JP2003261491A - Dicyclic compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To efficiently and simply obtain various multi-substituted biaryl compounds including compounds having large steric hindrances around the biaryl axes. <P>SOLUTION: A method for producing the biaryl compound represented by formula (1) (R<SP>1</SP>to R<SP>4</SP>are each identically or differently H, a hydrocarbon group, or the like; the ring A is an aromatic ring which may have one or more substituents) comprises reacting a cyclobutenone derivative represented by formula (2) with a ring represented by formula (3) (M is a monovalent or divalent metal, or the like) and then thermally refluxing the obtained reaction mixture. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polysubstituted bicyclic compound, and more specifically, a polysubstituted biaryl compound can be easily produced by utilizing a thermal ring expansion reaction of alkenylcyclobutene. On how to do.

[0002]

BACKGROUND OF THE INVENTION Many compounds having a biaryl bond exist in nature and many have important pharmacological activity. In addition, axially chiral biaryl compounds are often used for asymmetric identification and asymmetric synthesis. The conventional biaryl synthesis methods are not very general in terms of yield and reaction conditions in the synthesis of compounds having large steric hindrance around the biaryl axis, especially at the 2,2′-position and the 6,6′-position. It was

Therefore, it has been desired to provide a synthetic method for efficiently and conveniently obtaining various polysubstituted biaryls including compounds having large steric hindrance around the biaryl axis.

[0004]

The inventors of the present invention utilize a thermal ring-expansion reaction of an alkenylcyclobutene derivative to obtain various polysubstituted compounds including compounds with large steric hindrance around the biaryl axis. The inventors have found that biaryls can be obtained efficiently and simply, and have found that the method can be widely applied not only to biaryls but also to the synthesis of bicyclic compounds, and completed the present invention.

That is, the first aspect of the present invention provides a bicyclic compound represented by the following formula (1).

[Chemical 9] [In the formula, R¹, R², R³And R^FourAre independent of each other
Standing, identical or different, with a hydrogen atom; having a substituent
May be C₁~ C₂₀Hydrocarbon groups; having substituents
Good C₁~ C₂₀Alkoxy group; even if it has a substituent
Good C₆~ C₂₀Aryloxy group; having a substituent
Optionally an amino group; a silyl group which may have a substituent;
Alkylthio group which may have a substituent (-SY¹,
In the formula, Y¹Is C which may have a substituent₁~ C₂₀Archi
Represents a radical. ); Aryl which may have a substituent
O group (-SY², In the formula, Y²May have a substituent
C₆~ C₁₈Indicates an aryl group. ); Having a substituent
Good alkylsulfonyl group (-SO₂Y³, In the formula, Y³
Is C which may have a substituent₁~ C₂₀Indicates an alkyl group
You ); Arylsulfonyl which may have a substituent
Group (-SO₂Y^Four, In the formula, Y ^FourMay have a substituent
I C₆~ C₁₈Indicates an aryl group. ); Hydroxyl group; or halo
Gen atom, provided that R¹And R²Cross linked to each other
C_Four~ C_TenIt may form a saturated ring or an unsaturated ring,
The ring is composed of oxygen atom, sulfur atom, silicon atom, tin atom,
A rumanium atom or a group represented by the formula -N (B)-(formula
Where B is a hydrogen atom or C₁~ C_TenIt is a hydrocarbon group. )
May be interrupted by, and may have a substituent
Well, ring A represents an aromatic ring which may have a substituent.
You ]

In a second aspect of the present invention, a cyclobutenone derivative represented by the following formula (2):

[Chemical 10] [In the formula, R¹, R², R³And R^FourAre independent of each other
Standing, identical or different, with a hydrogen atom; having a substituent
May be C₁~ C₂₀Hydrocarbon groups; having substituents
Good C₁~ C₂₀Alkoxy group; even if it has a substituent
Good C₆~ C₂₀Aryloxy group; having a substituent
Optionally an amino group; a silyl group which may have a substituent;
Alkylthio group which may have a substituent (-SY¹,
In the formula, Y¹Is C which may have a substituent₁~ C₂₀Archi
Represents a radical. ); Aryl which may have a substituent
O group (-SY², In the formula, Y²May have a substituent
C₆~ C₁₈Indicates an aryl group. ); Having a substituent
Good alkylsulfonyl group (-SO₂Y³, In the formula, Y³
Is C which may have a substituent₁~ C₂₀Indicates an alkyl group
You ); Arylsulfonyl which may have a substituent
Group (-SO₂Y^Four, In the formula, Y ^FourMay have a substituent
I C₆~ C₁₈Indicates an aryl group. ); Hydroxyl group; or halo
Gen atom, provided that R¹And R²Cross linked to each other
C_Four~ C_TenIt may form a saturated ring or an unsaturated ring,
The ring is composed of oxygen atom, sulfur atom, silicon atom, tin atom,
A rumanium atom or a group represented by the formula -N (B)-(formula
Where B is a hydrogen atom or C₁~ C_TenIt is a hydrocarbon group. )
May be interrupted by, and may have a substituent
Good. ] With a ring represented by the following formula (3)

[Chemical 11] [In the formula, A ring represents an aromatic ring which may have a substituent, and M represents a metal halide of Group 2 of the periodic table or a metal of Group 1 of the periodic table. ] Is reacted to obtain a reaction mixture, and a step of heating and refluxing the reaction mixture is provided, and a method for producing a bicyclic compound represented by the following formula (1) is provided.

[Chemical 12] [In formula, R < ¹ >, R < ² >, R < ³ >, R < ⁴ > and A ring are synonymous with the above. ]

In a second aspect of the invention, the reaction is
It is preferably carried out in the presence of a protecting group-providing agent, and more preferably the protecting group-providing agent is an esterifying agent, an acylating agent, an alkylating agent or a silylating agent.

In the second aspect of the present invention, M is
It is preferably lithium or magnesium halide.

In the first and second aspects of the present invention, the following formula

[Chemical 13] [In the formula, the ring A has the same meaning as described above. ] Is a partial structure represented by the following formula

[Chemical 14] [In the formula, R^Five, R⁶, R⁷, R⁸And R⁹Are each
Independently, the same or different, a hydrogen atom;
C which may have₁~ C₂₀Hydrocarbon groups; having substituents
May be C₁~ C₂₀Alkoxy group; having a substituent
May be C₆~ C ₂₀Aryloxy group; having a substituent
Optionally substituted amino group; optionally substituted silyl group
Group; an alkylthio group which may have a substituent (-S
Y¹, In the formula, Y¹Is C which may have a substituent₁~ C₂₀
Indicates an alkyl group. ); An ant optionally having a substituent
Group (-SY², In the formula, Y²Has a substituent
Good C₆~ C₁₈Indicates an aryl group. ); Having a substituent
Optionally alkylsulfonyl group (-SO₂Y³,formula
Medium, Y³Is C which may have a substituent₁~ C₂₀Alkyl
Indicates a group. ); Arylsulu which may have a substituent
Honyl group (-SO₂Y^Four, In the formula, Y^FourHas a substituent
May be C₆~ C₁₈Indicates an aryl group. ); Hydroxyl group;
Is a halogen atom, provided that R^FiveAnd R⁶, R⁶as well as
R⁷, R⁷And R⁸, And R⁸And R⁹Respectively,
Crosslinked to each other C_Four~ C_TenForming a saturated or unsaturated ring
The ring may have an oxygen atom, a sulfur atom, a silicon atom,
Tin atom, germanium atom or represented by the formula -N (B)-
(Wherein B is a hydrogen atom or C₁~ C_{1 0}Hydrocarbon group
Is. ) And have a substituent.
You may have. ] Is preferred. in this case,
R^Five, R⁶, R⁷, R⁸And R⁹But each is independent of each other
And have the same or different hydrogen atom; a substituent
May be C₁~ C₂₀Hydrocarbon group; even if it has a substituent
Good C₁~ C₂₀Alkoxy group; or having a substituent
It is preferably an amino group.

