JP4238046B2 - Method for producing conjugated polycyclic compound - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a conjugated polycyclic compound, and more particularly to a method for producing a conjugated polycyclic compound capable of introducing a wide range of substituents.
[0002]
[Prior art and problems to be solved by the invention]
A technique for converting two aromatic rings connected by σ bonds into condensed rings is important for organic material development.
[0003]
Conventionally, a method of introducing acetylene using nickel for biphenylene and a method of introducing acetylene using palladium for 2-iodobiphenyl have been known. However, these methods have limitations on the substituents of acetylene and cannot use a wide range of substituents.
[0004]
Therefore, there has been a demand for a method for easily and efficiently converting two aromatic rings bonded by a σ bond into a condensed ring using a wide range of substituents.
[0005]
[Means for Solving the Problems]
The inventors of the present invention reacted two aromatic rings linked by σ bonds with acetylene having various substituents in the presence of alkyllithium and chromium halide, and obtained tricyclic condensation without any substituent limitation. The present inventors have found that a ring can be obtained, and found that the number of condensed rings can be increased by repeating the method, thereby completing the present invention.
[0006]
That is, in the first aspect of the present invention, there is provided a method for producing a conjugated tricyclic compound represented by the following formula (1),
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[Where A ¹ And A ² Are independently of each other, the same or different, a hydrogen atom; an optionally substituted C ₁ ~ C ₂₀ Hydrocarbon group; 5- to 10-membered heterocyclic group which may have a substituent; C which may have a substituent ₁ ~ C ₂₀ Alkoxy group; C which may have a substituent ₆ ~ C ₂₀ Aryloxy group; amino group optionally having substituent; silyl group optionally having substituent; C optionally having substituent ₇ ~ C ₂₀ Alkylaryloxy group; optionally substituted C ₂ ~ C ₂₀ An alkoxycarbonyl group; optionally substituted C ₇ ~ C ₂₀ Aryloxycarbonyl group; cyano group (—CN); carbamoyl group (—C (═O) NH ₂ ); Haloformyl group (—C (═O) —X, wherein X represents a halogen atom); formyl group (—C (═O) —H); isocyano group; isocyanato group; thiocyanato group or thioisocyanato group However, A ¹ And A ² Are cross-linked to form C _Four ~ C _Ten A saturated ring or an unsaturated ring may be formed, and the ring is an oxygen atom, a sulfur atom, a silicon atom, a tin atom, a germanium atom, or a group represented by the formula -N (B)-(wherein B is hydrogen). Atom or C ₁ ~ C _Ten It is a hydrocarbon group. ) And may have a substituent, X ^Three And X ^Four Are independently of each other and the same or different and each represents a leaving group; ¹ Ring and B ² Each of the rings is independently of each other and is the same or different and represents a 5- to 10-membered aromatic ring which may have a substituent. A bicyclic compound represented by the following formula (2) in the presence of alkyl lithium and chromium halide;
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[Where X ^Three , X ^Four , B ¹ Ring and B ² The ring has the above meaning. X ¹ And X ² Each independently represent the same or different and represents a leaving group. An alkyne represented by the following formula (3)
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[Where A ¹ And A ² Has the above meaning. ] Is made to react, The manufacturing method of the conjugated tricyclic compound characterized by the above-mentioned is provided.
[0007]
In the first aspect of the present invention, X ¹ , X ² , X ^Three And X ^Four Are independently of each other, the same or different, a hydrogen atom, a halogen atom, a tosylate group (—O—S (═O) ₂ -C ₆ H _Four -CH _Three ), Triflate group (—O—S (═O) ₂ -CF _Three Or C ₁ ~ C ₂₀ An alkoxy group is preferred.
[0008]
In the first aspect of the present invention, X ¹ And X ² Are the same groups and / or X ^Three And X ^Four May be the same group, and X ¹ And X ² At least one of is a hydrogen atom and / or X ^Three And X ^Four At least one of may be a hydrogen atom.
[0009]
In the first aspect of the present invention, A ¹ And A ² Are each independently the same or different and may have a substituent. ₁ ~ C ₂₀ Hydrocarbon group; 5- to 7-membered heterocyclic group which may have a substituent; C which may have a substituent ₁ ~ C ₂₀ Alkoxy group; C which may have a substituent ₆ ~ C ₂₀ Aryloxy group; optionally substituted C ₇ ~ C ₂₀ Alkylaryloxy group; optionally substituted C ₂ ~ C ₂₀ C which may have an alkoxycarbonyl group or a substituent ₇ ~ C ₂₀ An aryloxycarbonyl group is preferred.
[0010]
In the first aspect of the present invention, the bicyclic compound represented by the formula (2) is a biphenyl derivative represented by the following formula (2) ′;
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[Where X ¹ , X ² , X ^Three And X ^Four Has the above meaning. R ² , R ^Three , R ^Four , R ⁶ , R ⁷ And R ⁸ Are independently of each other, the same or different, a hydrogen atom; an optionally substituted C ₁ ~ C ₂₀ Hydrocarbon group; optionally substituted C ₁ ~ C ₂₀ Alkoxy group; C which may have a substituent ₆ ~ C ₂₀ An aryloxy group; an amino group which may have a substituent; a silyl group which may have a substituent; a hydroxyl group or a halogen atom; ^Three And R ² , R ² And R ^Three , R ^Three And R ^Four , X ^Four And R ⁶ , R ⁶ And R ⁷ And R ⁷ And R ⁸ Are cross-linked with each other to form C _Four ~ C ₂₀ A saturated ring or an unsaturated ring may be formed, and the ring is an oxygen atom, a sulfur atom, a silicon atom, a tin atom, a germanium atom, or a group represented by the formula -N (B)-(wherein B is hydrogen). Atom or C ₁ ~ C ₂₀ It is a hydrocarbon group. ) And may have a substituent. The conjugated tricyclic compound represented by the formula (1) is represented by the following formula (1) ′
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[Where A ¹ , A ² , X ^Three , R ² , R ^Three , R ^Four , X ^Four , R ⁶ , R ⁷ And R ⁸ Has the above meaning. ] The phenanthrene derivative shown by this may be sufficient.
[0011]
In this case, X ^Three , R ² , R ^Three , R ^Four , X ^Four , R ⁶ , R ⁷ And R ⁸ Is preferably a hydrogen atom.
[0012]
In the first aspect of the present invention, B ¹ Ring and B ² The rings may be the same ring.
[0013]
In the first aspect of the present invention, B ¹ Ring and B ² At least one of the rings may be an aromatic ring containing a nitrogen atom, a sulfur atom or an oxygen atom.
[0014]
In this case, the bicyclic compound represented by the formula (2) is a 1-phenylpyrrole derivative represented by the following formula (2) ",
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[Where X ¹ , X ² , X ^Three And X ^Four Has the above meaning. R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ And R ¹⁷ Are independently of each other, the same or different, a hydrogen atom; an optionally substituted C ₁ ~ C ₂₀ Hydrocarbon group; optionally substituted C ₁ ~ C ₂₀ Alkoxy group; C which may have a substituent ₆ ~ C ₂₀ An aryloxy group; an amino group which may have a substituent; a silyl group which may have a substituent; a hydroxyl group or a halogen atom; ^Three And R ¹² , R ¹² And R ¹³ , R ¹³ And R ¹⁴ , X ^Four And R ¹⁶ And R ¹⁶ And R ¹⁷ Are cross-linked with each other to form C _Four ~ C ₂₀ A saturated ring or an unsaturated ring may be formed, and the ring is an oxygen atom, a sulfur atom, a silicon atom, a tin atom, a germanium atom, or a group represented by the formula -N (B)-(wherein B is hydrogen). Atom or C ₁ ~ C ₂₀ It is a hydrocarbon group. ) And may have a substituent. The conjugated tricyclic compound represented by the formula (1) is represented by the following formula (1) "
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[Where A ¹ , A ² , X ^Three , R ¹² , R ¹³ , R ¹⁴ , X ^Four , R ¹⁶ And R ¹⁷ Has the above meaning. It is preferable that it is a compound shown by this.
[0015]
In this case, X ^Three , R ¹² , R ¹³ , R ¹⁴ , X ^Four , R ¹⁶ And R ¹⁷ Is more preferably a hydrogen atom.
[0016]
In the first embodiment of the present invention, the conjugated tricyclic compound represented by the formula (1) is 9-n-butylphenanthrene, 9-ethoxycarbonyl-10-methylphenanthrene, 9-ethyl-10- ( 3-butynyl) phenanthrene, 9-phenylphenanthrene, 9-methylphenanthrene, 9-methyl-10-phenylphenanthrene, pyrrole [1,2-a] -3,4-diethylquinoline, or pyrrole [1,2-a ] -3,4-diphenylquinoline is preferred.
[0017]
In the second aspect of the present invention, there is provided a process for producing a conjugated tetracyclic compound obtained by further condensing the conjugated tricyclic compound obtained in the first aspect, that is, the conjugate represented by the following formula (4). A method for producing a tetracyclic compound comprising:
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[Where A ¹ , A ² , A ^Three And A ^Four Are independently of each other, the same or different, a hydrogen atom; an optionally substituted C ₁ ~ C ₂₀ Hydrocarbon group; 5- to 10-membered heterocyclic group which may have a substituent; C which may have a substituent ₁ ~ C ₂₀ Alkoxy group; C which may have a substituent ₆ ~ C ₂₀ Aryloxy group; amino group optionally having substituent; silyl group optionally having substituent; C optionally having substituent ₇ ~ C ₂₀ Alkylaryloxy group; optionally substituted C ₂ ~ C ₂₀ An alkoxycarbonyl group; optionally substituted C ₇ ~ C ₂₀ Aryloxycarbonyl group; cyano group (—CN); carbamoyl group (—C (═O) NH ₂ ); Haloformyl group (—C (═O) —X, wherein X represents a halogen atom); formyl group (—C (═O) —H); isocyano group; isocyanato group; thiocyanato group or thioisocyanato group However, A ¹ And A ² And A ^Three And A ^Four Are cross-linked to form C _Four ~ C _Ten A saturated ring or an unsaturated ring may be formed, and the ring is an oxygen atom, a sulfur atom, a silicon atom, a tin atom, a germanium atom, or a group represented by the formula -N (B)-(wherein B is hydrogen). Atom or C ₁ ~ C _Ten It is a hydrocarbon group. ) And may have a substituent, B ¹ Ring and B ² Each of the rings is independently of each other and is the same or different and represents a 5- to 10-membered aromatic ring which may have a substituent. A conjugated tricyclic compound represented by the following formula (1) in the presence of alkyllithium and chromium halide;
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[Where A ¹ , A ² , B ¹ Ring and B ² The ring has the above meaning. X ^Three And X ^Four Each independently represent the same or different and represents a leaving group. The alkyne represented by the following formula (5)
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[Where A ^Three And A ^Four Has the above meaning. ] Is made to react, The manufacturing method of the conjugated tetracyclic compound characterized by the above-mentioned is provided.
