JP2022132090A - Production method of substituted poly(diphenylacetylene) and the like - Google Patents

Abstract

To provide a production method of substituted poly(diphenylacetylene) allowing control of the molecular mass in a wide range from a low molecular mass to a high molecular mass.SOLUTION: A production method of cyclic substituted poly(diphenylacetylene) having a repeating unit represented by the specified formula (II) comprises polymerizing a compound represented by the specified formula (I) in the presence of tetravalent halogenated tungsten, a cocatalyst with reducing capability, and substituted or unsubstituted triarylphosphine.SELECTED DRAWING: None

Description

The present invention relates to a novel process for producing substituted poly(diphenylacetylene)s having various functional groups, which is capable of controlling the molecular weight over a wide range of molecular weights and has good yields.

Substituted polyacetylene derivatives are one of the representative conjugated polymers. They have a structure in which various side chains are introduced into a rigid main chain, so they have unique properties not found in other polymer materials. In fact, many studies are being conducted toward the development of materials for gas separation membranes, organic ELs, liquid crystals, organic diodes, and the like. Among them, substituted poly(diphenylacetylene)s are high molecular compounds that are expected to have practical applications because they not only have extremely high thermal stability compared to other substituted polyacetylene derivatives but also exhibit strong luminescence properties. is.

Substituted poly(diphenylacetylene)s can be synthesized by chain polymerization of the corresponding diphenylacetylenes using a transition metal catalyst. It is often more difficult than other general polymerization methods of this kind. So far, as a polymerization method for diphenylacetylenes, a method using a catalyst system combining tantalum pentachloride (TaCl ₅ ) and an organotin reagent, or a catalyst system combining tungsten hexachloride (WCl ₆ ) and an organotin reagent has been used. However, these polymerization methods are limited in the range of applicable monomers, i.e., diphenylacetylenes, and yield poly(diphenylacetylene)s with desired molecular weights and functional groups. It was difficult to obtain it efficiently (Patent Documents 1 and 2, Non-Patent Documents 1 and 3).

Recently, by using tungsten oxytetrachloride (WOCl ₄ ) instead of WCl ₆ as a catalyst, poly(diphenyls) with various functional groups such as alkoxy-carbonyl groups, halogen atoms, alkoxy groups, etc. reported that acetylenes can be obtained in high yields (Non-Patent Document 4). However, the upper limit of the molecular weight of the poly(diphenylacetylene)s obtained by this method is about 20,000, and it is difficult to obtain functionalized poly(diphenylacetylene)s having a higher molecular weight. It was difficult.

JP-A-5-271338 JP-A-6-107737

Handbook of Metathesis, Grubbs, R. H., Ed. Wiley-VCH: Weinheim, 2003; Vol. 3, pp 375-406 J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 165-180 Polymer Reviews 2017, 57, 175-199 Angew. Chem. Int. Ed. 2020, 59, 14772-14780

Against this background, we have developed an effective method for producing substituted poly(diphenylacetylene)s, which can be applied to a wide range of monomers having desired functional groups and can control the molecular weight over a wide range of molecular weights. Development is desperately needed.

An object of the present invention is to provide a substituted poly(diphenylacetylene) having various functional groups and capable of controlling the molecular weight in a wide molecular weight range from several thousands to about 200,000 compared to conventional methods. To provide a production method with a good yield of the same.

Under such circumstances, the present inventors have made intensive studies and found that in the presence of a tetravalent tungsten halide, a cocatalyst having a reducing ability, and an optionally substituted triarylphosphine, the formula (I) :

[In the formula,
n R ¹ are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
m R ² are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
n represents an integer from 0 to 3, and m represents an integer from 0 to 3. ]
Formula (II), comprising a step of polymerizing a compound represented by (hereinafter sometimes referred to as "compound (I)"):

[Each symbol in the formula has the same meaning as defined above. ]
A method for producing a substituted poly(diphenylacetylene) (hereinafter sometimes referred to as "compound (II)") having a repeating unit represented by (hereinafter sometimes referred to as "the manufacturing method of the present invention") In the polymerization reaction of substituted diphenylacetylene, it was found for the first time that the molecular weight can be controlled to some extent over a wide range from low molecular weight to high molecular weight, and that the substituted poly(diphenylacetylene) obtained by this production method has a cyclic structure. , have completed the present invention.

That is, the present invention is as follows.
[1] In the presence of a tetravalent tungsten halide, a cocatalyst having reducing ability, and an optionally substituted triarylphosphine, formula (I):

[In the formula,
n R ¹ are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
m R ² are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
n represents an integer of 0-3, and m represents an integer of 0-3. ]
comprising the step of polymerizing a compound represented by formula (II):

[Each symbol in the formula has the same meaning as described above. ]
A method for producing a substituted poly(diphenylacetylene) having repeating units represented by
[2] In the presence of a tetravalent tungsten halide, a cocatalyst having reducing ability, and an optionally substituted triarylphosphine, formula (I):

[In the formula,
n R ¹ are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- represents a carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
m R ² are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- represents a carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
n represents an integer from 0 to 3, and m represents an integer from 0 to 3. ]
comprising the step of polymerizing a compound represented by formula (II):

