016] Examples of branched alkyl groups having 11 carbon atoms include branched alkyl groups whose main chain has 10 carbon atoms, branched alkyl groups whose main chain has 9 carbon atoms, branched alkyl groups whose main chain has 8 carbon atoms, branched alkyl groups whose main chain has 7 carbon atoms, branched alkyl groups whose main chain has 6 carbon atoms, branched alkyl groups whose main chain has 5 carbon atoms, and branched alkyl groups whose main chain has 4 carbon atoms. An example of a branched alkyl group whose main chain has 10 carbon atoms is a methyldecyl group. Examples of branched alkyl groups whose main chain has 9 carbon atoms are a dimethylnonyl group and an ethylnonyl group. Examples of branched alkyl groups whose main chain has 8 carbon atoms are a trimethyloctyl group, a methylethyloctyl group, and a propyloctyl group. Examples of branched alkyl groups having a main chain of 7 or less carbon atoms include tetramethylheptyl, dimethylethylheptyl, methylpropylheptyl, butylheptyl, heptamethylhexyl, dimethylpropylhexyl, trimethylethylhexyl, methylbutylhexyl, pentylhexyl, hexamethylpentyl, methylethylpropylpentyl, dimethyldiethylpentyl, dimethylbutylpentyl, dipropylpentyl, ethylbutylpentyl, pentamethylethylbutyl, tetramethylpropylbutyl, etc. In these branched alkyl groups having 11 carbon atoms, the alkyl group having 3 or more carbon atoms bonded to the main chain may be linear or branched.

[0017] Examples of branched alkyl groups having 12 carbon atoms include branched alkyl groups whose main chain has 11 carbon atoms, branched alkyl groups whose main chain has 10 carbon atoms, branched alkyl groups whose main chain has 9 carbon atoms, branched alkyl groups whose main chain has 8 carbon atoms, branched alkyl groups whose main chain has 7 carbon atoms, branched alkyl groups whose main chain has 6 carbon atoms, and branched alkyl groups whose main chain has 5 carbon atoms. An example of a branched alkyl group whose main chain has 11 carbon atoms is a methylundecyl group. Examples of branched alkyl groups whose main chain has 10 carbon atoms are a dimethyldecyl group and an ethyldecyl group. Examples of branched alkyl groups whose main chain has 9 carbon atoms are a trimethylnonyl group, a methylethylnonyl group, and a propylnonyl group. Examples of branched alkyl groups whose main chain has 8 carbon atoms are a tetramethyloctyl group, a dimethylethyloctyl group, a diethyloctyl group, a methylpropyloctyl group, and a butyloctyl group. Examples of branched alkyl groups having a main chain containing 7 or less carbon atoms include pentamethylheptyl, dimethylpropylheptyl, trimethylethylheptyl, methyldiethylheptyl, methylbutylheptyl, pentylheptyl, hexamethylhexyl, triethylhexyl, dimethyldiethylhexyl, methylethylpropylhexyl, trimethylpropylhexyl, dipropylhexyl, ethylbutylhexyl, heptamethylpentyl, methyltriethylpentyl, methylethylbutylpentyl, methyldipropylpentyl, dimethylethylpropylpentyl, trimethyldiethylpentyl, trimethylbutylpentyl, tetramethylpropylpentyl, and propylbutylpentyl groups. In these branched alkyl groups having 12 carbon atoms, the alkyl group having 3 or more carbon atoms bonded to the main chain may be linear or branched.