[0018]
In a second aspect of the invention, X ^Three And X ^Four Are independently of each other, the same or different, a hydrogen atom, a halogen atom, a tosylate group (—O—S (═O) ₂ -C ₆ H _Four -CH _Three ), Triflate group (—O—S (═O) ₂ -CF _Three Or C ₁ ~ C ₂₀ An alkoxy group is preferred.
[0019]
In the second aspect of the present invention, X ^Three And X ^Four May be the same group, and X ^Three And X ^Four At least one of may be a hydrogen atom.
[0020]
In the second aspect of the present invention, A ¹ , A ² , A ^Three And A ^Four Are each independently the same or different and may have a substituent. ₁ ~ C ₂₀ Hydrocarbon group; 5- to 7-membered heterocyclic group which may have a substituent; C which may have a substituent ₁ ~ C ₂₀ Alkoxy group; C which may have a substituent ₆ ~ C ₂₀ Aryloxy group; optionally substituted C ₇ ~ C ₂₀ Alkylaryloxy group; optionally substituted C ₂ ~ C ₂₀ C which may have an alkoxycarbonyl group or a substituent ₇ ~ C ₂₀ An aryloxycarbonyl group is preferred.
[0021]
In the second aspect of the present invention, the conjugated tricyclic compound represented by the formula (1) is a phenanthrene derivative represented by the following formula (1) ′.
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[Where A ¹ , A ² , X ^Three And X ^Four Has the above meaning. R ² , R ^Three , R ^Four , R ⁶ , R ⁷ And R ⁸ Are independently of each other, the same or different, a hydrogen atom; an optionally substituted C ₁ ~ C ₂₀ Hydrocarbon group; optionally substituted C ₁ ~ C ₂₀ Alkoxy group; C which may have a substituent ₆ ~ C ₂₀ An aryloxy group; an amino group which may have a substituent; a silyl group which may have a substituent; a hydroxyl group or a halogen atom; ² And R ^Three , R ^Three And R ^Four , R ⁶ And R ⁷ And R ⁷ And R ⁸ Are cross-linked with each other to form C _Four ~ C ₂₀ A saturated ring or an unsaturated ring may be formed, and the ring is an oxygen atom, a sulfur atom, a silicon atom, a tin atom, a germanium atom, or a group represented by the formula -N (B)-(wherein B is hydrogen). Atom or C ₁ ~ C ₂₀ It is a hydrocarbon group. ) And may have a substituent. The conjugated tetracyclic compound represented by the formula (4) is represented by the following formula (4) ′
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[Where A ¹ , A ² , A ^Three , A ^Four , R ² , R ^Three , R ^Four , R ⁶ , R ⁷ And R ⁸ Has the above meaning. ] The pyrene derivative shown by this may be sufficient.
[0022]
In this case, R ² , R ^Three , R ^Four , R ⁶ , R ⁷ And R ⁸ Is preferably a hydrogen atom.
[0023]
In the second aspect of the present invention, B ¹ Ring and B ² The rings may be the same ring.
[0024]
In the second aspect of the present invention, B ¹ Ring and B ² At least one of the rings may be an aromatic ring containing a nitrogen atom, a sulfur atom or an oxygen atom.
[0025]
In this case, the conjugated tricyclic compound represented by the formula (1) is a compound represented by the following formula (1) ",
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[Where A ¹ , A ² , X ^Three And X ^Four Has the above meaning.
R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ And R ¹⁷ Are independently of each other, the same or different, a hydrogen atom; an optionally substituted C ₁ ~ C ₂₀ Hydrocarbon group; optionally substituted C ₁ ~ C ₂₀ Alkoxy group; C which may have a substituent ₆ ~ C ₂₀ An aryloxy group; an amino group which may have a substituent; a silyl group which may have a substituent; a hydroxyl group or a halogen atom; ¹² And R ¹³ , R ¹³ And R ¹⁴ And R ¹⁶ And R ¹⁷ Are cross-linked with each other to form C _Four ~ C ₂₀ A saturated ring or an unsaturated ring may be formed, and the ring is an oxygen atom, a sulfur atom, a silicon atom, a tin atom, a germanium atom, or a group represented by the formula -N (B)-(wherein B is hydrogen). Atom or C ₁ ~ C ₂₀ It is a hydrocarbon group. ) And may have a substituent. The conjugated tetracyclic compound represented by the formula (4) is represented by the following formula (4) "
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[Where A ¹ , A ² , A ^Three , A ^Four , R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ And R ¹⁷ Has the above meaning. It is preferable that it is a compound shown by these.
[0026]
In this case, R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ And R ¹⁷ Is more preferably a hydrogen atom.
[0027]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, a bicyclic compound represented by the following formula (2) is reacted with an alkyne represented by the following formula (3) in the presence of alkyllithium and chromium halide. The manufacturing method of the conjugated tricyclic compound shown by these is provided.
[0028]
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[Where A ¹ , A ² , B ¹ Ring, B ² Ring, X ¹ , X ² , X ^Three And X ^Four Has the above meaning. ]
[0029]
In the above formula (1), A ¹ And A ² Are independently of each other, the same or different, a hydrogen atom; an optionally substituted C ₁ ~ C ₂₀ Hydrocarbon group; 5- to 10-membered heterocyclic group which may have a substituent; C which may have a substituent ₁ ~ C ₂₀ Alkoxy group; C which may have a substituent ₆ ~ C ₂₀ Aryloxy group; amino group optionally having substituent; silyl group optionally having substituent; C optionally having substituent ₇ ~ C ₂₀ Alkylaryloxy group; optionally substituted C ₂ ~ C ₂₀ An alkoxycarbonyl group; optionally substituted C ₇ ~ C ₂₀ Aryloxycarbonyl group; cyano group (—CN); carbamoyl group (—C (═O) NH ₂ ); Haloformyl group (—C (═O) —X, wherein X represents a halogen atom); formyl group (—C (═O) —H); isocyano group; isocyanato group; thiocyanato group or thioisocyanato group It is.
[0030]
In this specification, “C ₁ ~ C ₂₀ The hydrocarbon group of the “hydrocarbon group” may be saturated or unsaturated acyclic, or may be saturated or unsaturated cyclic. C ₁ ~ C ₂₀ When the hydrocarbon group is acyclic, it may be linear or branched. “C ₁ ~ C ₂₀ Hydrocarbon group includes C ₁ ~ C ₂₀ Alkyl group, C ₂ ~ C ₂₀ Alkenyl group, C ₂ ~ C ₂₀ Alkynyl group, C _Four ~ C ₂₀ Alkyldienyl group, C ₆ ~ C ₁₈ Aryl group, C ₆ ~ C ₂₀ Alkylaryl group, C ₆ ~ C ₂₀ Arylalkyl group, C _Four ~ C ₂₀ A cycloalkyl group, C _Four ~ C ₂₀ A cycloalkenyl group, (C _Three ~ C _Ten Cycloalkyl) C ₁ ~ C _Ten Alkyl groups and the like are included.
[0031]
In this specification, “C ₁ ~ C ₂₀ “Alkyl group” means C ₁ ~ C _Ten It is preferably an alkyl group, C ₁ ~ C ₆ More preferably, it is an alkyl group. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, dodecanyl and the like.
[0032]
In this specification, “C ₂ ~ C ₂₀ An alkenyl group is C ₂ ~ C _Ten An alkenyl group is preferred, and C ₂ ~ C ₆ More preferably, it is an alkenyl group. Examples of alkenyl groups include, but are not limited to, vinyl, allyl, propenyl, isopropenyl, 2-methyl-1-propenyl, 2-methylallyl, 2-butenyl and the like.
[0033]
In this specification, “C ₂ ~ C ₂₀ An alkynyl group is C ₂ ~ C _Ten Preferably it is an alkynyl group, C ₂ ~ C ₆ More preferably, it is an alkynyl group. Examples of alkynyl groups include, but are not limited to, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl and the like.
[0034]
In this specification, “C _Four ~ C ₂₀ An alkyldienyl group is C _Four ~ C _Ten It is preferably an alkyldienyl group, C _Four ~ C ₆ More preferably, it is an alkyldienyl group. Examples of alkyldienyl groups include, but are not limited to, 1,3-butadienyl and the like.
[0035]
In this specification, “C ₆ ~ C ₁₈ "Aryl group" means C ₆ ~ C _Ten An aryl group is preferred. Examples of the aryl group include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenylyl, anthryl, phenanthryl and the like.
[0036]
In this specification, “C ₆ ~ C ₂₀ An alkylaryl group is C ₆ ~ C ₁₂ An alkylaryl group is preferred. Examples of alkylaryl groups include, but are not limited to, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, o-cumenyl, m -Cumenyl, p-cumenyl, mesityl and the like can be mentioned.
[0037]
In this specification, “C ₆ ~ C ₂₀ An arylalkyl group is C ₆ ~ C ₁₂ An arylalkyl group is preferred. Examples of arylalkyl groups include, but are not limited to, benzyl, phenethyl, diphenylmethyl, triphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-phenyl Examples include phenylbutyl and 5-phenylpentyl.
[0038]
In this specification, “C _Four ~ C ₂₀ A cycloalkyl group is C _Four ~ C _Ten A cycloalkyl group is preferred. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
[0039]
In this specification, “C _Four ~ C ₂₀ “Cycloalkenyl group” means C _Four ~ C _Ten A cycloalkenyl group is preferred. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, and the like.
[0040]
In the present specification, the “5- to 10-membered heterocyclic group” includes a monovalent group formed by removing any one hydrogen atom from a 5- to 10-membered heterocyclic ring.
In the present specification, examples of the “5-membered to 10-membered heterocyclic ring” include aromatic rings containing nitrogen atom, sulfur atom or oxygen atom, and furan, thiophene, pyrrole, pyran, pyridine, pyrazine, pyridazine. , Pyrimidine, thiopyran, thiazole, isothiazole, imidazole, quinoline, isoquinoline, indole, indolizine, benzofuran, isobenzofuran, 1,3,5-triazine and the like.