[Each symbol in the formula has the same meaning as defined above. ]
A method for producing a substituted poly(diphenylacetylene) having repeating units represented by
[3] co-catalysts with reducing ability are tetraphenyltin, tetra-n-butyltin, bis(trimethylsilyl)cyclohexa-1,4-diene, bis(trimethylsilyl)2-methylcyclohexa-1,4-diene, aluminum hydride The production method according to the above [1] or [2], which is selected from the group consisting of reagents, boron hydride reagents, silane reagents, organomagnesium reagents, and organolithium reagents.
[4] Any one of the above [1] to [3], wherein the optionally substituted triarylphosphine is triphenylphosphine, tris(4-fluorophenyl)phosphine or tris(4-chlorophenyl)phosphine. manufacturing method.
[5] The production method according to any one of [1] to [4] above, wherein the tetravalent tungsten halide is tungsten tetrachloride.
[6] the tetravalent tungsten halide is tungsten tetrachloride,
The cocatalyst having reducing ability is selected from the group consisting of tetraphenyltin, tetra-n-butyltin and bis(trimethylsilyl)cyclohexa-1,4-diene, and the optionally substituted triarylphosphine is triphenylphosphine The manufacturing method according to the above [1] or [2].
[7] n R ¹ 's and m R ² 's in formula (I) are each independently absent or present at meta- and/or para-positions to the phenylethynyl group, and The production method according to any one of [1] to [6] above, wherein n and m are each independently an integer of 0 to 2.
[8] Formula (II'):

[In the formula,
R ^1' and R ^2' each independently represent a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted Alkylsulfanyl group, optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted It represents an alkoxy-carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group. ]
A substituted poly(diphenylacetylene) having a repeating unit represented by (hereinafter sometimes referred to as "compound (II')") or a salt thereof.
[9] Formula (II'):

[In the formula,
R ^1' and R ^2' each independently represent a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted Alkylsulfanyl group, optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted It represents an alkoxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group. ]
A substituted poly(diphenylacetylene) having a repeating unit represented by or a salt thereof.

According to the present invention, cyclic substituted poly(diphenylacetylene)s having various functional groups with high yield while controlling the molecular weight in a wide molecular weight range from several thousand to several hundred thousand by simple operation can be manufactured. In addition, according to the present invention, it is possible to obtain substituted poly(diphenylacetylene)s having a molecular weight controlled to some extent and desired functional groups, and having excellent thermal stability, for which no effective synthesis method has been available so far. Therefore, it is extremely useful as a raw material synthesis method for various functional polymer materials.

1A to 1D show compound (II-1) coated on a highly oriented pyrolytic graphite substrate, using an atomic force microscope (AFM) (Cypher (registered trademark)) manufactured by Asylum Research. Measured images and partially enlarged images are shown.

Definitions of terms and symbols used in this specification are explained below.

As used herein, "halogen atom" means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the present specification, "alkyl (group)" means a linear or branched alkyl group having 1 or more carbon atoms, and when there is no particular limitation on the carbon number range, preferably C It is a _1-20 alkyl group, and more preferably a C _1-6 alkyl group.

As used herein, “C _1-20 alkyl (group)” means a linear or branched alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl , sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, eicosyl and the like.

As used herein, "C _1-6 alkyl (group)" means a linear or branched alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl , sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, etc. mentioned.

As used herein, “cycloalkyl (group)” means a cyclic alkyl group, preferably a C _3-8 cycloalkyl group, unless the carbon number range is particularly limited.

As used herein, "C _3-8 cycloalkyl (group)" means a cyclic alkyl group having 3 to 8 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. are mentioned. Among them, a C _3-6 cycloalkyl group is preferred.

As used herein, the term "alkoxy (group)" means a group in which a straight-chain or branched-chain alkyl group is bonded to an oxygen atom, and the carbon number range is not particularly limited, but preferably C _1-20 alkoxy group, more preferably a C _1-8 alkoxy group, still more preferably a C _1-6 alkoxy group.

As used herein, "C _1-20 alkoxy (group)" means a linear or branched alkoxy group having 1 to 20 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, isohexyloxy, 1,1-dimethylbutoxy, 2,2-dimethylbutoxy, 3,3-dimethylbutoxy, 2 -ethylbutoxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, eicosyloxy and the like.

As used herein, "C _1-6 alkoxy (group)" means a linear or branched alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy and the like.

As used herein, the term "alkylsulfanyl (group)" means a group in which a straight-chain or branched-chain alkyl group is bonded to a sulfur atom, and the carbon number range is not particularly limited, but preferably C _1-6 It is an alkylsulfanyl group, more preferably a C _1-4 alkylsulfanyl group.

As used herein, the term “C _1-6 alkylsulfanyl (group)” refers to a group in which the above “C _1-6 alkyl” group is bonded to a sulfur atom, i.e., a linear or branched chain having 1-6 carbon atoms. means an alkylsulfanyl group. The "C _1-6 alkylsulfanyl (group)" includes, for example, methylsulfanyl, ethylsulfanyl, propylsulfanyl, isopropylsulfanyl, butylsulfanyl, isobutylsulfanyl, sec-butylsulfanyl, tert-butylsulfanyl, pentylsulfanyl, isopentyl sulfanyl, neopentylsulfanyl, 1-ethylpropylsulfanyl, hexylsulfanyl and the like.

