JP2021134151A - Diol, diketone, method for producing diol, and method for producing diketone - Google Patents

Abstract

To provide novel diol, diketone, method for producing diol and method for producing diketone.SOLUTION: Provided is a diol represented by the following formula. In the formula, R1 and R2 represent H, a hetero atom-containing group, a halogen atom, a linear alkyl group having 1 to 6 carbon atoms, and a group containing a branched alkyl group or aryl group having 3 to 6 carbon atoms and having 6 to 12 carbon atoms, R3 and R4 represent a heteroatom-containing group, a halogen atom, a linear alkyl group having 1 to 6 carbon atoms, and a group containing a branched alkyl group or aryl group having 3 to 6 carbon atoms and having 6 to 12 carbon atoms, and W represents an aromatic ring-containing group.SELECTED DRAWING: None

Description

The present invention relates to a diol, a diketone, a method for producing a diol, and a method for producing a diketone. In particular, it relates to a diol having a spiro ring structure and the like.

Conventionally, spiroglycol (3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane) has been studied. Further, in recent years, a diol having a spiro ring structure as shown in Patent Document 1 has also been studied.

International Publication No. 2018/074305

Diols having a spiro ring structure, such as spiroglycol and the diol described in Patent Document 1, are useful as raw materials for various resins and the like. With recent technological innovations, there are increasing cases where further performance is required, and new materials are also required for diols having a spiro ring structure.
An object of the present invention is to solve such a problem, a novel diol having a spiro ring structure and having beneficial properties, a diketone that can be a raw material of the diol, and the diol. It is an object of the present invention to provide the method for producing the diketone and the method for producing the diketone.

（式（１）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子、ヘテロ原子を含む基、ハロゲン原子、炭素数１〜６の直鎖のアルキル基、炭素数３〜６の分岐したアルキル基、または、アリール基を含み炭素数が６〜１２である基を表し、Ｒ³およびＲ⁴は、それぞれ独立に、ヘテロ原子を含む基、ハロゲン原子、炭素数１〜６の直鎖のアルキル基、炭素数３〜６の分岐したアルキル基、または、アリール基を含み炭素数が６〜１２である基を表し、Ｗは、式（２）で表される基から選択される。）
式（２）

（式（２）中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹およびＲ¹²は、それぞれ独立に、水素原子、炭素数１〜６の直鎖のアルキル基、炭素数３〜６の分岐したアルキル基、および、アリール基を含み炭素数が６〜２０である基からなる群から選ばれる基を表す。Ｒ⁵およびＲ⁶の少なくとも１つは、アリール基を含み炭素数が６〜２０である基である。＊は、結合部位である。）
＜２＞前記式（１）におけるＲ¹およびＲ²が、水素原子である、＜１＞に記載のジオール。
＜３＞前記式（１）におけるＲ³およびＲ⁴が、それぞれ独立に、炭素数１〜６の直鎖のアルキル基、または、炭素数３〜６の分岐したアルキル基を表す、＜１＞または＜２＞に記載のジオール。
＜４＞前記式（１）におけるＷが式（２２）で表される基から選択される、＜１＞〜＜３＞のいずれか１つに記載のジオール。
式（２２）

（式（２２）中、Ｒ⁵²は、水素原子、メチル基またはフェニル基を表し、Ｒ⁷²、Ｒ⁸²、Ｒ⁹²およびＲ¹⁰²は、それぞれ独立に、水素原子またはメチル基を表し、Ｒ¹¹²およびＲ¹²²は、それぞれ独立に、水素原子またはメチル基を表す。＊は、結合部位である。）
＜５＞下記ジオール。

＜６＞下記ジオール。

＜７＞下記ジオール。

＜８＞下記式（３）で表されるジケトン。
式（３）

（式（３）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子、ヘテロ原子を含む基、ハロゲン原子、炭素数１〜６の直鎖のアルキル基、炭素数３〜６の分岐したアルキル基、または、アリール基を含み炭素数が６〜１２である基を表し、Ｗは、式（２）で表される基から選択される。）
式（２）

（式（２）中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹およびＲ¹²は、それぞれ独立に、水素原子、炭素数１〜６の直鎖のアルキル基、炭素数３〜６の分岐したアルキル基、および、アリール基を含み炭素数が６〜２０である基からなる群から選ばれる基を表す。Ｒ⁵およびＲ⁶の少なくとも１つは、アリール基を含み炭素数が６〜２０である基である。＊は、結合部位である。）
＜９＞前記式（３）におけるＲ¹およびＲ²が、水素原子である、＜８＞に記載のジケトン。
＜１０＞前記式（３）におけるＷが式（２２）で表される基から選択される、＜８＞または＜９＞に記載のジケトン。
式（２２）

（式（２２）中、Ｒ⁵²は、水素原子、メチル基またはフェニル基を表し、Ｒ⁷²、Ｒ⁸²、Ｒ⁹²およびＲ¹⁰²は、それぞれ独立に、水素原子またはメチル基を表し、Ｒ¹¹²およびＲ¹²²は、それぞれ独立に、水素原子またはメチル基を表す。＊は、結合部位である。）
＜１１＞下記ジケトン。

＜１２＞下記ジケトン。

＜１３＞下記ジケトン。

＜１４＞下記式（３）で表されるジケトンと下記式（４）で表されるトリオールを脱水環化反応させることを含む、ジオールの製造方法。
式（３）

（式（３）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子、ヘテロ原子を含む基、ハロゲン原子、炭素数１〜６の直鎖のアルキル基、炭素数３〜６の分岐したアルキル基、または、アリール基を含み炭素数が６〜１２である基を表し、Ｗは、式（２）で表される基から選択される。）
式（２）

（式（２）中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹およびＲ¹²は、それぞれ独立に、水素原子、炭素数１〜６の直鎖のアルキル基、炭素数３〜６の分岐したアルキル基、および、アリール基を含み炭素数が６〜２０である基からなる群から選ばれる基を表す。Ｒ⁵およびＲ⁶の少なくとも１つは、アリール基を含み炭素数が６〜２０である基である。＊は、結合部位である。）
式（４）

（式（４）中、Ｒ¹³は、炭化水素基を表す。）
＜１５＞前記式（４）で表されるトリオールが、トリメチロールプロパン、トリメチロールエタンおよびα，α，α−トリス（ヒドロキシメチル）トルエンの少なくとも１種である、＜１４＞に記載のジオールの製造方法。
＜１６＞前記ジオールが、＜１＞〜＜７＞のいずれか１つに記載のジオールである、＜１４＞または＜１５＞に記載のジオールの製造方法。
＜１７＞下記式（５）で表される化合物を水素還元することを含む、＜８＞〜＜１３＞のいずれか１つに記載のジケトンの製造方法。
式（５）

（式（５）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子、ヘテロ原子を含む基、ハロゲン原子、炭素数１〜６の直鎖のアルキル基、炭素数３〜６の分岐したアルキル基、または、アリール基を含み炭素数が６〜１２である基を表し、Ｗは、式（２）で表される基から選択される。）
式（２）

（式（２）中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹およびＲ¹²は、それぞれ独立に、水素原子、炭素数１〜６の直鎖のアルキル基、炭素数３〜６の分岐したアルキル基、および、アリール基を含み炭素数が６〜２０である基からなる群から選ばれる基を表す。Ｒ⁵およびＲ⁶の少なくとも１つは、アリール基を含み炭素数が６〜２０である基である。＊は、結合部位である。） As a result of studies by the present inventor based on the above problems, it has been found that a new material having beneficial properties can be provided by the following means.
<1> A diol represented by the following formula (1).
Equation (1)

(In the formula (1), R ¹ and R ² are independently branched with a hydrogen atom, a group containing a hetero atom, a halogen atom, a linear alkyl group having 1 to 6 carbon atoms, and 3 to 6 carbon atoms, respectively. Represents an alkyl group or a group containing an aryl group and having 6 to 12 carbon atoms, and R ³ and R ⁴ are independently a heteroatom-containing group, a halogen atom, and a linear chain having 1 to 6 carbon atoms. Represents an alkyl group, a branched alkyl group having 3 to 6 carbon atoms, or a group containing an aryl group and having 6 to 12 carbon atoms, and W is selected from the groups represented by the formula (2).
Equation (2)

In formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , respectively, are independently hydrogen atoms and linear alkyl groups having 1 to 6 carbon atoms. Represents a group selected from the group consisting of a branched alkyl group having 3 to 6 carbon atoms and a group containing an aryl group and having 6 to 20 carbon atoms. At ^{least one of R 5} and R ⁶ is an aryl group. It is a group containing 6 to 20 carbon atoms. * Is a binding site.)
<2> The diol according to <1>, wherein ^{R 1} and R ² in the formula (1) are hydrogen atoms.
^{<3> R 3} and R ⁴ in the above formula (1) independently represent a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, respectively. <1> Or the diol according to <2>.
<4> The diol according to any one of <1> to <3>, wherein W in the formula (1) is selected from the groups represented by the formula (22).
Equation (22)

(In formula (22), R ⁵² represents a hydrogen atom, a methyl group or a phenyl group, and R ⁷² , R ⁸² , R ⁹² and R ¹⁰² independently represent a hydrogen atom or a methyl group, and R ¹¹² and R ¹²² independently represents a hydrogen atom or a methyl group. * Is a bond site.)
<5> The following diol.