[0041]
In this specification, “C ₁ ~ C ₂₀ “Alkoxy group” means C ₁ ~ C _Ten An alkoxy group is preferred, and C ₁ ~ C ₆ More preferably, it is an alkoxy group. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentyloxy and the like.
[0042]
In this specification, “C ₆ ~ C ₂₀ An aryloxy group is C ₆ ~ C _Ten An aryloxy group is preferred. Examples of aryloxy groups include, but are not limited to, phenyloxy, naphthyloxy, biphenyloxy, and the like.
[0043]
In this specification, “C ₇ ~ C ₂₀ An alkylaryloxy group is C ₇ ~ C ₁₂ An alkylaryloxy group is preferred. Examples of alkylaryloxy groups include, but are not limited to, methylphenyloxy, ethylphenyloxy, propylphenyloxy, butylphenyloxy, dimethylphenyloxy, diethylphenyloxy, dipropylphenyloxy, dibutylphenyloxy, methyl Examples thereof include ethylphenyloxy, methylpropylphenyloxy, ethylpropylphenyloxy and the like.
[0044]
In this specification, “C ₂ ~ C ₂₀ An alkoxycarbonyl group is C ₂ ~ C _Ten An alkoxycarbonyl group is preferred. Examples of alkoxycarbonyl groups include, but are not limited to, methoxycarbonyl, ethoxycarbonyl, 2-methoxyethoxycarbonyl, t-butoxycarbonyl, and the like.
[0045]
In this specification, “C ₇ ~ C ₂₀ An aryloxycarbonyl group is C ₇ ~ C ₁₂ An aryloxycarbonyl group is preferred. Examples of the aryloxycarbonyl group include, but are not limited to, phenoxycarbonyl, naphthoxycarbonyl, phenylphenoxycarbonyl, and the like.
[0046]
Note that the carbamoyl group (—C (═O) NH ₂ ), A haloformyl group (—C (═O) —X, wherein X represents a halogen atom), a formyl group (—C (═O) —H) and the like are mutually converted into a cyano group and an alkoxycarbonyl group. can do.
[0047]
A ¹ And R ² "C" ₁ ~ C ₂₀ "Hydrocarbon group", "5- to 10-membered heterocyclic group", "C ₁ ~ C ₂₀ Alkoxy group "," C ₆ ~ C ₂₀ Aryloxy group, amino group, silyl group, C ₇ ~ C ₂₀ Alkylaryloxy "," C ₂ ~ C ₂₀ Alkoxycarbonyl group "," C ₇ ~ C ₂₀ A substituent may be introduced into the “aryloxycarbonyl group”. As this substituent, for example, C ₁ ~ C _Ten Hydrocarbon group (eg, methyl, ethyl, propyl, butyl, phenyl, naphthyl, indenyl, tolyl, xylyl, benzyl, etc.), C ₁ ~ C _Ten An alkoxy group (for example, methoxy, ethoxy, propoxy, butoxy, etc.), C ₆ ~ C _Ten An aryloxy group (for example, phenyloxy, naphthyloxy, biphenyloxy, etc.), an amino group, a hydroxyl group, a halogen atom (for example, fluorine, chlorine, bromine, iodine) or a silyl group can be exemplified. In this case, one or more substituents may be introduced at substitutable positions, and preferably 1 to 4 substituents may be introduced. When the number of substituents is 2 or more, each substituent may be the same or different.
[0048]
In the present specification, examples of “optionally substituted amino group” include, but are not limited to, amino, dimethylamino, methylamino, methylphenylamino, phenylamino and the like.
[0049]
In this specification, examples of “optionally substituted silyl group” include, but are not limited to, dimethylsilyl, diethylsilyl, trimethylsilyl, triethylsilyl, trimethoxysilyl, triethoxysilyl, diphenyl Examples include methylsilyl, triphenylsilyl, triphenoxysilyl, dimethylmethoxysilyl, dimethylphenoxysilyl, and methylmethoxyphenyl.
[0050]
In the present invention, A ¹ And A ² Are cross-linked to form C _Four ~ C ₂₀ A saturated ring or an unsaturated ring may be formed. The ring formed by these substituents is preferably a 4-membered ring to a 16-membered ring, and more preferably a 4-membered ring to a 12-membered ring. This ring may be an aromatic ring such as a benzene ring or an aliphatic ring. One or more rings may be further formed on the ring formed by these substituents.
[0051]
The saturated ring or unsaturated ring is an oxygen atom, a sulfur atom, a silicon atom, a tin atom, a germanium atom, or a group represented by the formula —N (B) — (wherein B is a hydrogen atom or C ₁ ~ C ₂₀ It is a hydrocarbon group. ) May be interrupted. That is, the saturated ring or unsaturated ring may be a heterocyclic ring. And you may have a substituent. The unsaturated ring may be an aromatic ring such as a benzene ring.
[0052]
B is a hydrogen atom or C ₁ ~ C _Ten It is preferably a hydrocarbon group, a hydrogen atom or C ₁ ~ C ₇ More preferably, it is a hydrocarbon group, B is a hydrogen atom, C ₁ ~ C _Three More preferably, it is an alkyl group, a phenyl group or a benzyl group.
[0053]
This saturated ring or unsaturated ring may have a substituent, for example, C ₁ ~ C _Ten Hydrocarbon group (eg, methyl, ethyl, propyl, butyl, etc.), C ₁ ~ C _Ten An alkoxy group (for example, methoxy, ethoxy, propoxy, butoxy, etc.), C ₆ ~ C _Ten A substituent such as an aryloxy group (for example, phenyloxy, naphthyloxy, biphenyloxy, etc.), an amino group, a hydroxyl group, a halogen atom (for example, fluorine, chlorine, bromine, iodine) or a silyl group may be introduced.
[0054]
In the present invention, A ¹ And A ² Are each independently the same or different and may have a substituent. ₁ ~ C ₂₀ Hydrocarbon group; 5- to 7-membered heterocyclic group which may have a substituent; C which may have a substituent ₁ ~ C ₂₀ Alkoxy group; C which may have a substituent ₆ ~ C ₂₀ Aryloxy group; optionally substituted C ₇ ~ C ₂₀ Alkylaryloxy group; optionally substituted C ₂ ~ C ₂₀ C which may have an alkoxycarbonyl group or a substituent ₇ ~ C ₂₀ An aryloxycarbonyl group is preferred.
[0055]
A ¹ And A ² Is C ₁ ~ C _Ten Alkyl group; C ₁ ~ C _Ten Alkenyl group; C ₁ ~ C _Ten Alkynyl group; C ₆ ~ C _Ten Aryl group; 2- or 3-thienyl group; C ₁ ~ C _Ten Alkoxy group; C ₆ ~ C ₁₂ Aryloxy group; C ₇ ~ C ₁₂ Alkylaryloxy group; C ₂ ~ C _Ten Alkoxycarbonyl group; C ₇ ~ C ₁₂ An aryloxycarbonyl group or a silyl group which may have a substituent is more preferable, and methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, vinyl, allyl, propenyl, iso Propenyl, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, phenyl, 2-thienyl, 3-thienyl, phenyloxy, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, dimethylsilyl, diethyl More preferred is silyl, trimethylsilyl or triethylsilyl.
[0056]
In the above formula (1), X ^Three And X ^Four Each independently represent the same or different and represents a leaving group. Examples of the leaving group include a hydrogen atom, a halogen atom such as F, Cl, Br, and I, and a tosylate group (—O—S (═O). ₂ -C ₆ H _Four -CH _Three ), Triflate group (—O—S (═O) ₂ -CF _Three Or C ₁ ~ C ₂₀ An alkoxy group etc. are mentioned. In the present invention, X ^Three And X ^Four Are each preferably a hydrogen atom, a halogen atom, an alkoxy group or a tosylate group, more preferably a hydrogen atom, Cl, Br, I or a tosylate group.
In the present invention, X ^Three And X ^Four Are preferably the same group. Or X ^Three And X ^Four It is preferable that at least one of is a hydrogen atom.
[0057]
In the present invention, B ¹ Ring and B ² Each of the rings is independently of each other and is the same or different and represents a 5- to 10-membered aromatic ring which may have a substituent.
[0058]
In the present specification, examples of the “5- to 10-membered aromatic ring” include a benzene ring and a 5- to 10-membered heterocyclic ring.
[0059]
In the present invention, B ¹ Ring and B ² At least one of the rings may be a heteroaromatic ring containing a nitrogen atom, a sulfur atom or an oxygen atom. Examples of such a heteroaromatic ring include pyrrole, furan, thiophene, pyridine, pyrazine, pyridazine, pyrimidine, and thiazole. , Isothiazole, imidazole, quinoline, isoquinoline, indole, indolizine, benzofuran, isobenzofuran and the like.
[0060]
B ¹ Ring and B ² A substituent may be introduced into the “aromatic ring” represented by the ring. As this substituent, for example, C ₁ ~ C _Ten Hydrocarbon group (eg, methyl, ethyl, propyl, butyl, etc.), C ₁ ~ C _Ten An alkoxy group (for example, methoxy, ethoxy, propoxy, butoxy, etc.), C ₆ ~ C _Ten An aryloxy group (for example, phenyloxy, naphthyloxy, biphenyloxy, etc.), an amino group, a hydroxyl group, a halogen atom (for example, fluorine, chlorine, bromine, iodine) or a silyl group can be exemplified. In this case, one or more substituents may be introduced at substitutable positions, and preferably 1 to 4 substituents may be introduced. When the number of substituents is 2 or more, each substituent may be the same or different.
[0061]
In the first embodiment of the present invention, a bicyclic compound represented by the following formula (2) is used.
Embedded image
[Where X ^Three , X ^Four , B ¹ Ring and B ² The ring has the above meaning.
[0062]
In the present invention, X ¹ And X ² Each independently represent the same or different and represents a leaving group. Examples of the leaving group include a hydrogen atom, a halogen atom such as F, Cl, Br, and I, and a tosylate group (—O—S (═O). ₂ -C ₆ H _Four -CH _Three ), Triflate group (—O—S (═O) ₂ -CF _Three Or C ₁ ~ C ₂₀ An alkoxy group etc. are mentioned. In the present invention, X ¹ And X ² Are each preferably a hydrogen atom, a halogen atom, an alkoxy group or a tosylate group, more preferably a Cl, Br, I or tosylate group.
In the present invention, X ¹ And X ² Are preferably the same group. Or X ¹ And X ² It is preferable that at least one of is a hydrogen atom.