As used herein, the term "C _1-6 alkylsulfonyl (group)" refers to a group in which the above "C _1-6 alkyl" group is bonded to a sulfonyl group, i.e., a linear or branched chain having 1 to 6 carbon atoms. means an alkylsulfonyl group. The "C _1-6 alkylsulfonyl (group)" includes, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentyl sulfonyl, neopentylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl and the like.

As used herein, "alkoxy-carbonyl (group)" means a group in which the above alkoxy group is bonded to a carbonyl group, and the carbon number range is not particularly limited, but preferably a C _1-20 alkoxy-carbonyl group and more preferably a C _1-8 alkoxy-carbonyl group.

As used herein, "acyl (group)" means alkanoyl or aroyl, and although the carbon number range is not particularly limited, it is preferably C _1-7 alkanoyl group or C _7-11 aroyl.

As used herein, the term "C _1-7 alkanoyl (group)" refers to linear or branched formyl or alkylcarbonyl having 1 to 7 carbon atoms (that is, C _1-6 alkyl-carbonyl). , for example, formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl and the like.

As used herein, “C _7-11 aroyl (group)” is arylcarbonyl having 7 to 11 carbon atoms (ie, C _6-10 aryl-carbonyl), and includes benzoyl and the like.

As used herein, "acyloxy (group)" means a group in which the alkanoyl group or aroyl group is bonded to an oxygen atom, and the carbon number range is not particularly limited, but preferably a C _1-7 alkanoyloxy group or a C _7-11 aroyloxy group.

In the present specification, "C _1-7 alkanoyloxy (group)" includes, for example, formyloxy, acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyl oxy, tert-butylcarbonyloxy (pivaloyloxy), pentylcarbonyloxy, isopentylcarbonyloxy, neopentylcarbonyloxy, hexylcarbonyloxy and the like, preferably acetoxy or pivaloyloxy.

As used herein, “C _7-11 aroyloxy (group)” includes, for example, benzoyloxy, 1-naphthoyloxy, 2-naphthoyloxy and the like.

As used herein, the term "aryl (group)" means a monocyclic or polycyclic (condensed) hydrocarbon group exhibiting aromaticity, and specifically includes, for example, phenyl, 1-naphthyl, Examples thereof include C _6-14 aryl groups such as 2-naphthyl, biphenylyl, 2-anthryl and fluorenyl, with C _6-10 aryl groups being preferred.

As used herein, “C _6-10 aryl (group)” includes, for example, phenyl, 1-naphthyl and 2-naphthyl, with phenyl and 1-naphthyl being particularly preferred.

As used herein, "aryloxy (group)" means a group in which the above aryl group is bonded to an oxygen atom, preferably a C _6-14 aryloxy group, more preferably a C _6-10 It is an aryloxy group.

As used herein, "aryloxy-carbonyl (group)" means a group in which the above aryloxy group is bonded to a carbonyl group, and the carbon number range is not particularly limited, but preferably C _6-14 aryloxy -carbonyl group, more preferably C _6-10 aryloxy-carbonyl group, particularly preferably phenoxy-carbonyl group.

As used herein, “aralkyl (group)” means a group in which an alkyl group is substituted with an aryl group, and although the carbon number range is not particularly limited, it is preferably C _7-14 aralkyl.

As used herein, "C _7-22 aralkyl (group)" means a group in which a "C _1-4 alkyl group" is substituted with a "C _6-18 aryl group", such as benzyl, 1-phenyl ethyl, 2-phenylethyl, (naphthyl-1-yl)methyl, (naphthyl-2-yl)methyl, 1-(naphthyl-1-yl)ethyl, 1-(naphthyl-2-yl)ethyl, 2-( naphthyl-1-yl)ethyl, 2-(naphthyl-2-yl)ethyl, diphenylmethyl, fluorenylmethyl, trityl and the like.

As used herein, “arylsulfonyl (group)” means a group in which an aryl group is bonded to a sulfonyl group, and although the carbon number range is not particularly limited, it is preferably a C _6-10 arylsulfonyl group.

As used herein, “C _6-10 arylsulfonyl (group)” means a group in which “C _6-10 aryl group” is bonded to a sulfonyl group, such as phenylsulfonyl, 1-naphthylsulfonyl, 2- and naphthylsulfonyl.

As used herein, "alkylsulfonyloxy (group)" means a group in which an alkylsulfonyl group is bonded to an oxygen atom, and the carbon number range is not particularly limited, but preferably a C _1-6 alkylsulfonyloxy group is.

As used herein, "C _1-6 alkylsulfonyloxy (group)" means a group in which a C _1-6 alkylsulfonyl group is bonded to an oxygen atom, such as methylsulfonyloxy, ethylsulfonyloxy, propylsulfonyl oxy, isopropylsulfonyloxy, butylsulfonyloxy and the like.

As used herein, "arylsulfonyloxy (group)" means a group in which an arylsulfonyl group is bonded to an oxygen atom, and the carbon number range is not particularly limited, but preferably a C _6-10 arylsulfonyloxy group is.

As used herein, "C _6-10 arylsulfonyloxy (group)" means a group in which a C _6-10 arylsulfonyl group is bonded to an oxygen atom, such as phenylsulfonyloxy, 1-naphthylsulfonyloxy, 2-naphthylsulfonyloxy and the like.