<6> The following diol.

<7> The following diol.

<8> The diketone represented by the following formula (3).
Equation (3)

(In the formula (3), R ¹ and R ² are independently branched with a hydrogen atom, a group containing a hetero atom, a halogen atom, a linear alkyl group having 1 to 6 carbon atoms, and 3 to 6 carbon atoms, respectively. Represents an alkyl group or a group containing an aryl group and having 6 to 12 carbon atoms, and W is selected from the groups represented by the formula (2).
Equation (2)

In formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , respectively, are independently hydrogen atoms and linear alkyl groups having 1 to 6 carbon atoms. Represents a group selected from the group consisting of a branched alkyl group having 3 to 6 carbon atoms and a group containing an aryl group and having 6 to 20 carbon atoms. At ^{least one of R 5} and R ⁶ is an aryl group. It is a group containing 6 to 20 carbon atoms. * Is a binding site.)
<9> The diketone according to <8>, wherein ^{R 1} and R ² in the formula (3) are hydrogen atoms.
<10> The diketone according to <8> or <9>, wherein W in the formula (3) is selected from the groups represented by the formula (22).
Equation (22)

(In formula (22), R ⁵² represents a hydrogen atom, a methyl group or a phenyl group, and R ⁷² , R ⁸² , R ⁹² and R ¹⁰² independently represent a hydrogen atom or a methyl group, and R ¹¹² and R ¹²² independently represents a hydrogen atom or a methyl group. * Is a bond site.)
<11> The following diketone.

<12> The following diketone.

<13> The following diketone.

<14> A method for producing a diol, which comprises a dehydration cyclization reaction of a diketone represented by the following formula (3) and a triol represented by the following formula (4).
Equation (3)

(In the formula (3), R ¹ and R ² are independently branched with a hydrogen atom, a group containing a hetero atom, a halogen atom, a linear alkyl group having 1 to 6 carbon atoms, and 3 to 6 carbon atoms, respectively. Represents an alkyl group or a group containing an aryl group and having 6 to 12 carbon atoms, and W is selected from the groups represented by the formula (2).
Equation (2)

In formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , respectively, are independently hydrogen atoms and linear alkyl groups having 1 to 6 carbon atoms. Represents a group selected from the group consisting of a branched alkyl group having 3 to 6 carbon atoms and a group containing an aryl group and having 6 to 20 carbon atoms. At ^{least one of R 5} and R ⁶ is an aryl group. It is a group containing 6 to 20 carbon atoms. * Is a binding site.)
Equation (4)

(In formula (4), R ¹³ represents a hydrocarbon group.)
<15> The diol according to <14>, wherein the triol represented by the formula (4) is at least one of trimethylolpropane, trimethylolethane and α, α, α-tris (hydroxymethyl) toluene. Production method.
<16> The method for producing a diol according to <14> or <15>, wherein the diol is the diol according to any one of <1> to <7>.
<17> The method for producing a diketone according to any one of <8> to <13>, which comprises hydrogen-reducing a compound represented by the following formula (5).
Equation (5)

(In the formula (5), R ¹ and R ² are independently branched with a hydrogen atom, a group containing a hetero atom, a halogen atom, a linear alkyl group having 1 to 6 carbon atoms, and 3 to 6 carbon atoms, respectively. Represents an alkyl group or a group containing an aryl group and having 6 to 12 carbon atoms, and W is selected from the groups represented by the formula (2).
Equation (2)

In formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , respectively, are independently hydrogen atoms and linear alkyl groups having 1 to 6 carbon atoms. Represents a group selected from the group consisting of a branched alkyl group having 3 to 6 carbon atoms and a group containing an aryl group and having 6 to 20 carbon atoms. At ^{least one of R 5} and R ⁶ is an aryl group. It is a group containing 6 to 20 carbon atoms. * Is a binding site.)

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a novel diol having a spiro ring structure and having beneficial properties, a diketone that can be a raw material of the diol, a method for producing the diol, and a method for producing the diketone. became.
In particular, by successfully introducing an aromatic ring into a diol having a spiro ring structure, it has become possible to improve the refractive index and hardness.

Hereinafter, embodiments for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and the present invention is not limited to the present embodiment.
In addition, in this specification, "~" is used in the meaning that the numerical values described before and after it are included as the lower limit value and the upper limit value.
In the present specification, various physical property values and characteristic values shall be at 23 ° C. unless otherwise specified.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, the notation that does not describe substitution and non-replacement is preferably non-replacement.
As used herein, "(meth) acrylate" refers to both acrylate and methacrylate, or either.
In the present specification, Me stands for methyl group, Et stands for ethyl group, Pr stands for propyl group, and Bu stands for butyl group.

（式（１）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子、ヘテロ原子を含む基、ハロゲン原子、炭素数１〜６の直鎖のアルキル基、炭素数３〜６の分岐したアルキル基、または、アリール基を含み炭素数が６〜１２である基を表し、Ｒ³およびＲ⁴は、それぞれ独立に、ヘテロ原子を含む基、ハロゲン原子、炭素数１〜６の直鎖のアルキル基、炭素数３〜６の分岐したアルキル基、または、アリール基を含み炭素数が６〜１２である基を表し、Ｗは、式（２）で表される基から選択される。）
式（２）

（式（２）中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹およびＲ¹²は、それぞれ独立に、水素原子、炭素数１〜６の直鎖のアルキル基、炭素数３〜６の分岐したアルキル基、および、アリール基を含み炭素数が６〜２０である基からなる群から選ばれる基を表す。Ｒ⁵およびＲ⁶の少なくとも１つは、アリール基を含み炭素数が６〜２０である基である。＊は、結合部位である。） <Glycol>
The diol of the present embodiment is a diol represented by the formula (1).
Equation (1)

(In the formula (1), R ¹ and R ² are independently branched with a hydrogen atom, a group containing a hetero atom, a halogen atom, a linear alkyl group having 1 to 6 carbon atoms, and 3 to 6 carbon atoms, respectively. Represents an alkyl group or a group containing an aryl group and having 6 to 12 carbon atoms, and R ³ and R ⁴ are independently a heteroatom-containing group, a halogen atom, and a linear chain having 1 to 6 carbon atoms. Represents an alkyl group, a branched alkyl group having 3 to 6 carbon atoms, or a group containing an aryl group and having 6 to 12 carbon atoms, and W is selected from the groups represented by the formula (2).
Equation (2)

In formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , respectively, are independently hydrogen atoms and linear alkyl groups having 1 to 6 carbon atoms. Represents a group selected from the group consisting of a branched alkyl group having 3 to 6 carbon atoms and a group containing an aryl group and having 6 to 20 carbon atoms. At ^{least one of R 5} and R ⁶ is an aryl group. It is a group containing 6 to 20 carbon atoms. * Is a binding site.)

Diols having a spiro ring structure are known, such as spiroglycol and the diol described in Patent Document 1. However, with technological innovation, diols having a spiro ring structure may also be required to have a further improvement in refractive index and hardness. Here, in order to further improve the refractive index and hardness of the diol having a spiro ring structure, it is conceivable to introduce an aromatic ring into the diol having a spiro ring structure. Then, in the present embodiment, for example, with respect to bisphenol having an aromatic ring, hydrogenation was added to some of the aromatic rings, and for some of the aromatic rings, a diketone compound in which the aromatic was left was obtained. Then, it is considered that the diol having an aromatic ring and a spiro ring structure was successfully obtained by using such a diketone body as an intermediate material.

The diol represented by the formula (1) may have a geometric isomer, and in this embodiment, it represents a mixture of any one or more of the geometric isomers. The production ratio of the geometric isomer of the diol represented by the formula (1) varies depending on the reaction conditions (reaction solvent type, reaction catalyst type, reaction temperature) and the like, and is not particularly limited. The mixture of geometric isomers of the diol having a dispiro structure obtained in the present embodiment can be used as a mixture or separated into each geometric isomer by a conventionally known method.

The equation (1) will be described below.
In formula (1), R ¹ and R ² are independently hydrogen atom, heteroatom-containing group, halogen atom, linear alkyl group having 1 to 6 carbon atoms, and branched alkyl having 3 to 6 carbon atoms, respectively. Represents a group or a group containing an aryl group and having 6 to 12 carbon atoms.
R ¹ and R ² each contain a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or an aryl group, and have 6 to 12 carbon atoms. It is preferably a certain group, more preferably a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a branched alkyl group having 3 to 6 carbon atoms, and it is a hydrogen atom or a methyl group. Is even more preferable, and a hydrogen atom is even more preferable.

