JP5026739B2 - Process for producing β-naphthols - Google Patents

Description

  In the present invention, by dehydrogenating a 2-tetralone compound, the corresponding β-naphthols (hereinafter referred to as “2-naphthol compound” in the present specification without being influenced by by-produced hydrogen). This is related to a method of selectively manufacturing.

  Conventionally, as one method for producing a 2-naphthol compound, a method for dehydrogenating a 2-tetralone compound is known, and in particular, a method using a noble metal catalyst such as palladium carbon as a dehydrogenating agent is simple and useful. It is used as a method (see Non-Patent Document 1). However, in these methods, the 2-tetralone compound as a raw material becomes an undesired by-product such as a naphthalene compound due to the action of the noble metal catalyst used and the hydrogen generated in the system as the reaction proceeds. As a result, it was also known that the 2-naphthol compound, which is the target product, could not be obtained with good yield. In addition, when the 2-tetralone compound as a raw material has a substituent that can be reduced by hydrogen in the presence of the noble metal catalyst used, the target product yield can be easily reduced for the same reason. Predictable. In addition, a method is known in which reaction conditions are moderated by allowing a compound such as maleic acid to coexist in the reaction system (see Non-Patent Document 2). There is no description or suggestion of what compounds are effective in order to avoid the disadvantages caused by the action of hydrogen generated in the system.

Journal of Organic Chemistry, 63, 4140 (1998) "New Experimental Chemistry Course", Volume 15 [I-2], pp. 1088-1093, September 30, 1951, published by Maruzen Co., Ltd.

  The corresponding 2-naphthol compound is easily and efficiently produced from the 2-tetralone compound without causing a serious side reaction such as elimination of a substituent by the dehydrogenation reaction that solves the above-mentioned drawbacks of the prior art. A method was desired.

  In view of the above situation, the present inventors have conducted extensive research on a method for easily and efficiently producing a naphthol compound, and as a result, surprisingly, a palladium catalyst and an olefin compound that can react with by-produced hydrogen. The present inventors have found that the above-mentioned problems can be solved by dehydrogenating a 2-tetralone compound in the presence of, and that a 2-naphthol compound can be easily and efficiently produced, and the present invention has been completed based on this finding.

  The method of the present invention provides a method for easily and efficiently producing a 2-naphthol compound. According to the method of the present invention, an undesirable by-product such as a naphthalene compound is produced by dehydrogenating a 2-tetralone compound in the presence of a palladium catalyst and an olefin compound that can react with by-produced hydrogen. The target 2-naphthol compound can be efficiently produced with high selectivity and simple operation under mild conditions without using a special reaction apparatus.

  Hereinafter, the present invention will be described in detail.

  This invention solves the said subject by providing invention of the following [1] thru | or [6].

[1] General formula (1)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a fluorine atom, an alkyl group, a cyclic alkyl group, a trialkylsilyl group, a hydroxy group) , Alkoxy group, trialkylsiloxy group, hydroxyalkyl group, alkoxyalkyl group, alkylcarbonyl group, arylcarbonyl group which may have a substituent, heteroarylcarbonyl group which may have a substituent, carboxyl A group or a metal salt thereof, an alkoxycarbonyl group, an aryloxycarbonyl group which may have a substituent, a heteroaryloxycarbonyl group which may have a substituent, an aryl group which may have a substituent, An aryloxy group which may have a substituent, a heteroaryloxy group which may have a substituent, or a substituent. Shows a heteroaryl group, also ^{R 1, R 2, R 3} , R 4, R 5, may form a fused ring as a whole by any two of ^{R 6} and ^{R 7} binds.)

In represented by 2-tetralone compound, a palladium catalyst and, general formula (2) or general formula (3)

(In the formula, R ⁸ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁹ has 1 to 12 carbon atoms which may have a substituent. R represents an alkyl group or an aryl group which may have a substituent, and R ¹⁰ and R ¹¹ each independently represents a trifluoromethyl group, an acyl group, an aryl group which may have a substituent, or a substituent. A heteroaryl group, an alkylsulfonyl group, an arylsulfonyl group, a heteroarylsulfonyl group, an alkylsulfonyloxy group, an arylsulfonyl group, a heteroarylsulfonyl group, or a monovalent group (A)

(In the formula, R ¹⁴ represents an alkyl group having 1 to 12 carbon atoms which may have a substituent or an aryl group which may have a substituent.)

N represents an integer of 0 to 3. )

In olefin compound represented, and characterized in that it is at least one kind of the presence dehydrogenation selected from isophorone, formula (4)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently have the same meaning as in general formula (1).)

The manufacturing method of 2-naphthol compound represented by these.

[2] The 2-naphthol compound according to [1], wherein the palladium catalyst is a heterogeneous catalyst supported on at least one carrier selected from carbon, alumina, barium sulfate, calcium carbonate, hydroxyapatite, and hydrotalcite. Production method.

[3] The method for producing a 2-naphthol compound according to [1] or [2], wherein the palladium catalyst is palladium carbon.

[4] The method for producing a 2-naphthol compound according to any one of [1] to [3] , wherein the dehydrogenation is performed in the presence of at least one selected from maleic acid diester, fumaric acid diester, and isophorone. .

[5] The 2-naphthol compound according to any one of [1] to [4], wherein R ₁ , R ₂ and R _{3 of the 2} -tetralone compound represented by the general formula (1) are all hydrogen. Manufacturing method.

[6] 2 in any one of [1] to [5], wherein the 2-tetralone compound represented by the general formula (1) is 2-tetralone or 7,8-difluoro-2-tetralone. -Manufacturing method of a naphthol compound.

  Hereinafter, the present invention will be described in detail.

  In the method of the present invention, the 2-tetralone compound represented by the general formula (1) can react with the noble metal catalyst and hydrogen produced as a by-product, and the coexistence represented by the general formula (2) or the general formula (3). A method for producing a 2-naphthol compound represented by the general formula (4), wherein the dehydrogenation is performed in the presence of the compound.

  First, the 2-tetralone compound (raw material compound) represented by the general formula (1) or used as a raw material of the method of the present invention will be described.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ in the general formula (1) are each independently
Hydrogen atom;

Fluorine atom;

For example, straight or branched carbon number such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc. 1 to 6 (Hereinafter, in the present specification, for example, in the case of 1 to 6 carbon atoms, this is abbreviated as “C1 to C6”.) C1 to C6 alkyl group (the alkyl group is Cyclic C1-C6 alkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group; for example, tri (straight or branched C1-C6 alkyl) silyl group such as trimethylsilyl group, t-butyldimethylsilyl group, etc. A tri (linear or branched C1-C6 alkyl) silyloxy group such as, for example, a trimethylsilyloxy group or a t-butyldimethylsilyloxy group; Linear or branched C1-C6 alkylamino group such as mino group, ethylamino group, dimethylamino group; for example, linear or branched C1-C6 alkylcarbonylamino group such as methylcarbonylamino group, ethylcarbonylamino group; For example, a linear or branched C1-C6 alkylcarbonyl group such as a methylcarbonyl group or an ethylcarbonyl group; a carboxyl group or a metal salt thereof; for example, a linear or branched C1-C6 alkoxy such as a methoxycarbonyl group or an ethoxycarbonyl group Carbonyl group; aminocarbonyl group; linear or branched C1-C6 alkylaminocarbonyl group such as methylaminocarbonyl group, ethylaminocarbonyl group and dimethylaminocarbonyl group; aryl group such as phenyl group and naphthyl group; phenoxy group , Naphthyloxy group, etc. Aryloxy group; a pyridyl group, a thienyl group, which may have a substituent such as a heteroaryl group such as furanyl group).;

An aryl group such as a phenyl group or a naphthyl group (the aryl group is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, or an n-pentyl group) Linear or branched C1-C6 alkyl group such as n-hexyl group; cyclic C1-C6 alkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group; for example, trimethylsilyl group, t-butyldimethylsilyl A tri (linear or branched C1-C6 alkyl) silyl group such as a group; a hydroxy group; for example, a linear or branched C1-C6 alkoxy group such as a methoxy group, ethoxy group, n-propoxy group, isopropoxy group; For example, tri (linear or branched C1-C6 alkyl) such as trimethylsilyloxy group, t-butyldimethylsilyloxy group, etc. Silyloxy group; for example, linear or branched C1-C6 hydroxyalkyl group such as hydroxymethyl group, hydroxyethyl group; for example, linear or branched (C1-C6) such as methoxymethyl group, methoxyethyl group, ethoxyethyl group Alkoxy)-(C1-C6 alkyl) group; for example, linear or branched C1-C6 haloalkyl group such as fluoromethyl group, difluoromethyl group, trifluoromethyl group; for example, methylamino group, ethylamino group, dimethylamino A linear or branched C1-C6 alkylamino group such as a group; for example, a linear or branched C1-C6 alkylcarbonylamino group such as a methylcarbonylamino group or an ethylcarbonylamino group; for example, a methylcarbonyl group or an ethylcarbonyl group Linear or branched C1-C6 alkylcarbonyl groups such as Xyl group or metal salt thereof; for example, linear or branched C1-C6 alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group; aminocarbonyl group; for example, methylaminocarbonyl group, ethylaminocarbonyl group, dimethylaminocarbonyl group Linear or branched C1-C6 alkylaminocarbonyl groups such as: aryl groups such as phenyl groups and naphthyl groups; aryloxy groups such as phenoxy groups and naphthyloxy groups; heteroaryl groups such as pyridyl groups, thienyl groups and furanyl groups And may have a substituent such as