As used herein, the term "substituted amino group" means a group in which at least one of the two hydrogen atoms of the amino group is substituted with a group other than a hydrogen atom, and both of the two hydrogen atoms are When substituted by substituents, the substituents may be the same or different.

As used herein, "trisubstituted silyl (group)" means a silyl group substituted with three identical or different substituents (e.g., C _1-6 alkyl group, C _6-10 aryl group, etc.) The group includes a trialkylsilyl group such as a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group (preferably a tri-C _1-6 alkylsilyl group, more preferably a tri-C _1-4 alkylsilyl group), tert-butyldiphenylsilyl group, triphenylsilyl group and the like are preferred.

As used herein, the term "trisubstituted silyloxy (group)" means a group in which a trisubstituted silyl group is bonded to an oxygen atom, and the group includes a trimethylsilyloxy group, a triethylsilyloxy group, and a triisopropylsilyloxy group. , a trialkylsilyloxy group such as a tert-butyldimethylsilyloxy group (preferably a tri-C _1-6 alkylsilyloxy group, more preferably a tri-C _1-4 alkylsilyloxy group), tert-butyldiphenylsilyloxy groups, triphenylsilyloxy groups and the like are preferred.

In the present specification, the substituents constituting the "substituted amino group" include, for example, protective groups for amino groups described in Protective Groups in Organic Synthesis, John Wiley and Sons (3rd edition, 1999). For example, C _1-6 alkyl group, C _1-6 alkylsulfonyl group, C _7-22 aralkyl group, C _6-10 aryl group, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group, C _1-6 alkoxy-carbonyl group, C _7-14 aralkyloxy-carbonyl group, C _6-10 arylsulfonyl group, tri-C _1-6 alkylsilyl group (e.g., tri-C _1-6 alkylsilyl protecting groups such as groups (eg, trimethylsilyl, tert-butyl(dimethyl)silyl)). The protecting groups above may be further substituted with a halogen atom, a C _1-6 alkyl group, a C _1-6 alkoxy group or a nitro group. Specific examples of the amino-protecting group include methyl (monomethyl or dimethyl), benzyl, trityl, acetyl, trifluoroacetyl, pivaloyl, tert-butoxycarbonyl, benzyloxycarbonyl, trifluoromethanesulfonyl, p-toluenesulfonyl and the like. mentioned.

"Optionally substituted" means having 1 to 5 (preferably 1 to 3) substituents at unsubstituted or substitutable positions, and each substituent is the same may be different.

Examples of substituents "optionally substituted" include (1) a halogen atom, (2) a hydroxy group, (3) a cyano group, (4) a nitro group, (5) an azide group, and (6) a substituted amino group, (7) C _1-6 alkyl group, (8) C _1-6 alkoxy group, (9) C _3-8 cycloalkyl group, (10) C _6-10 aryl group, (11) C _{7- 22} aralkyl group, (12) C _1-7 alkanoyl group, (13) C _7-11 aroyl group, (14) C _1-7 alkanoyloxy group, (15) C _7-11 aroyloxy group, (16) C _{1 -6} alkoxy-carbonyl group, (17) carbamoyl group optionally mono- or di-substituted with C _1-6 alkyl group, (18) C _1-6 alkylsulfonyloxy group, (19) C _6-10 aryl sulfonyloxy group, (20) C _1-6 alkylsulfanyl, (21) tri-substituted silyl group, (22) tri-substituted silyloxy group, (23) C _6-10 aryloxy-carbonyl group and the like. Among them, halogen atoms, C _1-6 alkyl, C _1-6 alkoxy, acetyl, formyl, carbamoyl, azide, trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, tert-butyldimethylsilyloxy, phenyl, cyclohexyl , dimethylamino, acetylamino, tert-butoxycarbonylamino, benzyloxycarbonylamino, methoxycarbonyl, methylsulfanyl and the like are preferred.
Substituents of "optionally substituted alkyl" or "optionally substituted alkoxy" include "(7) C _1-6 alkyl group" and "(11) C _7-22 Substituents other than "aralkyl group" can be mentioned.

Each of the above substituents may be further substituted with one or more of hydroxy group, C _1-6 alkyl group, C _1-6 alkoxy group, halogen atom, cyano group, nitro group, phenyl group, etc. good.

As used herein, "triarylphosphine" means a compound in which three identical or different aryl groups are attached to a phosphorus atom. The "optionally substituted triarylphosphine" is not particularly limited, and examples thereof include triphenylphosphine, tris(methylphenyl)phosphine, tris(fluorophenyl)phosphine, tris(chlorophenyl)phosphine and the like. Among them, triphenylphosphine, tris(4-fluorophenyl)phosphine or tris(4-chlorophenyl)phosphine is preferred, and triphenylphosphine is more preferred.

As used herein, the term "repeating unit" means a partial unit structure that constitutes a polymer compound. A plurality of such repeating units are continuously present in the substituted poly(diphenylacetylene) obtained by the production method of the present invention. When multiple types of repeating units are present in the polyacetylene of the present invention, these multiple types of repeating units are present forming multiple blocks in the substituted poly(diphenylacetylene).

As used herein, "cyclic substituted poly(diphenylacetylene)" means substituted poly(diphenylacetylene) having no molecular ends. It is presumed that the cyclic substituted poly(diphenylacetylene) of the present invention is formed by a ring-expansion polymerization reaction according to the examples described later.