In the first and second aspects of the present invention, R ¹ , R ² , R ³ and R ⁴ are each independently of the same or different and each is a hydrogen atom; a C ₁ -C ₂₀ alkyl group. ; C ₆ -C ₁₈ aryl group; C ₁ -C ₂₀ alkoxy groups;
It is preferably a silyl group which may have a substituent; or a halogen atom.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In a first aspect of the present invention, a bicyclic compound represented by the following formula (1) is provided.

[Chemical 15] [In the formula, R ¹ , R ² , R ³ , R ⁴ and A ring have the above meanings. ]

R¹, R², R³And R^FourAre each other
Independently of each other, the same or different, a hydrogen atom;
C which may be₁~ C₂₀Hydrocarbon groups; having substituents
May be C₁~ C₂₀Alkoxy group; having a substituent
May be C₆~ C₂₀Aryloxy group; having a substituent
Optionally substituted amino group; optionally substituted silyl
Group; an alkylthio group which may have a substituent (-SY
¹, In the formula, Y¹Is C which may have a substituent₁~ C₂₀A
Indicates a rukyl group. ); An aryl which may have a substituent
Ruthio group (-SY², In the formula, Y²Has a substituent
Good C₆~ C₁₈Indicates an aryl group. ); Having a substituent
Alkylsulfonyl group (-SO ₂Y³, In the formula,
Y³Is C which may have a substituent₁~ C₂₀Alkyl group
Show. ); Aryl sulfonyl which may have a substituent
Group (-SO₂Y^Four, In the formula, Y^FourHas a substituent
Good C₆~ C₁₈Indicates an aryl group. ); Hydroxyl group; halogen
Atom.

In the present specification, the hydrocarbon group of "C ₁ -C ₂₀ hydrocarbon group" may be saturated or unsaturated acyclic, or saturated or unsaturated cyclic. Good. When the C ₁ -C ₂₀ hydrocarbon group is acyclic, it may be linear or branched. The "C ₁ -C ₂₀ hydrocarbon group", C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₄ -C ₂₀ alkadienyl group, C ₆ ~ C ₁₈ aryl group, C ₆ -C ₂₀ alkylaryl group, C ₆ -C ₂₀ arylalkyl group, C ₄ ~C _{2 0} cycloalkyl group, C ₄ -C ₂₀ cycloalkenyl group, (C ₃ -C
₁₀ cycloalkyl) C ₁ -C ₁₀ alkyl groups and the like are included.

In the present specification, the "C ₁ -C ₂₀ alkyl group" is preferably C ₁ -C ₁₀ alkyl group,
And more preferably a C ₁ -C ₆ 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 can be mentioned. In this specification,
"C ₂ -C ₂₀ alkenyl group" is preferably C ₂ -C ₁₀ alkenyl group, more preferably a C ₂ -C ₆ 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. In the present specification, “C ₂ -C ₂₀ alkynyl group” means C ₂ -C ₁₀
It is preferably an alkynyl group, and more preferably a C ₂ -C ₆ alkynyl group. Examples of alkynyl groups include, but are not limited to, ethynyl, 2-propynyl, 2-butynyl, and the like. In the present specification, "C ₄ -C ₂₀ alkyldienyl group", C ₄ ~
It is preferably a C ₁₀ alkyldienyl group, C ₄ ~
More preferably, it is a C ₆ alkyldienyl group. Examples of alkyldienyl groups include, but are not limited to, 1,3-butadienyl and the like.

In the present specification, the "C ₆ -C ₁₈ aryl group" is preferably C ₆ -C ₁₀ aryl group.
Examples of aryl groups include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenylyl, anthryl, phenanthryl and the like. In the present specification, the “C ₆ -C ₂₀ alkylaryl group” is preferably C ₆ -C ₁₂ alkylaryl group. Examples of alkylaryl groups include, but are not limited to, o-tolyl, m-tolyl, p-
Trilyl, 2,3-xylyl, 2,4-xylyl, 2,5
-Xylyl, o-cumenyl, m-cumenyl, p-cumenyl, mesityl and the like can be mentioned. In the present specification, the “C ₆ -C ₂₀ arylalkyl group” is preferably C ₆ -C ₁₂ arylalkyl group. Examples of arylalkyl groups include, but are not limited to, benzyl, phenethyl, diphenylmethyl, triphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2.
-Diphenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl and the like can be mentioned. In the present specification, the “C ₄ -C ₂₀ cycloalkyl group” is preferably C ₄ -C ₁₀ cycloalkyl group. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. In the present specification, the “C ₄ -C ₂₀ cycloalkenyl group” means C ₄
It is preferably a C ₁₀ cycloalkenyl group. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3
-Cyclohexen-1-yl etc. can be mentioned.

In the present specification, the "C ₁ -C ₂₀ alkoxy group" is preferably C ₁ -C ₁₀ alkoxy group, and more preferably C ₁ -C ₆ alkoxy group.
Examples of alkoxy groups include, but are not limited to,
Examples include methoxy, ethoxy, propoxy, butoxy and pentyloxy.

In the present specification, the "C ₆ -C ₂₀ aryloxy group" is preferably C ₆ -C ₁₀ aryloxy group. Examples of aryloxy groups include, but are not limited to, phenyloxy, naphthyloxy, biphenyloxy and the like.

In the present specification, "alkylthio group (-
SY ¹ , wherein Y ¹ is a C ₁ -C which may have a substituent.
_{20 represents} an alkyl group. ) ”And“ alkylsulfonyl group (—SO ₂ Y ³ , in which Y ³ represents a C _{1 to} C ₂₀ alkyl group which may have a substituent) ”, Y ¹ and Y
³ is preferably a C ₁ -C ₁₀ alkyl group, C ₁
More preferably, it is a C ₆ 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 can be mentioned.

In the present specification, "arylthio group (-
SY ² , wherein Y ² is a C ₆ -C which may have a substituent.
₁₈ Indicates an aryl group. ) ”And“ arylsulfonyl group (—SO ₂ Y ⁴ , in which Y ⁴ represents a C _{6 to} C ₁₈ aryl group which may have a substituent) ”, Y ² and Y
⁴ is preferably a C ₆ -C ₁₀ aryl group. Examples of aryl groups include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenylyl, anthryl, phenanthryl and the like.