[0018] Examples of branched alkyl groups having 13 carbon atoms include branched alkyl groups whose main chain has 12 carbon atoms, branched alkyl groups whose main chain has 11 carbon atoms, branched alkyl groups whose main chain has 10 carbon atoms, branched alkyl groups whose main chain has 9 carbon atoms, branched alkyl groups whose main chain has 8 carbon atoms, branched alkyl groups whose main chain has 7 carbon atoms, branched alkyl groups whose main chain has 6 carbon atoms, and branched alkyl groups whose main chain has 5 carbon atoms. An example of a branched alkyl group whose main chain has 12 carbon atoms is a methyldodecyl group. Examples of branched alkyl groups whose main chain has 11 carbon atoms are a dimethylundecyl group and an ethylundecyl group. Examples of branched alkyl groups whose main chain has 10 carbon atoms are a trimethyldecyl group, a methylethyldecyl group, and a propyldecyl group. Examples of branched alkyl groups whose main chain has 9 carbon atoms are a tetramethylnonyl group, a dimethylethylnonyl group, a methylpropylnonyl group, a diethylnonyl group, and a butylnonyl group. Examples of branched alkyl groups having a main chain of 8 carbon atoms include pentamethyloctyl, trimethylethyloctyl, methyldiethyloctyl, methylbutyloctyl, ethylpropyloctyl, dimethylpropyloctyl, and pentyloctyl groups. Examples of branched alkyl groups having a main chain containing 7 or less carbon atoms include a hexamethylheptyl group, a methylpentylheptyl group, a dimethylbutylheptyl group, a trimethylpropylheptyl group, a tetramethylethylheptyl group, a triethylheptyl group, an ethylbutylheptyl group, a dipropylheptyl group, a hexylheptyl group, a heptamethylhexyl group, a methyltriethylhexyl group, a methyldipropylhexyl group, a methylethylbutylhexyl group, a dimethylethylpropylhexyl group, a trimethyldiethylhexyl group, a trimethylbutylhexyl group, a tetramethylpropylhexyl group, an ethylpentylhexyl group, a diethylpropylhexyl group, a propylbutylhexyl group, an octamethylpentyl group, a dimethyltriethylpentyl group, a dimethylethylbutylpentyl group, a dimethyldipropylpentyl group, a trimethylethylpropylpentyl group, a tetramethyldiethylpentyl group, a tetramethylbutylpentyl group, a pentamethylpropylpentyl group, a diethylbutylpentyl group, and a dibutylpentyl group. In these branched alkyl groups having 13 carbon atoms, the alkyl groups having 3 or more carbon atoms bonded to the main chain may be linear or branched.

[0019] When the compound represented by the general formula (A) is used as an antioxidant, R １ When R has 6 to 13 carbon atoms, the compound A can be stabilized by radical resonance during the oxidation reaction described below, thereby exhibiting a sufficient antioxidant effect. １ The number of carbon atoms is preferably 8 to 13, more preferably 10 to 13, and even more preferably 8, because when used as a colorant or antioxidant, these functions are easily exhibited.

[0020] In order to improve the stabilization of the compound represented by the general formula (A) by radical resonance, R １ is preferably a branched alkyl group, more preferably a branched alkyl group having 8 carbon atoms. １ is a branched alkyl group having 8 carbon atoms, R １ is preferably a 1,1,2,2-tetramethylbutyl group, a 1,2,2,3-tetramethylbutyl group, a 1,1,2,3-tetramethylbutyl group, or a 1,1,3,3-tetramethylbutyl group, and is more preferably a 1,1,3,3-tetramethylbutyl group because of its high stability and ease of production.

[0021] In the above general formula (A), R ２ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. R ２ When the two R are used as a coloring agent or an antioxidant, these functions are easily exhibited, so that the two R are preferably hydrogen atoms. ２ may be the same or different.

[0022] Compound A represented by the general formula (A) is preferably a dimer formed by condensation of two molecules of 4-[[alkylphenyl]imino]-1(4H)-naphtharenone, which is formed by oxidation of compound B represented by the general formula (B). This dimer is typically formed by condensation of two molecules of 4-[[alkylphenyl]imino]-1(4H)-naphtharenone, which is formed by oxidation of compound B represented by the general formula (B). １is a 1,1,3,3-tetramethylbutyl group, and R ２ is a hydrogen atom, 1,4-naphtharenediamine,N1-1-naphthalenyl-N1,N4-bis[4-(1,1,3,3-tetramethylbutyl)phenyl]. 1,4-naphtharenediamine,N1-1-naphthalenyl-N1,N4-bis[4-(1,1,3,3-tetramethylbutyl)phenyl] is represented by the following formula (A-1).