For example, a heteroaryl group such as pyridyl group, thienyl group, furanyl group (the heteroaryl group is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, Linear or branched C1-C6 alkyl group such as butyl group, n-pentyl group, n-hexyl group; cyclic C1-C6 alkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group; A tri (straight or branched C1-C6 alkyl) silyl group such as a t-butyldimethylsilyl group; a hydroxy group; for example, a straight chain or a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, or the like Branched C1-C6 alkoxy group; for example, tri (trimethylsilyloxy group, t-butyldimethylsilyloxy group, etc. Linear or branched C1-C6 alkyl) silyloxy group; for example, a linear or branched C1-C6 hydroxyalkyl group such as hydroxymethyl group, hydroxyethyl group; for example, a methoxymethyl group, methoxyethyl group, ethoxyethyl group, etc. A linear or branched (C1-C6 alkoxy)-(C1-C6 alkyl) group; for example, a linear or branched C1-C6 haloalkyl group such as a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group; Linear or branched C1-C6 alkylamino group such as amino group, ethylamino group, dimethylamino group; for example, linear or branched C1-C6 alkylcarbonylamino group such as methylcarbonylamino group, ethylcarbonylamino group; For example, linear or branched C1 such as methylcarbonyl group and ethylcarbonyl group C6 alkylcarbonyl group; carboxyl group or metal salt thereof; linear or branched C1-C6 alkoxycarbonyl group such as methoxycarbonyl group or ethoxycarbonyl group; aminocarbonyl group; for example, methylaminocarbonyl group, ethylaminocarbonyl group Linear or branched C1-C6 alkylaminocarbonyl group such as dimethylaminocarbonyl group; aryl group such as phenyl group and naphthyl group; aryloxy group such as phenoxy group and naphthyloxy group; pyridyl group, thienyl group and furanyl group May have a substituent such as a heteroaryl group, etc.);

An aryloxy group in which the aryl moiety has the above-mentioned meaning, such as a phenoxy group, a naphthyloxy group (the aryloxy group is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl A linear or branched C1-C6 alkyl group such as a group, t-butyl group, n-pentyl group, n-hexyl group; a cyclic C1-C6 alkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group A tri (linear or branched C1-C6 alkyl) silyl group such as a trimethylsilyl group or a t-butyldimethylsilyl group; a hydroxy group; such as a methoxy group, an ethoxy group, an n-propoxy group or an isopropoxy group; A linear or branched C1-C6 alkoxy group; for example, a trimethylsilyloxy group, t-butyldimethylsilyl Tri (linear or branched C1-C6 alkyl) silyloxy group such as a loxy group; for example, a linear or branched C1-C6 hydroxyalkyl group such as a hydroxymethyl group or a hydroxyethyl group; for example, a methoxymethyl group, methoxyethyl A straight chain or branched (C1-C6 alkoxy)-(C1-C6 alkyl) group such as a group or ethoxyethyl group; for example, a straight chain or branched C1 such as a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group C6 haloalkyl group; linear or branched C1-C6 alkylamino group such as methylamino group, ethylamino group, dimethylamino group; linear or branched C1 such as methylcarbonylamino group and ethylcarbonylamino group -C6 alkylcarbonylamino group; for example, methylcarbonyl group, ethylcarbonyl group, etc. A linear or branched C1-C6 alkylcarbonyl group; a carboxyl group or a metal salt thereof; for example, a linear or branched C1-C6 alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group; an aminocarbonyl group; Linear or branched C1-C6 alkylaminocarbonyl groups such as carbonyl group, ethylaminocarbonyl group, dimethylaminocarbonyl group; aryl groups such as phenyl group and naphthyl group; aryloxy groups such as phenoxy group and naphthyloxy group; pyridyl A substituent such as a heteroaryl group such as a group, thienyl group, furanyl group, etc.);

A heteroaryloxy group having a heteroaryl moiety as defined above, such as a 2-pyridyloxy group, a 2-thienyloxy group, or a 2-furyloxy group. Linear or branched C1-C6 alkyl group such as propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group; cyclopropyl group, cyclobutyl group, Cyclic C1-C6 alkyl group such as cyclopentyl group and cyclohexyl group; for example, tri (linear or branched C1-C6 alkyl) silyl group such as trimethylsilyl group and t-butyldimethylsilyl group; hydroxy group; Linear or branched C1-C6 alkoxy groups such as ethoxy group, n-propoxy group, isopropoxy group; For example, tri (linear or branched C1-C6 alkyl) silyloxy group such as trimethylsilyloxy group, t-butyldimethylsilyloxy group; for example, linear or branched C1-C6 such as hydroxymethyl group, hydroxyethyl group, etc. Hydroxyalkyl group; for example, linear or branched (C1-C6 alkoxy)-(C1-C6 alkyl) group such as methoxymethyl group, methoxyethyl group, ethoxyethyl group; for example, fluoromethyl group, difluoromethyl group, tri Linear or branched C1-C6 haloalkyl group such as fluoromethyl group; for example, linear or branched C1-C6 alkylamino group such as methylamino group, ethylamino group, dimethylamino group; for example, methylcarbonylamino group, Linear or branched C1-C6 alkylcarbonylamino group such as ethylcarbonylamino group For example, a linear or branched C1-C6 alkylcarbonyl group such as a methylcarbonyl group or an ethylcarbonyl group; a carboxyl group or a metal salt thereof; for example, a linear or branched C1-C6 alkoxy such as a methoxycarbonyl group or an ethoxycarbonyl group Carbonyl group; aminocarbonyl group; linear or branched C1-C6 alkylaminocarbonyl group such as methylaminocarbonyl group, ethylaminocarbonyl group and dimethylaminocarbonyl group; aryl group such as phenyl group and naphthyl group; phenoxy group An aryloxy group such as a naphthyloxy group; it may have a substituent such as a heteroaryl group such as a pyridyl group, a thienyl group or a furanyl group);

C3-C6 cyclic alkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group (the cyclic alkyl group is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec Linear or branched C1-C6 alkyl group such as -butyl group, t-butyl group, n-pentyl group, n-hexyl group; cyclic C1-C6 such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group Alkyl group; for example, tri (linear or branched C1-C6 alkyl) silyl group such as trimethylsilyl group, t-butyldimethylsilyl group; hydroxy group; for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group Linear or branched C1-C6 alkoxy groups such as trimethylsilyloxy group, t-butyl Tri (linear or branched C1-C6 alkyl) silyloxy group such as rudimethylsilyloxy group; for example, linear or branched C1-C6 hydroxyalkyl group such as hydroxymethyl group, hydroxyethyl group; for example, methoxymethyl group A linear or branched (C1-C6 alkoxy)-(C1-C6 alkyl) group such as a methoxyethyl group or an ethoxyethyl group; for example, a linear or branched group such as a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group Branched C1-C6 haloalkyl group; for example, linear or branched C1-C6 alkylamino group such as methylamino group, ethylamino group, dimethylamino group; for example, linear chain such as methylcarbonylamino group, ethylcarbonylamino group Or branched C1-C6 alkylcarbonylamino group; for example, methylcarbonyl group, ethyl A linear or branched C1-C6 alkylcarbonyl group such as a sulfonyl group; a carboxyl group or a metal salt thereof; for example, a linear or branched C1-C6 alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group; an aminocarbonyl group; For example, a linear or branched C1-C6 alkylaminocarbonyl group such as a methylaminocarbonyl group, an ethylaminocarbonyl group, or a dimethylaminocarbonyl group; an aryl group such as a phenyl group or a naphthyl group; an aryl such as a phenoxy group or a naphthyloxy group An oxy group; may have a substituent such as a heteroaryl group such as a pyridyl group, a thienyl group, or a furanyl group);

For example, a tri (C1-C6 alkyl) silyl group in which the alkyl portion has the above-mentioned meaning, such as a trimethylsilyl group and a t-butyldimethylsilyl group;