Examples of the hetero atom contained in the group containing the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom.
Preferred examples of the group containing a hetero atom include an alkoxy group, an alkylthioether group, an amino group, and a nitro group. The alkyl chain constituting the alkoxy group or the alkylthioether group is preferably a linear alkyl chain having 1 to 6 carbon atoms, and more preferably a straight chain alkyl chain having 1 to 3 carbon atoms.

As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a chlorine atom, a bromine atom and an iodine atom are more preferable.

The linear alkyl group having 1 to 6 carbon atoms is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and a methyl group. Alternatively, it is more preferably an ethyl group, and even more preferably a methyl group.

The branched alkyl group having 3 to 6 carbon atoms is preferably a branched alkyl group having 3 to 5 carbon atoms, more preferably a branched alkyl group having 3 or 4 carbon atoms, and the branched alkyl group having 3 carbon atoms. It is more preferable that it is an alkyl group.

The group containing an aryl group and having 6 to 12 carbon atoms is preferably a phenyl group, an alkyl group having 6 to 12 carbon atoms and substituted with a phenyl group, and more preferably a phenyl group. The number of carbon atoms of the alkyl group constituting the alkyl group substituted with the phenyl group is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

^{Specific examples of R 1} and R ² in the formula (1) include hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group and 2-, respectively. Methylpropyl group, 1,1-dimethylethyl group (tert-butyl group), n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl Group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group (neopentyl group), n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group , 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1 -Ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group, fluorine Examples thereof include atom, chlorine atom, bromine atom, iodine atom, methoxy group, ethoxy group, prochioxy group, butoxy group, methylthioether group, ethylthioether group, amino group, nitro group, phenyl group and benzyl group.
Of these, R ¹ and R ² are more preferably hydrogen atoms, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, and n-butyl groups, respectively. Further, from the viewpoint of industrial availability, it is particularly preferable that ^{R 1} and R ^{2 are hydrogen atoms.}

In the formula (1), R ³ and R ⁴ are independently a group containing a hetero atom, a halogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a branched alkyl group having 3 to 6 carbon atoms. , Representing a group containing an aryl group and having 6 to 12 carbon atoms, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or an aryl group having 6 carbon atoms. It is preferably a group having 1 to 12 carbon atoms, more preferably a linear alkyl group having 1 to 6 carbon atoms, or a group containing an aryl group and having 6 to 12 carbon atoms, and 1 to 6 carbon atoms. It is more preferably a straight chain alkyl group, and even more preferably an ethyl group.
A preferred range of groups containing a heteroatom, a halogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a group containing an aryl group and having 6 to 12 carbon atoms. Examples thereof include those having the same preferable range as the group containing a heteroatom described in ^{R 1} and R ² of the formula (1).

^{Specific examples of R 3} and R ⁴ in the formula (1) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group and 2-methylpropyl group, respectively. , 1,1-Dimethylethyl group (tert-butyl group), n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1 , 2-Dimethylpropyl group, 2,2-dimethylpropyl group (neopentyl group), n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1, 1-Dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group , 2-Ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group, n-heptyl group , 1-Methylhexyl group, 2-Methylhexyl group, 3-Methylhexyl group, 4-Methylhexyl group, 5-Methylhexyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3 -Dimethylpentyl group, 1,4-dimethylpentyl group, 1,5-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethyl Pentyl group, 3,4-dimethylpentyl group, 4,4-dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-propylbutyl group, 2-propylbutyl group, 3 -Propylbutyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-2-methylbutyl group, Examples thereof include 2-ethyl-3-methylbutyl group, 1,2,3-trimethylbutyl group, phenyl group, naphthyl group, anthracenyl group and the like.
Among these, R ³ and R ⁴ are more preferably methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group, respectively, and further preferably methyl group or ethyl group. It is also preferable that at least one of ^{R 3} and R ^{4 is a phenyl group.} From the viewpoint of the production method is particularly convenient, it is preferred that R ³ and R ⁴ are the same, a R ³ and R ⁴ are the same, and particularly preferably a methyl group or an ethyl group. It is also preferable that both ^{R 3} and R ^{4 are phenyl groups.}

In formula (1), W is selected from the groups represented by formula (2).
In formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , respectively, are independent hydrogen atoms and linear alkyl groups having 1 to 6 carbon atoms. Represents a group selected from the group consisting of a branched alkyl group having 3 to 6 carbon atoms and a group containing an aryl group and having 6 to 20 carbon atoms, and ^{at least one of R 5} and R ⁶ contains an aryl group. It is a group having 6 to 20 carbon atoms.

In formula (2), R ⁵ and R ⁶ are independently groups containing a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or an aryl group and having 6 to 20 carbon atoms. Is more preferable, a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms (preferably an aryl group having 6 to 12 carbon atoms), and a hydrogen atom and methyl. More preferably, it is a group or a phenyl group.
At ^{least one of R 5} and R ⁶ is a group containing an aryl group and having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and further preferably a phenyl group. preferable.
Preferred combinations of R ⁵ and R ⁶ in the present embodiment, (preferably a phenyl group), while the aryl group having 6 to 12 carbon atoms of R ⁵ and R ⁶ is and the other is a hydrogen atom, 1 to carbon atoms It is preferably a linear alkyl group of 6 (preferably a methyl or ethyl group, more preferably a methyl group) or an aryl group having 6 to 12 carbon atoms (preferably a phenyl group), which is one of R ⁵ and R ⁶ . Is more preferably an aryl group having 6 to 12 carbon atoms, and the other is a linear alkyl group having 1 to 6 carbon atoms.

In the formula (2), R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are preferably hydrogen atoms or linear alkyl groups having 1 to 6 carbon atoms, respectively, and are directly having 1 to 6 carbon atoms. It is more preferably an alkyl group of the chain, further preferably a methyl group, an ethyl group or a propyl group, further preferably a methyl group or an ethyl group, and even more preferably a methyl group.

In formula (2), R ¹¹ and R ¹² are independently hydrogen atoms, linear alkyl groups having 1 to 6 carbon atoms, or groups containing an aryl group and having 6 to 12 carbon atoms. Is preferable, a hydrogen atom, a linear alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 12 carbon atoms is more preferable, and a hydrogen atom, a methyl group or a phenyl is further preferable, and hydrogen is more preferable. It is more preferably an atom or a methyl group, and even more preferably a hydrogen atom.

^{Specific examples of R 5} , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ^{12 in} the formula (2) are independently hydrogen atom, methyl group, ethyl group and n-propyl. Group, isopropyl group, n-butyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group (tert-butyl group), n-pentyl group, 1-methylbutyl group, 2-methylbutyl group , 3-Methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group (neopentyl group), n-hexyl group, 1-methylpentyl group , 2-Methylpentyl group, 3-Methylpentyl group, 4-Methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group , 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl -1-Methylpropyl group, 1-ethyl-2-methylpropyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl Group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4-dimethylpentyl group, 1,5-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-Dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3,4-dimethylpentyl group, 4,4-dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group Group, 3-ethylpentyl group, 1-propylbutyl group, 2-propylbutyl group, 3-propylbutyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-3 Methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-2-methylbutyl group, 2-ethyl-3-methylbutyl group, and 1,2,3-trimethylbutyl group, phenyl group, naphthyl group, anthracenyl group, etc. Can be mentioned.

（式（２２）中、Ｒ⁵²は、水素原子、メチル基またはフェニル基を表し、Ｒ⁷²、Ｒ⁸²、Ｒ⁹²およびＲ¹⁰²は、それぞれ独立に、水素原子またはメチル基を表し、Ｒ¹¹²およびＲ¹²²は、それぞれ独立に、水素原子またはメチル基を表す。＊は、結合部位である。） The formula (2) is also preferably selected from the groups represented by the formula (22).
Equation (22)

(In formula (22), R ⁵² represents a hydrogen atom, a methyl group or a phenyl group, and R ⁷² , R ⁸² , R ⁹² and R ¹⁰² independently represent a hydrogen atom or a methyl group, and R ¹¹² and R ¹²² independently represents a hydrogen atom or a methyl group. * Is a bond site.)

In formula (22), R ⁵² is preferably a hydrogen atom or a methyl group, more preferably a methyl group.

In formula (22), R ⁷² , R ⁸² , R ⁹² and R ¹⁰² are preferably methyl groups. R ¹¹² and R ¹²² are preferably hydrogen atoms.

As a preferred embodiment of the diol represented by the formula (1), R ¹ and R ² in the formula (1) are hydrogen atoms, and R ³ and R ⁴ are independently ethyl group, methyl group or phenyl group, respectively. (More preferably, an ethyl group or a methyl group, further preferably an ethyl group), and diols in which W is selected from the groups represented by the formula (22) are exemplified.

The diols preferably used in this embodiment are shown below. Needless to say, the present embodiment is not limited to these.

The molecular weight of the diol represented by the formula (1) is preferably 400 to 1100. Within such a range, the effect of the present invention is more effectively exhibited.
The diol represented by the formula (1) can be produced by a known method. For example, a dehydration cyclization reaction of a diketone represented by the formula (3) described later and a triol represented by the formula (4) described later. Obtained by letting. Details of the method for producing the diol will be described later.