"C _{1 represented by} R ¹ , R ² , R ³ and R ⁴
-C ₂₀ hydrocarbon group "," C ₁ -C ₂₀ alkoxy group "
"C ₆ -C ₂₀ aryloxy group", "amino group", "silyl group", "alkylthio group", "arylthio group",
"Alkylsulfonyl group", "arylsulfonyl group"
Into, a substituent may be introduced. Examples of this substituent include a C _{1 to} C ₁₀ hydrocarbon group (eg, methyl, ethyl, propyl, butyl, phenyl, naphthyl,
Indenyl, tolyl, xylyl, benzyl, etc.), C _1-
C ₁₀ alkoxy group (eg, methoxy, ethoxy, propoxy, butoxy, etc.), C _{6 to} C ₁₀ aryloxy group (eg, phenyloxy, naphthyloxy, biphenyloxy, etc.), amino group, hydroxyl group, halogen atom (eg, fluorine) , Chlorine, bromine, iodine) or a silyl group. In this case, one or more substituents may be introduced at the substitutable position, and preferably one to four substituents may be introduced. When the number of substituents is 2 or more, each substituent may be the same or different.

In the present specification, examples of the "amino group which may have a substituent (s)" include, but are not limited to, amino, dimethylamino, methylamino, methylphenylamino, phenylamino and the like. .

In the present specification, examples of the "silyl group which may have a substituent (s)" include, but are not limited to, trimethylsilyl, triethylsilyl, trimethoxysilyl, triethoxysilyl, diphenylmethylsilyl, Examples include triphenylsilyl, triphenoxysilyl, dimethylmethoxysilyl, dimethylphenoxysilyl, and methylmethoxyphenyl.

In the present invention, R ¹ and R ² may be bridged with each other to form a C ₄ -C ₂₀ saturated ring or unsaturated ring. The ring formed by these substituents is preferably a 4-membered ring to a 16-membered ring, 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. Further, the ring formed by these substituents may further have a single ring or a plurality of rings. 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 a C _{1 to} C ₂₀ carbon atom). It is a hydrogen group.) That is, the saturated ring or unsaturated ring may be a heterocycle. Moreover, it may have a substituent.
The unsaturated ring may be an aromatic ring such as a benzene ring.
B is preferably a hydrogen atom or a C _{1 to} C ₁₀ hydrocarbon group, more preferably a hydrogen atom or a C _{1 to} C ₇ hydrocarbon group, and B is a hydrogen atom or a C _{1 to} C ₃ alkyl group. Still more preferably, it is a phenyl group or a benzyl group. This saturated ring or unsaturated ring may have a substituent, for example, a C _{1 to} C ₁₀ hydrocarbon group (for example,
Methyl, ethyl, propyl, butyl, etc.), C ₁ -C ₁₀ alkoxy group (e.g., methoxy, ethoxy, propoxy, butoxy, etc.), C ₆ ~C _{1 0} aryloxy group (e.g., phenyloxy, naphthyloxy, biphenyloxy Etc.), an amino group, a hydroxyl group, a halogen atom (for example, fluorine, chlorine, bromine, iodine), or a substituent such as a silyl group may be introduced.

In the present invention, R¹, R², R³And R^Four
Are, independently of each other, the same or different,
Atom; C₁~ C₂₀Alkyl group; C₆~ C₁₈Aryl group; C
₁~ C₂₀Alkoxy group; Sili which may have a substituent
Group; or a halogen atom, preferably hydrogen atom
Child; C₁~ C_TenAlkyl group; C₆~ C_TenAryl group; C ₁
~ C_TenAlkoxy group; Silyl which may have a substituent
More preferably, it is a group; or a halogen atom. R¹
And R²Are independent of each other and are the same or different
And hydrogen atom; C₁~ C_TenAlkyl group or C₆~ C_TenAnts
Group, preferably a hydrogen atom, methyl or ethyl.
Ru, propyl, isopropyl, n-butyl, sec-bu
Tyl, tert-butyl, pentyl, hexyl or phen
More preferably, it is nil. R³Is C₁~ C_TenAl
Kill group, C₆~ C₁₈Having an aryl group or a substituent
Is preferably a silyl group such as methyl or ethyl.
Ru, propyl, isopropyl, n-butyl, sec-bu
Tyl, tert-butyl, phenyl, trimethylsilyl
Alternatively, triethylsilyl is more preferable. R^Four
Is preferably a halogen atom and chlorine.
And are more preferable.

In the above formula (1), ring A is an aromatic ring which may have a substituent.

In the present specification, examples of the "aromatic ring" include a monocyclic aromatic ring and a polycyclic aromatic ring. Examples of the "monocyclic aromatic ring" include a benzene ring, a 5-membered or a 6-membered heterocyclic ring. "5- or 6-membered heterocycle"
Examples thereof include furan, thiophene, pyrrole, pyran, thiopyran, pyridine, thiazole, imidazole, pyrimidine, 1,3,5-triazine and the like. Examples of the "polycyclic aromatic ring" include polycyclic aromatic hydrocarbons and polycyclic heteroaromatic rings. Examples of the "polycyclic aromatic hydrocarbon" include biphenyl, triphenyl, naphthalene, indene, anthracene, phenanthrene and the like. Examples of the "polycyclic heteroaromatic ring" include indole, quinoline, purine and the like.

A substituent may be introduced into the "aromatic ring" represented by ring A. As this substituent, for example,
C ₁ -C ₁₀ hydrocarbon group (e.g., methyl, ethyl, propyl, butyl, etc.), C ₁ -C ₁₀ alkoxy group (e.g.,
Methoxy, ethoxy, propoxy, butoxy, etc.), C ₆
To C ₁₀ aryloxy groups (eg, phenyloxy, naphthyloxy, biphenyloxy, etc.), amino groups, hydroxyl groups, halogen atoms (eg, fluorine, chlorine, bromine, iodine) or silyl groups. In this case, one or more substituents may be introduced at the substitutable position, and preferably one to four substituents may be introduced. When the number of substituents is 2 or more, each substituent may be the same or different.

In the present invention, a partial structure containing ring A

[Chemical 16] Is the following formula

[Chemical 17] [In the formula, R^Five, R⁶, R⁷, R⁸And R⁹Means the above
Have. ] Is preferred. R^Five, R⁶, R⁷,
R⁸And R⁹Are the same or different
And a hydrogen atom; C which may have a substituent₁~ C
₂₀Hydrocarbon group; C which may have a substituent₁~ C₂₀A
Lucoxy group; C which may have a substituent₆~ C₂₀Ants
Group; oxy group; optionally substituted amino group;
A silyl group which may have a substituent; which has a substituent
Good alkylthio group (-SY¹, In the formula, Y¹Is a substituent
C which may have₁~ C₂₀Indicates an alkyl group. );
Arylthio group which may have a substituent (-SY²,formula
Medium, Y²Is C which may have a substituent₆~ C₁₈Aryl
Indicates a group. ); Alkyl sulfone which may have a substituent
Honyl group (-SO₂Y³, In the formula, Y³Has a substituent
May be C₁~ C₂₀Indicates an alkyl group. ); With a substituent
Optionally substituted arylsulfonyl group (-SO₂Y^Four,formula
Medium, Y ^FourIs C which may have a substituent₆~ C₁₈Aryl
Indicates a group. ); A hydroxyl group; or a halogen atom.