A hydroxy group;

A carboxyl group or a metal salt thereof;

For example, a C1-C6 alkoxy group in which the alkyl moiety has the above-mentioned meaning, such as a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group;

For example, a C2-C7 alkoxycarbonyl group in which an alkoxy moiety has the above-mentioned meaning, such as a methoxycarbonyl group or an ethoxycarbonyl group;

For example, an aryloxycarbonyl group in which the aryloxy moiety has the above-mentioned meaning, such as a phenoxycarbonyl group and a naphthyloxycarbonyl group;

For example, a heteroaryloxycarbonyl group in which the heteroaryloxy moiety has the above-mentioned meaning, such as 2-pyridyloxycarbonyl group, 2-thienyloxycarbonyl group, 2-furyloxycarbonyl group;

For example, a tri (C1-C6 alkyl) silyloxy group in which the alkyl moiety has the above-mentioned meaning, such as a trimethylsilyloxy group and a t-butyldimethylsilyloxy group;

For example, a C1-C6 hydroxyalkyl group in which the alkyl moiety has the above-mentioned meaning, such as a hydroxymethyl group, a hydroxyethyl group;

For example, an alkyl moiety such as a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group, an alkoxy moiety has the above meaning (C1-C6 alkoxy)-(C1-C6 alkyl) group;

For example, a C1-C7 alkylcarbonyl group in which the alkyl portion has the above-mentioned meaning, such as a methylcarbonyl group, an ethylcarbonyl group;

For example, an arylcarbonyl group in which the aryl moiety has the above-mentioned meaning, such as a phenylcarbonyl group or a naphthylcarbonyl group;

For example, a heteroarylcarbonyl group in which the heteroaryl moiety has the above-mentioned meaning, such as a 2-pyridylcarbonyl group, a 2-thienylcarbonyl group, and a 2-furanylcarbonyl group;

Indicates.

As the 2-tetralone compound (raw material compound) represented by the general formula (1) that can be used in this reaction, specifically, for example,
2-tetralone, 5-fluoro-2-tetralone, 6-fluoro-2-tetralone, 7-fluoro-2-tetralone, 8-fluoro-2-tetralone, 5,6-difluoro-2-tetralone, 5,7- Difluoro-2-tetralone, 5,8-difluoro-2-tetralone, 6,7-difluoro-2-tetralone, 6,8-difluoro-2-tetralone, 7,8-difluoro-2-tetralone,

1-methyl-2-tetralone, 3-methyl-2-tetralone, 4-methyl-2-tetralone, 5-methyl-2-tetralone, 6-methyl-2-tetralone, 7-methyl-2-tetralone, 8- Methyl-2-tetralone, 1-ethyl-2-tetralone, 3-ethyl-2-tetralone, 4-ethyl-2-tetralone, 5-ethyl-2-tetralone, 6-ethyl-2-tetralone, 7-ethyl- 2-tetralone, 8-ethyl-2-tetralone,

1-cyclopropyl-2-tetralone, 3-cyclopropyl-2-tetralone, 4-cyclopropyl-2-tetralone, 5-cyclopropyl-2-tetralone, 6-cyclopropyl-2-tetralone, 7-cyclopropyl- 2-tetralone, 8-cyclopropyl-2-tetralone,

1-trimethylsilyl-2-tetralone, 3-trimethylsilyl-2-tetralone, 4-trimethylsilyl-2-tetralone, 5-trimethylsilyl-2-tetralone, 6-trimethylsilyl-2-tetralone, 7-trimethylsilyl-2-tetralone, 8- Trimethylsilyl-2-tetralone, 1-t-butyldimethylsilyl-2-tetralone, 3-t-butyldimethylsilyl-2-tetralone, 4-t-butyldimethylsilyl-2-tetralone, 5-t-butyldimethylsilyl- 2-tetralone, 6-t-butyldimethylsilyl-2-tetralone, 7-t-butyldimethylsilyl-2-tetralone, 8-t-butyldimethylsilyl-2-tetralone,

5-hydroxy-2-tetralone, 6-hydroxy-2-tetralone, 7-hydroxy-2-tetralone, 8-hydroxy-2-tetralone,

5-methoxy-2-tetralone, 6-methoxy-2-tetralone, 7-methoxy-2-tetralone, 8-methoxy-2-tetralone, 5-ethoxy-2-tetralone, 6-ethoxy-2-tetralone, 7- Ethoxy-2-tetralone, 8-ethoxy-2-tetralone,

5-trimethylsilyloxy-2-tetralone, 6-trimethylsilyloxy-2-tetralone, 7-trimethylsilyloxy-2-tetralone, 8-trimethylsilyloxy-2-tetralone, 5-t-butyldimethylsilyloxy-2 -Tetralone, 6-t-butyldimethylsiloxy-2-tetralone, 7-t-butyldimethylsiloxy-2-tetralone, 8-t-butyldimethylsiloxy-2-tetralone,

1-hydroxymethyl-2-tetralone, 3-hydroxymethyl-2-tetralone, 4-hydroxymethyl-2-tetralone, 5-hydroxymethyl-2-tetralone, 6-hydroxymethyl-2-tetralone, 7-hydroxymethyl- 2-tetralone, 8-hydroxymethyl-2-tetralone,

1-methoxymethyl-2-tetralone, 3-methoxymethyl-2-tetralone, 4-methoxymethyl-2-tetralone, 5-methoxymethyl-2-tetralone, 6-methoxymethyl-2-tetralone, 7-methoxymethyl- 2-tetralone, 8-methoxymethyl-2-tetralone,

1-acetyl-2-tetralone, 3-acetyl-2-tetralone, 4-acetyl-2-tetralone, 5-acetyl-2-tetralone, 6-acetyl-2-tetralone, 7-acetyl-2-tetralone, 8- Acetyl-2-tetralone, 1-ethylcarbonyl-2-tetralone, 3-ethylcarbonyl-2-tetralone, 4-ethylcarbonyl-2-tetralone, 5-ethylcarbonyl-2-tetralone, 6-ethylcarbonyl-2-tetralone 7-ethylcarbonyl-2-tetralone, 8-ethylcarbonyl-2-tetralone,

1-benzoyl-2-tetralone, 3-benzoyl-2-tetralone, 4-benzoyl-2-tetralone, 5-benzoyl-2-tetralone, 6-benzoyl-2-tetralone, 7-benzoyl-2-tetralone, 8- Benzoyl-2-tetralone,

1- (2-pyridylcarbonyl) -2-tetralone, 3- (2-pyridylcarbonyl) -2-tetralone, 4- (2-pyridylcarbonyl) -2-tetralone, 5- (2-pyridylcarbonyl) -2- Tetralone, 6- (2-pyridylcarbonyl) -2-tetralone, 7- (2-pyridylcarbonyl) -2-tetralone, 8- (2-pyridylcarbonyl) -2-tetralone, 1- (2-thienylcarbonyl)- 2-tetralone, 3- (2-thienylcarbonyl) -2-tetralone, 4- (2-thienylcarbonyl) -2-tetralone, 5- (2-thienylcarbonyl) -2-tetralone, 6- (2-thienylcarbonyl) ) -2-tetralone, 7- (2-thienylcarbonyl) -2-tetralone, 8- (2-thienylcarbonyl) -2-tetra 1- (2-furanylcarbonyl) -2-tetralone, 3- (2-furanylcarbonyl) -2-tetralone, 4- (2-furanylcarbonyl) -2-tetralone, 5- (2-furanyl) Nylcarbonyl) -2-tetralone, 6- (2-furanylcarbonyl) -2-tetralone, 7- (2-furanylcarbonyl) -2-tetralone, 8- (2-furanylcarbonyl) -2-tetralone,

2-tetralone-1-carboxylic acid, 2-tetralone-3-carboxylic acid, 2-tetralone-4-carboxylic acid, 2-tetralone-5-carboxylic acid, 2-tetralone-6-carboxylic acid,
And alkali metal salts such as sodium salts and potassium salts thereof,

1-methoxycarbonyl-2-tetralone, 3-methoxycarbonyl-2-tetralone, 4-methoxycarbonyl-2-tetralone, 5-methoxycarbonyl-2-tetralone, 6-methoxycarbonyl-2-tetralone, 7-methoxycarbonyl- 2-tetralone, 8-methoxycarbonyl-2-tetralone, 1-ethoxycarbonyl-2-tetralone, 3-ethoxycarbonyl-2-tetralone, 4-ethoxycarbonyl-2-tetralone, 5-ethoxycarbonyl-2-tetralone, 6 -Ethoxycarbonyl-2-tetralone, 7-ethoxycarbonyl-2-tetralone, 8-ethoxycarbonyl-2-tetralone,

