JP5371545B2 - Method for producing naphthalene derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for preparing a naphthalene derivative without any difficult operation. <P>SOLUTION: A compound (II) represented by formula (II) is produced by reducing a compound (I) represented by formula (I) in the presence of a catalyst and hydrogen (in the formulae, at least one of R<SB>7</SB>and R<SB>8</SB>is -Q<SP>1</SP>-CHO, while the remaining R<SB>7</SB>or R<SB>8</SB>and R<SB>1</SB>-R<SB>6</SB>are each independently a hydrogen atom, 1-6C monovalent hydrocarbon group, -Q<SP>2</SP>-OH or -Q<SP>3</SP>-OR'; R<SB>7</SB>' and R<SB>8</SB>' are identical to R<SB>7</SB>and R<SB>8</SB>, respectively, provided that when R<SB>7</SB>is -Q<SP>1</SP>-CHO, R<SB>7</SB>' is -Q<SP>1</SP>-CH<SB>2</SB>OH, and when R<SB>8</SB>is -Q<SP>1</SP>-CHO, R<SB>8</SB>' is -Q<SP>1</SP>-CH<SB>2</SB>OH; Q<SP>1</SP>-Q<SP>3</SP>are each independently a single bond or 1-6C bivalent hydrocarbon group; and R' is a 1-6C monovalent hydrocarbon group). <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

The present invention relates to a method for producing a naphthalene derivative having —CH ₂ OH as a substituent.

The method for producing a naphthalene derivative having a -CH 2 _OH substituent, the following Patent Document 1, 6-hydroxy-2-naphthalene carboxylic acid, and reduced with boranes, manufacturing intermediate member such as pharmaceutical and agricultural chemicals A process for producing 6-hydroxy-2-naphthalenemethanol useful as
Non-Patent Document 1 below describes a method for producing 6-hydroxy-2-naphthalenemethanol by reducing 6-hydroxy-2-naphthylaldehyde with lithium aluminum hydride.

International Publication No. 00/73252 Pamphlet

Tetrahedron, 2001, 57, p. 7349-7359

  However, both of the methods described in Patent Document 1 and Non-Patent Document 1 are difficult to handle because of the high cost of the reducing agent and are difficult to say as industrially easy production methods.

The present invention has been made in consideration of the above situation, and an object thereof is to allow a naphthalene derivative having a -CH 2 _OH substituent, can be prepared in a simple manner without the difficult operation.

In order to solve the above-mentioned problems, a first aspect of the present invention is to reduce a compound (I) represented by the following general formula (I) in the following general formula (II) in the presence of a catalyst and hydrogen. A compound characterized in that the compound (II) is produced , wherein the catalyst includes a metal catalyst composed of palladium or a supported catalyst in which palladium is supported on a support, and the reaction temperature during the reduction is 0 It is a manufacturing method of the naphthalene derivative which is more than 50 degreeC.

(Wherein at least one of R ₇ and R ₈ represents ^-Q 1 -CHO, is not an ^-Q 1 -CHO of the R ₇ and R _8, and _R 1 to R ₆ are each independently, Represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, —Q ² —OH, or —Q ³ —OR ′, wherein Q ¹ represents a single bond, and Q ² and Q ³ are independent of each other. Represents a single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms, and R ′ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms.)

_(Wherein, R 1 to R ₆ are respectively the same as _R 1 to R ₆ in formula _{(I), R 7 ',} R 8' are respectively the same as _R 7, _{R 8} in formula (I) Provided that when R ₇ is —Q ¹ —CHO, R ₇ ′ represents —Q ¹ —CH ₂ OH, and when R ₈ is —Q ¹ —CHO, R ₈ ′ represents —Q ¹ —CH _2. Represents OH, Q ¹ is the same as Q ¹ in formula (I).

The second aspect of the present invention is a method for producing a naphthalene derivative, wherein the reaction temperature in the first aspect is 0 ° C. or higher and 40 ° C. or lower .
In the third aspect of the present invention, the hydrogen pressure in the reaction system when performing the reduction in the first or second aspect is in the range of 1.0 × 10 ⁴ Pa to 5.0 × 10 ⁵ Pa. A method for producing a naphthalene derivative.

According to the present invention, a naphthalene derivative represented by the above formula (II), that is, a naphthalene derivative having —CH ₂ OH as a substituent can be produced by an easy method without any difficult operation.