"C ₁ -C ₂₀ hydrocarbon group", "C ₁ -C ₂₀ alkoxy group" and "C ₆ -C ₂₀ aryloxy group" represented by R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ ",""Aminogroup","silylgroup","alkylthiogroup","arylthiogroup","alkylsulfonylgroup","arylsulfonylgroup" may have a substituent introduced. Examples of this substituent include a C _{1 to} C ₁₀ hydrocarbon group (eg, methyl, ethyl, propyl, butyl, phenyl, naphthyl, indenyl, tolyl, xylyl, benzyl, etc.), a C _{1 to} C ₁₀ alkoxy group (eg, , Methoxy, ethoxy, propoxy, butoxy), C ₆ -C ₁₀ aryloxy groups (eg, phenyloxy, naphthyloxy, biphenyloxy, etc.), amino groups, hydroxyl groups, halogen atoms (eg, fluorine, chlorine, bromine, iodine). ) Or a silyl group. In this case, one or more substituents may be introduced at substitutable positions,
Preferably, 1 to 4 may be introduced. When the number of substituents is 2 or more, each substituent may be the same or different.

In the present invention, R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ , and R ⁸ and R ⁹ are respectively
C ₄ -C ₁₀ may form a saturated or unsaturated ring crosslinked with each other. The ring formed by these substituents is a 4-membered ring to 1
A 6-membered ring is preferred, and a 4-membered to 12-membered ring is more preferred. This ring may be an aromatic ring such as a benzene ring or an aliphatic ring. Further, the ring formed by these substituents may further have a single ring or a plurality of rings. The saturated ring or unsaturated ring is
Suspended with 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 ₂₀ hydrocarbon group). May be. That is, the saturated ring or unsaturated ring may be a heterocycle. Moreover, it may have a substituent. The unsaturated ring may be an aromatic ring such as a benzene ring. B is preferably a hydrogen atom or a C _{1 to} C ₁₀ hydrocarbon group, more preferably a hydrogen atom or a C _{1 to} C ₇ hydrocarbon group, and B is a hydrogen atom or a C _{1 to} C ₃ alkyl group. Still more preferably, it is a phenyl group or a benzyl group. This saturated ring or unsaturated ring may have a substituent, for example, a C _{1 to} C ₁₀ hydrocarbon group (eg, methyl, ethyl, propyl, butyl, etc.), C ₁ to
C ₁₀ alkoxy group (e.g., methoxy, ethoxy, propoxy, butoxy, etc.), C ₆ -C _{1 0} aryl group (e.g., phenyloxy, naphthyloxy, biphenyloxy, etc.), an amino group, a hydroxyl group, a halogen atom (e.g., Fluorine, chlorine, bromine, iodine) or a substituent such as a silyl group may be introduced.

In the present invention, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently of the same or different and are a hydrogen atom; C ₁ -C ₂₀ which may have a substituent. Hydrocarbon group; C ₁ -C ₂₀ alkoxy group optionally having substituent group; or amino group optionally having substituent group, hydrogen atom; optionally having substituent group good C ₁ -C ₁₀ hydrocarbon radical; an optionally substituted C ₁ ~
C ₁₀ alkoxy group; or an amino group which may have a substituent is more preferable, and a hydrogen atom, a C ₁ -C ₁₀ hydrocarbon group which may have a substituent or a substituent It is more preferably a C ₁ -C ₁₀ alkoxy group which may be present, and particularly preferably a hydrogen atom, methyl, methoxy, ethoxy, propoxy or butoxy. Further, in the present invention, it is preferable that R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ or R ⁸ and R ⁹ are cross-linked with each other to form an aromatic ring. Is more preferably formed.

In a second aspect of the present invention, there is provided one aspect of a method for producing a bicyclic compound according to the first aspect of the present invention,
A method comprising: reacting a cyclobutenone derivative represented by the following formula (2) with a ring represented by the following formula (3) to obtain a reaction mixture; and heating the reaction mixture under reflux. Provided is a method for producing a bicyclic compound represented by formula (1).

[Chemical 18] [In the formula, R ¹ , R ² , R ³ , R ⁴ , M and A rings have the same meanings as described above. ]

In the second embodiment of the present invention, the following formula (2)
The cyclobutenone derivative represented by is used.

[Chemical 19] [In the formula, R ¹ , R ² , R ³ and R ⁴ have the above meanings. ]

R ¹ , R ² , R ³ and R in the above formula (2)
⁴ is a first embodiment of the present invention, wherein R ¹ in the above formula (1),
It is the same as described for R ² , R ³ and R ⁴ .

The cyclobutenone derivative represented by the above formula (2) can be synthesized by a known method. For example, cyclobutenes obtained by utilizing a [2 + 2] cycloaddition reaction of alkyne and dichloroketene are added. Then, it can be obtained by acting a nucleophile such as vinyllithium or vinylmagnesium halide.

In the second aspect of the present invention, the following formula (3)
The ring shown by is used.

[Chemical 20] [In the formula, M and A rings have the above-mentioned meanings. ]

In the above formula (3), the ring A is the same as described in the above formula (1) in the first aspect of the present invention.

In the above formula (3), M represents a halide of a metal of Group 2 of the periodic table or a metal of Group 1 of the periodic table. M
Examples thereof include alkali metals such as lithium, sodium and potassium; MgX (X is a halogen atom) and the like. Of these, lithium and MgX (X is a halogen atom) are preferable.

The amount of the ring represented by the above formula (3) is 1 mol to 10 mols, preferably 1 mol to 3 mols, and more preferably 1 mols to 1 mol of the cyclobutenone derivative (2). 2 mol.

In the method for producing a bicyclic compound according to the second aspect of the present invention, the reaction between the cyclobutenone derivative represented by the above formula (2) and the ring represented by the above formula (3) is carried out by the above formula (2). From the viewpoint of protecting the oxygen atom in the cyclobutenone derivative represented by, it is preferable to carry out in the presence of a protecting group-providing agent. Examples of the protecting group-providing agent include esterifying agents, acylating agents, alkylating agents, silylating agents, and the like. Examples of the "esterifying agent" include halogenated esters, and particularly preferably methyl chloroformate. "Acylating agent"
Examples thereof include acyl halides, carboxylic acid anhydrides, and the like, with benzoyl chloride being particularly preferable. Examples of the “alkylating agent” include alkyl halides, alkyl sulfonates, dialkyl sulfates, epoxides, and the like, and particularly preferably methyl triflate. Examples of the “silylating agent” include silyl halide and silyl triflate, and particularly preferable is trimethylsilyl chloride. In the present invention, it is preferable to use an esterifying agent or an acylating agent as the protective group-providing agent, and it is more preferable to use methyl chloroformate or benzoyl chloride.