1-phenyl-2-tetralone, 3-phenyl-2-tetralone, 4-phenyl-2-tetralone, 5-phenyl-2-tetralone, 6-phenyl-2-tetralone, 7-phenyl-2-tetralone, 8- Phenyl-2-tetralone,

1- (2-pyridyl) -2-tetralone, 3- (2-pyridyl) -2-tetralone, 4- (2-pyridyl) -2-tetralone, 5- (2-pyridyl) -2-tetralone, 6- (2-pyridyl) -2-tetralone, 7- (2-pyridyl) -2-tetralone, 8- (2-pyridyl) -2-tetralone, 1- (2-thienyl) -2-tetralone, 3- (2 -Thienyl) -2-tetralone, 4- (2-thienyl) -2-tetralone, 5- (2-thienyl) -2-tetralone, 6- (2-thienyl) -2-tetralone, 7- (2-thienyl) ) -2-tetralone, 8- (2-thienyl) -2-tetralone, 1- (2-furanyl) -2-tetralone, 3- (2-furanyl) -2-tetralone, 4- (2-furanyl)- 2-tetralone, 5- (2-furanyl) 2-tetralone, 6- (2-furanyl) -2-tetralone, 7- (2-furanyl) -2-tetralone, 8- (2-furanyl) -2-tetralone

1-phenoxy-2-tetralone, 3-phenoxy-2-tetralone, 4-phenoxy-2-tetralone, 5-phenoxy-2-tetralone, 6-phenoxy-2-tetralone, 7-phenoxy-2-tetralone, 8- Phenoxy-2-tetralone,

1- (2-pyridyloxy) -2-tetralone, 3- (2-pyridyloxy) -2-tetralone, 4- (2-pyridyloxy) -2-tetralone, 5- (2-pyridyloxy) -2- Tetralone, 6- (2-pyridyloxy) -2-tetralone, 7- (2-pyridyloxy) -2-tetralone, 8- (2-pyridyloxy) -2-tetralone, 1- (2-thienyloxy)- 2-tetralone, 3- (2-thienyloxy) -2-tetralone, 4- (2-thienyloxy) -2-tetralone, 5- (2-thienyloxy) -2-tetralone, 6- (2-thienyloxy) ) -2-tetralone, 7- (2-thienyloxy) -2-tetralone, 8- (2-thienyloxy) -2-tetralone, 1- (2-furanyloxy) -2-tetralone, 3- ( -Furanyloxy) -2-tetralone, 4- (2-furanyloxy) -2-tetralone, 5- (2-furanyloxy) -2-tetralone, 6- (2-furanyloxy) -2-tetralone, 7- (2-furanyloxy) ) -2-tetralone, 8- (2-furanyloxy) -2-tetralone

1-phenoxycarbonyl-2-tetralone, 3-phenoxycarbonyl-2-tetralone, 4-phenoxycarbonyl-2-tetralone, 5-phenoxycarbonyl-2-tetralone, 6-phenoxycarbonyl-2-tetralone, 7-phenoxycarbonyl- 2-tetralone, 8-phenoxycarbonyl-2-tetralone,

1- (2-pyridyloxycarbonyl) -2-tetralone, 3- (2-pyridyloxycarbonyl) -2-tetralone, 4- (2-pyridyloxycarbonyl) -2-tetralone, 5- (2-pyridyloxycarbonyl) ) -2-tetralone, 6- (2-pyridyloxycarbonyl) -2-tetralone, 7- (2-pyridyloxycarbonyl) -2-tetralone, 8- (2-pyridyloxycarbonyl) -2-tetralone, 1- (2-thienyloxycarbonyl) -2-tetralone, 3- (2-thienyloxycarbonyl) -2-tetralone, 4- (2-thienyloxycarbonyl) -2-tetralone, 5- (2-thienyloxycarbonyl)- 2-tetralone, 6- (2-thienyloxycarbonyl) -2-tetralone, 7- (2-thienyl) Xycarbonyl) -2-tetralone, 8- (2-thienyloxycarbonyl) -2-tetralone, 1- (2-furanyloxycarbonyl) -2-tetralone, 3- (2-furanyloxycarbonyl) -2- Tetralone, 4- (2-furanyloxycarbonyl) -2-tetralone, 5- (2-furanyloxycarbonyl) -2-tetralone, 6- (2-furanyloxycarbonyl) -2-tetralone, 7- ( 2-furanyloxycarbonyl) -2-tetralone, 8- (2-furanyloxycarbonyl) -2-tetralone,

Etc.,
Furthermore, these compounds include, for example, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, sec-butyl groups, t-butyl groups, n-pentyl groups, and n-hexyl groups. Chain or branched C1-C6 alkyl group; cyclic C1-C6 alkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group; for example, tri (linear or linear) such as trimethylsilyl group, t-butyldimethylsilyl group A branched C1-C6 alkyl) silyl group; a hydroxy group; for example, a linear or branched C1-C6 alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group; for example, a trimethylsilyloxy group, t- A tri (linear or branched C1-C6 alkyl) silyloxy group, such as a butyldimethylsilyloxy group; A linear or branched C1-C6 hydroxyalkyl group such as a methyl group or a hydroxyethyl group; for example, a linear or branched (C1-C6 alkoxy)-(C1-C6) such as a methoxymethyl group, a methoxyethyl group or an ethoxyethyl group; C6 alkyl) group; for example, linear or branched C1-C6 haloalkyl group such as fluoromethyl group, difluoromethyl group, trifluoromethyl group; for example, linear chain such as methylamino group, ethylamino group, dimethylamino group Or a branched C1-C6 alkylamino group; for example, a linear or branched C1-C6 alkylcarbonylamino group such as a methylcarbonylamino group or an ethylcarbonylamino group; for example, a straight chain such as a methylcarbonyl group or an ethylcarbonyl group Branched C1-C6 alkylcarbonyl group; carboxyl group or metal salt thereof; A linear or branched C1-C6 alkoxycarbonyl group such as methoxycarbonyl group or ethoxycarbonyl group; an aminocarbonyl group; ~ C6 alkylaminocarbonyl group; phenyl group; phenoxy group; heteroaryl group such as pyridyl group, thienyl group, furanyl group; heteroaryloxy group such as 2-pyridyloxy group, 2-thienyloxy group, 2-furanyloxy group, etc. It may have a substituent.

  Since the 2-tetralone compound (raw material compound) represented by the general formula (1) is a known compound, it can be produced according to a known method.

  Then, the palladium catalyst used for this invention method is demonstrated. The palladium catalyst used in the dehydrogenation reaction may be any catalyst that can perform the dehydrogenation reaction. Specific examples of the palladium catalyst that can be used in the dehydrogenation reaction include palladium carbon and palladium support. Examples include heterogeneous catalysts such as alumina, palladium-supported barium sulfate, and palladium-supported calcium carbonate. The use of palladium carbon and palladium-supported alumina, which are highly reactive and can easily recover the palladium catalyst after the reaction, is preferred. From the viewpoints of availability, ease of handling, reactivity, and the like, the use of palladium carbon is preferred. These palladium catalysts may be used alone or as a mixed catalyst in an arbitrary ratio. These palladium catalysts are known compounds.

  The palladium catalyst in the method of the present invention can be reacted at any molar ratio with respect to the 2-tetralone compound (raw material compound) represented by the general formula (1), but the amount used is represented by the general formula (1). The molar ratio is usually 0.00001 to 1.0 mol, preferably 0.0001 to 0.1 mol, more preferably 0.0001 to 0.05 mol, relative to 2-tetralone (raw compound). Can be illustrated.

  Furthermore, in the method of the present invention, the reaction is carried out in the presence of an olefin compound that can be itself reduced by hydrogen for the purpose of suppressing side reactions due to hydrogen by-produced as the dehydrogenation proceeds.

Examples of the olefin compound used for this purpose include compounds represented by the above general formula (2) or general formula (3) , or isophorone .