[0063]
In the first aspect of the present invention, the formula (2) may be a biphenyl derivative represented by the following formula (2) ′.
Embedded image
[Where X ¹ , X ² , X ^Three And X ^Four Has the above meaning. ]
[0064]
R ² , R ^Three , R ^Four , R ⁶ , R ⁷ And R ⁸ Are independently of each other, the same or different, a hydrogen atom; optionally substituted C ₁ ~ C ₂₀ Hydrocarbon group; optionally substituted C ₁ ~ C ₂₀ Alkoxy group; C which may have a substituent ₆ ~ C ₂₀ An aryloxy group; an amino group which may have a substituent; a silyl group which may have a substituent; a hydroxyl group; or a halogen atom.
[0065]
R ² , R ^Three , R ^Four , R ⁶ , R ⁷ And R ⁸ "C" ₁ ~ C ₂₀ Hydrocarbon group ”,“ C ₁ ~ C ₂₀ Alkoxy group "," C ₆ ~ C ₂₀ Substituents may be introduced into the “aryloxy group”, “amino group”, and “silyl group”. As this substituent, for example, C ₁ ~ C _Ten Hydrocarbon group (eg, methyl, ethyl, propyl, butyl, phenyl, naphthyl, indenyl, tolyl, xylyl, benzyl, etc.), C ₁ ~ C _Ten An alkoxy group (for example, methoxy, ethoxy, propoxy, butoxy, etc.), C ₆ ~ C _Ten An aryloxy group (for example, phenyloxy, naphthyloxy, biphenyloxy, etc.), an amino group, a hydroxyl group, a halogen atom (for example, fluorine, chlorine, bromine, iodine) or a silyl group can be exemplified. In this case, one or more substituents may be introduced at substitutable positions, and preferably 1 to 4 substituents may be introduced. When the number of substituents is 2 or more, each substituent may be the same or different.
[0066]
In the present invention, X ^Three And R ² , R ² And R ^Three , R ^Three And R ^Four , X ^Four And R ⁶ , R ⁶ And R ⁷ And R ⁷ And R ⁸ Are cross-linked with each other to form C _Four ~ C _Ten A saturated ring or an unsaturated ring may be formed. The ring formed by these substituents is preferably a 4-membered ring to a 16-membered ring, and more preferably a 4-membered ring to a 12-membered ring. This ring may be an aromatic ring such as a benzene ring or an aliphatic ring. One or more rings may be further formed on the ring formed by these substituents. The saturated ring or unsaturated ring is an oxygen atom, a sulfur atom, a silicon atom, a tin atom, a germanium atom, or a group represented by the formula —N (B) — (wherein B is a hydrogen atom or C ₁ ~ C ₂₀ It is a hydrocarbon group. ) May be interrupted. That is, the saturated ring or unsaturated ring may be a heterocyclic ring. And you may have a substituent. The unsaturated ring may be an aromatic ring such as a benzene ring.
[0067]
B is a hydrogen atom or C ₁ ~ C _Ten It is preferably a hydrocarbon group, a hydrogen atom or C ₁ ~ C ₇ More preferably, it is a hydrocarbon group, B is a hydrogen atom, C ₁ ~ C _Three More preferably, it is an alkyl group, a phenyl group or a benzyl group.
[0068]
This saturated ring or unsaturated ring may have a substituent, for example, C ₁ ~ C _Ten Hydrocarbon group (eg, methyl, ethyl, propyl, butyl, etc.), C ₁ ~ C _Ten An alkoxy group (for example, methoxy, ethoxy, propoxy, butoxy, etc.), C ₆ ~ C _Ten A substituent such as an aryloxy group (for example, phenyloxy, naphthyloxy, biphenyloxy, etc.), an amino group, a hydroxyl group, a halogen atom (for example, fluorine, chlorine, bromine, iodine) or a silyl group may be introduced.
[0069]
In the present invention, in the above formula (2) ′, X ^Three , R ² , R ^Three , R ^Four , X ^Four , R ⁶ , R ⁷ And R ⁸ Is preferably a hydrogen atom.
[0070]
In the present invention, when the above formula (2) is a biphenyl derivative represented by the above formula (2) ′, the compound obtained by the production method of the present invention is a phenanthrene derivative represented by the following formula (1) ′. It becomes.
Embedded image
[Where A ¹ , A ² , X ^Three , R ² , R ^Three , R ^Four , X ^Four , R ⁶ , R ⁷ And R ⁸ Has the above meaning. ]
[0071]
In the first aspect of the present invention, the formula (2) may be a 1-phenylpyrrole derivative represented by the following formula (2) ″.
Embedded image
[Where X ¹ , X ² , X ^Three And X ^Four Has the above meaning.
[0072]
R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ And R ¹⁷ Are independently of each other, the same or different, a hydrogen atom; optionally substituted C ₁ ~ C ₂₀ Hydrocarbon group; optionally substituted C ₁ ~ C ₂₀ Alkoxy group; C which may have a substituent ₆ ~ C ₂₀ An aryloxy group; an amino group which may have a substituent; a silyl group which may have a substituent; a hydroxyl group; or a halogen atom.
[0073]
R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ And R ¹⁷ "C" ₁ ~ C ₂₀ Hydrocarbon group ”,“ C ₁ ~ C ₂₀ Alkoxy group "," C ₆ ~ C ₂₀ Substituents may be introduced into the “aryloxy group”, “amino group”, and “silyl group”. As this substituent, for example, C ₁ ~ C _Ten Hydrocarbon group (eg, methyl, ethyl, propyl, butyl, phenyl, naphthyl, indenyl, tolyl, xylyl, benzyl, etc.), C ₁ ~ C _Ten An alkoxy group (for example, methoxy, ethoxy, propoxy, butoxy, etc.), C ₆ ~ C _Ten An aryloxy group (for example, phenyloxy, naphthyloxy, biphenyloxy, etc.), an amino group, a hydroxyl group, a halogen atom (for example, fluorine, chlorine, bromine, iodine) or a silyl group can be exemplified. In this case, one or more substituents may be introduced at substitutable positions, and preferably 1 to 4 substituents may be introduced. When the number of substituents is 2 or more, each substituent may be the same or different.
[0074]
In the present invention, X ^Three And R ¹² , R ¹² And R ¹³ , R ¹³ And R ¹⁴ , X ^Four And R ¹⁶ And R ¹⁶ And R ¹⁷ Are cross-linked with each other to form C _Four ~ C _Ten A saturated ring or an unsaturated ring may be formed. The ring formed by these substituents is preferably a 4-membered ring to a 16-membered ring, and more preferably a 4-membered ring to a 12-membered ring. This ring may be an aromatic ring such as a benzene ring or an aliphatic ring. One or more rings may be further formed on the ring formed by these substituents.
The saturated ring or unsaturated ring is an oxygen atom, a sulfur atom, a silicon atom, a tin atom, a germanium atom, or a group represented by the formula —N (B) — (wherein B is a hydrogen atom or C ₁ ~ C ₂₀ It is a hydrocarbon group. ) May be interrupted. That is, the saturated ring or unsaturated ring may be a heterocyclic ring. And you may have a substituent. The unsaturated ring may be an aromatic ring such as a benzene ring.
[0075]
B is a hydrogen atom or C ₁ ~ C _Ten It is preferably a hydrocarbon group, a hydrogen atom or C ₁ ~ C ₇ More preferably, it is a hydrocarbon group, B is a hydrogen atom, C ₁ ~ C _Three More preferably, it is an alkyl group, a phenyl group or a benzyl group.
[0076]
This saturated ring or unsaturated ring may have a substituent, for example, C ₁ ~ C _Ten Hydrocarbon group (eg, methyl, ethyl, propyl, butyl, etc.), C ₁ ~ C _Ten An alkoxy group (for example, methoxy, ethoxy, propoxy, butoxy, etc.), C ₆ ~ C _Ten A substituent such as an aryloxy group (for example, phenyloxy, naphthyloxy, biphenyloxy, etc.), an amino group, a hydroxyl group, a halogen atom (for example, fluorine, chlorine, bromine, iodine) or a silyl group may be introduced.
[0077]
In the present invention, in the above formula (2) ", X ^Three , R ¹² , R ¹³ , R ¹⁴ , X ^Four , R ¹⁶ And R ¹⁷ Is preferably a hydrogen atom.
[0078]
In the present invention, when the above formula (2) is a 1-phenylpyrrole derivative represented by the above formula (2) ″, the compound obtained by the production method of the present invention is represented by the following formula (1) ″. It becomes a compound.
Embedded image
[Where A ¹ , A ² , X ^Three , R ¹² , R ¹³ , R ¹⁴ , X ^Four , R ¹⁶ And R ¹⁷ Has the above meaning. ]
[0079]
In the present invention, the tricyclic compound represented by the above formula (1) is 9-n-butylphenanthrene, 9-ethoxycarbonyl-10-methylphenanthrene, 9-ethyl-10- (3-butynyl) phenanthrene, 9- Phenylphenanthrene, 9-methylphenanthrene, 9-methyl-10-phenylphenanthrene, pyrrole [1,2-a] -3,4-diethylquinoline, or pyrrole [1,2-a] -3,4-diphenylquinoline It is preferable that
[0080]
In the method for producing a tricyclic compound according to the first aspect of the present invention, an alkyne represented by the following formula (3) is used.
Embedded image
[Where A ¹ And A ² Has the above meaning. ]
[0081]
In the present invention, the amount of the alkyne represented by the above formula (3) is 0.1 mol to 100 mol, preferably 0.5 mol, per 1 mol of the bicyclic compound represented by the above formula (2). It is -3 mol, More preferably, it is 0.8 mol-1.5 mol.
[0082]
In the method for producing a tricyclic compound according to the first aspect of the present invention, the reaction is performed in the presence of alkyllithium and a chromium halide.
[0083]
In the first aspect of the present invention, the alkyl lithium includes C ₁ ~ C ₆ Alkyl lithium can be mentioned, and n-butyl lithium, s-butyl lithium, t-butyl lithium and the like can be preferably mentioned.
[0084]
In the first embodiment of the present invention, the amount of alkyl lithium is 0.1 mol to 100 mol, preferably 0.5 mol to 5 mol, relative to 1 mol of the bicyclic compound represented by the above formula (2). More preferably, it is 0.8 mol-3 mol.
In the method for producing a tricyclic compound of the present invention, a normal activator of alkyl lithium may be added to the reaction system. An example of such an activator is tetramethylethylenediamine (TMEDA). The amount of activator is preferably from 1 mol to 5 mol.