The amount of the protective group-providing agent is 1 mol to 10 mol, preferably 1 mol to 5 mol, and more preferably 1.5 mol to 3 mol, per 1 mol of the cyclobutenone derivative (2). is there.

In the second embodiment of the present invention, the bicyclic compound is typically added to a solution of the ring represented by the above formula (3),
The cyclobutenone derivative represented by the above formula (2) and, if necessary, a protecting group-providing agent are respectively added to obtain a reaction mixture. Subsequently, the reaction mixture is heated under reflux to produce the bicyclic compound represented by the above formula (1). The ring (3) does not need to be isolated, and the ring (3) prepared in the solution may be used as it is.

In the second embodiment of the present invention, when a protecting group-providing agent is used, the cyclobutenone derivative (2) is reacted with the ring (3) to give an intermediate (4) according to the reaction mechanism shown below. , Intermediate (5) is obtained (hereinafter,
This step is also referred to as "first step". ), And further by heating and refluxing the obtained reaction mixture, the final product, the bicyclic compound (1), is obtained through the intermediate (6) (hereinafter, this step is also referred to as “second step”). )it is conceivable that.

[Chemical 21] [Wherein R ¹ , R ² , R ³ , R ⁴ , M and A rings have the above meanings. R ¹⁰ represents an ester group, an acyl group, an alkyl group or a silyl group provided by a protecting group-providing agent. ]

The above reaction mechanism is only a hypothesis, and the present invention is not limited to the above reaction mechanism.

In the first step of the second aspect of the present invention, the reaction is preferably carried out in the temperature range of -100 ° C to 150 ° C, particularly preferably -80 ° C to 80 ° C, and further preferably- It is performed in a temperature range of 80 ° C to 40 ° C.

In the first step of the second aspect of the present invention, the solvent is preferably a solvent capable of dissolving the ring represented by the above formula (3). As the solvent, an aliphatic or aromatic organic solvent is used. Ethereal 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 dimethylsulfoxide; Aromatic hydrocarbons such as benzene and toluene are used.

In the second step of the second aspect of the present invention, the heating under reflux is preferably carried out in the temperature range of 80 ° C to 300 ° C, particularly preferably in the temperature range of 100 ° C to 250 ° C.
More preferably, it is carried out in the temperature range of 120 ° C to 200 ° C. The heating reflux time is preferably 1 hour to 150.
It is carried out in a temperature range of time, particularly preferably 1 hour to 10 hours.
It is carried out in a temperature range of 0 hour, more preferably in a temperature range of 2 hours to 50 hours.

In the second step of the second aspect of the present invention, the solvent is preferably a solvent capable of dissolving the reaction mixture obtained in the first step. As the solvent, xylene, mesitylene, pyridine, 2,6-lutidine, o-dichlorobenzene, dimethyl sulfoxide (DMSO), 1-butanol and the like can be used alone or in combination,
Xylene-pyridine solution, mesitylene-pyridine solution,
It is preferable to use a mesitylene-lutidine solution.

[0049]

EXAMPLES The present invention will be described below based on examples.
However, the present invention is not limited to the following examples.

Tetrahydrofuran (THF) (dehydrated),
Xylene (special grade), pyridine (special grade), t-BuLi
(1.64M pentane solution), benzoyl chloride,
The one purchased from Kanto Chemical Co., Inc. was used. 2, 4,
6-Trimethoxybromobenzene was synthesized by a known method, and 2,4-dimethoxybromobenzene, 4-methoxybromobenzene and 1-bromonaphthalene were purchased from Aldrich Chemical. As for the other reagents, commercially available products were purchased and used as they were. ¹ H and ¹³ C NMR spectra are 2
Deuterated chloroform solution at 7 ° C (heavy acetone only in Example 3)
Was measured with a JEOL JNM LA-400 nuclear magnetic resonance spectrum analyzer (400/100 MHz). Preparative thin layer chromatography on silica gel is Merck silica
gel 60PF254 (Art 7747) was used. Also, infrared absorption (IR)
PerkinElmer Japan 1600 spectroscopic FT / IR
A 200 infrared absorption spectrometer was used.

Reference Example 1

[Chemical formula 22] Zn-Cu (3
9.2 g, 0.60 mol) and phenylacetylene (20.4 g, 0.20
A solution of trichloroacetyl chloride (44.6 mL, 0.40 mol) in dimethoxyethane (125 mL) was slowly added dropwise to a diethyl ether solution (400 mL) of (mol) in 2 hours at room temperature. After stirring for 30 hours, the reaction mixture was filtered through Celite,
It was washed with hexane (200 mL). The filtrate was washed with a 0.5 M aqueous hydrochloric acid solution, further washed with a 5% aqueous sodium hydroxide solution, and then dried using anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the obtained residue was purified by silica gel chromatography (hexane / ethyl acetate = 8/2) to give dichlorocyclobutenone (37.0 g, 87%). Dichlorocyclobutenone (10.1 g, 52.4 mmol) in benzene (60
mL) at room temperature with ethylene glycol (4.4 mL, 79 mmo
l) and p-toluenesulfonic acid (4.98 g, 26.2 mmol) were added, and the mixture was stirred with heating under reflux for 30 hr. After setting the reaction temperature to room temperature, a saturated aqueous sodium hydrogen carbonate solution was added at 0 ° C. to stop the reaction. After the product was extracted with ethyl acetate, the extract was washed with saturated saline and dried with anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel chromatography (hexane / methylene chloride / diethyl ether = 90/5/5), and the acetal (1
1.6 g, 86%) was obtained. In a 200 mL 3-neck reaction vessel under an argon atmosphere, 2-bromopropene (799 mg, 6.61 mmol) E was added.
t-BuLi (1.54 M pentane solution, 7.15 mL, 11.7 mmol) was added to the t ₂ O solution (15 mL) at −78 ° C., and the mixture was stirred for 1 hour. At this temperature, acetal (1.14 g, 4.40 mmol) in Et ₂ O (1
5 mL) was added. After stopping the reaction with pH 7 phosphate buffer solution, the product was extracted with ethyl acetate. The extract was washed with saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain a crude product. _{THF-H 2 O (5.0 mL} -0.5 mL) with a solution to 0 ° C. TFA of the crude product (10.0
mL) was added. The reaction temperature was raised to room temperature and the mixture was stirred for 4 hours, and then saturated aqueous sodium hydrogen carbonate solution was added to stop the reaction. The product was extracted with ethyl acetate, the extract was washed with saturated brine and dried over anhydrous sodium sulfate. The obtained residue is subjected to silica gel chromatography (hexane /
Purify using ethyl acetate = 95/5) to give the title compound (1.07
g, 92%).

The reaction scheme of Reference Example 1 is shown below.

[Chemical formula 23] However, in the above reaction scheme, vinyl lithium was generated using a halogen-metal exchange reaction between vinyl bromide and t-BuLi.