In the present specification, "molecular weight distribution" means the value ( _Mw / _Mn ) obtained by dividing the weight average molecular weight ( _Mw ) by the number average molecular weight ( _Mn ), and the closer to 1 , meaning that the molecular weight of the polymer compound (ie, the substituted poly(diphenylacetylene)) is consistent. Molecular weight distributions given in the examples below were estimated by gel permeation chromatography with a UV-visible detector and calibrated with polystyrene standards.

As used herein, the term "co-catalyst having reducing ability" means a co-catalyst capable of reducing tetravalent tungsten halide as a catalyst. By "promoter" is meant a substance that does not act as a catalyst by itself, but which, when used in conjunction with a catalyst, has the effect of assisting the reaction that the catalyst accelerates.

As used herein, "tetravalent tungsten halide" means tetravalent tungsten to which four halogen atoms are bonded, specifically, for example, tungsten tetrafluoride, tungsten tetrachloride, tetravalent tungsten Among them, tungsten tetraiodide and tungsten tetraiodide are mentioned, and among them, tungsten tetrachloride (hereinafter also referred to as "WCl ₄ ") is preferable.

As used herein, "somewhat controlled molecular weight" means that there is a substantial correlation between the molar ratio of catalyst to monomer used and the molecular weight (M _n ) of the polymer produced. In the production method of the present invention, the molecular weight (M _n ) of the substituted poly(diphenylacetylene) obtained varies depending on the types of monomers and co-catalysts used in a wide molecular weight range from several thousand to about 200,000. They can be produced differently by changing the molar ratio of the catalyst and the monomer. Thus, any molecular weight (M _n ) that can be obtained with relatively high accuracy is referred to herein as a "somewhat controlled molecular weight."

(Manufacturing method of the present invention)
The production method of the present invention is
tetravalent tungsten halide,
In the presence of a cocatalyst having reducing ability and an optionally substituted triarylphosphine,
Formula (I):

[In the formula,
n R ¹ are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
m R ² are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
n represents an integer of 0-3, and m represents an integer of 0-3. ]
and polymerizing a compound represented by (compound (I)).

Preferred embodiments of the tetravalent tungsten halide are described below.
The tetravalent tungsten halide includes tungsten tetrafluoride, tungsten tetrachloride, tungsten tetrabromide and tungsten tetraiodide, preferably tungsten tetrachloride. As the tetravalent tungsten halide, a commercially available product can be used as it is, or one prepared by a method known per se can be used.

Preferred embodiments of the co-catalyst having reducing ability are described below.
The co-catalyst having reducing ability is not particularly limited as long as it is a compound having the ability to reduce tetravalent tungsten halide, but is preferably tetraphenyltin; tetra-n-butyltin; bis(trimethylsilyl)cyclohexa-1 ,4-diene; bis(trimethylsilyl)2-methylcyclohexa-1,4-diene; aluminum hydride reagents such as sodium bis(2-methoxyethoxy)aluminum hydride; 9-borabicyclo[3.3.1]nonane and the like silane reagents such as triethylsilane; organomagnesium reagents such as methylmagnesium bromide; and organolithium reagents such as butyllithium. A promoter selected from the group consisting of n-butyltin and bis(trimethylsilyl)cyclohexa-1,4-diene.

Preferred embodiments of optionally substituted triarylphosphine are described below.
Triarylphosphine which may be substituted includes triphenylphosphine, tris(methylphenyl)phosphine, tris(fluorophenyl)phosphine, tris(chlorophenyl)phosphine and the like, preferably triphenylphosphine, tris(4 -fluorophenyl)phosphine or tris(4-chlorophenyl)phosphine, more preferably triphenylphosphine. As the optionally substituted triarylphosphine, commercially available products can be used as they are.

In the production method of the present invention, the combination of a reactant (catalyst system) consisting of a tetravalent tungsten halide; a cocatalyst having reducibility; and an optionally substituted triarylphosphine,
Preferably, tungsten tetrachloride; tetraphenyltin, tetra-n-butyltin, bis(trimethylsilyl)cyclohexa-1,4-diene, bis(trimethylsilyl)2-methylcyclohexa-1,4-diene, hydrogenated bis(2- methoxyethoxy)aluminum sodium, boron hydride reagents such as 9-borabicyclo[3.3.1]nonane, silane reagents such as triethylsilane, organomagnesium reagents such as methylmagnesium bromide, and organic reagents such as butyllithium. a promoter selected from the group consisting of lithium reagents; and a combination consisting of triphenylphosphine, tris(4-fluorophenyl)phosphine or tris(4-chlorophenyl)phosphine;
More preferred is a combination consisting of tungsten tetrachloride; a promoter selected from the group consisting of tetraphenyltin, tetra-n-butyltin and bis(trimethylsilyl)cyclohexa-1,4-diene; and triphenylphosphine.