（式（３）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子、ヘテロ原子を含む基、ハロゲン原子、炭素数１〜６の直鎖のアルキル基、炭素数３〜６の分岐したアルキル基、または、アリール基を含み炭素数が６〜１２である基を表し、Ｗは、式（２）で表される基から選択される。）
式（２）

（式（２）中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹およびＲ¹²は、それぞれ独立に、水素原子、炭素数１〜６の直鎖のアルキル基、炭素数３〜６の分岐したアルキル基、および、アリール基を含み炭素数が６〜２０である基からなる群から選ばれる基を表す。Ｒ⁵およびＲ⁶の少なくとも１つは、アリール基を含み炭素数が６〜２０である基である。＊は、結合部位である。） <Diketone>
The diketone of the present embodiment is the diketone represented by the formula (3).
Equation (3)

(In the formula (3), R ¹ and R ² are independently branched with a hydrogen atom, a group containing a hetero atom, a halogen atom, a linear alkyl group having 1 to 6 carbon atoms, and 3 to 6 carbon atoms, respectively. Represents an alkyl group or a group containing an aryl group and having 6 to 12 carbon atoms, and W is selected from the groups represented by the formula (2).
Equation (2)

In formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , respectively, are independently hydrogen atoms and linear alkyl groups having 1 to 6 carbon atoms. Represents a group selected from the group consisting of a branched alkyl group having 3 to 6 carbon atoms and a group containing an aryl group and having 6 to 20 carbon atoms. At ^{least one of R 5} and R ⁶ is an aryl group. It is a group containing 6 to 20 carbon atoms. * Is a binding site.)

^{R 1} and R ² in the formula (3) are ^{synonymous with R 1} and R ² in the formula (1), respectively, and the preferable range is also the same.
The W in the formula (3), that is, the group represented by the formula (2) is synonymous with the W in the formula (1), and the preferable range is also the same.
The diketone preferably used in this embodiment is shown below. Needless to say, the present embodiment is not limited to these.

The molecular weight of the diketone represented by the formula (3) is preferably 200 to 800. The melting point of the diketone represented by the formula (3) can be 40 ° C. or higher, and may be 230 ° C. or lower.
The diketone represented by the formula (3) can be produced by a known method. For example, it can be produced by hydrogenating bisphenol having an aromatic ring structure. Further, a method of reducing bisphenol to diol and then oxidizing it to diketone can also be adopted. Details of the method for producing the diketone will be described later.

<Hydrogenation catalyst>
When hydrogenating, it is preferable to use a hydrogenation catalyst. Examples of the active ingredient of the hydrogenation catalyst used in the present embodiment include a metal element having a catalytic hydrogenation ability (hereinafter, referred to as “specific metal component”). Specific metal components include, for example, nickel, cobalt, iron, ruthenium, rhodium, palladium, platinum, iridium, copper, silver, molybdenum, tungsten, chromium and rhenium. The specific metal component may be in a metal state or a cation state as long as it exhibits hydrogenation ability. Of these, in general, the metallic state is preferable because it has a stronger hydrogenating ability and is stable in a reducing atmosphere. The specific metal component can be used alone or in combination of two or more in a state of being contained in a solid catalyst. When two or more kinds of specific metal components are used, there is no particular limitation on their combination, mixing ratio and form, and they can be used in the form of a mixture of individual metals or an alloy or an intermetallic compound. In the present embodiment, the hydrogenation catalyst is preferably a solid catalyst containing at least one selected from the group consisting of palladium, platinum, nickel and copper, and particularly preferably a solid catalyst containing palladium.

In the hydrogenation catalyst of the present embodiment, a non-metal substance can be used in combination with a specific metal component. Examples of non-metal substances mainly include elemental substances, carbides, nitrides, oxides, hydroxides, sulfates, carbonates and phosphates (hereinafter referred to as "specific non-metal components"). .. Specific examples thereof include graphite, diamond, activated carbon, silicon carbide, silicon nitride, aluminum nitride, boron nitride, boron oxide, aluminum oxide (alumina), silicon oxide (silica), titanium oxide, zirconium oxide, and hafnium oxide. Lantern oxide, cerium oxide, yttrium oxide, niobium oxide, magnesium silicate, calcium silicate, magnesium aluminate, calcium aluminate, zinc oxide, chromium oxide, aluminosilicate, aluminosiricophosphate, aluminophosphate, borophosphate, magnesium phosphate , Calcium Phosphate, Strontium Phosphate, Apatite Hydroxide (Calcium Hydroxyl Phosphate), Apatite Chloride, Apatite Fluoride, Calcium Sulfate, Barium Sulfate and Barium Carbonate. The specific non-metal component may be used alone or in combination of two or more. When two or more kinds are used in combination, the combination, mixing ratio, and form are not particularly limited, and can be used in a form such as a mixture of individual compounds, a complex compound, or a double salt.

From the viewpoint of industrial use, a specific non-metal component that can be easily and inexpensively obtained is preferable. Preferred as such a specific non-metal component are activated carbon, a zirconium compound, and an aluminum compound, and more preferably activated carbon and a zirconium compound.

As the hydrogenation catalyst of the present embodiment, the specific metal component may be used alone, or the specific metal component and the specific non-metal component may be used in combination. The method for producing the hydrogenation catalyst of the present embodiment is not particularly limited, and a conventionally known method can be used. As an example, a method of impregnating a specific non-metal component with a raw material compound of a specific metal component (supporting method), a method of dissolving the raw material compound of the specific metal component and the raw material compound of the specific non-metal component together in an appropriate solvent. Later, a method of simultaneously precipitating using an alkaline compound or the like (co-precipitation method), a method of mixing and homogenizing the raw material compound of the specific metal component and the specific non-metal component at an appropriate ratio (kneading method) and the like can be mentioned. Further, more simply, an industrially distributed hydrogenation catalyst can be used as it is.

Depending on the composition of the hydrogenation catalyst or the convenience of the catalyst preparation method, a specific metal component may be prepared in a cation state and then reduced to obtain a metal state. As the reducing method and reducing agent for that purpose, conventionally known ones can be used, and there is no particular limitation. Reducing agents include, for example, reducing inorganic gases such as hydrogen gas, carbon monoxide gas, ammonia, hydrazine, phosphine and silane, lower oxygenated compounds such as methanol, formaldehyde and formic acid, sodium borohydride and hydrogenation. Examples include hydrides such as lithium aluminum. By reducing the specific metal component in the cation state in the gas phase or the liquid phase in which these reducing agents are present, the specific metal component is converted into the metal state. The reduction treatment conditions at this time can be set to suitable conditions depending on the type and amount of the specific metal component and the reducing agent. The operation of this reduction treatment may be carried out separately by using a catalytic reduction device before the hydrogenation reduction in the production method of the present embodiment, before the reaction is started in the reactor used in the production method of the present embodiment, or before the reaction is started. It may be performed at the same time as the reaction operation.

Further, the metal content and shape of the hydrogenation catalyst of the present embodiment are not particularly limited. The shape may be powdery or molded, and there are no particular restrictions on the shape and molding method when molded. For example, a spherical product, a tableted molded product, an extruded molded product, and a product obtained by crushing them to an appropriate size can be appropriately selected and used.

（式（３）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子、ヘテロ原子を含む基、ハロゲン原子、炭素数１〜６の直鎖のアルキル基、炭素数３〜６の分岐したアルキル基、または、アリール基を含み炭素数が６〜１２である基を表し、Ｗは、式（２）で表される基から選択される。）
式（２）

（式（２）中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹およびＲ¹²は、それぞれ独立に、水素原子、炭素数１〜６の直鎖のアルキル基、炭素数３〜６の分岐したアルキル基、および、アリール基を含み炭素数が６〜２０である基からなる群から選ばれる基を表す。Ｒ⁵およびＲ⁶の少なくとも１つは、アリール基を含み炭素数が６〜２０である基である。＊は、結合部位である。）
式（４）

（式（４）中、Ｒ¹³は、炭化水素基を表す。） <Glycol manufacturing method>
The method for producing a diol of the present embodiment includes a dehydration cyclization reaction of a diketone represented by the following formula (3) and a triol represented by the following formula (4).
Equation (3)

(In the formula (3), R ¹ and R ² are independently branched with a hydrogen atom, a group containing a hetero atom, a halogen atom, a linear alkyl group having 1 to 6 carbon atoms, and 3 to 6 carbon atoms, respectively. Represents an alkyl group or a group containing an aryl group and having 6 to 12 carbon atoms, and W is selected from the groups represented by the formula (2).
Equation (2)

In formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , respectively, are independently hydrogen atoms and linear alkyl groups having 1 to 6 carbon atoms. Represents a group selected from the group consisting of a branched alkyl group having 3 to 6 carbon atoms and a group containing an aryl group and having 6 to 20 carbon atoms. At ^{least one of R 5} and R ⁶ is an aryl group. It is a group containing 6 to 20 carbon atoms. * Is a binding site.)
Equation (4)

(In formula (4), R ¹³ represents a hydrocarbon group.)