[Chemical formula 24]

Reference Example 2

[Chemical 25] The procedure was the same as in Reference Example 1. However, 2-bromo-cis-2-butene was used instead of 2-bromopropene.

Reference Example 3

[Chemical formula 26] The procedure was the same as in Reference Example 1. However, trimethylsilylacetylene was used instead of phenylacetylene. In addition, 2-bromo-cis-2-butene was used instead of 2-bromopropene.

Reference Example 4

[Chemical 27] The procedure was the same as in Reference Example 1. However, 1-hexyne was used instead of phenylacetylene.

Example 1

[Chemical 28] Under an argon atmosphere, in a 50 mL 2-neck reaction vessel, 2.
4,6-trimethoxybromobenzene (47.4 mg,
-78 in a THF solution (2 mL) of 0.192 mmol).
T-BuLi (1.64M pentane solution, 0.22
(mL, 0.35 mmol) was added and stirred for 1 hour. At this temperature, the compound obtained in Reference Example 1 (30.9 mg,
0.141 mmol) in THF (2.0 mL) was added, and the mixture was stirred for 5 minutes, and then benzoyl chloride (29.8) was added.
mg, 0.212 mmol) in THF (0.5 m
L) was added. Raise the reaction temperature to room temperature over 1 hour,
Stir for another 20 minutes. After quenching the reaction with water, the mixture was extracted with ethyl acetate (10 mL × 3) and the solvent was evaporated under reduced pressure to give an intermediate product. 30 in an argon atmosphere
The xylene-pyridine solution (2.5 mL-0.2 mL) of the intermediate product was heated under reflux for 26 hours in a mL 1-neck reaction container. After setting the reaction temperature to room temperature, 2M HCL (20
mL) was added, the mixture was extracted with ethyl acetate (10 mL × 3), the solvent was evaporated under reduced pressure, and the obtained crude product was purified by silica gel preparative thin layer chromatography (hexane / ethyl acetate = 7).
/ 3) to give the title compound (40.2 mg, isolated yield 77% (based on Reference Example 1)).

¹ H NMR (CDCl ₃ , δ) 2.36 (s, 3H), 3.74
(s, 6H), 3.86 (s, 3H), 6.23 (s, 2H), 7.04 (d, 1H,
J = 2.2 Hz), 7.11 (d, 1H, J = 2.2 Hz), 7.32−7.51
(m, 5H); ¹³ C NMR (CDCl ₃ , δ) 20.9, 55.3, 56.0, 90.8, 110.8, 1
27.1, 127.8, 130.0, 130.4, 131.0, 132.4, 134.3, 13
5.5, 140.3, 140.6, 158.5, 161.1; IR (neat) 2937, 2838, 1609, 1587, 1505, 1456, 1408,
1337, 1225, 1205, 1160, 1144, 1128, 1058, 1036, 95
1, 866, 811, 768 cm ^-1 ; Calculated by elemental analysis C ₂₂ H ₂₁ O ₃ Cl: C, 71.64; H, 5.74. Found: C, 71.54; H, 6.03.

The reaction scheme of Example 1 is shown below.

[Chemical 29]

Example 2

[Chemical 30] The procedure was similar to that in Example 1. However, 2, 4, 6-
2,4-Dimethoxybromobenzene was used instead of trimethoxybromobenzene. Further, instead of the compound obtained in Reference Example 1, the compound obtained in Reference Example 2 was used. Further, instead of heating the intermediate product xylene-pyridine solution (2.5 mL-0.2 mL) under reflux for 26 hours, the intermediate product mesitylene-pyridine solution (2.
(5 mL-0.2 mL) was heated under reflux for 12 hours. Isolated yield 51% (reference example 2).

¹ H NMR (CDCl ₃ , δ) 2.00 (s, 3H), 2.32
(s, 3H), 3.72 (s, 3H), 3.78 (s, 3H), 6.69 (d, 1H,
J = 2.9 Hz), 6.90 (dd, 1H, J ₁ = 2.9, J ₂ = 8.9 Hz),
6.94 (d, 1H, J = 8.9 Hz), 7.15 (s, 1H), 7.32−7.48
(m, 5H); ¹³ C NMR (CDCl ₃ , δ) 17.4, 20.2, 55.7, 56.4, 112.4, 1
13.6, 116.6, 127.1, 127.8, 129.6, 129.7,129.9, 13
1.7, 134.9, 136.4, 137.7, 137.8, 140.3, 151.0, 15
3.6; IR (neat) 2940, 2832, 1604, 1580, 1497, 1463, 1421,
1381, 1273, 1222, 1174, 1048,1027, 936, 880, 810,
768 cm ^-1 .

Example 3

[Chemical 31] The procedure was similar to that in Example 1. However, 2, 4, 6-
1-Bromonaphthalene was used instead of trimethoxybromobenzene. Further, instead of the compound obtained in Reference Example 1, the compound obtained in Reference Example 2 was used. Also,
Xylene-pyridine solution of intermediate product (2.5 mL-
Instead of heating (0.2 mL) under reflux for 26 hours, a mesitylene-pyridine solution of the intermediate product (2.5 mL-0.2
(mL) was heated to reflux for 45 hours. Isolation yield 74% (based on Reference Example 2).

¹ H NMR (acetone-d ₆ , δ) 1.86 (s, 3H),
2.39 (s, 3H), 7.29−7.63 (m, 11H), 7.96−8.00 (m,
2H).

Example 4

[Chemical 32] The procedure was similar to that in Example 1. However, 2, 4, 6-
4-methoxybromobenzene was used instead of trimethoxybromobenzene. Further, instead of the compound obtained in Reference Example 1, the compound obtained in Reference Example 2 was used.
In addition, a xylene-pyridine solution of an intermediate product (2.5 m
L-0.2 mL) was heated under reflux for 26 hours, and a mesitylene-pyridine solution of the intermediate product (2.5 mL-
(0.2 mL) was heated under reflux for 10 hours. Isolation yield 66%
(Based on Reference Example 2).

¹ H NMR (CDCl ₃ , δ) 2.01 (s, 3H), 2.31
(s, 3H), 3.86 (s, 3H), 6.98 (d, 2H, J = 8.8 Hz),
7.13 (d, 2H, J = 8.8 Hz), 7.14 (s, 1H), 7.32−7.46
(m, 5H); ¹³ C NMR (CDCl ₃ , δ) 17.9, 20.3, 55.2, 113.7, 127.2,
127.9, 129.6, 129.7, 130.5, 131.4, 132.6, 135.1, 1
36.4, 138.0, 140.3, 140.9, 158.6; IR (neat) 3058, 2973, 2864, 1610, 1575, 1514, 1456,
1381, 1287, 1245, 1175, 1138, 1115, 1074, 1037, 99
6, 926, 881, 835, 788 cm ^-1 ; Calculated by elemental analysis C ₂₁ H ₁₉ OCl: C, 78.13; H, 5.93. Found: C, 77.83; H, 6.04.

The reaction scheme of Example 4 is shown below.