(Compound (I))
Preferred embodiments of the raw material monomer, that is, the compound (I) are described below.
As the compound (I), n R ^1s in the formula (I) are preferably each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g. methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy , hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), C _1-7 alkanoyl groups optionally substituted by halogen atoms (e.g., acetyl, trifluoroacetyl), substituted by halogen atoms optionally C _1-7 alkanoyloxy group (e.g., acetoxy, trifluoroacetoxy), C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), an arylsulfonyloxy group (e.g., benzenesulfonyloxy, 4- _{fluorobenzenesulfonyloxy} , 2- nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), tri-C _1-6 alkylsilyl groups (e.g. trimethylsilyl, triethylsilyl, tri isopropylsilyl), or C _1-6 alkylsulfonyl group, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group, C _1-6 alkoxy-carbonyl group, C _7-14 an amino group substituted with a group selected from the group consisting of an aralkyloxy-carbonyl group and a C _6-10 arylsulfonyl group;
More preferably, each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (eg, methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _{1- 6} alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl) or tri-C _1-4 alkylsilyl a group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl);
m R ² are preferably each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g. methyl, ethyl, propyl, isopropyl, butyl, pentyl , hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy , trifluoroacetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and a C _1-6 alkyl an arylsulfonyloxy group optionally substituted by a group selected from the group consisting of groups (eg, benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _{1- 8} alkoxy-carbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), tri-C _1-6 alkylsilyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, from C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group, C _1-6 alkoxy-carbonyl group, C _7-14 aralkyloxy-carbonyl group and C _6-10 arylsulfonyl group an amino group substituted with a group selected from the group consisting of
More preferably, each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (eg, methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _{1- 6} alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl) or tri-C _1-4 alkylsilyl a group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl);
n is preferably an integer from 0 to 2, more preferably 0 or 1; and m is preferably an integer from 0 to 2, more preferably 0 or 1.
In addition, it is preferred that n R ¹ and m R ² are each independently absent or present in the meta-position and/or para-position relative to the phenylethynyl group, absent or It is more preferred to be in the meta or para position relative to the phenylethynyl group.

As another aspect of compound (I), n R ¹ in the formula (I) are preferably each independently C ₁ optionally substituted with a halogen atom, a cyano group or a halogen atom. _-6 alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), C _1-7 alkanoyl groups optionally substituted by halogen atoms (e.g., acetyl, trifluoroacetyl), halogen atoms C _1-7 alkanoyloxy groups optionally substituted by (e.g., acetoxy, trifluoroacetoxy), C _1-6 alkylsulfonyloxy groups optionally substituted by halogen atoms (e.g., methanesulfonyloxy, trifluoromethane sulfonyloxy), a halogen atom, a nitro group, a cyano group and an arylsulfonyloxy group optionally substituted by a group selected from the group consisting of a C _1-6 alkyl group (e.g., benzenesulfonyloxy, 4-fluorobenzenesulfonyl oxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6-10 optionally substituted by halogen atoms aryloxy-carbonyl group (eg pentafluorophenoxy-carbonyl), tri-C _1-6 alkylsilyl group (eg trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1-7 selected from the group consisting of an alkanoyl group, a C _7-11 aroyl group, a C _7-14 aralkyl-carbonyl group, a C _1-6 alkoxy-carbonyl group, a C _7-14 aralkyloxy-carbonyl group and a C _6-10 arylsulfonyl group; is an amino group substituted by a group
More preferably, each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (eg, methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _{1- 6} alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), substituted by halogen atoms a C _6-10 aryloxy-carbonyl group (e.g. pentafluorophenoxy-carbonyl) or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropylsilyl);
m R ² are preferably each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g. methyl, ethyl, propyl, isopropyl, butyl, pentyl , hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy , trifluoroacetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and a C _1-6 alkyl an arylsulfonyloxy group optionally substituted by a group selected from the group consisting of groups (eg, benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _{1- 8} alkoxy-carbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6-10 aryloxy-carbonyl groups optionally substituted by halogen atoms (eg, pentafluorophenoxy-carbonyl), tri-C _{1 -6} alkylsilyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group , a C _1-6 alkoxy-carbonyl group, a C _7-14 aralkyloxy-carbonyl group and an amino group substituted by a group selected from the group consisting of a C _6-10 arylsulfonyl group,
More preferably, each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (eg, methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _{1- 6} alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), substituted by halogen atoms a C _6-10 aryloxy-carbonyl group (e.g. pentafluorophenoxy-carbonyl), or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropylsilyl);
n is preferably an integer from 0 to 2, more preferably 0 or 1; and m is preferably an integer from 0 to 2, more preferably 0 or 1.
In addition, it is preferred that n R ¹ and m R ² are each independently absent or present in the meta-position and/or para-position relative to the phenylethynyl group, absent or It is more preferred to be in the meta or para position relative to the phenylethynyl group.

Suitable compounds (I) include the following compounds.
[Compound IA]
n R ¹ in the above formula (I) are each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl , butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy, trifluoroacetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and C an arylsulfonyloxy group optionally substituted by a group selected from the group consisting of _1-6 alkyl groups (e.g., benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy) , C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), tri-C _1-6 alkylsilyl groups (e.g. trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group, C _1-6 alkoxy-carbonyl group, C _7-14 aralkyloxy-carbonyl group and C _6-10 an amino group substituted with a group selected from the group consisting of an arylsulfonyl group;
m R ² are each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy ), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy, trifluoro acetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and a C _1-6 alkyl group an arylsulfonyloxy group optionally substituted by a group selected from the group (e.g., benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _1-8 alkoxy- carbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), tri-C _1-6 alkylsilyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1- from the group consisting of ₇ alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group, C _1-6 alkoxy-carbonyl group, C _7-14 aralkyloxy-carbonyl group and C _6-10 arylsulfonyl group an amino group substituted by a selected group;
n is an integer from 0 to 2;
m is an integer of 0 to 2; and n R ¹ and m R ² are each independently absent or present in meta and/or para positions relative to the phenylethynyl group. do,
Compound (I).