[0023]

[0024] <Production Method> Compound A represented by the above general formula (A) can be obtained by using N-alkylphenyl-α-naphthylamine represented by the following general formula (B) (referred to as "compound B") as a raw material and reacting compound B with an oxidizing agent by the following production method (1) or production method (2). In the production of compound A, one type of compound B may be used alone as a raw material, or R ３ and R ４ A mixture of two or more compounds B having different structures may be used. When a mixture of two or more compounds B is used as a raw material, the resulting compound A may also have the structure R １ and R ２ When a mixture of two or more compounds B is used as a raw material for producing compound A, R ３ is preferably a mixture of compounds B with different R ３ The number of carbon atoms is preferably 10 to 13.

[0025]

[0026] In the above general formula (B), R ３ represents R in the above general formula (A). １ and the preferred embodiments thereof are the same as those of compound A. In the above general formula (B), R ４ represents R in the above general formula (A). ２ The preferred embodiments thereof are the same as those of Compound A.

[0027] (Production Method (1)) Production Method (1) is a method in which Fremy's salt, which is an oxidizing agent, is reacted with N-alkylphenyl-α-naphthylamine represented by the above general formula (B) to obtain a compound represented by the above general formula (A) (referred to as "Compound A"). The reaction involved in Production Method (1) is shown in Figure 1.

[0028] First, compound B is dissolved in a solvent to obtain a solution of compound B. To the solution of compound B, potassium nitrosodisulfonate dissolved in water is added. A pH adjusting buffer is further added to the resulting mixture to adjust the pH to about 4 to 5. This mixture is stirred at 15 to 60°C, preferably at room temperature, for 1 to 5 hours. The progress of the reaction during stirring is observed, and the stirring time is adjusted as necessary to continue the reaction.

[0029] In the production method (1), examples of the solvent for dissolving Compound B include acetone, methanol, and ethanol, and acetone is preferred from the viewpoint of workability. As the pH adjusting buffer, potassium dihydrogen phosphate and sodium dihydrogen phosphate can be used, and potassium dihydrogen phosphate is preferred.

[0030] Fremy's salt is a nitrosodisulfonate, and is derived from disodium nitrosodisulfonate (Na ４ [ON(SO ３ ) ２ ] ２ ) or dipotassium nitrosodisulfonate (K ４ [ON(SO ３ ) ２ ] ２ The amount of Fremy's salt is preferably 1.5 to 3 mol per 1 mol of compound B.

[0031] After the reaction is completed, the solvent is removed from the reaction mixture by evaporation. An extract is added to the aqueous residue after solvent removal, and the reaction product is extracted into the extract layer. The extract layer is then separated and washed with water as needed, and the extract is removed by vacuum distillation or a rotary evaporator to obtain a reaction product containing Compound A. Compound A can then be purified from this reaction product by silica gel column chromatography, as described below. Chloroform is a typical extract, but dichloromethane may also be used.

[0032] (Production Method (2)) Production Method (2) is a method for obtaining a compound represented by the above general formula (A) (Compound A) by reacting butyl hydroperoxide, which is an oxidizing agent, with the above compound B. The reaction involved in Production Method (2) is shown in Figure 2.

[0033] First, compound B is dissolved in a solvent. To the solution of compound B, butyl hydroperoxide and cobalt toluate as a catalyst are added. This mixed solution is stirred at room temperature for about 5 hours. The progress of the reaction is observed during stirring, and the stirring time is adjusted as necessary to continue the reaction.

[0034] The solvent used in Production Method (2) is the same as in Production Method (1). The amount of butyl hydroperoxide is preferably 3 to 5 mol per 1 mol of Compound B. The butyl hydroperoxide contains a linear or branched butyl group, preferably a branched butyl group, and more preferably tert-butyl hydroperoxide. The amount of cobalt toluate is a catalytic amount, and is, for example, 0.005 to 0.05 mol per mol of Compound B. In addition to cobalt toluate, potassium permanganate may also be used as the catalyst.