In the present embodiment, a diketone having an aromatic ring structure is used to obtain a diol having a spiro ring structure and an aromatic ring structure.

The diketone represented by the formula (3) is the diketone of the present embodiment described above.
In the method for producing a diol of the present embodiment, only one type of diketone may be used, or two or more types of diketone may be used.

In the formula (4), R ¹³ represents a hydrocarbon group, preferably a linear alkyl group having 1 to 6 carbon atoms, and a branched alkyl group or an aryl group having 3 to 6 carbon atoms, more preferably. , A linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, and a linear alkyl group having 1 to 6 carbon atoms is more preferable.
The hydrocarbon group as R ¹³ preferably does not contain an ether bond.
The linear alkyl group having 1 to 6 carbon atoms is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and a methyl group. Alternatively, it is more preferably an ethyl group, and even more preferably an ethyl group.
The branched alkyl group having 3 to 6 carbon atoms is preferably a branched alkyl group having 3 to 5 carbon atoms, more preferably a branched alkyl group having 3 or 4 carbon atoms, and the branched alkyl group having 3 carbon atoms. It is more preferable that it is an alkyl group.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, a phenyl group, a naphthyl group and an anthracenyl group are more preferable, and a phenyl group is further preferable.

^{Examples of R 13} in the formula (4) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methylpropyl group, a 2-methylpropyl group, and a 1,1-dimethylethyl group. (Tart-butyl group), n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2 , 2-Dimethylpropyl group (neopentyl group), n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1, 2-Dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1, 1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group, n-heptyl group, 1-methylhexyl group, 2 -Methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4 -Dimethylpentyl group, 1,5-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3,4-dimethyl Pentyl group, 4,4-dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-propylbutyl group, 2-propylbutyl group, 3-propylbutyl group, 1-ethyl -1-Methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-2-methylbutyl group, 2-ethyl-3-methylbutyl group , And 1,2,3-trimethylbutyl group, phenyl group, naphthyl group, anthracenyl group and the like.
Among these, R ¹³ is more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or an n-butyl group, more preferably a methyl group or an ethyl group, and even more preferably an ethyl group. Further, as another embodiment, it is also preferable that ^{R 13 is a phenyl group.}

In the present embodiment, the triol represented by the formula (4) is preferably at least one of trimethylolpropane, trimethylolethane and α, α, α-tris (hydroxymethyl) toluene, and is preferably trimethylolpropane. More preferably.
In the method for producing a diol of the present embodiment, only one type of triol represented by the formula (4) may be used, or two or more types may be used.

In the dehydration cyclization reaction of the present embodiment, the amount of triol represented by the formula (4) with respect to the amount of the diketone represented by the formula (3) is not particularly limited as long as it can produce a desired diol. .. However, since it is industrially advantageous to have a small amount of unreacted components, the amount of triol used by the formula (4) relative to the amount of the diketone represented by the formula (3) is the lower limit on a molar basis. The value is preferably 2.00 equivalents or more, more preferably 2.50 equivalents or more, further preferably 2.70 equivalents or more, and even more preferably 3.00 equivalents or more. The upper limit of the amount used is preferably 5.00 equivalents or less, more preferably 4.50 equivalents or less, further preferably 4.00 equivalents or less, and 3.50 equivalents or less. Is even more preferable. Within such a range, diol can be produced more economically.

The dehydration cyclization reaction (acetalization reaction) in the present embodiment is preferably carried out in the presence of an acid catalyst. As the acid catalyst, a known acid catalyst may be used, and there is no particular limitation. Specific examples of such acid catalysts include organic acids such as paratoluene sulfonic acid and methane sulfonic acid, mineral acids such as hydrochloric acid, sulfuric acid, nitrate and phosphoric acid, Nafion (manufactured by Sigma-Aldrich, trade name) and yang. A solid acid catalyst such as an ion exchange resin can be used. In particular, organic acids are preferable as the acid catalyst used in the present invention. Further, the acid catalyst is preferably a homogeneous acid catalyst. Furthermore, the acid catalyst may be a hydrate.
In the present embodiment, the acid catalyst preferably contains at least one of methanesulfonic acid, paratoluenesulfonic acid, sulfuric acid, hydrochloric acid, nitrate and phosphoric acid, and at least one of methanesulfonic acid, paratoluenesulfonic acid and sulfuric acid. It is more preferable to contain at least one of methanesulfonic acid and paratoluenesulfonic acid. Two or more kinds of acid catalysts may be used in combination.
The amount of the acid catalyst used is not particularly limited, but is preferably 0.00001 to 0.1 equivalent on a molar basis with respect to the amount of the diketone represented by the formula (3). From the viewpoint of reaction time, 0.00005 equivalent or more is more preferable, 0.0001 equivalent or more is further preferable, and from the viewpoint of suppressing the production of by-products and removing the catalyst, 0.1 equivalent or less is more preferable, and 0.05 equivalent or less is used. Is even more preferable.

In the dehydration cyclization reaction in the present embodiment, an organic solvent may be used as the reaction solvent in addition to the diketone represented by the formula (3), the triol represented by the formula (4), and the acid catalyst. By using an organic solvent, water generated by the dehydration cyclization reaction can be easily removed from the reaction system, and the progress of the dehydration cyclization reaction can be accelerated. Therefore, the organic solvent is not particularly limited as long as it does not cause a side reaction with the raw material, and an organic solvent that separates two layers from water and azeotropes with water is preferable. In the present invention, it is preferable that water derived from the raw material is also removed in addition to the water produced by the dehydration cyclization reaction.
That is, in the method for producing a diol of the present embodiment, it is preferable to include removing water produced by the dehydration cyclization reaction from the reaction system. The method for removing water from the reaction system is not particularly limited, and a method generally known as a method for removing water produced by the dehydration reaction from the reaction system can be adopted. In the present embodiment, the water produced by the dehydration cyclization reaction is preferably removed by azeotropic boiling with an organic solvent as described above, but when the water is removed, the water derived from the raw material is also removed. Is preferable.
When azeotropically boiling with an organic solvent, a method of distilling off the organic solvent and water as an azeotropic fraction and then removing only the water separated into two layers from the above system is exemplified. When an organic solvent capable of forming an azeotropic mixture with water is used, the reaction temperature for removing water is not particularly limited as long as the temperature is such that the water and the organic solvent azeotrope.

Further, from the viewpoint of facilitating the removal of water from the reaction system, the organic solvent is preferably water-insoluble or sparingly water-soluble, and a hydrocarbon solvent is more preferable. As the hydrocarbon solvent, paraffins, aromatic hydrocarbons and alicyclic hydrocarbons are preferable, and pentane, hexane, heptane, octane, benzene, toluene, xylene, cyclohexane, ligroine and petroleum ether are more preferable, and toluene is preferable. And cyclohexane are more preferred. As the organic solvent, one type may be used alone, or two or more types may be mixed and used.
Here, "water-insoluble or sparingly water-soluble" refers to a property in which the solubility in water at room temperature (for example, 25 ° C.) is 2 g / L or less.

The amount of the organic solvent used is not particularly limited, but is preferably 10 to 10000 parts by mass with respect to 100 parts by mass of the total amount of the diketone represented by the formula (3) and the triol represented by the formula (4). It is more preferably 20 to 5000 parts by mass, still more preferably 30 to 1000 parts by mass. When the amount of the organic solvent used is within the above numerical range, water can be more effectively and surely removed from the above system when the organic solvent can form an azeotropic mixture with water.

The reaction temperature of the dehydration cyclization reaction of the present embodiment depends on the boiling point of the organic solvent, but is, for example, 50 to 180 ° C, preferably 70 to 150 ° C, and more. The temperature is preferably 85 to 125 ° C. When the reaction temperature is 50 ° C. or higher, the reaction time can be shortened, and when the reaction temperature is 180 ° C. or lower, coloring due to side reactions can be suppressed more effectively. The reaction pressure of the dehydration cyclization reaction is not particularly limited as long as it is a pressure at which the dehydration cyclization reaction proceeds at the above reaction temperature, and may be normal pressure, and in some cases, the reaction is carried out under reduced pressure. That is also effective. The atmosphere around the reaction system at the time of this reaction is not particularly limited, and may be, for example, any of an air atmosphere, a nitrogen atmosphere, and a nitrogen flow. The reaction time may be appropriately adjusted depending on the amount of catalyst and the reaction temperature, but is usually preferably 2 to 48 hours, more preferably 5 to 20 hours.

The diol obtained by the production method of the present embodiment is preferably the diol represented by the above formula (1).