[0085]
In the first aspect of the present invention, the chromium halide includes CrX. _Three (X is a halogen atom such as F, Cl, Br, or I), CrCl _Three Can be preferably mentioned.
[0086]
In the first aspect of the present invention, the amount of chromium halide is 0.1 mol to 100 mol, preferably 0.5 mol to 5 mol, per 1 mol of the bicyclic compound represented by the above formula (2). Mol, and more preferably 0.8 mol to 3 mol.
[0087]
In the first embodiment of the present invention, the tricyclic compound is typically obtained by adding alkyllithium, chromium halide, alkyne (3) to a solution of the bicyclic compound represented by the above formula (2), Stir to produce. The order of addition is preferably the order of alkyl lithium, chromium halide and alkyne (3).
[0088]
In the first embodiment of the present invention, when the alkyllithium and the bicyclic compound (2) react, first, the leaving group near the axis in the bicyclic compound (2) exchanges with lithium. Subsequently, it is thought that chromium exchange causes a metal exchange reaction from lithium to chromium, and alkyne (3) reacts with this to produce tricyclic compound (1).
[0089]
In addition, the said reaction mechanism is only a hypothesis and this invention is not limited to these reaction mechanisms.
[0090]
In the first embodiment of the present invention, the reaction is preferably performed in a temperature range of −100 ° C. to 300 ° C., particularly preferably in a temperature range of −80 ° C. to 200 ° C., and more preferably in a temperature range of −80 ° C. to 60 ° C. Done in a range. The pressure is, for example, in the range from 0.1 bar to 2500 bar, preferably in the range from 0.5 bar to 10 bar.
[0091]
In the first aspect of the present invention, the solvent is preferably a solvent capable of dissolving the bicyclic compound represented by the above formula (2). As the solvent, an aliphatic or aromatic organic solvent is used. Ether solvents such as tetrahydrofuran or diethyl ether; halogenated hydrocarbons such as methylene chloride; halogenated aromatic hydrocarbons such as o-dichlorobenzene; amides such as N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxide; Aromatic hydrocarbons such as benzene and toluene are used.
[0092]
In the second aspect of the present invention, there is provided a process for producing a conjugated tetracyclic compound in which the conjugated tricyclic compound obtained in the first aspect is further condensed. In the presence of alkyllithium and chromium halide, Provided is a method for producing a conjugated tetracyclic compound represented by the following formula (4), which comprises reacting a conjugated tricyclic compound represented by 1) with an alkyne represented by the following formula (5): Is done.
Embedded image
[Where A ¹ , A ² , B ¹ Ring, B ² Ring, X ^Three And X ^Four Has the above meaning. ]
[0093]
A ^Three And A ^Four Are independently of each other, the same or different, a hydrogen atom; an optionally substituted C ₁ ~ C ₂₀ Hydrocarbon group; optionally substituted 5- to 10-membered heteroaromatic ring group; optionally substituted C ₁ ~ C ₂₀ Alkoxy group; C which may have a substituent ₆ ~ C ₂₀ Aryloxy group; amino group optionally having substituent; silyl group optionally having substituent; C optionally having substituent ₇ ~ C ₂₀ Alkylaryloxy group; optionally substituted C ₂ ~ C ₂₀ An alkoxycarbonyl group; optionally substituted C ₇ ~ C ₂₀ Aryloxycarbonyl group; cyano group (—CN); carbamoyl group (—C (═O) NH ₂ ); Haloformyl group (—C (═O) —X, wherein X represents a halogen atom); formyl group (—C (═O) —H); isocyano group; isocyanato group; thiocyanato group or thioisocyanato group It is.
[0094]
A ^Three And R ^Four "C" ₁ ~ C ₂₀ "Hydrocarbon group", "5- to 10-membered heterocyclic group", "C ₁ ~ C ₂₀ Alkoxy group "," C ₆ ~ C ₂₀ Aryloxy group, amino group, silyl group, C ₇ ~ C ₂₀ Alkylaryloxy "," C ₂ ~ C ₂₀ Alkoxycarbonyl group "," C ₇ ~ C ₂₀ A substituent may be introduced into the “aryloxycarbonyl group”. As this substituent, for example, C ₁ ~ C _Ten Hydrocarbon group (eg, methyl, ethyl, propyl, butyl, phenyl, naphthyl, indenyl, tolyl, xylyl, benzyl, etc.), C ₁ ~ C _Ten An alkoxy group (for example, methoxy, ethoxy, propoxy, butoxy, etc.), C ₆ ~ C _Ten An aryloxy group (for example, phenyloxy, naphthyloxy, biphenyloxy, etc.), an amino group, a hydroxyl group, a halogen atom (for example, fluorine, chlorine, bromine, iodine) or a silyl group can be exemplified. In this case, one or more substituents may be introduced at substitutable positions, and preferably 1 to 4 substituents may be introduced. When the number of substituents is 2 or more, each substituent may be the same or different.
[0095]
In the present invention, A ^Three And A ^Four Are cross-linked to form C _Four ~ C ₂₀ A saturated ring or an unsaturated ring may be formed. The ring formed by these substituents is preferably a 4-membered ring to a 16-membered ring, and more preferably a 4-membered ring to a 12-membered ring. This ring may be an aromatic ring such as a benzene ring or an aliphatic ring. One or more rings may be further formed on the ring formed by these substituents.
[0096]
The saturated ring or unsaturated ring is an oxygen atom, a sulfur atom, a silicon atom, a tin atom, a germanium atom, or a group represented by the formula —N (B) — (wherein B is a hydrogen atom or C ₁ ~ C ₂₀ It is a hydrocarbon group. ) May be interrupted. That is, the saturated ring or unsaturated ring may be a heterocyclic ring. And you may have a substituent. The unsaturated ring may be an aromatic ring such as a benzene ring.
[0097]
B is a hydrogen atom or C ₁ ~ C _Ten It is preferably a hydrocarbon group, a hydrogen atom or C ₁ ~ C ₇ More preferably, it is a hydrocarbon group, B is a hydrogen atom, C ₁ ~ C _Three More preferably, it is an alkyl group, a phenyl group or a benzyl group.
[0098]
This saturated ring or unsaturated ring may have a substituent, for example, C ₁ ~ C _Ten Hydrocarbon group (eg, methyl, ethyl, propyl, butyl, etc.), C ₁ ~ C _Ten An alkoxy group (for example, methoxy, ethoxy, propoxy, butoxy, etc.), C ₆ ~ C _Ten A substituent such as an aryloxy group (for example, phenyloxy, naphthyloxy, biphenyloxy, etc.), an amino group, a hydroxyl group, a halogen atom (for example, fluorine, chlorine, bromine, iodine) or a silyl group may be introduced.
[0099]
In the present invention, A ^Three And A ^Four Are each independently the same or different and may have a substituent. ₁ ~ C ₂₀ Hydrocarbon group; 5- to 7-membered heterocyclic group which may have a substituent; C which may have a substituent ₁ ~ C ₂₀ Alkoxy group; C which may have a substituent ₆ ~ C ₂₀ Aryloxy group; optionally substituted C ₇ ~ C ₂₀ Alkylaryloxy group; optionally substituted C ₂ ~ C ₂₀ C which may have an alkoxycarbonyl group or a substituent ₇ ~ C ₂₀ An aryloxycarbonyl group is preferred.
[0100]
A ^Three And A ^Four Is C ₁ ~ C _Ten Alkyl group; C ₁ ~ C _Ten Alkenyl group; C ₁ ~ C _Ten Alkynyl group; C ₆ ~ C _Ten Aryl group; 2- or 3-thienyl group; C ₁ ~ C _Ten Alkoxy group; C ₆ ~ C ₁₂ Aryloxy group; C ₇ ~ C ₁₂ Alkylaryloxy group; C ₂ ~ C _Ten Alkoxycarbonyl group; C ₇ ~ C ₁₂ An aryloxycarbonyl group or a silyl group which may have a substituent is more preferable, and methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, vinyl, allyl, propenyl, iso Propenyl, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, phenyl, 2-thienyl, 3-thienyl, phenyloxy, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, dimethylsilyl, diethyl More preferred is silyl, trimethylsilyl or triethylsilyl.
[0101]
The above formula (1) used in the second aspect of the present invention may be a phenanthrene derivative represented by the following formula (1) ′.
Embedded image
[Where A ¹ , A ² , X ^Three , R ² , R ^Three , R ^Four , X ^Four , R ⁶ , R ⁷ And R ⁸ Has the above meaning. ]
[0102]
In the above formula (1) ′, R ² , R ^Three , R ^Four , R ⁶ , R ⁷ And R ⁸ Is preferably a hydrogen atom.
[0103]
In the present invention, when the above formula (1) is a phenanthrene derivative represented by the above formula (1) ′, the product obtained by the production method of the present invention is pyrene represented by the following formula (4) ′. It becomes a derivative.
Embedded image
[Where A ¹ , A ² , A ^Three , A ^Four , R ² , R ^Three , R ^Four , R ⁶ , R ⁷ And R ⁸ Has the above meaning. ]
[0104]
The following formula (1) used in the second embodiment of the present invention may be a compound represented by the following formula (1) ″.
Embedded image
[Where A ¹ , A ² , X ^Three , X ^Four , R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ And R ¹⁷ Has the above meaning. ]
[0105]
In the above formula (1) ", R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ And R ¹⁷ Is preferably a hydrogen atom.
[0106]
In the present invention, when the above formula (1) is a compound represented by the above formula (1) ″, the product obtained by the production method of the present invention is a compound represented by the following formula (4) ″: Become.
Embedded image
[Where A ¹ , A ² , A ^Three , A ^Four , R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ And R ¹⁷ Has the above meaning. ]
[0107]
In the method for producing a tetracyclic compound according to the second aspect of the present invention, an alkyne represented by the following formula (5) is used.
Embedded image
[Where A ^Three And A ^Four Has the above meaning. ]
[0108]
In the present invention, the amount of the alkyne represented by the above formula (5) is 0.1 mol to 100 mol, preferably 0.5 mol, per 1 mol of the tricyclic compound represented by the above formula (1). It is -3 mol, More preferably, it is 0.8 mol-1.5 mol.
[0109]
In the method for producing a tetracyclic compound according to the second aspect of the present invention, the reaction is carried out in the presence of alkyllithium and a chromium halide.
[0110]
In the second embodiment of the present invention, the alkyl lithium includes C ₁ ~ C ₆ Alkyl lithium can be mentioned, and n-butyl lithium, s-butyl lithium, t-butyl lithium and the like can be preferably mentioned.