In the production method of the present invention, the compound (I) represented by the general formula (I) is reduced in the presence of a catalyst and hydrogen to obtain the compound (II) represented by the general formula (II) ( Hereinafter, it may be referred to as a reduction step).
[Compound (I)]
In the general formula (I), at least one of R ₇ and R ₈ represents —Q ¹ —CHO, and Q ¹ represents a single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms.
The C 1-6 divalent hydrocarbon group as the linking group Q ¹ may be linear or branched, and may be saturated or unsaturated. The hydrocarbon group may have a heteroatom such as oxygen, sulfur, or nitrogen in the middle of the carbon chain or at the end of the branched chain.

In General Formula (I), R ₇ and R ₈ that are not —Q ¹ —CHO and R _{1 to} R ₆ are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, — Q ² —OH or —Q ³ —OR ′ is represented.
The monovalent hydrocarbon group having 1 to 6 carbon atoms as R _{1 to} R ₈ may be linear or branched, and may be saturated or unsaturated. The hydrocarbon group may have a heteroatom such as oxygen, sulfur, or nitrogen in the middle or at the end of the carbon chain.
Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert -Pentyl group, neopentyl group, n-hexyl group, isohexyl group and the like.

The linking groups Q ² and Q ³ are the same as Q ¹ . When two or more selected from Q ^{1 to} Q ³ are present in one molecule, they may be the same as or different from each other.
R ′ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms. The hydrocarbon group as R ′ may be linear or branched and may be saturated or unsaturated. The hydrocarbon group may have a heteroatom such as oxygen, sulfur, or nitrogen in the middle or at the end of the carbon chain.
Specific examples of the hydrocarbon group as R ′ are the same as the specific examples of the hydrocarbon group as R _{1 to} R ₈ .

[Compound (II)]
In the general formula (II), R _{1 to} R ₆ are the same as R _{1 to} R ₆ in the formula (I), respectively.
In formula (I), when R ₇ is —Q ¹ —CHO, R ₇ ′ in formula (II) is —Q ¹ —CH ₂ OH, and Q ¹ is the same as Q ¹ in formula (I). It is. When R ₇ is not -Q ¹ -CHO, R ₇ ′ is the same as R ₇ in formula (I).
Similarly, when R ₈ is —Q ¹ —CHO, R ₈ ′ is —Q ¹ —CH ₂ OH, and Q ¹ is the same as Q ¹ in formula (I). When R ₈ is not -Q ¹ -CHO, R ₈ ′ is the same as R ₈ in formula (I).
Specific examples of the compound (II) include 2-hydroxy-6-naphthalenemethanol, which is useful as an intermediate for the monomer constituting the photoresist polymer compound.

[catalyst]
The catalyst used in the reduction step is preferably a metal catalyst containing a metal selected from the group consisting of nickel, palladium, platinum, ruthenium and cobalt. There may be one kind of metal or two or more kinds of metals. In particular, it is preferable to contain palladium in that a high yield is easily obtained.
As the metal catalyst, a metal may be used as it is, or a supported catalyst in which a metal is supported on a carrier can be used. Although it does not specifically limit as a support | carrier, For example, activated carbon, a silica, an alumina etc. are mentioned.
One type of catalyst may be used, or two or more types may be used in combination.
The addition amount of the catalyst is not particularly limited, but from the viewpoint of economy, reaction rate, and product selectivity, the amount of metal contained in the catalyst is 0.01 mass relative to the amount of compound (I) used as the reaction substrate. It is preferable that it is% -10 mass%, and 0.05 mass%-5 mass% are more preferable.
In the reduction step, the entire amount of the catalyst used may be added all at once or in several portions.

[solvent]
In the reduction step, a solvent may be appropriately used. Examples of the solvent include alcohols having 1 to 4 carbon atoms such as methanol, ethanol and 2-propanol; ethers having 4 to 6 carbon atoms such as 1,4-dioxane and tetrahydrofuran; 1 to 1 carbon atoms such as acetic acid and formic acid. 3 carboxylic acids; or water or the like. These may be used alone or in combination of two or more.

[Cocatalyst]
In the reduction step, a promoter may be added. The selectivity can be improved by adding a cocatalyst. As the promoter, for example, lead, cadmium, antimony, bismuth, zinc, iron, lead, copper, tin or the like is used. These may be used alone or in combination of two or more. Although the addition amount of a co-catalyst is not specifically limited, 0.1-50 mass% of the metal amount in the catalyst used is preferable.