In the production method of the present embodiment, the purity of the obtained diol represented by the formula (1) by GC analysis (HPLC analysis when measurement by GC analysis is difficult) is 70% by mass or more, and further 90% by mass. It can also be the above. Further, the isolated yield of the obtained diol represented by the formula (1) can be 60% by mass or more, further 80% by mass or more.
The diol obtained by the production method of the present embodiment can be isolated by a known purification method after performing appropriate post-treatment such as neutralization, filtration, washing, and concentration. Specific examples thereof include crystallization, distillation, adsorption treatment, column chromatography, preparative HPLC (liquid chromatography), preparative gas chromatography and the like. Further, depending on the use of the diol, it can be used as it is unpurified only by the post-treatment in the production method of the present embodiment without performing an isolation operation.

（式（５）中、Ｒ¹およびＲ²は、それぞれ独立に、水素原子、ヘテロ原子を含む基、ハロゲン原子、炭素数１〜６の直鎖のアルキル基、炭素数３〜６の分岐したアルキル基、または、アリール基を含み炭素数が６〜１２である基を表し、Ｗは、式（２）で表される基から選択される。）
式（２）

（式（２）中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹およびＲ¹²は、それぞれ独立に、水素原子、炭素数１〜６の直鎖のアルキル基、炭素数３〜６の分岐したアルキル基、および、アリール基を含み炭素数が６〜２０である基からなる群から選ばれる基を表す。Ｒ⁵およびＲ⁶の少なくとも１つは、アリール基を含み炭素数が６〜２０である基である。＊は、結合部位である。）
本実施形態では、芳香環構造を有するジケトンを用いることにより、所望のジオールが得られる。 <Manufacturing method of diketone>
The method for producing the diketone of the present embodiment includes hydrogen reduction of the compound represented by the following formula (5).
Equation (5)

(In the formula (5), R ¹ and R ² are independently branched with a hydrogen atom, a group containing a hetero atom, a halogen atom, a linear alkyl group having 1 to 6 carbon atoms, and 3 to 6 carbon atoms, respectively. Represents an alkyl group or a group containing an aryl group and having 6 to 12 carbon atoms, and W is selected from the groups represented by the formula (2).
Equation (2)

In formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , respectively, are independently hydrogen atoms and linear alkyl groups having 1 to 6 carbon atoms. Represents a group selected from the group consisting of a branched alkyl group having 3 to 6 carbon atoms and a group containing an aryl group and having 6 to 20 carbon atoms. At ^{least one of R 5} and R ⁶ is an aryl group. It is a group containing 6 to 20 carbon atoms. * Is a binding site.)
In this embodiment, a desired diol can be obtained by using a diketone having an aromatic ring structure.

In formula (5), R ¹ and R ^{2 are synonymous with R 1} and R ² in formula (1), and the preferred range is also the same.
In the formula (5), W is synonymous with W in the formula (1), and the preferable range is also the same.
As the compound represented by the formula (5), only one kind may be used, or two or more kinds may be used.

A reaction solvent may be used for the hydrogenation reduction of the present embodiment. When the reaction solvent is used, its type and concentration are not particularly limited as long as it is in an inactive state for hydrogenation reduction. However, if a reaction solvent that interacts more strongly with the specific metal component in the hydrogenation catalyst than the compound represented by the formula (5) is used, the reaction rate may be extremely reduced or the reaction may be stopped. be. From this point of view, for example, a compound containing phosphorus, nitrogen, and sulfur is preferably not used as a reaction solvent, but may be used as long as it is a trace amount that does not significantly affect the reaction rate. Preferred reaction solvents are hydrocarbon compounds, ester compounds and ether compounds, which may be used alone or in combination of two or more. Examples of the reaction solvent include n-pentane, iso-pentane, n-hexane, iso-hexane, 2,2-dimethyl-butane, n-heptane, iso-heptane, 2,2,4- as hydrocarbon compounds. Trimethylpentane, n-octane, iso-octane, n-nonan and iso-nonane and their isomers, n-decane, n-pentadecane, cyclohexane, methylcyclohexane, dimethylcyclohexane and its isomers, decalin, benzene, toluene, xylene , Trimethylbenzene, as an ester compound, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, methyl n-butyrate, ethyl n-butyrate, butyl n-butyrate, methyl i-butyrate, cyclohexyl n-butyrate, cyclohexyl i-butyrate And methyl valerate and its isomers, as ether compounds, as dimethyl ether, diethyl ether, din-propyl ether, diiso-propruether, din-butyl ether, diiso-butyl ether, disec-butyl ether, methylpropyl ether, Ethylpropyl ether, methylbutyl ether, methylpentyl ether, ethylbutyl ether, propylbutyl ether, methylcyclopentyl ether, methylcyclohexyl ether, ethylcyclopentyl ether, ethylcyclohexyl ether, propylcyclopentyl ether, propylcyclohexyl ether, butylcyclopentyl ether, butylcyclohexyl ether, ethylene Glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofuran, methyl tetrahydrofuran, tetrahydropyran, methyltetrahydropyran, 1, Examples thereof include 4-dioxane and dimethyl-1,4-dioxane and their isomers. Among these, benzene, toluene, xylene, ethyl acetate, butyl acetate, ethylene glycol dimethyl ether, tetrahydrofuran and 1,4-dioxane are preferable, and xylene is particularly preferable, from the viewpoint of solubility of the raw material.

The hydrogenation-reduction reaction system in the present embodiment is formed from a compound represented by the formula (5), a liquid phase containing the compound and a reaction solvent, a gas phase of hydrogen gas, and a solid phase of a hydrogenation catalyst. There is no particular limitation as long as the reaction form is carried out in coexistence. As the type of the reaction vessel in the hydrogenation reduction of the present embodiment, a conventionally known type such as a tube type, a tank type, and a kettle type can be used. Further, the method of supplying the raw material composition may be either a distribution method or a batch method. As the hydrogenation catalyst, conventionally known methods such as a fixed bed, a fluidized bed and a suspended bed can be adopted, and there is no particular limitation. In the case of the fixed bed flow method, the reaction can be carried out in the irrigation flow state and the bubble flow state. The flow direction of the raw material liquid may be either a downflow that flows in the direction of gravity or an upflow that flows in the opposite direction, and the supply direction of the raw material gas is either parallel flow or countercurrent flow with respect to the raw material liquid. It may be.

The reaction temperature in the hydrogenation reduction of the present embodiment is preferably 50 to 350 ° C, more preferably 100 to 250 ° C, and even more preferably 150 to 200 ° C. When the reaction temperature is 50 ° C. or higher, a higher hydrogenation rate can be easily obtained, and when the reaction temperature is 350 ° C. or lower, side reactions accompanied by decomposition of raw materials can be further suppressed, and the yield of the target product can be further increased. ..

The reaction pressure in the hydrogenation reduction of the present embodiment is preferably 0.1 to 10 MPa, more preferably 0.5 to 5 MPa. When the reaction pressure is 0.1 MPa or more, a higher hydrogenation rate can be easily obtained, the conversion rate of the compound represented by the formula (5) is improved, and when it is 10 MPa or less, the reaction equipment cost is further increased. It can be kept low and is economically preferable.

The hydrogen gas used for the hydrogenation reduction of the present embodiment does not have to be purified to a particularly high purity, and may be of the quality usually used for an industrial hydrogenation reaction. Further, since the hydrogenation reaction is promoted depending on the hydrogen partial pressure, it is preferable that the purity of the hydrogen gas used is high, but the hydrogen gas is mixed with a gas inert to the reaction such as helium, argon, nitrogen and methane. It may be mixed. The ratio of hydrogen gas to the compound represented by the formula (5) in the reaction system is the molar ratio of hydrogen gas charged to the compound represented by the formula (5) in the case of a batch reaction, and in the case of a distribution reaction, the formula ( Expressed as the molar supply rate ratio of hydrogen gas to the compound represented by 5), it is preferably 0.1 to 300, more preferably 0.5 to 100. When the molar ratio of hydrogen gas is 0.1 or more, the hydrogenation reaction is further promoted, and when the molar ratio of hydrogen gas is 300 or less, the equipment cost for circulating excess hydrogen gas is suppressed to a lower level. be able to.

In the production method of the present embodiment, the purity of the obtained diketone represented by the formula (3) by GC analysis (HPLC analysis when measurement by GC analysis is difficult) is 70% by mass or more, and further 85% by mass. As mentioned above, it can be 90% by mass or more. Further, the isolated yield of the obtained diketone represented by the formula (3) can be 60% by mass or more, further 80% by mass or more.
The diketone obtained by the production method of the present embodiment can be isolated by a known purification method after performing appropriate post-treatment such as neutralization, filtration, washing and concentration. Specific examples thereof include crystallization, distillation, adsorption treatment, column chromatography, preparative HPLC (liquid chromatography), preparative gas chromatography and the like. Further, depending on the use of the diketone, it can be used as it is unpurified only by the post-treatment in the production method of the present embodiment without performing an isolation operation.