[Chemical 33]

Example 5

[Chemical 34] The procedure was similar to that in Example 1. However, 2, 4, 6-
4-methoxybromobenzene was used instead of trimethoxybromobenzene. Further, instead of the compound obtained in Reference Example 1, the compound obtained in Reference Example 3 was used.
In addition, a xylene-pyridine solution of an intermediate product (2.5 m
L-0.2 mL) was heated under reflux for 26 hours, and a mesitylene-pyridine solution of the intermediate product (2.5 mL-
(0.2 mL) was heated under reflux for 10 hours. 82% isolated yield
(Based on Reference Example 3).

¹ H NMR (CDCl ₃ , δ) 0.36 (s, 9H), 1.96
(s, 3H), 2.28 (s, 3H), 3.86 (s, 3H), 6.97 (d, 2H,
J = 8.7 Hz), 7.09 (d, 2H, J = 8.7 Hz), 7.22 (s, 1
H); ¹³ C NMR (CDCl ₃ , δ) −0.49, 18.0, 20.3, 55.2, 113.6,
130.5, 132.5, 134.5, 135.5, 135.7, 138.3, 138.6,
140.2, 158.5; IR (neat) 3037, 2953, 2835, 1611, 1574, 1514, 1456,
1360, 1289, 1245, 1174, 1106,1039, 937, 856, 839,
785, 756 cm ^-1 ; Calculated by elemental analysis C ₁₈ H ₂₃ OClSi: C, 67.79; H, 7.27. Found: C, 67.64; H, 7.41.

Example 6

[Chemical 35] The procedure was similar to that in Example 1. However, instead of the compound obtained in Reference Example 1, the compound obtained in Reference Example 4 was used. Also, instead of heating the intermediate product xylene-pyridine solution (2.5 mL-0.2 mL) under reflux for 26 hours, the intermediate product xylene-pyridine solution (2.5
(mL-0.2 mL) was heated under reflux for 32 hours. Isolation yield 54% (based on Reference Example 4).

¹ H NMR (CDCl ₃ , δ) 0.95 (t, 3H, J = 7.3
Hz), 1.38-1.67 (m, 4H), 2.31 (s, 3H), 2.74 (t, 2
H, J = 7.8 Hz), 3.71 (s, 6H), 3.86 (s, 3H), 6.22
(s, 2H), 6.87 (d, 1H, J = 2.0 Hz), 7.00 (d, 1H, J =
2.0 Hz); ¹³ C NMR (CDCl ₃ , δ) 14.0, 20.9, 22.7, 32.0, 34.0, 5
5.3, 56.0, 90.9, 111.2, 129.8, 130.8, 131.8, 133.
7, 135.2, 140.1, 158.4, 160.9; IR (neat) 2999, 2958, 2859, 1610, 1587, 1504, 1466,
1413, 1337, 1225, 1205, 1157, 1129, 1058, 1040, 95
1, 860, 811 cm ^-1 ; Calculated by elemental analysis C ₂₀ H ₂₅ O ₃ Cl: C, 68.86; H, 7.22. Found: C, 69.11; H, 7.46.

The reaction scheme of Example 6 is shown below.

[Chemical 36]

Example 7

[Chemical 37] The procedure was similar to that in Example 1. However, 2, 4, 6-
2,4-Dimethylbromobenzene was used instead of trimethoxybromobenzene. Further, instead of the compound obtained in Reference Example 1, the compound obtained in Reference Example 3 was used. In addition, a xylene-pyridine solution (2.
Instead of heating (5 mL-0.2 mL) under reflux for 26 hours, a solution of an intermediate product in xylene-pyridine (2.5 mL)
-0.2 mL) was heated to reflux for 18 hours. Isolated yield 54
% (Based on Reference Example 3).

¹ H NMR (CDCl ₃ , δ) 0.36 (s, 9H), 1.88
(s, 3H), 1.96 (s, 3H), 2.28 (s, 3H), 2.38 (s, 3H),
6.90 (d, 1H, J = 7.6 Hz), 7.06 (d, 1H, J = 7.6 H
z), 7.10 (s, 1H), 7.22 (s, 1H); ¹³ C NMR (CDCl ₃ , δ) −0.48, 17.4, 19.4, 20.2, 21.2,
126.6, 129.0, 130.6, 134.4, 135.5, 135.6, 135.8, 1
36.88, 136.92, 138.0, 138.2, 139.9; IR (neat) 2951, 2921, 1614, 1574, 1503, 1456, 1357,
1288, 1249, 1147, 937, 840, 766 cm ^-1 ; Elemental analysis calculated C ₁₉ H ₂₅ ClSi: C, 72.00; H, 7.95. Found: C, 71.88; H, 8.19.

The reaction scheme of Example 7 is shown below.

[Chemical 38]

[0074]

INDUSTRIAL APPLICABILITY By the method of the present invention, various polysubstituted bicyclic compounds including compounds having large steric hindrance around the axis can be obtained efficiently and easily.

Claims (11)