[Reaction conditions]
The reaction temperature in the reduction step refers to a reaction substrate (compound (I)), a catalyst, and, if necessary, a co-catalyst, a solvent, etc. added to a reaction solution to make a reaction solution, and then coexist with hydrogen. Indicates the temperature of the reaction solution when consuming. Although reaction temperature receives restrictions, such as the boiling point of the solvent to be used, the inside of the range of 0-150 degreeC is preferable from a viewpoint of operativity and economical efficiency. Furthermore, when the reaction rate and product selectivity are taken into consideration, the range of 20 to 100 ° C. is preferable. When the reaction temperature is 20 ° C. or higher, the reaction rate is moderately high and the remaining raw materials are suppressed. It is preferable that the remaining of the raw material is small because a load such as removal purification in a subsequent process is reduced. When the reaction temperature exceeds 100 ° C., in the produced compound (II), particularly when Q ¹ of —Q ¹ —CHO in R ₇ or R ₈ of compound (I) is a single bond, the hydroxyl group at the benzyl position is reduced. The selectivity may be greatly reduced.
The reaction temperature may be constant from the start to the end of the reduction step, or may be changed stepwise.

The reaction time in the reduction step is not particularly limited, but if it is too short, the yield will be low. On the other hand, if the reaction time becomes longer than necessary, the hydroxyl group at the benzyl position in the produced compound (II), particularly when Q ¹ of —Q ¹ —CHO in R ₇ or R ₈ of compound (I) is a single bond, May be gradually reduced over time, and the selectivity may be greatly reduced. Therefore, the reaction time is preferably 0.1 hour to 50 hours, more preferably 1 hour to 30 hours.

Hydrogen is present in the reaction system in the reduction step. The gas present in the reaction system is preferably composed of only hydrogen gas or a mixed gas of hydrogen gas and an inert gas other than hydrogen. For example, nitrogen gas can be used as the inert gas.
The method for supplying hydrogen gas or mixed gas to the reaction system is not particularly limited as long as the reaction substrate can come into contact with hydrogen. For example, it may be blown into the reaction solution, may be circulated to the gas phase portion in the reaction system, or may be intermittently supplied to the gas phase portion.

The hydrogen pressure in the reaction system is preferably in the range of 1.0 × 10 ⁴ Pa to 5.0 × 10 ⁵ Pa at the temperature of the gas in the reaction system.
In the present invention, the hydrogen pressure in the reaction system is the pressure of the gas in the reaction system when the gas existing in the reaction system is only hydrogen gas, and the mixed gas in the case of a mixed gas. Refers to the hydrogen partial pressure in the gas.
If the hydrogen pressure in the reaction system is too low, a sufficient reaction rate cannot be obtained. If it is too high, the reduction reaction is excessively promoted, and in particular, when Q ¹ of —Q ¹ —CHO in R ₇ or R ₈ of Compound (I) is a single bond, the hydroxyl group at the benzyl position in the produced Compound (II) is further increased. There is a possibility that the selectivity of the target product is greatly reduced due to reduction.
A more preferable range of the hydrogen pressure in the reaction system is a range of 2.0 × 10 ⁴ Pa to 4.0 × 10 ⁵ Pa, and a more preferable range is 3.0 × 10 ⁴ Pa to 3.0 × 10 ⁵ Pa. It is a range.

[Post-processing]
As post-treatment after the reduction reaction, the catalyst and, if necessary, the co-catalyst are solid-liquid separated by operations such as filtration, centrifugation, and precipitation separation, and then the reaction is generated by means such as distilling off the solvent. Product can be isolated. Thereafter, it can be purified by a known method such as recrystallization or distillation.

  According to the method of the present invention, since it is not necessary to use a reducing agent that is difficult to handle, the target product can be produced by an easy method that does not involve difficult operations. In addition, as shown in Examples described later, high yield and high selectivity can be achieved.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In the following, “%” is “% by mass” unless otherwise specified.

  The analysis of the reaction solution was performed by the following method. First, a mixed solution of acetonitrile and water (acetonitrile: water mixed volume ratio = 1: 1) was prepared as a dilution solvent. Next, the reaction solution was sampled, and a 10-fold amount of the dilution solvent was added thereto to obtain a dilution solution. Subsequently, the diluted solution was filtered through a membrane filter to remove the catalyst, and then analyzed by high performance liquid chromatography (HPLC). A differential refraction detector (RI detector) was used as a detector.