<Use>
The diketone represented by the formula (3) of the present embodiment is preferably used as a raw material for producing the diol represented by the formula (1) of the present embodiment. Further, the diketone of the present embodiment can also be used as a raw material for pharmaceuticals, a raw material for industrial chemicals, a raw material for polymers, a raw material for a polymerization initiator, an antioxidant, and a heat resistance improver.
The diol of this embodiment can be used as a raw material for various industrial materials. For example, the diol of the present embodiment can be used as a raw material for a resin or a raw material for (meth) acrylate.
Examples of the resin include polycarbonate resin, polyester resin, epoxy resin, polyurethane resin, polyacrylic acid ester resin, and polymethacrylic acid ester resin.
The resin obtained from the diol of the present embodiment has a high refractive index and high hardness, and is therefore preferably used as an optical material.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
Unless otherwise specified, the indication of "%" in the examples is based on mass.

The method of analyzing the physical properties in the examples is as follows.
(1) Reaction yield and product purity The reaction yield and product purity were quantified by high performance liquid chromatography (HPLC). The column was an Inertsil Diol manufactured by GL Sciences (silica gel particle diameter 3 μm, inner diameter 4.6 mm, length 250 mm filled in the column), and the eluent was a mixed solution of 80% hexane / 20% ethanol (volume ratio).
For high performance liquid chromatography, L2000 series manufactured by Hitachi High-Tech Fielding was used.
(2) Nuclear Magnetic Resonance (NMR)
NMR was used to determine the structure of the compound.
As the nuclear magnetic resonance apparatus, a model: JNM-ECA500 manufactured by JEOL Ltd. was used. The deuterated solvent used and the measurement frequency are described in the attribution of each compound.

(3) High-resolution mass spectrometry High-resolution mass (millimeter, MS) analysis of the compound was performed by the DART (Direct Analysis in Real Time) -MS method.
DART device: DART-Os (manufactured by AMR)
MS device: LTQ Orbitrap Discovery (manufactured by Thermo Fisher Scientific)
Measurement conditions when using DART Ion source temperature: 400 ° C
MS measurement conditions (during DART)
Ionization method: DART
Ionization mode: Positive
Capillary temperature: 275 ° C
Capillary voltage: 35V
Tube lens voltage: 110V

(4) Melting point The melting point of the compound was measured by using a differential scanning calorimeter, placing about 10 mg of a sample in an unsealed aluminum container, and measuring the temperature rise rate at 10 ° C./min in a nitrogen gas stream.
As the differential scanning calorimeter, a model: DSC7020 manufactured by Hitachi High-Tech Science Corporation was used.

Example 1 Synthesis of Diketone A by Hydrogenation A palladium catalyst supported on activated carbon in a 500 mL stainless steel (SUS) reactor (hereinafter sometimes referred to as “Pd / C catalyst”, manufactured by N.E.Chemcat) 1 It contained .01 g, bisphenol M (reagent manufactured by Tokyo Kasei Kogyo Co., Ltd.) 45.0 g, sodium carbonate (manufactured by Fuji Film Wako Junyaku Co., Ltd.) 0.1 g, and metaxylene (manufactured by Mitsubishi Gas Chemicals Co., Ltd.) 256.0 g. Then, the reactor was filled with hydrogen gas until it reached 1.0 MPa, and the temperature was raised to 170 ° C., which is the reaction temperature. The reaction was carried out at 170 ° C. for 6 hours while supplying hydrogen gas so that the reaction pressure was 1.0 MPa. After that, the contents of the reactor were collected by cooling and filtered to remove the catalyst. The filtrate was analyzed by HPLC according to the method described in (1) Reaction Yield and Product Purity section above. The conversion rate of the raw material bispheno M was 100.0%, and the selectivity of the target diketone substance A was 85.6%.
When the contents were concentrated and left at room temperature, a white solid was formed. The product was filtered, washed with hexane, and dried under reduced pressure to obtain 36.0 g of the diketone compound A (HPLC purity 91.6%, isolation yield 79.4%). The melting point of the diketone body A was 102 ° C. The reaction scheme of Example 1 is shown below.

The structure of the diketone A obtained in Example 1 was ^{identified from various spectra of 1} HNMR, ¹³ CNMR, DEPT method (Distorsionless Enhancement by Polarization Transfer), H-HCOSY spectrum (Correlation Spectroscopy), and HMQC (Heteronuclear Multiple Quantum Correlation). bottom.

Furthermore, the molecular weight of diketone A was measured by high-resolution mass spectrometry and the DART method. In high-resolution mass spectrometry, molecules are ionized with almost no fragmentation for mass spectrometry, so that information on molecular weight can be obtained, and at the same time, high-resolution mass spectrometry can be verified as a composition formula. Since the mass number (molecular weight M + 1) of ^{[M + H] +} protonated while maintaining the molecular structure was _{355.26316 (C 24} H ₃₅ O ₂ ), the composition formula of the diketone A is C ₂₄ H _34. It was requested as _{O 2.}

Example 2 Ketalization of Diketone A 20.0 g of Diketone A obtained in Example 1, 22.7 g of trimethylolpropane (manufactured by Mitsubishi Gas Chemical Industries, Ltd.), and toluene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., special grade reagent). 200 g and 0.35 g of paratoluenesulfonic acid monohydrate (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) are housed in a 500 mL round bottom flask, and the temperature inside the kettle is in the range of 100 ° C to 112 ° C under normal pressure. The dehydration cyclization reaction was carried out by heating as described above. While maintaining the above temperature, the water produced by the reaction was azeotropically boiled with toluene and removed from the inside of the system to the outside of the system using a Dean-Stark trap, and the reaction was carried out for 7 hours until the distillate of water stopped. The reaction solution was cooled to room temperature, washed with aqueous sodium hydrogen carbonate, and concentrated to obtain a viscous fluid. Hexane was added to the viscous fluid, and the mixture was stirred and then left at room temperature to form a white solid. The product was filtered, washed with hexane, and dried under reduced pressure to obtain 29.9 g of compound B (HPLC purity 96.9%, isolation yield 87%). The melting point of compound B was 181 ° C. The reaction scheme of Example 2 is shown below.

The structure of compound B obtained in Example 2 was ^{identified from various spectra of 1} HNMR, ¹³ CNMR, DEPT method, H-HCOSY spectrum, and HMQC.

Furthermore, the molecular weight of compound B was measured by high-resolution mass spectrometry and the DART method. Since the mass number of [M + H] ⁺ (molecular weight M + 1) was 587.43027 (C ₃₆ H ₅₉ O ₆ ), the composition formula of compound B was determined to be C ₃₆ H ₅₈ O ₆ .

Example 3 Synthesis of Diketone C by Hydrogenation In Example 1, 45.0 g of bisphenol M was changed to 45.0 g of bisphenol AP (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), and the amount of Pd / C catalyst was changed from 1.0 g to 0. The reaction was carried out under the same conditions as in Example 1 except that the reaction time was changed to 9 g and the reaction time was extended from 6 hours to 7.5 hours. When the product was analyzed by HPLC, the conversion rate of the raw material bispheno AP was 100.0%, and the selectivity of the target diketone C was 65.9%. The contents were concentrated and washed with isopropanol to give a white solid. The product was filtered and dried under reduced pressure to obtain 30.0 g of the diketone compound C (HPLC purity 92.3%, isolation yield 63.0%). The melting point of the diketone body C was 166 ° C. The reaction scheme of Example 3 is shown below.

The structure of the diketone body C obtained in Example 3 was ^{identified from various spectra of 1} HNMR, ¹³ CNMR, DEPT, H-HCOSY spectrum, and HMQC.

Furthermore, the molecular weight of the diketone body C was measured by high-resolution mass spectrometry and the DART method. Since the mass number of [M + H] ⁺ (molecular weight M + 1) was 299.20049 (C ₂₀ H ₂₇ O ₂ ), the composition formula of the diketone body C was determined to be C ₂₀ H ₂₆ O ₂ .

Example 4 Ketalization of diketone C In Example 2, 20.0 g of the diketone body A was changed to 4.0 g of the diketone body C, the trimethylol propane was changed from 22.7 g to 3.8 g, and the toluene was changed from 200 g to 150 g. The reaction was carried out under the same conditions as in Example 2 except that 0.35 g of toluene sulfonic acid was changed to 0.11 g of methane sulfonic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd., reagent). The reaction mixture was cooled to room temperature, washed with aqueous sodium hydrogen carbonate, and concentrated to obtain 6.0 g of a viscous fluid (HPLC purity 79.0%, HPLC yield 66.6%). After adding 50 g of toluene to the viscous fluid to dissolve it, hexane was added and the mixture was stirred. The supernatant was filtered, washed with hexane, and dried under reduced pressure to give compound D. No melting point of compound D was found. Since the melting point was higher than the decomposition point, it was presumed that no melting point was observed. The reaction scheme of Example 4 is shown below.

The structure of compound D obtained in Example 4 was ^{identified from various spectra of 1} HNMR, ¹³ CNMR, DEPT method, H-HCOSY spectrum, and HMQC.