[Claims] 1. A bicyclic compound represented by the following formula (1): [Chemical 1] [In the formula, R¹, R², R³And R^FourAre independent of each other
Standing, identical or different, with a hydrogen atom; having a substituent
May be C₁~ C₂₀Hydrocarbon groups; having substituents
Good C₁~ C₂₀Alkoxy group; even if it has a substituent
Good C₆~ C₂₀Aryloxy group; having a substituent
Optionally an amino group; a silyl group which may have a substituent;
Alkylthio group which may have a substituent (-SY¹,
In the formula, Y¹Is C which may have a substituent₁~ C₂₀Archi
Represents a radical. ); Aryl which may have a substituent
O group (-SY², In the formula, Y²May have a substituent
C₆~ C₁₈Indicates an aryl group. ); Having a substituent
Good alkylsulfonyl group (-SO₂Y³, In the formula, Y³
Is C which may have a substituent₁~ C₂₀Indicates an alkyl group
You ); Arylsulfonyl which may have a substituent
Group (-SO₂Y^Four, In the formula, Y ^FourMay have a substituent
I C₆~ C₁₈Indicates an aryl group. ); Hydroxyl group; or halo
Gen atom, However, R¹And R²Are cross-linked with each other and C_Four~ C_TenSaturation
It may form a ring or an unsaturated ring, and the ring is an oxygen source.
Child, sulfur atom, silicon atom, tin atom, germanium atom
Or a group represented by the formula -N (B)-(wherein B is a hydrogen atom)
Or C₁~ C_TenIt is a hydrocarbon group. ) Has been suspended
And may have a substituent, Ring A represents an aromatic ring which may have a substituent. ] 2. The following formula [Chemical 2] [In the formula, the ring A has the same meaning as in claim 1. ]
The partial structure is [Chemical 3] [In the formula, R^Five, R⁶, R⁷, R⁸And R⁹Are each
Independently, the same or different, a hydrogen atom;
C which may have₁~ C₂₀Hydrocarbon groups; having substituents
May be C₁~ C₂₀Alkoxy group; having a substituent
May be C₆~ C ₂₀Aryloxy group; having a substituent
Optionally substituted amino group; optionally substituted silyl group
Group; an alkylthio group which may have a substituent (-S
Y¹, In the formula, Y¹Is C which may have a substituent₁~ C₂₀
Indicates an alkyl group. ); An ant optionally having a substituent
Group (-SY², In the formula, Y²Has a substituent
Good C₆~ C₁₈Indicates an aryl group. ); Having a substituent
Optionally alkylsulfonyl group (-SO₂Y³,formula
Medium, Y³Is C which may have a substituent₁~ C₂₀Alkyl
Indicates a group. ); Arylsulu which may have a substituent
Honyl group (-SO₂Y^Four, In the formula, Y^FourHas a substituent
May be C₆~ C₁₈Indicates an aryl group. ); Hydroxyl group;
Is a halogen atom, However, R^FiveAnd R⁶, R⁶And R⁷, R⁷And R⁸, Line
And R⁸And R⁹Are respectively cross-linked to C_Four~ C
_TenIt may form a saturated ring or an unsaturated ring, and the ring is an acid.
Elemental atom, sulfur atom, silicon atom, tin atom, germanium
An atom or a group represented by the formula -N (B)-(in the formula, B is hydrogen
Atom or C₁~ C_TenIt is a hydrocarbon group. ) Suspended by
It may be present and may have a substituent. ]
The bicyclic compound according to claim 1, wherein 3. R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are independently of each other, the same or different, a hydrogen atom; a C ₁ -C ₂₀ hydrocarbon which may have a substituent. The group according to claim 2, which is a group; a C ₁ -C ₂₀ alkoxy group which may have a substituent; or an amino group which may have a substituent.
Cyclic compound. 4. R ¹ , R ² , R ³ and R ⁴ are each independently of the same or different and each is a hydrogen atom; C ₁ -C ₂₀
Alkyl group; C ₆ -C ₁₈ aryl group; C ₁ -C ₂₀ alkoxy groups; bicyclic according to any of claims 1 to 3 or a halogen atom; an optionally substituted silyl group Compound. 5. A cyclobutenone derivative represented by the following formula (2):
A conductor, [Chemical 4] [In the formula, R¹, R², R³And R^FourAre independent of each other
Standing, identical or different, with a hydrogen atom; having a substituent
May be C₁~ C₂₀Hydrocarbon groups; having substituents
Good C₁~ C₂₀Alkoxy group; even if it has a substituent
Good C₆~ C₂₀Aryloxy group; having a substituent
Optionally an amino group; a silyl group which may have a substituent;
Alkylthio group which may have a substituent (-SY¹,
In the formula, Y¹Is C which may have a substituent₁~ C₂₀Archi
Represents a radical. ); Aryl which may have a substituent
O group (-SY², In the formula, Y²May have a substituent
C₆~ C₁₈Indicates an aryl group. ); Having a substituent
Good alkylsulfonyl group (-SO₂Y³, In the formula, Y³
Is C which may have a substituent₁~ C₂₀Indicates an alkyl group
You ); Arylsulfonyl which may have a substituent
Group (-SO₂Y^Four, In the formula, Y ^FourMay have a substituent
I C₆~ C₁₈Indicates an aryl group. ); Hydroxyl group; or halo
Gen atom, However, R¹And R²Are cross-linked with each other and C_Four~ C_TenSaturation
It may form a ring or an unsaturated ring, and the ring is an oxygen source.
Child, sulfur atom, silicon atom, tin atom, germanium atom
Or a group represented by the formula -N (B)-(wherein B is a hydrogen atom)
Or C₁~ C_TenIt is a hydrocarbon group. ) Has been suspended
And may have a substituent. ] A ring represented by the following formula (3) [Chemical 5] [In the formula, ring A represents an aromatic ring which may have a substituent.
Where M is a halide of a metal of Group 2 of the periodic table, or
Table 1 shows metals of Group 1. ] To react to obtain a reaction mixture
And heating the reaction mixture to reflux.
A bicyclic compound represented by the following formula (1), characterized in that
Manufacturing method. [Chemical 6] [In the formula, R¹, R², R³, R^FourAnd A ring has the same meaning as above.
Show. ] 6. The method for producing a bicyclic compound according to claim 5, wherein the reaction is carried out in the presence of a protecting group-providing agent. 7. The method for producing a bicyclic compound according to claim 6, wherein the protecting group-providing agent is an esterifying agent, an acylating agent, an alkylating agent or a silylating agent. 8. The method for producing a bicyclic compound according to claim 5, wherein M is lithium or magnesium halide. 9. The following formula [Chemical 7] [In the formula, the ring A has the same meaning as in claim 5. ]
The partial structure is [Chemical 8] [In the formula, R^Five, R⁶, R⁷, R⁸And R⁹Are each
Independently, the same or different, a hydrogen atom;
C which may have₁~ C₂₀Hydrocarbon groups; having substituents
May be C₁~ C₂₀Alkoxy group; having a substituent
May be C₆~ C ₂₀Aryloxy group; having a substituent
Optionally substituted amino group; optionally substituted silyl group
Group; an alkylthio group which may have a substituent (-S
Y¹, In the formula, Y¹Is C which may have a substituent₁~ C₂₀
Indicates an alkyl group. ); An ant optionally having a substituent
Group (-SY², In the formula, Y²Has a substituent
Good C₆~ C₁₈Indicates an aryl group. ); Having a substituent
Optionally alkylsulfonyl group (-SO₂Y³,formula
Medium, Y³Is C which may have a substituent₁~ C₂₀Alkyl
Indicates a group. ); Arylsulu which may have a substituent
Honyl group (-SO₂Y^Four, In the formula, Y^FourHas a substituent
May be C₆~ C₁₈Indicates an aryl group. ); Hydroxyl group;
Is a halogen atom, However, R^FiveAnd R⁶, R⁶And R⁷, R⁷And R⁸, Line
And R⁸And R⁹Are respectively cross-linked to C_Four~ C
_TenIt may form a saturated ring or an unsaturated ring, and the ring is an acid.
Elemental atom, sulfur atom, silicon atom, tin atom, germanium
An atom or a group represented by the formula -N (B)-(in the formula, B is hydrogen
Atom or C₁~ C_TenIt is a hydrocarbon group. ) Suspended by
It may be present and may have a substituent. ]
The production of the bicyclic compound according to any one of claims 5 to 8.
Method. 10. R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently of the same or different, a hydrogen atom; a C ₁ -C ₂₀ hydrocarbon which may have a substituent. The method for producing a bicyclic compound according to claim 9, wherein the group is a C ₁ -C ₂₀ alkoxy group which may have a substituent; or an amino group which may have a substituent. 11. R ¹ , R ² , R ³ and R ⁴ are each independently of the same or different and each is a hydrogen atom; C ₁ -C
₂₀ alkyl group; C ₆ -C ₁₈ aryl group; C ₁ -C ₂₀ alkoxy group; silyl group which may have a substituent; or halogen atom, 2 ring according to any one of claims 5 to 10. Method for producing formula compound.