Example 1
A palladium / activated carbon supported catalyst having a water content of 50% was prepared by adding the same mass of water to a supported catalyst (palladium content 5%, manufactured by Wako Pure Chemical Industries, Ltd.) having palladium supported on activated carbon.
Prepared in an eggplant flask at room temperature (20 ° C.), 50.0 g of methanol as a solvent, 5.0 g (29.1 mmol) of 2-hydroxy-6-naphthaldehyde (manufactured by Aldrich) as a reaction substrate, and the above 0.25 g of the palladium / activated carbon supported catalyst (water content 50%) was added. Then, after reducing the pressure in the flask, the operation of replacing the gas in the flask with nitrogen was repeated three times. Furthermore, the operation of substituting the gas in the flask with hydrogen in the same procedure was performed three times. The hydrogen pressure in the flask at that time was 1.0 × 10 ⁵ Pa.
Then, it heated up until the liquid temperature became 40 degreeC which is reaction temperature, stirring the liquid in a flask. Subsequently, the liquid temperature was kept at 40 ° C., and stirring was continued. After 4 hours, the mixture was cooled to room temperature, and the gas in the flask was replaced with nitrogen to obtain a reaction liquid. A pressure filtration using Celite was performed to remove the catalyst from the reaction solution, and the solvent was distilled off from the obtained filtrate under reduced pressure to obtain 5.80 g of a reaction product.
When the reaction solution was analyzed by the above method, the reaction product contained 2-hydroxy-6-naphthalenemethanol (represented by the following formula (III)), which was the target product. It was confirmed that the yield was 91%, purity was 84% (HPLC area percentage), and the content of the by-product represented by the following formula (IV) (hereinafter referred to as by-product (IV)) was 6% (HPLC area percentage). It was done.

( Reference Example 2)
In Example 1, the same operation as in Example 1 was performed except that the reaction temperature was changed to 50 ° C.
As a result, 4.80 g of a solid containing 2-hydroxy-6-naphthalenemethanol, the target product, was obtained. As a result of the analysis, the yield was 73%, purity was 78% (HPLC area percentage), and by-product (IV) was 20% (HPLC area percentage).
In this example, since the reaction temperature was higher than in Example 1, the product was further reduced to produce more by-products, and as a result, the purity of the target product was lower than that in Example 1.

(Example 3)
First, in Example 1, the solvent was changed to 1,4-dioxane 60.0 g, the addition amount of 2-hydroxy-6-naphthaldehyde was changed to 2.50 g (14.5 mmol), and the palladium / activated carbon supported catalyst. The reaction was conducted for 4 hours at 40 ° C. in the same manner as in Example 1 except that the amount of addition was changed to 0.10 g, and then cooled to room temperature until the gas in the flask was replaced with nitrogen. It was.
Subsequently, 0.24 g of the same palladium / activated carbon supported catalyst as described above was added and reacted at 40 ° C. for 4 hours, and then 0.22 g of palladium / activated carbon supported catalyst was added and reacted at 60 ° C. for 3 hours. It was. When the catalyst was added, nitrogen substitution and hydrogen substitution after addition of the catalyst were performed before the addition of the catalyst (same as in Example 1).
From the obtained reaction solution, the catalyst was removed in the same manner as in Example 1, and further the solvent was distilled off.
2.52 g of a solid containing 2-hydroxy-6-naphthalenemethanol was obtained. As a result of the analysis, the yield was 95%, the purity was 93% (HPLC area percentage), and the by-product (IV) was 2% (HPLC area percentage).

Claims (3)

The following general formula (I)

(Wherein at least one of R ₇ and R ₈ represents ^-Q 1 -CHO, is not an ^-Q 1 -CHO of the R ₇ and R _8, and _R 1 to R ₆ are each independently, Represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, —Q ² —OH, or —Q ³ —OR ′, wherein Q ¹ represents a single bond, and Q ² and Q ³ are independent of each other. Represents a single bond or a divalent hydrocarbon group having 1 to 6 carbon atoms, and R ′ represents a monovalent hydrocarbon group having 1 to 6 carbon atoms.)
The compound (I) represented by the following general formula (II) is reduced by reduction in the presence of a catalyst and hydrogen:

_(Wherein, R 1 to R ₆ are respectively the same as _R 1 to R ₆ in formula _{(I), R 7 ',} R 8' are respectively the same as _R 7, _{R 8} in formula (I) Provided that when R ₇ is —Q ¹ —CHO, R ₇ ′ represents —Q ¹ —CH ₂ OH, and when R ₈ is —Q ¹ —CHO, R ₈ ′ represents —Q ¹ —CH _2. Represents OH, Q ¹ is the same as Q ¹ in formula (I).
A compound (II) represented by the formula:
The catalyst comprises a metal catalyst comprising palladium or a supported catalyst in which palladium is supported on a carrier;
A method for producing a naphthalene derivative, wherein a reaction temperature during the reduction is 0 ° C or higher and lower than 50 ° C.   The method for producing a naphthalene derivative according to claim 1, wherein the reaction temperature during the reduction is 0 ° C or higher and 40 ° C or lower. The manufacturing method of the naphthalene derivative of Claim 1 or 2 whose hydrogen pressure in the reaction system at the time of the said reduction | restoration is the range of 1.0 * 10 < ⁴ > Pa-5.0 * 10 < ⁵ > Pa.