[0035] After the reaction is completed, the solvent is removed from the reaction mixture by evaporation, and an extract is added to the residue obtained by evaporating the solvent, and the reaction product is extracted into the extract layer. The extract layer is then separated and washed with water as necessary, and the extract is removed by vacuum distillation or a rotary evaporator to obtain a reaction product containing Compound A. Compound A can then be separated and purified from this reaction product by silica gel column chromatography, as described below. The extract used in Production Method (2) is typically chloroform, as in Production Method (1), but dichloromethane may also be used.

[0036] (Purification of Compound A from Reaction Product) Compound A is separated from the reaction product obtained by the above-mentioned Production Method (1) or Production Method (2) by silica gel column chromatography. Specifically, the reaction product is first developed with hexane. Thereafter, if necessary, by-products are separated using an eluent in which hexane, toluene, and acetone are mixed in a predetermined ratio. Furthermore, Compound A can be separated and purified using an eluent of acetone-toluene (volume ratio 1:1). The obtained Compound A is analyzed for its compositional formula by liquid chromatography mass spectrometry (LC / MS), and then the following is obtained: １ H-NMR, １３ The structure can be identified using C-NMR and two-dimensional NMR (one or more of COSY, HSQC, HMBC, and INADEQUATE). Compound A thus obtained is orange, brown, or red in color and is a liquid at room temperature.

[0037] Compound A can be used, for example, as an antioxidant, colorant, or pigment. In particular, the unshared electron pair on the nitrogen atom of Compound A is easily able to catch radicals, and it is thought that when Compound A is contained in an oil-based composition, Compound A itself is oxidized, thereby providing the composition with an antioxidant function. The chemical reaction formula presumed for this radical-catching reaction is shown in Figure 3.

[0038] The present invention will be described in more detail below with reference to examples. The scope of the present invention is not limited to the following examples, and the materials, reagents, amounts and proportions of substances, and procedures shown in the examples can be suitably changed without departing from the spirit of the present invention.

[0039] In the examples, silica gel column chromatography was performed using an open column packed with Wakosil C-200 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as silica gel. LC / MS was performed using a Synapt G2-S (manufactured by Waters) with ESI+ ionization and a mass range of m / z from 50 to 2000, and the composition formula was estimated. １ The H-NMR spectrum was measured using tetramethylsilane as the chemical shift standard with an AVANCE III HD 600 MHz CryoNMR (manufactured by Bruker), and all δ values ​​are shown in ppm. １３ C-NMR spectra were measured using deuterated chloroform (CDCl) as the chemical shift standard. ３ (77.1 ppm)) was measured using an AVANCE III HD 600 MHz CryoNMR (manufactured by Bruker) by the 1H-inverse gated decoupling method, and all δ values ​​were expressed in ppm. INADEQUATE measurements were performed using deuterated chloroform (CDCl) as the chemical shift standard. ３ (77.1 ppm) was used.

[0040] Example 1 In Example 1, 1,4-naphthalenediamine, N1-1-naphthalenyl-N1,N4-bis[4-(1,1,3,3-tetramethylbutyl)phenyl] (hereinafter referred to as "dimer") was produced by a method for producing Compound A (Production Method (1)) in which Fremy's Salt was used as an oxidizing agent to react with N-alkylphenyl-α-naphthylamine. Specifically, the dimer was produced using n-(4-Tert-octylphenyl)-1-naphthylamine (hereinafter referred to as "APAN") as a raw material and potassium nitrosodisulfonate. The reaction according to Example 1 is shown in FIG. 4.

[0041] To a solution of 0.3 g (1 mmol) of APAN in 30 mL of acetone, 0.7 g (2.5 mmol) of potassium nitrosodisulfonate in 40 mL of water was added, and after stirring, 4 mL of 0.16 M aqueous potassium dihydrogen phosphate solution was added. The mixture was stirred at room temperature (25°C) for 1 to 5 hours to react. After the reaction, the acetone was removed by vacuum distillation at room temperature, and the aqueous residue was extracted with chloroform. After removing the chloroform from the extract, the product was purified by silica gel column chromatography using hexane-toluene (1:1) as an eluent to obtain 0.1 g (yield 10%) of a dimer as a brown liquid. The purified compound was １ H-NMR, １３ The structure was identified by C-NMR and INADEQUATE analysis, and it was confirmed that it was a dimer. １ The H-NMR spectrum is shown in Figure 5. １３ The C-NMR spectrum is shown in Figure 6, and the INADEQUATE spectrum is shown in Figure 7. Note that the peaks marked with "*1" in Figures 5 and 6 are not derived from the dimer. The peaks marked with "*2" in Figure 6 are derived from deuterated chloroform as the chemical shift standard.