[0111]
In the second embodiment of the present invention, the amount of alkyl lithium is 0.1 mol to 100 mol, preferably 0.5 mol to 5 mol, relative to 1 mol of the tricyclic compound represented by the above formula (1). More preferably, it is 0.8 mol-3 mol.
In the method for producing a tetracyclic compound of the present invention, a normal activator of alkyl lithium may be added to the reaction system. An example of such an activator is tetramethylethylenediamine (TMEDA). The amount of activator is preferably from 1 mol to 5 mol.
[0112]
In the second aspect of the present invention, the chromium halide includes CrX. _Three (X is a halogen atom such as F, Cl, Br, or I), CrCl _Three Can be preferably mentioned.
[0113]
In the second embodiment of the present invention, the amount of the chromium halide is 0.1 mol to 100 mol, preferably 0.5 mol to 5 mol, relative to 1 mol of the tricyclic compound represented by the above formula (1). Mol, and more preferably 0.8 mol to 3 mol.
[0114]
In the second embodiment of the present invention, the tetracyclic compound is typically obtained by adding alkyl lithium, chromium halide, alkyne (5) to a solution of the tricyclic compound represented by the above formula (1), Stir to produce. The order of addition is preferably the order of alkyl lithium, chromium halide and alkyne (5).
[0115]
In the second embodiment of the present invention, the leaving group X in the tricyclic compound (1) is first reacted by reacting alkyllithium with the tricyclic compound (1). ^Three And / or X ^Four Replace with lithium. Subsequently, it is thought that chromium exchange causes a metal exchange reaction from lithium to chromium, and this reacts with alkyne (5) to produce tetracyclic compound (4).
[0116]
In addition, the said reaction mechanism is only a hypothesis and this invention is not limited to these reaction mechanisms.
[0117]
In the second embodiment of the present invention, the reaction is preferably performed in a temperature range of −100 ° C. to 300 ° C., particularly preferably a temperature range of −80 ° C. to 200 ° C., and more preferably a temperature of −80 ° C. to 60 ° C. Done in a range. The pressure is, for example, in the range from 0.1 bar to 2500 bar, preferably in the range from 0.5 bar to 10 bar.
[0118]
In the second aspect of the present invention, the solvent is preferably a solvent capable of dissolving the tricyclic compound represented by the above formula (1). As the solvent, an aliphatic or aromatic organic solvent is used. Ether solvents such as tetrahydrofuran or diethyl ether; halogenated hydrocarbons such as methylene chloride; halogenated aromatic hydrocarbons such as o-dichlorobenzene; amides such as N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxide; Aromatic hydrocarbons such as benzene and toluene are used.
[0119]
【Example】
Hereinafter, the present invention will be described based on examples. However, the present invention is not limited to the following examples.
[0120]
All reactions were performed under a dry nitrogen atmosphere unless otherwise stated. Tetrahydrofuran (THF) used as a solvent was distilled off with sodium metal and benzophenone under nitrogen flow to make it anhydrous. As other reagents, commercially available products were purchased and used as they were.
[0121]
¹ H and ¹³ C NMR spectrum is CDCl at 25 ° C. _Three Measurements were made on a Bruker ARX-400 or JEOL JNM-AL 300 NMR spectrometer using a solution (containing 1% TMS). The measurement was performed with a SHIMADZU GC-14A gas chromatograph equipped with a silica glass capillary column SHIMADZU CBP1-M25-O25 and SHIMADZU C-R6A-Chromatopac integrator.
[0122]
Example 1
9-n-Butylphenanthrene
Embedded image
THF (10 ml) in which 2,2′-dibromobiphenyl (312 mg, 1.0 mmol) was dissolved was cooled to −78 ° C., and n-BuLi (2.0 eq.) Was added dropwise thereto. 1 hour later, CrCl _Three (317 mg, 2.0 mmol) was added, and the mixture was stirred at room temperature for 1 hour, 1-hexyne (2 eq.) Was added, and the mixture was stirred at 50 ° C. for 12 hours, followed by hydrolysis with 3N HCl aqueous solution. Then, it extracted and dried with magnesium sulfate. Removal of solvent and isolation by column chromatography gave the title compound. GC yield: 75%, isolated yield: 58%
[0123]
¹ H NMR (300 MHz, CDCl _Three , Me _Four Si): δ0.95 (t, J = 7.0 Hz, 3H), 1.43 (qt, 2H), 1.74 (tt, 2H), 3.03 (t, 2H), 7.50-7.56 (m, 5H), 7.74 (d , 1H), 8.04 (d, J = 7.0 Hz, 1H), 8.55 (d, J = 4.4 Hz, 1H), 8.63 (d, J = 4.4 Hz, 1H); ¹³ C NMR (75 MHz, CDCl _Three , Me _Four Si): δ14.04, 22.91, 32.36, 33.13, 122.41, 123.18, 124.45, 125.79, 125.91, 126.02, 126.39, 126.50, 127.98, 129.62, 130.72, 131.36, 131.98, 136.90.Calculated value C ₁₈ H ₁₈ 234.1385, found 234.1409.
[0124]
Example 2
9-Ethoxycarbonyl-10-methylphenanthrene
Embedded image
The same procedure as in Example 1 was performed. However, 2 equivalent of TMEDA was added together with n-BuLi. Further, 1-hexyne was added and, instead of stirring at 50 ° C. for 12 hours, 1-ethoxycarbonyl-1-propyne was added and stirred at 50 ° C. for 24 hours. GC yield: 46%, isolated yield: 31%
[0125]
¹ H NMR (300 MHz, CDCl _Three , Me _Four Si): δ1.40 (t, J = 7.2 Hz, 3H), 2.62 (s, 3H), 4.47 (q, J = 7.1 Hz, 2H), 7.48-7.69 (m, 5H), 8.02-8.05 (dd , 1H), 8.58-8.61 (d, 1H), 8.63 (d, J = 2.2 Hz, 1H); ¹³ C NMR (75 MHz, CDCl _Three , Me _Four Si): δ14.36, 17.06, 61.47, 122.70, 122.94, 125.08, 125.17, 126.39, 127.00, 127.12, 127.23, 128.13, 129.40, 129.56, 130.37, 130.39, 130.95, 170.35.Calculated value C ₁₈ H ₁₆ O ₂ 264.1132, found 264.1150.
[0126]
Example 3
9-ethyl-10- (3-butynyl) phenanthrene
Embedded image
The same procedure as in Example 1 was performed. However, instead of adding 1-hexyne and stirring at 50 ° C. for 12 hours, octa-3,5-diyne was added and stirred at 50 ° C. for 24 hours. GC yield: 67%, isolated yield: 47%.
[0127]
¹ H NMR (300 MHz, CDCl _Three , Me _Four Si): δ1.41 (tt, 6H), 2.66 (q, J = 7.46, 2H), 4.43 (q, J = 7.5 Hz, 2H), 7.58-7.67 (m, 4H), 8.10-8.14 (dd, 1H), 8.48-8.51 (dd, 1H), 8.63-8.72 (m, 2H); ¹³ C NMR (75 MHz, CDCl _Three , Me _Four Si): δ13.65, 14.27, 14.39, 24.88, 77.17, 100.59, 118.55, 122.36, 123.09, 124.88, 126.11, 126.48, 126.73, 126.83, 127.01, 129.12, 130.11, 130.33, 131.52, 142.18. Value C ₂₀ H ₁₈ 258.1421, found value 258.1409.
[0128]
Example 4
9-phenylphenanthrene
Embedded image
The same procedure as in Example 1 was performed. However, instead of adding 1-hexyne and stirring at 50 ° C. for 12 hours, phenylacetylene was added and stirred at 50 ° C. for 24 hours. GC yield: 63%, isolated yield: 45%.
[0129]
¹ H NMR (300 MHz, CDCl _Three , Me _Four Si): δ7.28-7.55 (m, 10H), 7.73-7.82 (dd, 2H), 8.55 (dd, J = 8.08, 1H), 8.61 (d, J = 8.26, 2H); ¹³ C NMR (75 MHz, CDCl _Three , Me _Four Si): δ122.50, 122.87, 126.41, 126.47, 126.54, 126.80, 126.89, 127.32, 127.49, 128.27, 128.63, 129.93, 130.04, 130.60, 131.10, 131.53, 138.74, 140.77.Calculated value C ₂₀ H ₁₈ 254.1098, found 254.1096.
[0130]
Example 5
9-methylphenanthrene
Embedded image
The same procedure as in Example 1 was performed. However, instead of adding 1-hexyne and stirring at 50 ° C. for 12 hours, 1-propyne was added and stirred at 50 ° C. for 24 hours. Isolated yield: 58%.
[0131]
¹ H NMR (300 MHz, CDCl _Three , Me _Four Si): δ2.78 (s, 3H), 7.63-7.74 (m, 10H), 7.85-7.86 (dd, 1H), 8.09-8.12 (dd, 1H), 8.68-8.71 (d, 1H), 8.75- 8.78 (d, 1H); ¹³ C NMR (75 MHz, CDCl _Three , Me _Four Si): δ 19.96, 122.41, 122.96, 124.60, 125.75, 126.15, 126.46, 126.52, 126.69, 127.79, 129.64, 130.33, 131.98, 132.03, 132.41.
[0132]
Example 6
9-Methyl-10-phenylphenanthrene
Embedded image
The same procedure as in Example 1 was performed. However, instead of adding 1-hexyne and stirring at 50 ° C. for 12 hours, 1-phenyl-1-propyne was added and stirred at 50 ° C. for 24 hours. GC yield: 75%, isolated yield: 58%.
[0133]
¹ H NMR (300 MHz, CDCl _Three , Me _Four Si): δ2.40 (s, 3H), 7.18-7.66 (m, 10H), 8.08-8.12 (dd, 1H), 8..66-8.74 (m, 2H); ¹³ C NMR (75 MHz, CDCl _Three , Me _Four Si): δ 17.31, 122.31, 122.85, 125.07, 125.60, 126.19, 126.33, 126.80, 127.02, 127.42, 128.39, 129.33, 129.936, 130.35, 131.88, 132.30, 137.06, 140.70.
[0134]
Example 7
Pyrrole [1,2-a] -3,4-diethyl-quinoline
Embedded image
The same procedure as in Example 1 was performed. However, 2,2′-dibromo-1-phenylpyrrole was used in place of 2,2′-dibromobiphenyl. Moreover, instead of adding 1-hexyne and stirring at 50 ° C. for 12 hours, 3-hexyne was added and stirred at 50 ° C. for 24 hours. GC yield: 73%, isolated yield: 68%.