Wherein R ⁸ , R ¹² and R ¹³ are each independently
Hydrogen atom;

Or a C1-C3 alkyl group including a methyl group, an ethyl group, an n-propyl group, and an isopropyl group;

R ⁹ is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n -C1-C12 alkyl group such as octyl group, n-decyl group, n-dodecyl group (the alkyl group is a cyclic C1-C6 alkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group; Tri (linear or branched C1-C6 alkyl) silyl group such as trimethylsilyl group, t-butyldimethylsilyl group; hydroxy group; for example, linear chain such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group Or a branched C1-C6 alkoxy group; for example, tri (linear or branched) such as trimethylsilyloxy group, t-butyldimethylsilyloxy group 1-C6 alkyl) silyloxy group; for example, linear or branched C1-C6 hydroxyalkyl group such as hydroxymethyl group, hydroxyethyl group; for example, linear or branched such as methoxymethyl group, methoxyethyl group, ethoxyethyl group Branched (C1-C6 alkoxy)-(C1-C6 alkyl) group; for example, linear or branched C1-C6 haloalkyl group such as fluoromethyl group, difluoromethyl group, trifluoromethyl group; for example, methylamino group, ethyl Linear or branched C1-C6 alkylamino group such as amino group, dimethylamino group; for example, linear or branched C1-C6 alkylcarbonylamino group such as methylcarbonylamino group, ethylcarbonylamino group; Straight chain or branched C1-C6 alkyl such as ethylcarbonyl group A carbonyl group; a carboxyl group or a metal salt thereof; for example, a linear or branched C1-C6 alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group; an aminocarbonyl group; for example, a methylaminocarbonyl group, an ethylaminocarbonyl group, dimethyl Linear or branched C1-C6 alkylaminocarbonyl group such as aminocarbonyl group; phenyl group; phenoxy group; heteroaryl group such as pyridyl group, thienyl group, furanyl group; 2-pyridyloxy group, 2-thienyloxy group, May have a substituent such as a heteroaryloxy group such as a 2-furanyloxy group);

An aryl group such as a phenyl group or a naphthyl group (the aryl group is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, or an n-pentyl group) Linear or branched C1-C6 alkyl group such as n-hexyl group; cyclic C1-C6 alkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group; for example, trimethylsilyl group, t-butyldimethylsilyl A tri (linear or branched C1-C6 alkyl) silyl group such as a group; a hydroxy group; for example, a linear or branched C1-C6 alkoxy group such as a methoxy group, ethoxy group, n-propoxy group, isopropoxy group; For example, tri (linear or branched C1-C6 alkyl) such as trimethylsilyloxy group, t-butyldimethylsilyloxy group, etc. Silyloxy group; for example, linear or branched C1-C6 hydroxyalkyl group such as hydroxymethyl group, hydroxyethyl group; for example, linear or branched (C1-C6) such as methoxymethyl group, methoxyethyl group, ethoxyethyl group Alkoxy)-(C1-C6 alkyl) group; for example, linear or branched C1-C6 haloalkyl group such as fluoromethyl group, difluoromethyl group, trifluoromethyl group; for example, methylamino group, ethylamino group, dimethylamino A linear or branched C1-C6 alkylamino group such as a group; for example, a linear or branched C1-C6 alkylcarbonylamino group such as a methylcarbonylamino group or an ethylcarbonylamino group; for example, a methylcarbonyl group or an ethylcarbonyl group Linear or branched C1-C6 alkylcarbonyl groups such as Xyl group or metal salt thereof; for example, linear or branched C1-C6 alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group; aminocarbonyl group; for example, methylaminocarbonyl group, ethylaminocarbonyl group, dimethylaminocarbonyl group Linear or branched C1-C6 alkylaminocarbonyl groups such as: aryl groups such as phenyl groups and naphthyl groups; aryloxy groups such as phenoxy groups and naphthyloxy groups; heteroaryl groups such as pyridyl groups, thienyl groups and furanyl groups And may have a substituent such as

Or, for example, a heteroaryl group such as pyridyl group, thienyl group, furanyl group (the heteroaryl group is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t -Linear or branched C1-C6 alkyl group such as butyl group, n-pentyl group, n-hexyl group; cyclic C1-C6 alkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group; Tri (linear or branched C1-C6 alkyl) silyl group such as trimethylsilyl group, t-butyldimethylsilyl group; hydroxy group; for example, linear chain such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group Or a branched C1-C6 alkoxy group; for example, a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, Li (linear or branched C1-C6 alkyl) silyloxy group; for example, a linear or branched C1-C6 hydroxyalkyl group such as hydroxymethyl group, hydroxyethyl group; for example, methoxymethyl group, methoxyethyl group, ethoxyethyl group A linear or branched (C1-C6 alkoxy)-(C1-C6 alkyl) group such as, for example, a linear or branched C1-C6 haloalkyl group such as a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group; A linear or branched C1-C6 alkylamino group such as methylamino group, ethylamino group, dimethylamino group; for example, a linear or branched C1-C6 alkylcarbonylamino group such as methylcarbonylamino group, ethylcarbonylamino group, etc. Group; for example, linear or branched, such as methylcarbonyl group, ethylcarbonyl group, etc. 1-C6 alkylcarbonyl group; carboxyl group or metal salt thereof; for example, linear or branched C1-C6 alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group; aminocarbonyl group; for example, methylaminocarbonyl group, ethylamino Linear or branched C1-C6 alkylaminocarbonyl group such as carbonyl group and dimethylaminocarbonyl group; aryl group such as phenyl group and naphthyl group; aryloxy group such as phenoxy group and naphthyloxy group; pyridyl group, thienyl group, (It may have a substituent such as a heteroaryl group such as a furanyl group.)
Indicate

R ¹⁰ and R ¹¹ are each independently
A trifluoromethyl group;

A C2-C13 alkylcarbonyl group in which the alkyl moiety is a C1-C12 alkyl group having the same meaning as the C1-C12 alkyl group of the substituent R ⁹ ;
May have a substituent the aryl moiety is an aryl group having the same meaning as the aryl group of the substituent R ⁹ aryl group,
An acyl group including a heteroarylcarbonyl group in which the heteroaryl moiety may have a substituent which is the same as the heteroaryl group defined above for the substituent R ⁹ ;

An aryl group which may have a substituent in which the aryl moiety is the same as the aryl group of the substituent R ⁹ ;

A heteroaryl group which may have a substituent, wherein the heteroaryl moiety is a heteroaryl group having the same meaning as the heteroaryl group of the substituent R ⁹ ;

Alkyl part wherein the substituents C1~C12 alkyl group and C1~C12 alkyl group is a substituted group of include optionally may C1~C12 alkylsulfonyl group synonymous ^{R 9;}

Aryl moiety the substituents aryl group as defined aryl group is a which may have a substituent arylsulfonyl group R ^9;

A heteroarylsulfonyl group in which the heteroaryl moiety may have a substituent which is the same as the heteroaryl group defined above for the substituent R ⁹ ;

Alkyl part wherein the substituents C1~C12 alkylsulfonyloxy group which may have a substituent is a C1~C12 alkyl group C1~C12 alkyl group as defined for ^{R 9;}

An arylsulfonyloxy group in which the aryl moiety may have a substituent which is the same as the aryl group of the substituent R ⁹ ;

A heteroarylsulfonyloxy group optionally having a substituent, wherein the heteroaryl moiety is a heteroaryl group having the same meaning as the heteroaryl group of the substituent R ⁹ ;

Or monovalent group (A)

(Wherein R ¹⁴ is

Alkyl group in the alkyl moiety wherein the substituent ^{R 9} of C1~C12 alkyl group as defined in C1~C12 alkyl group is a substituted group of 1 to carbon atoms which may have 12;

An aryl group which may have a substituent in which the aryl moiety is the same as the aryl group of the substituent R ⁹ ;

Or a heteroaryl moiety the substituents heteroaryl group as defined heteroaryl which may have a substituent is heteroaryl group of R ^9. )

n represents an integer of 0 to 3.