[0042] Example 2 In Example 2, a dimer was produced by a method (Production Method (2)) in which tert-butyl hydroperoxide was used as an oxidizing agent to react with N-alkylphenyl-α-naphthylamine to produce Compound A. Specifically, APAN was used as a raw material and was oxidized to produce a dimer. The reaction according to Example 2 is shown in FIG. 7.

[0043] To a solution of 0.2 g (0.56 mmol) of APAN in 30 mL of acetone, 0.2 g (2 mmol) of tert-butyl hydroperoxide was added and stirred at room temperature (25°C). Next, 2 mg of cobalt toluate was added to this mixture. The resulting mixture was stirred at room temperature for 12 hours. After that, 0.2 g (2 mmol) of tert-butyl hydroperoxide and 2 mg of cobalt toluate were added, in that order, to the mixture, and the mixture was stirred at room temperature for 12 hours. The acetone was removed by distillation under reduced pressure at room temperature, and the aqueous residue was extracted with chloroform. After removing the chloroform from the extract, the product was purified by silica gel column chromatography using hexane-toluene (1:1) as an eluent to obtain a dimer (yield 10%) as a brown oil. In Example 2, the purified compound was also １ H-NMR, １３ Analysis was performed by C-NMR and INADEQUATE, and the same results as in Example 1 were obtained. １ H-NMR spectrum and １３ A C-NMR spectrum was obtained, which allowed the structure of the purified compound to be identified and confirmed to be a dimer.

[0044] The antioxidant properties of the compounds obtained in the examples were measured by differential scanning calorimetry (OIT). The measuring device used was a P-DSC (high-pressure differential scanning calorimeter) manufactured by TA Instruments. The OIT measurement conditions were as follows: Measurement temperature conditions: The temperature was raised from room temperature to 210°C at a rate of 100°C / min and maintained at 210°C. Measurement atmosphere gas: air Measurement pressure: 1 MPa

[0045] The obtained compound was added to α-olefin oil at a concentration of 1% by mass, and the differential scanning calorimetry (OIT) measurement was performed three times to calculate the average value. In this measurement, the average mass of the measurement sample was 5.55 mg, and the oxidation induction time (OIT) of the dimer was 9.58 minutes on average. The oxidation induction time of the dimer was determined based on the oxidation induction time of the α-olefin oil alone (less than 1 minute). The longer the oxidation induction time, the greater the antioxidant function.

[0046] Example 3 In Example 3, 1,4-naphtharenediamine, N1-1-naphthalenyl-N1,N4-bis[4-(X)phenyl] (X is an alkyl group having 10 to 13 carbon atoms, hereinafter referred to as "dimer mixture") was produced by the above-mentioned production method (1) using Fremy's Salt as an oxidizing agent to react with N-alkylphenyl-α-naphthylamine (a mixture of alkyl groups having 10 to 13 carbon atoms). In this example, potassium nitrosodisulfonate was used as the oxidizing agent. The reaction according to Example 3 is shown in Figure 9. Hereinafter, "N-alkylphenyl-α-naphthylamine (a mixture of alkyl groups having 10 to 13 carbon atoms)" will be referred to as "APAN mixture." In Figure 9, the alkyl group bonded to the phenyl group (R in general formula (B)) is ３ and R in general formula (A) １ (an alkyl group corresponding to R １０－１３ This indicates:

[0047] To a solution of 0.4 g (1 mmol) of the APAN mixture in 30 mL of acetone, 0.7 g (2.5 mmol) of potassium nitrosodisulfonate in 40 mL of water was added, and after stirring, 4 mL of 0.16 M aqueous potassium dihydrogen phosphate was added. The mixture was stirred at room temperature (25°C) for 1 to 5 hours to react. After the reaction, the acetone was removed by vacuum distillation at room temperature, and the aqueous residue was extracted with chloroform. After removing the chloroform from the extract, the product was purified by silica gel column chromatography using hexane-toluene (1:1) as an eluent to obtain 0.1 g (10% yield) of a brown liquid dimer mixture.