[0135]
¹ H NMR (300 MHz, CDCl _Three , Me _Four Si): δ1.01-1.26 (m, 6H), 2.75-2.90 (m, 4H), 6.42 (dd, J = 2.75 1H), 7.16-7.39 (m, 2H), 7.73 (d, J = 8.44, 1H), 7.79 (d, J = 8.26, 1H); ¹³ C NMR (75 MHz, CDCl _Three , Me _Four Si): δ 14.23, 14.92, 20.35, 22.52, 100.46, 111.47, 112.31, 114.37, 123.32, 123.76, 125.04, 126.22, 126.50, 129.88, 131.79, 132.83.
[0136]
Example 8
Pyrrole [1,2-a] -3,4-diphenylquinoline
Embedded image
The same procedure as in Example 1 was performed. However, 2,2′-dibromo-1-phenylpyrrole was used in place of 2,2′-dibromobiphenyl. Moreover, instead of adding 1-hexyne and stirring at 50 ° C. for 12 hours, 1,2-diphenylacetylene was added and stirred at 50 ° C. for 24 hours. GC yield: 100%, isolated yield: 83%.
[0137]
¹ H NMR (300 MHz, CDCl _Three , Me _Four Si): δ6.24-6.25 (dd, 1H), 6.77-6.80 (d, 1H), 7.15-7.29 (m, 11H), 7.41-7.44 (m, 1H), 7.49-7.55 (m, 1H), 7.96 (d, J = 8.07, 2H); ¹³ C NMR (75 MHz, CDCl _Three , Me _Four Si): δ104.27, 112.26, 112.91, 114.04, 123.38, 124.74, 126.71, 126.93, 127.56, 127.69 (2C), 127.76 (2C), 128.11, 128.41, 130.20 (2C), 130.83, 131.47 (2C), 131.99 , 132.71, 137.60, 137.72.
[0138]
Example 9
3,4,8,9-tetraethyl-9b-aza-cyclopenta [cd] phenalene
Embedded image
Hexane (5 ml) in which pyrrole [1,2-a] -3,4-diethyl-quinoline (190 mg, 0.5 mmol) obtained in Example 7 was dissolved was cooled to 0 ° C., and n-BuLi (2.0 eq.) was added dropwise. 1 hour later, CrCl _Three (79 mg, 0.5 mmol) and THF (5 ml) were added, and the mixture was stirred at room temperature for 1 hour. Then, 3-hexyne (2 eq.) Was added, stirred at 50 ° C. for 3-24 hours, and then hydrolyzed with 3N HCl aqueous solution. Then, it extracted and dried with magnesium sulfate. Removal of solvent and isolation by column chromatography gave the title compound. Isolation yield: 29%
[0139]
¹ H NMR (300 MHz, benzene-d ₆ ): δ1.18 (t, 3H), 1.26 (t, 3H), 2.75-2.82 (q, 8H), 6.98 (m, 2H), 7.47 (m, 3H); ¹³ C NMR (75 MHz, benzene-d ₆ ): δ 13.34, 14.93, 21.03, 22.68, 103.46, 116.10, 123.48, 125.57, 127.17, 127.43, 128.29, 130.17.
[0140]
Example 10
3,4-Diethyl-8,9-diphenyl-9b-aza-cyclopenta [cd] phenalene
Embedded image
[0141]
The same procedure as in Example 9 was performed. However, 1,2-diphenylacetylene was used in place of 3-hexyne. Isolation yield: 40%.
[0142]
¹ H NMR (300 MHz, CDCl _Three , Me _Four Si): δ1.25 (t, 3H), 1.31 (t, 3H), 2.90-2.99 (q, 8H), 6.66 (d, 1H), 6.89 (d, 1H), 7.13-7.35 (m, 11H) , 7.50 (d, 1H).; ¹³ C NMR (75 MHz, CDCl _Three , Me _Four Si): δ13.34, 14.93, 21.03, 22.68, 103.46, 116.10, 123.48, 125.57, 127.17, 127.43, 128.29, 130.17.; High resolution mass spectrometry: calculated C ₃₀ H _{twenty five} N 399.1964, measured value 399.1987.
[0143]
Example 11
3,4-Diethyl-8,9-di-p-tolyl-9b-aza-cyclopenta [cd] phenalene
Embedded image
[0144]
The same procedure as in Example 9 was performed. However, 1,2-di-p-tolyl-acetylene was used instead of 3-hexyne. Isolated yield: 49%.
[0145]
¹ H NMR (300 MHz, benzene-d ₆ ): δ1.21 (t, 3H), 1.28 (t, 3H), 2.01 (s, 3H), 2.05 (s, 3H), 2.74-2.85 (q, 8H), 6.93-6.99 (dd, 2H), 7.17-7.98 (m, 3H), 7.32 (d, 4H), 7.17 (d, 4H), 7.42-7.47 (m, 3H). ¹³ C NMR (75 MHz, benzene-d ₆ ): δ13.24, 14.88, 21.07, 21.13, 21.17, 22.68, 104.08, 106.62, 116.73, 118.89, 123.47, 125.32, 127.20, 128.29, 128.98, 129.39, 129.53, 130.42, 130.62, 131.25, 131.31, 132.48, 135.53, 135.80, 136.36, 136.66.
[0146]
Example 12
3,4-Diethyl-8,9-di-thiophen-2-yl-9b-aza-cyclopenta [cd] phenalene
Embedded image
[0147]
The same procedure as in Example 9 was performed. However, 1,2-di-thiophen-2-yl-acetylene was used instead of 3-hexyne. Isolation yield: 38%.
[0148]
¹ H NMR (300 MHz, benzene-d ₆ ): δ0.87 (t, 3H), 0.94 (t, 3H), 2.37-2.49 (q, 4H), 6.43-6.46 (m, 1H), 6.52-6.55 (m, 1H), 6.61 (d, 1H ), 6.68 (d, 1H), 6.82-6.84 (m, 2H), 6.96 (t, 1H), 7.05 (d, 1H), 7.16 (d, 1H). ¹³ C NMR (75 MHz, benzene-d ₆ ): δ 13.18, 14.82, 21.01, 22.60, 104.40, 107.68, 117.15, 119.07, 122.53, 123.62, 125.02, 126.17, 126.62, 127.08, 127.28, 128.29, 128.67, 128.73, 129.20, 130.28, 132.14, 138.73, 139.32.
[0149]
【The invention's effect】
By the method of the present invention, two aromatic rings bonded by a σ bond can be easily and efficiently converted into a condensed ring.

Claims (21)

A method for producing a conjugated tricyclic compound represented by the following formula (1):
[Wherein, A ¹ and A ² are each independently the same or different and are each a hydrogen atom; an optionally substituted C ₁ -C ₂₀ hydrocarbon group; it may also be 5-10 membered heterocyclic group; which may have a substituent C ₁ -C ₂₀ alkoxy groups; which may have a substituent C ₆ -C ₂₀ aryloxy group; substituted An optionally substituted amino group; an optionally substituted silyl group; an optionally substituted C _{7 to} C ₂₀ alkylaryloxy group; an optionally substituted C ₂ to C ₂₀ alkoxycarbonyl group; C ₇ -C ₂₀ aryloxycarbonyl group optionally having substituent; cyano group (—CN); carbamoyl group (—C (═O) NH ₂ ); haloformyl group (—C (= O) -X, wherein X represents a halogen atom); a formyl group (-C (= O)- H); isocyano group; isocyanato group; thiocyanate group or thioisocyanato group, provided that A ¹ and A ² may be bridged with each other to form a C _{4 to} C ₁₀ saturated ring or unsaturated ring, The ring is an oxygen atom, a sulfur atom, a silicon atom, a tin atom, a germanium atom, or a group represented by the formula —N (B) — (wherein B is a hydrogen atom or a C _{1 to} C ₁₀ hydrocarbon group). And may have a substituent, and X ³ and X ⁴ , independently of one another, are the same or different and each represents a hydrogen atom or a halogen atom , and a ring B ¹ and The B ² rings are each independently the same or different and each represents a 5- to 10-membered aromatic ring which may have a substituent. ]
A bicyclic compound represented by the following formula (2) in the presence of alkyl lithium and chromium halide;
[Wherein, X ³ , X ⁴ , B ¹ ring and B ² ring have the above-mentioned meanings. X ¹ and X ² are bonded to carbon atoms adjacent to the bond axes of the B ¹ ring and the B ² ring, respectively, and are independently of each other, the same or different, and represent a hydrogen atom or a halogen atom . ]
Alkyne represented by the following formula (3)
[Wherein A ¹ and A ² have the above-mentioned meanings. ] Is made to react. The manufacturing method of the conjugated tricyclic compound characterized by the above-mentioned. X ¹ and X ² are identical groups, and / or, X ³ and X ⁴ are the same group, the manufacturing method of the conjugated tricyclic compounds object of claim 1. At least one hydrogen atom of X ¹ and X ^2, and / or at least one of X ³ and X ⁴ is a hydrogen atom, a manufacturing method of the conjugated tricyclic compounds object of claim 1. A ¹ and A ² are each independently the same or different and may have a C ₁ -C ₂₀ hydrocarbon group which may have a substituent; ring group; which may have a substituent C ₁ -C ₂₀ alkoxy groups; which may have a substituent C ₆ -C ₂₀ aryloxy group; which may have a substituent C ₇ ~ C ₂₀ alkylaryl group; an optionally substituted C ₂ -C ₂₀ alkoxycarbonyl group or optionally substituted C ₇ -C ₂₀ aryloxycarbonyl group, claim 1 either conjugated tricyclic compounds object manufacturing method according to the 3. The bicyclic compound represented by the formula (2) is a biphenyl derivative represented by the following formula (2) ′,
[Wherein X ¹ , X ² , X ³ and X ⁴ have the above-mentioned meanings. R ² , R ³ , R ⁴ , R ⁶ , R ⁷ and R ⁸ are each independently the same or different and are each a hydrogen atom; a C ₁ -C ₂₀ hydrocarbon group optionally having substituent (s) ; it may have a substituent group C ₁ -C ₂₀ alkoxy groups; which may have a substituent C ₆ -C ₂₀ aryloxy group; optionally substituted amino group; substituents A silyl group optionally having a hydroxyl group or a halogen atom, provided that X ³ and R ² , R ² and R ³ , R ³ and R ⁴ , X ⁴ and R ⁶ , R ⁶ and R ⁷ , and , R ⁷ and R ⁸ may be bridged with each other to form a C _{4 to} C ₂₀ saturated ring or unsaturated ring, and the ring is an oxygen atom, a sulfur atom, a silicon atom, a tin atom, or a germanium atom. or the formula -N (B) - group represented by (. wherein, B is a hydrogen atom or a C ₁ -C ₂₀ hydrocarbon group) is interrupted in At best, and it may have a substituent. ]
The conjugated tricyclic compound represented by the formula (1) is represented by the following formula (1) ′.