[Compound IB]
n R ¹ in the above formula (I) are each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _1-6 alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxy carbonyl) or a tri-C _1-4 alkylsilyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl);
m R ² are each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _1-6 alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl) or triC _{1- 4} alkylsilyl groups (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl);
n is 0 or 1;
m is 0 or 1; and n R ¹ and m R ² are each independently absent or are meta or para to the phenylethynyl group,
Compound (I).

[Compound IA']
n R ¹ in the above formula (I) are each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl , butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy, trifluoroacetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and C an arylsulfonyloxy group optionally substituted by a group selected from the group consisting of _1-6 alkyl groups (e.g., benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy) , C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6-10 aryloxy-carbonyl groups optionally substituted by halogen atoms (e.g. pentafluorophenoxy-carbonyl) , tri-C _1-6 alkylsilyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 an amino group substituted by a group selected from the group consisting of an aralkyl-carbonyl group, a C _1-6 alkoxy-carbonyl group, a C _7-14 aralkyloxy-carbonyl group and a C _6-10 arylsulfonyl group;
m R ² are each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy ), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy, trifluoro acetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and a C _1-6 alkyl group an arylsulfonyloxy group optionally substituted by a group selected from the group (e.g., benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _1-8 alkoxy- carbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6-10 aryloxy-carbonyl group optionally substituted by a halogen atom (eg, pentafluorophenoxy-carbonyl), tri-C _1-6 alkyl silyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group, C _{1 -6} an alkoxy-carbonyl group, a C _7-14 aralkyloxy-carbonyl group and an amino group substituted by a group selected from the group consisting of a C _6-10 arylsulfonyl group;
n is an integer from 0 to 2;
m is an integer of 0 to 2; and n R ¹ and m R ² are each independently absent or present in meta and/or para positions relative to the phenylethynyl group. do,
Compound (I).

[Compound IB']
n R ¹ in the above formula (I) are each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _1-6 alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxy carbonyl), a C _6-10 aryloxy-carbonyl group optionally substituted by a halogen atom (e.g. pentafluorophenoxy-carbonyl), or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropyl Cyril);
m R ² are each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _1-6 alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), substituted by halogen atoms a C _6-10 aryloxy-carbonyl group (e.g. pentafluorophenoxy-carbonyl), or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropylsilyl) which may be optionally
n is 0 or 1;
m is 0 or 1; and n R ¹ and m R ² are each independently absent or are meta or para to the phenylethynyl group,
Compound (I).

Preferable specific examples of compound (I) include the following formula:

Compounds represented by and the like.

Compound (I) can be easily obtained commercially and used as it is, or by a method known per se (e.g., Molecules 2016, 21, 1487; Chem. Lett. 2016, 45, 1063-1065; Angew. Chem. Int. Ed. 2020, 59, 14772-14780, etc.) or a method equivalent thereto.

(Compound (II))
The compound obtained by the production method of the present invention has the following formula (II):

[Each symbol in the formula has the same meaning as described above. ]
It is a cyclic substituted poly(diphenylacetylene) (compound (II)) having a repeating unit represented by.

Preferred embodiments of compound (II) are described below.
As the compound (II), n R ^1s in the formula (II) are preferably each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted with a halogen atom (e.g. methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy , hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), C _1-7 alkanoyl groups optionally substituted by halogen atoms (e.g., acetyl, trifluoroacetyl), substituted by halogen atoms optionally C _1-7 alkanoyloxy group (e.g., acetoxy, trifluoroacetoxy), C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), an arylsulfonyloxy group (e.g., benzenesulfonyloxy, 4- _{fluorobenzenesulfonyloxy} , 2- nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), tri-C _1-6 alkylsilyl groups (e.g. trimethylsilyl, triethylsilyl, tri isopropylsilyl), or C _1-6 alkylsulfonyl group, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group, C _1-6 alkoxy-carbonyl group, C _7-14 an amino group substituted with a group selected from the group consisting of an aralkyloxy-carbonyl group and a C _6-10 arylsulfonyl group;
More preferably, each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (eg, methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _{1- 6} alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl) or tri-C _1-4 alkylsilyl a group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl);
m R ² are preferably each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g. methyl, ethyl, propyl, isopropyl, butyl, pentyl , hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy , trifluoroacetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and a C _1-6 alkyl an arylsulfonyloxy group optionally substituted by a group selected from the group consisting of groups (eg, benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _{1- 8} alkoxy-carbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), tri-C _1-6 alkylsilyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, from C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group, C _1-6 alkoxy-carbonyl group, C _7-14 aralkyloxy-carbonyl group and C _6-10 arylsulfonyl group an amino group substituted with a group selected from the group consisting of
More preferably, each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (eg, methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _{1- 6} alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl) or tri-C _1-4 alkylsilyl a group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl);
n is preferably an integer from 0 to 2, more preferably 0 or 1; and m is preferably an integer from 0 to 2, more preferably 0 or 1.
In addition, it is preferred that n R ¹ and m R ² are each independently absent or present in the meta- and/or para-position relative to the substituted styryl group, absent or It is more preferred to be in the meta or para position relative to the substituted styryl group.