Furthermore, the molecular weight of compound D was measured by high-resolution mass spectrometry and the DART method. Since the mass number of [M + H] ⁺ (molecular weight M + 1) was 531.36802 (C ₃₂ H ₅₁ O ₆ ), the composition formula of compound D was determined to be C ₃₂ H ₅₀ O ₆ .

Example 5 Synthesis of Diketone E by Addition of Hydrogen In Example 1, 45.0 g of bisphenol M was changed to 25.0 g of bisphenol fluorene (reagent manufactured by Tokyo Chemical Industry Co., Ltd.), and the amount of Pd / C catalyst was changed from 1.0 g to 0. The reaction time was shortened from 6 hours to 5 hours by changing to 5 g, changing the amount of meta-xylene from 256 g to 225 g, changing sodium carbonate from 0.1 g to 0.05 g. The reaction was carried out under the same conditions as in Example 1 for the reaction temperature and reaction pressure. When the product was analyzed by HPLC, the conversion rate of the raw material bisphenofluorene was 95.2%, and the selectivity of the target diketone E was 38.4%. The contents were concentrated and washed with isopropanol to give a white solid. The product was filtered and dried under reduced pressure to obtain 7.94 g of the diketone compound E (HPLC purity 61.2%, isolation yield 19.0%). The melting point of the diketone body E was 264 ° C. The reaction scheme of Example 5 is shown below.

The structure of the diketone body E obtained in Example 5 was ^{identified from various spectra of 1} HNMR, ¹³ CNMR, DEPT, H-HCOSY spectrum, and HMQC.

Furthermore, the molecular weight of the diketone body E was measured by high-resolution mass spectrometry and the DART method. Since the mass number of [M + H] ⁺ (molecular weight M + 1) was 359.20007 (C ₂₅ H ₂₇ O ₂ ), the composition formula of the diketone body E was determined to be C ₂₀ H ₂₆ O ₂ .

Example 6 Ketalization of diketone E In Example 2, 20.0 g of the diketone body A was changed to 3.0 g of the diketone body E, the trimethylol propane was changed from 22.7 g to 3.4 g, and the toluene was changed from 200 g to 33.0 g. Then, the reaction was carried out under the same conditions as in Example 2 except that 0.35 g of toluene sulfonic acid was changed to 0.05 g. The reaction mixture was cooled to room temperature, washed with aqueous sodium hydrogen carbonate and concentrated to obtain 4.9 g of compound F. (HPLC purity 83.5%, isolation yield 82.6%). The melting point of compound F was 285 ° C. The reaction scheme of Example 6 is shown below.

The structure of compound F obtained in Example 6 was ^{identified from various spectra of 1} HNMR, ¹³ CNMR, DEPT method, H-HCOSY spectrum, and HMQC.

Furthermore, the molecular weight of compound F was measured by high-resolution mass spectrometry and the DART method. Since the mass number of [M + H] ⁺ (molecular weight M + 1) was 591.36792 (C ₃₇ H ₅₁ O ₆ ), the composition formula of compound F was determined to be C ₃₇ H ₅₀ O ₆ .

The compounds obtained in Examples 2, 4 and 6 have a spiro ring structure and an aromatic ring, and are refracted while maintaining various performances of conventionally known spiro glycols. It has become possible to improve the rate.
Further, the materials using the compounds obtained in Examples 2, 4 and 6 have made it possible to improve the hardness.

The diol obtained in the present embodiment has a high refractive index and can improve the hardness. Therefore, improvement in physical properties (optical characteristics such as high hardness and refractive index) of various resins (thermoplastic resins) using a diol component as a raw material can be expected. Therefore, the industrial applicability of the present invention is great.

Claims (17)

A diol represented by the following formula (1).
Equation (1)

(In the formula (1), R ¹ and R ² are independently branched with a hydrogen atom, a group containing a hetero atom, a halogen atom, a linear alkyl group having 1 to 6 carbon atoms, and 3 to 6 carbon atoms, respectively. Represents an alkyl group or a group containing an aryl group and having 6 to 12 carbon atoms, and R ³ and R ⁴ are independently a heteroatom-containing group, a halogen atom, and a linear chain having 1 to 6 carbon atoms. Represents an alkyl group, a branched alkyl group having 3 to 6 carbon atoms, or a group containing an aryl group and having 6 to 12 carbon atoms, and W is selected from the groups represented by the formula (2).
Equation (2)

In formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , respectively, are independently hydrogen atoms and linear alkyl groups having 1 to 6 carbon atoms. Represents a group selected from the group consisting of a branched alkyl group having 3 to 6 carbon atoms and a group containing an aryl group and having 6 to 20 carbon atoms. At ^{least one of R 5} and R ⁶ is an aryl group. It is a group containing 6 to 20 carbon atoms. * Is a binding site.) The diol according to claim 1, wherein ^{R 1} and R ² in the formula (1) are hydrogen atoms. ^{According to claim 1 or 2, R 3} and R ⁴ in the formula (1) independently represent a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms. The diol described. The diol according to any one of claims 1 to 3, wherein W in the formula (1) is selected from the groups represented by the formula (22).
Equation (22)

(In formula (22), R ⁵² represents a hydrogen atom, a methyl group or a phenyl group, and R ⁷² , R ⁸² , R ⁹² and R ¹⁰² independently represent a hydrogen atom or a methyl group, and R ¹¹² and R ¹²² independently represents a hydrogen atom or a methyl group. * Is a bond site.) The following diols.

The following diols.

The following diols.

The diketone represented by the following formula (3).
Equation (3)

(In the formula (3), R ¹ and R ² are independently branched with a hydrogen atom, a group containing a hetero atom, a halogen atom, a linear alkyl group having 1 to 6 carbon atoms, and 3 to 6 carbon atoms, respectively. Represents an alkyl group or a group containing an aryl group and having 6 to 12 carbon atoms, and W is selected from the groups represented by the formula (2).
Equation (2)

In formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , respectively, are independently hydrogen atoms and linear alkyl groups having 1 to 6 carbon atoms. Represents a group selected from the group consisting of a branched alkyl group having 3 to 6 carbon atoms and a group containing an aryl group and having 6 to 20 carbon atoms. At ^{least one of R 5} and R ⁶ is an aryl group. It is a group containing 6 to 20 carbon atoms. * Is a binding site.) The diketone according to claim 8, wherein ^{R 1} and R ² in the formula (3) are hydrogen atoms. The diketone according to claim 8 or 9, wherein W in the formula (3) is selected from the groups represented by the formula (22).
Equation (22)

(In formula (22), R ⁵² represents a hydrogen atom, a methyl group or a phenyl group, and R ⁷² , R ⁸² , R ⁹² and R ¹⁰² independently represent a hydrogen atom or a methyl group, and R ¹¹² and R ¹²² independently represents a hydrogen atom or a methyl group. * Is a bond site.) The following diketone.

The following diketone.

The following diketone.

A method for producing a diol, which comprises a dehydration cyclization reaction of a diketone represented by the following formula (3) and a triol represented by the following formula (4).
Equation (3)

(In the formula (3), R ¹ and R ² are independently branched with a hydrogen atom, a group containing a hetero atom, a halogen atom, a linear alkyl group having 1 to 6 carbon atoms, and 3 to 6 carbon atoms, respectively. Represents an alkyl group or a group containing an aryl group and having 6 to 12 carbon atoms, and W is selected from the groups represented by the formula (2).
Equation (2)

In formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , respectively, are independently hydrogen atoms and linear alkyl groups having 1 to 6 carbon atoms. Represents a group selected from the group consisting of a branched alkyl group having 3 to 6 carbon atoms and a group containing an aryl group and having 6 to 20 carbon atoms. At ^{least one of R 5} and R ⁶ is an aryl group. It is a group containing 6 to 20 carbon atoms. * Is a binding site.)
Equation (4)

(In formula (4), R ¹³ represents a hydrocarbon group.) The method for producing a diol according to claim 14, wherein the triol represented by the formula (4) is at least one of trimethylolpropane, trimethylolethane and α, α, α-tris (hydroxymethyl) toluene. The method for producing a diol according to claim 14 or 15, wherein the diol is the diol according to any one of claims 1 to 7. The method for producing a diketone according to any one of claims 8 to 13, which comprises hydrogen-reducing the compound represented by the following formula (5).
Equation (5)

(In the formula (5), R ¹ and R ² are independently branched with a hydrogen atom, a group containing a hetero atom, a halogen atom, a linear alkyl group having 1 to 6 carbon atoms, and 3 to 6 carbon atoms, respectively. Represents an alkyl group or a group containing an aryl group and having 6 to 12 carbon atoms, and W is selected from the groups represented by the formula (2).
Equation (2)

In formula (2), R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , respectively, are independently hydrogen atoms and linear alkyl groups having 1 to 6 carbon atoms. Represents a group selected from the group consisting of a branched alkyl group having 3 to 6 carbon atoms and a group containing an aryl group and having 6 to 20 carbon atoms. At ^{least one of R 5} and R ⁶ is an aryl group. It is a group containing 6 to 20 carbon atoms. * Is a binding site.)