More specifically, as the olefin compound,
Dimethyl maleate, diethyl maleate, di-n-propyl maleate, diisopropyl maleate, diphenyl maleate, di (1-naphthyl) maleate, di (2-naphthyl) maleate, dimethyl 2,3-dimethyl maleate Diethyl 2,3-dimethylmaleate, di-n-propyl 2,3-dimethylmaleate, diisopropyl 2,3-dimethylmaleate, diphenyl 2,3-dimethylmaleate, di (2,3-dimethylmaleate) 1-naphthyl), di (2-naphthyl) 2,3-dimethylmaleate, dimethyl 2,3-diethylmaleate, diethyl 2,3-diethylmaleate, di-n-propyl 2,3-diethylmaleate, 2,3-diethyl maleate diisopropyl, 2,3-diethyl maleate diphenyl, 2,3 Di (1-naphthyl) diethyl maleate, di (2-naphthyl) 2,3-diethyl maleate, dimethyl 2,3-di-n-propyl maleate, diethyl 2,3-di-n-propyl maleate, 2,3-di-n-propyl maleate di-n-propyl, 2,3-di-n-propyl maleate diisopropyl, 2,3-di-n-propyl maleate diphenyl, 2,3-di-n -Di (1-naphthyl) propyl maleate, di (2-naphthyl) 2,3-di-n-propyl maleate, dimethyl 2,3-diisopropyl maleate, diethyl 2,3-diisopropyl maleate, 2,3 -Di-n-propyl diisopropyl maleate, diisopropyl 2,3-diisopropyl maleate, diphenyl 2,3-diisopropyl maleate, 2,3-di Isopropyl maleate, di (1-naphthyl), 2,3-diisopropyl maleate, di maleic diesters represented by (2-naphthyl),
Dimethyl fumarate, diethyl fumarate, di-n-propyl fumarate, diisopropyl fumarate, diphenyl fumarate, di (1-naphthyl) fumarate, di (2-naphthyl) fumarate, dimethyl 2,3-dimethyl fumarate Diethyl 2,3-dimethyl fumarate, di-n-propyl 2,3-dimethyl fumarate, diisopropyl 2,3-dimethyl fumarate, diphenyl 2,3-dimethyl fumarate, di (2,3-dimethyl fumarate ( 1-naphthyl), 2,3-dimethyl fumarate di (2-naphthyl), dimethyl 2,3-diethyl fumarate, diethyl 2,3-diethyl fumarate, di-n-propyl 2,3-diethyl fumarate, 2,3-diethyl fumarate diisopropyl, 2,3-diethyl fumarate diphenyl, 2,3-diethyl fumarate di (1-naphthyl), , 3-Diethyl fumarate di (2-naphthyl), dimethyl 2,3-di-n-propyl fumarate, diethyl 2,3-di-n-propyl fumarate, 2,3-di-n-propyl fumaric acid Di-n-propyl, diisopropyl 2,3-di-n-propyl fumarate, diphenyl 2,3-di-n-propyl fumarate, di (1-naphthyl) 2,3-di-n-propyl fumarate, 2,3-di-n-propyl fumarate di (2-naphthyl), dimethyl 2,3-diisopropyl fumarate, diethyl 2,3-diisopropyl fumarate, di-n-propyl 2,3-diisopropyl fumarate, 2 , 3-diisopropyl fumarate diisopropyl, 2,3-diisopropyl fumarate diphenyl, 2,3-diisopropyl fumarate di (1-naphthyl), 2,3-diisopropyl fuma Fumaric acid diesters represented by di (2-naphthyl),
Methyl cinnamate, ethyl cinnamate, n-propyl cinnamate, isopropyl cinnamate, phenyl cinnamate, 1-naphthyl cinnamate), 2-naphthyl cinnamate, α-methyl cinnamate Methyl acrylate, ethyl α-methyl cinnamate, α-methyl cinnamate-n-propyl, isopropyl α-methyl cinnamate, phenyl α-methyl cinnamate, α-methyl cinnamate-1-naphthyl, α -Methyl cinnamate-2-naphthyl, methyl α-ethyl cinnamate, ethyl α-ethyl cinnamate, α-ethyl cinnamate-n-propyl, isopropyl α-ethyl cinnamate, α-ethyl cinnamate Phenyl acid, α-ethyl cinnamate-1-naphthyl, α-ethyl cinnamate-2-naphthyl, methyl α-n-propyl cinnamate, ethyl α-n-propyl cinnamate, α-n-propyl Cinnamic acid-n-propyl, α-n-propyl cinnamate isopropyl, α-n-propyl cinnamate phenyl, α-n-propyl cinnamate-1-naphthyl, α-n-propyl cinnamate-2-naphthyl, α-isopropyl cinnamate Methyl cinnamate, ethyl α-isopropyl cinnamate, α-isopropyl cinnamate-n-propyl, isopropyl α-isopropyl cinnamate, phenyl α-isopropyl cinnamate, 1-naphthyl α-isopropyl cinnamate, alkenoic acid ester compounds including cinnamic acid esters represented by α-isopropylcinnamic acid-2-naphthyl;

α-methyl trifluoromethyl acrylate, methyl β-trifluoromethyl acrylate, ethyl α-trifluoromethyl acrylate, ethyl β-trifluoromethyl acrylate, α-trifluoromethyl acrylate-n-propyl, β- N-propyl trifluoromethyl acrylate, isopropyl α-trifluoromethyl acrylate, isopropyl β-trifluoromethyl acrylate, phenyl α-trifluoromethyl acrylate, phenyl β-trifluoromethyl acrylate, α-trifluoro Methyl acrylic acid (1-naphthyl), β-trifluoromethyl acrylic acid (1-naphthyl), α-trifluoromethyl acrylic acid (2-naphthyl), β-trifluoromethyl acrylic acid (2-naphthyl),
Trifluoromethyl alkenoic acid ester compounds represented by:

β-methyl acrylate, β-ethyl acrylate, β-acetyl acrylate-n-propyl, β-acetyl acrylate, β-acetyl acrylate, β-acetyl acrylate (1-naphthyl), β -Β- (alkylcarbonyl) acrylic acid ester compounds represented by acetylacrylic acid (2-naphthyl),
β-benzoyl methyl acrylate, β-benzoyl ethyl acrylate, β-benzoyl acrylate-n-propyl, β-benzoyl isopropyl acrylate, β-benzoyl acrylate phenyl, β-benzoyl acrylate (1-naphthyl), β -Β- (arylcarbonyl) acrylic acid ester compounds represented by benzoylacrylic acid (2-naphthyl),
β- (2-pyridylcarbonyl) methyl acrylate, β- (2-pyridylcarbonyl) ethyl acrylate, β- (2-pyridylcarbonyl) acrylate-n-propyl, β- (2-pyridylcarbonyl) isopropyl , Β- (2-pyridylcarbonyl) acrylic acid phenyl, β- (2-pyridylcarbonyl) acrylic acid (1-naphthyl), β- (2-pyridylcarbonyl) acrylic acid (2-naphthyl),
Β-acyl alkenoic acid ester compounds including β- (heteroarylcarbonyl) acrylic acid ester compounds represented by:

β-methylsulfonylmethyl acrylate, β-methylsulfonylethyl acrylate, β-methylsulfonylacrylate-n-propyl, isopropyl β-methylsulfonylacrylate, phenyl β-methylsulfonylacrylate, β-methylsulfonylacrylate ( 1-naphthyl), β-methylsulfonylacrylic acid (2-naphthyl),
Β- (alkylsulfonyl) acrylic acid ester compounds represented by
β-phenylsulfonylmethyl acrylate, β-phenylsulfonylethyl acrylate, β-phenylsulfonylacrylate-n-propyl, β-phenylsulfonylacrylate isopropyl, β-phenylsulfonylacrylate phenyl, β-phenylsulfonylacrylate ( 1-naphthyl), β-phenylsulfonylacrylic acid (2-naphthyl),
Β- (arylsulfonyl) acrylic acid ester compounds represented by
β- (2-pyridyl) sulfonyl acrylate methyl, β- (2-pyridyl) sulfonyl acrylate ethyl, β- (2-pyridyl) sulfonyl acrylate-n-propyl, β- (2-pyridyl) sulfonyl acrylate , Β- (2-pyridyl) sulfonylacrylic acid phenyl, β- (2-pyridyl) sulfonylacrylic acid (1-naphthyl), β- (2-pyridyl) sulfonylacrylic acid (2-naphthyl),
Β- (substituted sulfonyl) alkenoic acid ester compounds including β- (heteroarylsulfonyl) acrylic acid ester compounds represented by:

β-methylsulfonyloxyacrylate methyl, β-methylsulfonyloxyacrylate ethyl, β-methylsulfonyloxyacrylate-n-propyl, β-methylsulfonyloxyacrylate isopropyl, β-methylsulfonyloxyacrylate phenyl, β- Methylsulfonyloxyacrylic acid (1-naphthyl), β- (alkylsulfonyloxy) acrylic acid ester alkylsulfonyloxyethylene compounds represented by β-methylsulfonyloxyacrylic acid (2-naphthyl),
β-phenylsulfonyloxyacrylate methyl, β-phenylsulfonyloxyacrylate ethyl, β-phenylsulfonyloxyacrylate-n-propyl, β-phenylsulfonyloxyacrylate, β-phenylsulfonyloxyacrylate, β- Β- (arylsulfonyloxy) acrylic acid ester compounds represented by phenylsulfonyloxyacrylic acid (1-naphthyl), β-phenylsulfonyloxyacrylic acid (2-naphthyl),
β- (2-pyridyl) sulfonyloxyacrylate methyl, β- (2-pyridyl) sulfonyloxyacrylate ethyl, β- (2-pyridyl) sulfonyloxyacrylate-n-propyl, β- (2-pyridyl) sulfonyl Isopropyl oxyacrylate, phenyl β- (2-pyridyl) sulfonyloxyacrylate, β- (2-pyridyl) sulfonyloxyacrylic acid (1-naphthyl), β- (2-pyridyl) sulfonyloxyacrylic acid (2-naphthyl) Β- (substituted sulfonyloxy) alkenoic acid ester compounds including β- (heteroarylsulfonyloxy) acrylic acid ester compounds represented by

Cyclic α-alkenones represented by isophorone, cyclopenten-3-one, cyclohexen-3-one, cyclohepten-3-one, and cycloocten-3-one;

Etc. can be illustrated.