[0048] The purified compound is １ H-NMR, １３ The structure was identified by C-NMR and it was confirmed that it was a dimer mixture. １ The H-NMR spectrum is shown in FIG. １３ The C-NMR spectrum is shown in Figure 11. The peaks marked with (*2) in Figure 11 are those obtained using chloroform as the chemical shift standard. These confirmed the presence of 1,4-naphthalenediamine, N1-1-naphthalenyl-N1,N4-bis[4-(X)phenyl] (X is an alkyl group with 10 to 13 carbon atoms).

[0049] Here, the APAN mixture has an alkyl group bonded to a phenyl group having 10 to 13 carbon atoms, and R １０－１３ But, -C １０ H ２１ , -C １1 H ２３ , -C １2 H ２５ and -C １３ H ２７ The dimer mixture is in a mixed state. Therefore, the NMR analysis result of the dimer mixture will be a spectrum that is a mixture of these. When APAN before the reaction was analyzed by X-ray structural analysis using a crystalline sponge, a typical alkyl structure (1,1,2,6-tetramethylbutyl group) was identified. As shown in Figure 9, the structure of the alkyl group bonded to the phenyl group does not change before and after the reaction, so one of the structures of the dimer mixture after the reaction was identified. The identified structure is shown in structural formula C below. Furthermore, the crystal data from the X-ray structural analysis using a crystalline sponge is shown in Table 1.

[0050]

[0051]

[0052] The novel compound (dimer) of the present embodiment can be used, for example, as an antioxidant, a colorant, or a pigment, and is particularly expected to be used as an antioxidant, a colorant, or a pigment for oil-based compositions, or a colorant or pigment for synthetic resins.

Claims

1. A compound represented by the following general formula (A): (In general formula (A), R １ represents an alkyl group having 6 to 13 carbon atoms, and R ２ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. １ may be the same or different, and two R 2 may be the same or different.) 2. R １ The compound according to claim 1, wherein is a branched alkyl group having 8 to 13 carbon atoms.

3. R ２ The compound according to claim 1 or 2, wherein is a hydrogen atom.

4. R １ The compound according to claim 1 or 2, wherein is a 1,1,3,3-tetramethylbutyl group.

5. The compound according to claim 1 or 2, which is 1,4-naphthalenediamine, N1-1-naphthalenyl-N1,N4-bis[4-(1,1,3,3-tetramethylbutyl)phenyl].

6. A method for producing a compound represented by the following general formula (A) by reacting a compound represented by the following general formula (B) with an oxidizing agent. １ represents an alkyl group having 6 to 13 carbon atoms, and R ２ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. １ may be the same or different, and two R 2 may be the same or different. ３ represents an alkyl group having 6 to 13 carbon atoms, and R ４ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

7. The method of claim 6, wherein the oxidizing agent comprises nitrosodisulfonic acid or butyl hydroperoxide.

8. The method of claim 6, wherein the oxidizing agent comprises potassium nitrosodisulfonate or tert-butyl hydroperoxide.

9. R １ and R ３ is a 1,1,3,3-tetramethylbutyl group, and R ２ and R ４ The method according to claim 6 or 7, wherein is a hydrogen atom.

10. An antioxidant containing the compound according to claim 1 as an active ingredient.

11. R １ The antioxidant according to claim 10, wherein R is a branched alkyl group having 8 to 13 carbon atoms.

12. R ２ The antioxidant according to claim 10, wherein is a hydrogen atom.

13. R １ The antioxidant according to claim 10, wherein is a 1,1,3,3-tetramethylbutyl group.

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