[Wherein A ¹ , A ² , X ³ , R ² , R ³ , R ⁴ , X ⁴ , R ⁶ , R ⁷ and R ⁸ have the above-mentioned meanings. ] The manufacturing method of the conjugated tricyclic compound body in any one of Claims 1-4 which is a phenanthrene derivative shown by these. The method for producing a conjugated tricyclic compound according to claim 5 , wherein X ³ , R ² , R ³ , R ⁴ , X ⁴ , R ⁶ , R ⁷ and R ⁸ are hydrogen atoms. The method for producing a conjugated tricyclic compound according to any one of claims 1 to 6 , wherein the B ¹ ring and the B ² ring are the same ring. The method for producing a conjugated tricyclic compound body according to any one of claims 1 to 4 , wherein at least one of the B ¹ ring and the B ² ring is an aromatic ring containing a nitrogen atom, a sulfur atom or an oxygen atom. The bicyclic compound represented by the formula (2) is a 1-phenylpyrrole derivative represented by the following formula (2) '',
[Wherein X ¹ , X ² , X ³ and X ⁴ have the above-mentioned meanings. R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ and R ¹⁷ are each independently the same or different and represent a hydrogen atom; an optionally substituted C ₁ -C ₂₀ hydrocarbon group; a substituent. good C ₁ -C ₂₀ alkoxy group optionally having; may have a substituent group C ₆ -C ₂₀ aryloxy group; optionally substituted amino group; substituted An optionally substituted silyl group; a hydroxyl group or a halogen atom, provided that X ³ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , X ⁴ and R ¹⁶ , and R ¹⁶ and R ¹⁷ are May be bridged with each other to form a C _{4 to} C ₂₀ saturated ring or unsaturated ring, and the ring may be an oxygen atom, a sulfur atom, a silicon atom, a tin atom, a germanium atom, or a formula —N (B) —. (wherein, B is a hydrogen atom or a C ₁ -C ₂₀ hydrocarbon group.) a group represented may be interrupted by And it may have a substituent. ]
The conjugated tricyclic compound represented by the formula (1) is represented by the following formula (1) ''
[Wherein, A ¹ , A ² , X ³ , R ¹² , R ¹³ , R ¹⁴ , X ⁴ , R ¹⁶ and R ¹⁷ have the above-mentioned meanings. The manufacturing method of the conjugated tricyclic compound body of Claim 8 which is a compound shown by these. The method for producing a conjugated tricyclic compound according to claim 9 , wherein X ³ , R ¹² , R ¹³ , R ¹⁴ , X ⁴ , R ¹⁶ and R ¹⁷ are hydrogen atoms. The conjugated tricyclic compound represented by the formula (1) is 9-n-butylphenanthrene, 9-ethoxycarbonyl-10-methylphenanthrene, 9-ethyl-10- (3-butynyl) phenanthrene, 9-phenylphenanthrene. 9-methylphenanthrene, 9-methyl-10-phenylphenanthrene, pyrrole [1,2-a] -3,4-diethylquinoline, or pyrrole [1,2-a] -3,4-diphenylquinoline. The manufacturing method of the conjugated tricyclic compound in any one of Claims 1-3 . A method for producing a conjugated tetracyclic compound represented by the following formula (4):
[Wherein, A ¹ , A ² , A ³ and A ⁴ are each independently the same or different and are each a hydrogen atom; an optionally substituted C ₁ -C ₂₀ hydrocarbon group; heterocyclic group may 5-10 membered have a group; which may have a substituent group C ₁ -C ₂₀ alkoxy groups; which may have a substituent C ₆ -C ₂₀ aryloxy group An amino group which may have a substituent; a silyl group which may have a substituent; a C _{7 to} C ₂₀ alkylaryloxy group which may have a substituent; which may be C ₂ -C ₂₀ alkoxycarbonyl group; optionally substituted C ₇ -C ₂₀ aryloxycarbonyl group; a cyano group (-CN); a carbamoyl group _{(-C (= O) NH 2} ) A haloformyl group (—C (═O) —X, wherein X represents a halogen atom); a formyl group (— C (= O) -H); isocyanato group; isocyanato group; thiocyanato group or thioisocyanato group, provided that A ¹ and A ² , and A ³ and A ⁴ are cross-linked with each other, and C _{4 to} C ₁₀ A saturated ring or an unsaturated ring may be formed, and the ring is an oxygen atom, a sulfur atom, a silicon atom, a tin atom, a germanium atom, or a group represented by the formula —N (B) — (wherein B is hydrogen). An atom or a C _{1 to} C ₁₀ hydrocarbon group) and may have a substituent, and the B ¹ ring and the B ² ring are independent of each other and are the same. Or it is different and shows the 5- to 10-membered aromatic ring which may have a substituent. ]
A conjugated tricyclic compound represented by the following formula (1) in the presence of alkyllithium and chromium halide;
[Wherein, A ¹ , A ² , B ¹ ring and B ² ring have the above-mentioned meanings. X ³ and X ⁴ are bonded to carbon atoms adjacent to the bond axes of the B ¹ ring and the B ² ring, respectively, and are each independently the same or different and each represents a hydrogen atom or a halogen atom . ]
Alkyne represented by the following formula (5)
[Wherein A ³ and A ⁴ have the above-mentioned meanings. ]. The manufacturing method of the conjugated tetracyclic compound characterized by the above-mentioned. The method for producing a conjugated tetracyclic compound body according to claim 12 , wherein X ³ and X ⁴ are the same group. The method for producing a conjugated tetracyclic compound body according to claim 12 , wherein at least one of X ³ and X ⁴ is a hydrogen atom. A ¹ , A ² , A ³ and A ⁴ are each independently the same or different and may have a C _{1 to} C ₂₀ hydrocarbon group which may have a substituent; A suitable 5- to 7-membered heterocyclic group; an optionally substituted C _{1 to} C ₂₀ alkoxy group; an optionally substituted C _{6 to} C ₂₀ aryloxy group; and a substituted group An optionally substituted C ₇ -C ₂₀ alkylaryloxy group; an optionally substituted C ₂ -C ₂₀ alkoxycarbonyl group or an optionally substituted C ₇ -C ₂₀ aryloxycarbonyl group there, according to claim 12-14 conjugated 4 cyclics object method according to any one of. The conjugated tricyclic compound represented by the formula (1) is a phenanthrene derivative represented by the following formula (1) ′,
[Wherein A ¹ , A ² , X ³ and X ⁴ have the above-mentioned meanings. R ² , R ³ , R ⁴ , R ⁶ , R ⁷ and R ⁸ are each independently the same or different and are each a hydrogen atom; a C ₁ -C ₂₀ hydrocarbon group optionally having substituent (s) ; it may have a substituent group C ₁ -C ₂₀ alkoxy groups; which may have a substituent C ₆ -C ₂₀ aryloxy group; optionally substituted amino group; substituents A silyl group optionally having a hydroxyl group or a halogen atom, provided that R ² and R ³ , R ³ and R ⁴ , R ⁶ and R ⁷ , and R ⁷ and R ⁸ are cross-linked with each other. To form a C _{4 to} C ₂₀ saturated ring or an unsaturated ring, wherein the ring is an oxygen atom, a sulfur atom, a silicon atom, a tin atom, a germanium atom, or a group represented by the formula —N (B) —. (wherein, B is a hydrogen atom or a C ₁ -C ₂₀ hydrocarbon group.) may be interrupted by, and, a substituent It may be in. ]
The conjugated tetracyclic compound represented by the formula (4) is represented by the following formula (4) ′.
[Wherein, A ¹ , A ² , A ³ , A ⁴ , R ² , R ³ , R ⁴ , R ⁶ , R ⁷ and R ⁸ have the above-mentioned meanings. A pyrene derivative represented by, the production method of the conjugated 4 cyclics Object according to any one of claims 12-15. The method for producing a conjugated tetracyclic compound according to claim 16 , wherein R ² , R ³ , R ⁴ , R ⁶ , R ⁷ and R ⁸ are hydrogen atoms. The method for producing a conjugated tetracyclic compound according to any one of claims 12 to 17 , wherein the B ¹ ring and the B ² ring are the same ring. The method for producing a conjugated tetracyclic compound body according to any one of claims 12 to 15 , wherein at least one of the B ¹ ring and the B ² ring is an aromatic ring containing a nitrogen atom, a sulfur atom or an oxygen atom. The conjugated tricyclic compound represented by the formula (1) is a compound represented by the following formula (1) ″,
[Wherein A ¹ , A ² , X ³ and X ⁴ have the above-mentioned meanings. R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ and R ¹⁷ are each independently the same or different and are each a hydrogen atom; an optionally substituted C ₁ -C ₂₀ hydrocarbon group; a substituent good C ₁ -C ₂₀ alkoxy group optionally having; may have a substituent group C ₆ -C ₂₀ aryloxy group; optionally substituted amino group; substituted An optionally substituted silyl group; a hydroxyl group or a halogen atom, provided that R ¹² and R ¹³ , R ¹³ and R ¹⁴ , and R ¹⁶ and R ¹⁷ are each bridged with each other to form a C _{4 to} C ₂₀ saturated ring. Alternatively, an unsaturated ring may be formed, and the ring is an oxygen atom, a sulfur atom, a silicon atom, a tin atom, a germanium atom, or a group represented by the formula —N (B) — (wherein B is a hydrogen atom or a C ₁ -C ₂₀ hydrocarbon group.) may be interrupted by, and may have a substituent There. ]
The conjugated tetracyclic compound represented by the formula (4) is represented by the following formula (4) ''
[Wherein, A ¹ , A ² , A ³ , A ⁴ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ and R ¹⁷ have the above-mentioned meanings. The manufacturing method of the conjugated tetracyclic compound body of Claim 19 which is a compound shown by these. The method for producing a conjugated tetracyclic compound according to claim 20 , wherein R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ and R ¹⁷ are hydrogen atoms.