  Among these olefin compounds, olefin compounds such as maleate esters represented by diethyl maleate, cyclic α-alkenones represented by isophorone, and cinnamic acid esters represented by ethyl cinnamate are used. Among them, maleic esters represented by diethyl maleate and cyclic α-alkenones represented by isophorone are particularly preferred, and specifically diethyl maleate and isophorone give particularly preferred results. In addition, even when “maleic acid” described in Non-Patent Document 3 is used in place of the olefin compound used in the method of the present invention, the target 2-naphthol compound is produced at all. Not possible (see Comparative Example 3 below).

  The olefin compound in the method of the present invention shows the effect of suppressing side reactions at any molar ratio relative to the raw material compound represented by the general formula (1), but the raw material compound represented by the general formula (1) A molar ratio of 0.1 to 5.0 mol, preferably 0.3 to 3.0 mol, more preferably 0.5 to 1.5 mol can be exemplified as the amount of the olefin compound used.

  In the dehydrogenation reaction in the method of the present invention, it is preferable to use an appropriate solvent in order to make the reaction proceed smoothly. The solvent that can be used in the dehydrogenation reaction is not particularly limited as long as it does not inhibit the reaction. For example, ethers such as diphenyl ether and anisole; aromatic hydrocarbons such as mesitylene and xylene; ethanol, 2-ethyl-1- Examples include alcohols such as hexanol and ethylene glycol; aprotic polar solvents such as tetramethylurea, hexamethylphosphoric triamide (HMPA) and propylene carbonate; and aliphatic hydrocarbons such as pentane and n-hexane. . It is preferable to use ethers such as diphenyl ether and anisole, and it is particularly preferable to use diphenyl ether as a solvent. A solvent can be used individually or as a mixed solvent of arbitrary mixing ratios.

  The amount of the solvent may be an amount that can sufficiently stir the reaction system, but is usually 0.05 to 10 l, preferably 0.3 to 1 mol per mol of the raw material compound represented by the general formula (1). It may be in the range of 2l.

  The reaction temperature of the dehydrogenation reaction in the method of the present invention can be exemplified by the range of 0 ° C. to the reflux temperature of the solvent to be used, preferably 70 ° C. to 280 ° C.

  Although the reaction time of the dehydrogenation reaction in the method of the present invention is not particularly limited, it is preferably 1 hour to 30 hours from the viewpoint of suppressing by-products.

  According to this reaction, a 2-naphthol compound represented by the general formula (3) is produced with high selectivity under mild conditions without using a special reaction apparatus. The obtained naphthol compound represented by the general formula (3) is a useful compound as an intermediate raw material for medical and agricultural chemicals or liquid crystals.

  Next, although the Example is given and the manufacturing method of this invention compound is demonstrated concretely, this invention is not limited at all by these Examples.

Example 1 (Invention described in [1]): Production of 2-naphthol To a 50 ml eggplant-shaped flask equipped with a magnetic stirrer, a toroidal connecting tube equipped with an eggplant-shaped flask for water trap, and a reflux tube After adding 1.46 g (10 mmol) of 2-tetralone, 1.72 g (10 mmol) of diethyl maleate, and then 3 ml of diphenyl ether, the system was replaced with nitrogen, and 10% palladium carbon (M) (manufactured by Kawaken Fine Chemical Co., Ltd., 0.15 g (water content of about 50%) (10 wt% with respect to 2-tetralone, 0.5 wt% as Pd) was added, and the mixture was stirred at a bath temperature of 180 ° C. for 20 hours. The product derived from the raw material compound in the reaction solution at this time contained 99% of 2-naphthol by gas chromatography. After cooling to room temperature, 50 ml of toluene was added to the system, followed by filtration to separate palladium carbon. The operation of extracting the filtrate with 50 ml of 5% aqueous sodium hydroxide was repeated twice. The aqueous layer was washed with 50 ml of toluene. Next, 35% hydrochloric acid was added to the aqueous layer until the reaction system became acidic, followed by extraction with 50 ml of toluene. The toluene layer was washed with water and then with a saturated saline solution. After the toluene layer was dried over anhydrous sodium sulfate, toluene was distilled off under reduced pressure. 1.3 g of brown crystals were obtained. The obtained brown crystals were purified by silica gel column chromatography to obtain 1.2 g of the desired product. Yield 83%. The purity of the desired product in the crystals was> 99% by gas chromatography.

m. p: 120-121 ° C
¹ H-NMR (300 MHz, CDCl ₃ ): δ = 7.78-7.67 (m, 3H), 7.45-7.30 (m, 2H), 7.16-7.08 (m, 2H) ), 5.03 (br, 1H) (ppm)
¹³ C-NMR (300 MHz, CDCl ₃ ): δ = 153.5, 134.8, 130.1, 129.2, 128.0, 126.8, 126.6, 123.9, 118.0, 109 .8 (ppm)
IR (KBr): 3291.9, 1629.6, 1602.6, 1510.0, 1467.6, 1216.9, 844.7, 813.8, 742.5 (cm ⁻¹ )
GC-MS: M ⁺ = 144

Comparative Example 1: Production of 2-naphthol Into a 50 ml eggplant-shaped flask equipped with a magnetic stirrer, a eggplant-shaped flask for water trap and a reflux tube, 1.46 g (10 mmol) of 2-tetralone Then, after adding 5 ml of diphenyl ether, the inside of the system was replaced with nitrogen, and 0.15 g of 10% palladium carbon (M) (manufactured by Kawaken Fine Chemical Co., Ltd., water content of about 50%) (10 wt% with respect to 2-tetralone, Pd As 0.5 wt%) and stirred at a bath temperature of 185 ° C. for 10 hours. The product derived from the raw material compound in the reaction solution at this time contained 66% of 2-naphthol by gas chromatography and 5% of 2-tetralone and 21% of tetralin-2-ol. . After cooling to room temperature, 50 ml of toluene was added to the system, followed by filtration to separate palladium carbon. The operation of extracting the filtrate with 25 ml of 10% aqueous sodium hydroxide was repeated twice. The aqueous layer was washed with 30 ml of toluene. Next, 35% hydrochloric acid was added to the aqueous layer until the system became acidic, followed by extraction with 30 ml of ethyl acetate. The ethyl acetate layer was washed with water and then with saturated brine. The ethyl acetate layer was dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. 1.33 g of brown crystals were obtained. Crude yield 92%. The components in this crystal were 77% 2-naphthol and 23% tetralin-2-ol by gas chromatography.

Example 2 (Invention described in [1]): Production of 7,8-difluoro-2-naphthol 50 ml equipped with a magnetic stirrer, a toroidal connection tube equipped with a eggplant-shaped flask for water trap, and a reflux tube 7,8-difluoro-2-tetralone 3.64 g (20 mmol), diethyl maleate 3.44 g (20 mmol), and then 5 ml of diphenyl ether were added, and the system was replaced with nitrogen. Add 0.36 g of palladium carbon (M) (made by Kawaken Fine Chemical Co., Ltd., water content of about 50%) (10 wt% with respect to 7,8-difluoro-2-tetralone, 0.5 wt% as Pd), bath temperature 180 Stir at 16 ° C. for 16 hours. After cooling to room temperature, 30 ml of toluene was added to the system, followed by filtration to separate palladium carbon. The operation of extracting the filtrate with 25 ml of 10% aqueous sodium hydroxide was repeated twice. The aqueous layer was washed with 30 ml of toluene. Next, 35% hydrochloric acid was added to the aqueous layer until the system became acidic, followed by extraction with 50 ml of ethyl acetate. The ethyl acetate layer was washed with water and then with saturated brine. The ethyl acetate layer was dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. 3.8 g of brown crystals were obtained. The obtained brown crystals were purified by Kugelrohr distillation to obtain 2.8 g of the desired product. Yield 78%. The purity of the desired product in the crystals was 98% by high performance liquid chromatography.

m. p: 99-100 ° C
¹ H-NMR (300 MHz, CDCl ₃ ): δ = 7.74 (dd, J = 9.0, 1.8 Hz, 1H), 7.51 (ddd, J = 9.0, 4.8, 1. 5Hz, 1H), 7.34 (d, J = 2.7Hz, 1H), 7.25-7.08 (m, 2H), 5.34 (br, 1H) (ppm)
¹³ C-NMR (300 MHz, CDCl ₃ ): δ = 154.7, 149.0, 145.9, 145.7, 142.4, 130.1, 126.7, 124.4, 124.31, 124 .27, 124.2, 118.21, 118.18, 114.5, 114.2, 102.4, 102.35, 102.28 (ppm)
IR (KBr): 3322.8, 1648.8, 1627.6, 1531.2, 1483.0, 1456.0, 1388.5, 1359.6, 1257.4, 1218.8, 1137.8, 1072 .2,1010.5,891.0,837.0,821.5,719.3 (cm ⁻¹ )
GC-MS: M ⁺ = 180

Comparative Example 2: Production of 7,8-difluoro-2-naphthol Into a 50 ml eggplant type flask equipped with a magnetic stirrer, a toroidal connection tube equipped with a eggplant type flask for water trap, and a reflux tube, -After adding 1.82 g (10 mmol) of difluoro-2-tetralone and then 5 ml of diphenyl ether, the inside of the system was replaced with nitrogen, and 10% palladium carbon (M) (manufactured by Kawaken Fine Chemical Co., Ltd., about 50% moisture). 36 g (20 wt% with respect to 7,8-difluoro-2-tetralone, 1 wt% as Pd) was added, and the mixture was stirred at a bath temperature of 180 ° C. for 10 hours. After cooling to room temperature, 30 ml of toluene was added to the system, followed by filtration to separate palladium carbon. The operation of extracting the filtrate with 25 ml of 10% aqueous sodium hydroxide was repeated twice. The aqueous layer was washed with 30 ml of toluene. Next, 35% hydrochloric acid was added to the aqueous layer until the system became acidic, followed by extraction with 50 ml of ethyl acetate. The ethyl acetate layer was washed with water and then with saturated brine. The ethyl acetate layer was dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. The residue was purified by Kugelrohr distillation to obtain 1.3 g of the desired product. Yield 72%. The purity of the target product in this crystal was 79% by high performance liquid chromatography, and it contained 19% of a defluorinated monofluoro product as a by-product.

Comparative Example 3: Production of 7,8-difluoro-2-naphthol Into a 50 ml eggplant type flask equipped with a magnetic stirrer, a toroidal connecting tube equipped with a eggplant shaped flask for water trap, and a reflux tube, -After adding 3.64 g (20 mmol) of difluoro-2-tetralone, 2.32 g (20 mmol) of maleic acid and then 3 ml of diphenyl ether, the inside of the system was replaced with nitrogen, and 10% palladium carbon (M) (manufactured by Kawaken, moisture About 50%) 0.36 g (10 wt%, 0.5 wt% as Pd) was added, and the mixture was stirred at a bath temperature of 180 ° C. for 20 hours. When this reaction solution was analyzed by gas chromatography, 72.4% diphenyl ether, 18.8% 7,8-difluoro-2-tetralone, and 7,8-difluoro-2-naphthol were not produced at all.

Example 3 (Invention described in [1]): Production of 7,8-difluoro-2-naphthol Magnetic stirrer, toroidal connecting pipe equipped with eggplant-shaped flask for water trap, and 50 ml equipped with a reflux pipe After adding 1.82 g (10 mmol) of 7,8-difluoro-2-tetralone, 1.38 g (10 mmol) of isophorone and 3 ml of diphenyl ether to the eggplant-shaped flask, the system was replaced with nitrogen, and 10% palladium carbon was added. (M) 0.18 g (10 wt% with respect to 7,8-difluoro-2-tetralone, 0.5 wt% as Pd) was added at Kawaken Fine Chemical Co., Ltd., and the bath temperature was 180 ° C. Stir for 20 hours. As a product derived from the raw material compound in this reaction solution, 75% of 7,8-difluoro-2-naphthol, 21% of 7,8-difluoro-2-tetralone and 2% of defluorinated monofluoro product were obtained by gas chromatography. Met.

Example 4 (Invention described in [1]): Production of 7,8-difluoro-2-naphthol Magnetic stirrer, toroidal connecting tube equipped with eggplant-shaped flask for water trap, and 50 ml equipped with a reflux tube To the eggplant-shaped flask, 1.82 g (10 mmol) of 7,8-difluoro-2-tetralone, 0.61 g (5 mmol) of nitrobenzene, and 2 ml of diphenyl ether were added, and the system was replaced with nitrogen, and 10% palladium carbon was added. (M) 0.18 g (10 wt% with respect to 7,8-difluoro-2-tetralone, 0.5 wt% as Pd) was added at Kawaken Fine Chemical Co., Ltd., and the bath temperature was 180 ° C. Stir for 16 hours. The product derived from the raw material compound in this reaction liquid includes 53% 7,8-difluoro-2-naphthol and 13% 7,8-difluoro-2-tetralone by gas chromatography, as well as a condensate of the raw material compound and aniline. Was 27%.

Example 5 (Invention described in [1]): Production of 7,8-difluoro-2-naphthol 50 ml equipped with a magnetic stirrer, a toroidal connecting tube equipped with an eggplant-shaped flask for water trap, and a reflux tube After adding 1.82 g (10 mmol) of 7,8-difluoro-2-tetralone, 1.06 g (10 mmol) of benzaldehyde, and 3 ml of diphenyl ether to the eggplant type flask, the inside of the system was replaced with nitrogen, and 10% palladium carbon was added. (M) 0.18 g (10 wt% with respect to 7,8-difluoro-2-tetralone, 0.5 wt% as Pd) was added at Kawaken Fine Chemical Co., Ltd., and the bath temperature was 180 ° C. Stir for 18 hours. The product derived from the raw material compound in this reaction solution includes 37% of 7,8-difluoro-2-naphthol and 51% of 7,8-difluoro-2-tetralone by gas chromatography, and the target product and ether of benzyl alcohol. Condensate was contained 12%.

Claims (6)

General formula (1)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom, a fluorine atom, an alkyl group, a cyclic alkyl group, a trialkylsilyl group, a hydroxy group) , Alkoxy group, trialkylsiloxy group, hydroxyalkyl group, alkoxyalkyl group, alkylcarbonyl group, arylcarbonyl group which may have a substituent, heteroarylcarbonyl group which may have a substituent, carboxyl A group or a metal salt thereof, an alkoxycarbonyl group, an aryloxycarbonyl group which may have a substituent, a heteroaryloxycarbonyl group which may have a substituent, an aryl group which may have a substituent, An aryloxy group which may have a substituent, a heteroaryloxy group which may have a substituent, or a substituent. Shows a heteroaryl group, also ^{R 1, R 2, R 3} , R 4, R 5, may form a fused ring as a whole by any two of ^{R 6} and ^{R 7} binds.)
In represented by 2-tetralone compound, a palladium catalyst and, general formula (2) or general formula (3)

(In the formula, R ⁸ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁹ has 1 to 12 carbon atoms which may have a substituent. An alkyl group or an aryl group which may have a substituent or a heteroaryl group which may have a substituent; R ¹⁰ and R ¹¹ each independently represents a trifluoromethyl group, an acyl group, a substituted group; Aryl group which may have a group, heteroaryl group which may have a substituent, alkylsulfonyl group, arylsulfonyl group, heteroarylsulfonyl group, alkylsulfonyloxy group, arylsulfonyloxy group, heteroarylsulfonyl Oxy group or monovalent group (A)

(In the formula, R ¹⁴ represents an alkyl group having 1 to 12 carbon atoms which may have a substituent or an aryl group which may have a substituent.)
N represents an integer of 0 to 3. )
Dehydrogenation in the presence of at least one selected from the group consisting of an olefin compound and isophorone represented by the general formula (4)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently have the same meaning as in general formula (1).)
The manufacturing method of 2-naphthol compound represented by these. The method for producing a 2-naphthol compound according to claim 1, wherein the palladium catalyst is a heterogeneous catalyst supported on at least one carrier selected from carbon, alumina, barium sulfate, calcium carbonate, hydroxyapatite and hydrotalcite. The method for producing a 2-naphthol compound according to claim 1 or 2, wherein the palladium catalyst is palladium carbon. The method for producing a 2-naphthol compound according to any one of claims 1 to 3 , wherein the dehydrogenation is performed in the presence of at least one selected from maleic acid diester, fumaric acid diester, and isophorone . The method for producing a 2-naphthol compound according to any one of claims 1 to 4, wherein all of R ¹ , R ² and R ^{3 of the 2} -tetralone compound represented by the general formula (1) are hydrogen. The production of a 2-naphthol compound according to any one of claims 1 to 5, wherein the 2-tetralone compound represented by the general formula (1) is 2-tetralone or 7,8-difluoro-2-tetralone. Method.