In another preferred embodiment of compound (II), n R ¹ in formula (II) are preferably each independently a halogen atom, a cyano group or a halogen atom C _1-6 alkyl groups (e.g. methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g. methoxy, ethoxy, propoxy , butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), halogen C _1-7 alkanoyloxy groups optionally substituted by atoms (e.g., acetoxy, trifluoroacetoxy), C _1-6 alkylsulfonyloxy groups optionally substituted by halogen atoms (e.g., methanesulfonyloxy, trifluoro methanesulfonyloxy), a halogen atom, a nitro group, a cyano group and an arylsulfonyloxy group optionally substituted by a group selected from the group consisting of a C _1-6 alkyl group (e.g., benzenesulfonyloxy, 4-fluorobenzene sulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _1-8 alkoxy-carbonyl groups (e.g., methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6- optionally substituted by halogen atoms ₁₀ aryloxy-carbonyl group (e.g., pentafluorophenoxy-carbonyl), tri-C _1-6 alkylsilyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1- from the group consisting of ₇ alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group, C _1-6 alkoxy-carbonyl group, C _7-14 aralkyloxy-carbonyl group and C _6-10 arylsulfonyl group an amino group substituted by a selected group;
More preferably, each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (eg, methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _{1- 6} alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), substituted by halogen atoms a C _6-10 aryloxy-carbonyl group (e.g. pentafluorophenoxy-carbonyl), or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropylsilyl);
m R ² are preferably each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g. methyl, ethyl, propyl, isopropyl, butyl, pentyl , hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy , trifluoroacetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and a C _1-6 alkyl an arylsulfonyloxy group optionally substituted by a group selected from the group consisting of groups (eg, benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _{1- 8} alkoxy-carbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6-10 aryloxy-carbonyl groups optionally substituted by halogen atoms (eg, pentafluorophenoxy-carbonyl), tri-C _{1 -6} alkylsilyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group , a C _1-6 alkoxy-carbonyl group, a C _7-14 aralkyloxy-carbonyl group and an amino group substituted by a group selected from the group consisting of a C _6-10 arylsulfonyl group,
More preferably, each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (eg, methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _{1- 6} alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), substituted by halogen atoms a C _6-10 aryloxy-carbonyl group (e.g. pentafluorophenoxy-carbonyl), or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropylsilyl);
n is preferably an integer from 0 to 2, more preferably 0 or 1; and m is preferably an integer from 0 to 2, more preferably 0 or 1.
In addition, it is preferred that n R ¹ and m R ² are each independently absent or present in the meta- and/or para-position relative to the substituted styryl group, absent or It is more preferred to be in the meta or para position relative to the substituted styryl group.

Suitable compounds (II) include the following compounds.
[Compound II-A]
n R ¹ in the above formula (II) are each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl , butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy, trifluoroacetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and C an arylsulfonyloxy group optionally substituted by a group selected from the group consisting of _1-6 alkyl groups (e.g., benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy) , C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), tri-C _1-6 alkylsilyl groups (e.g. trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group, C _1-6 alkoxy-carbonyl group, C _7-14 aralkyloxy-carbonyl group and C _6-10 an amino group substituted with a group selected from the group consisting of an arylsulfonyl group;
m R ² are each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy ), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy, trifluoro acetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and a C _1-6 alkyl group an arylsulfonyloxy group optionally substituted by a group selected from the group (e.g., benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _1-8 alkoxy- carbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), tri-C _1-6 alkylsilyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1- from the group consisting of ₇ alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group, C _1-6 alkoxy-carbonyl group, C _7-14 aralkyloxy-carbonyl group and C _6-10 arylsulfonyl group an amino group substituted by a selected group;
n is an integer from 0 to 2;
m is an integer of 0 to 2; and n R ¹ and m R ² are each independently absent or present in meta and/or para positions relative to the substituted styryl group. has a repeating unit,
Compound (II).

[Compound II-B]
n R ¹ in the formula (II) are each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _1-6 alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxy carbonyl) or a tri-C _1-4 alkylsilyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl);
m R ² are each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _1-6 alkoxy group (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl group (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl) or triC _{1- 4} alkylsilyl groups (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl);
n is 0 or 1;
m is 0 or 1; and n R ¹ and m R ² are each independently absent or present at the meta-position or para-position relative to the substituted styryl group. has a
Compound (II).

[Compound II-A']
n R ¹ in the above formula (II) are each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl , butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g., methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy, trifluoroacetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and C an arylsulfonyloxy group optionally substituted by a group selected from the group consisting of _1-6 alkyl groups (e.g., benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy) , C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6-10 aryloxy-carbonyl groups optionally substituted by halogen atoms (e.g. pentafluorophenoxy-carbonyl) , tri-C _1-6 alkylsilyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 an amino group substituted by a group selected from the group consisting of an aralkyl-carbonyl group, a C _1-6 alkoxy-carbonyl group, a C _7-14 aralkyloxy-carbonyl group and a C _6-10 arylsulfonyl group;
m R ² are each independently a halogen atom, a cyano group or a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, trifluoromethyl), C _1-8 alkoxy groups optionally substituted by halogen atoms (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, trifluoromethoxy, trifluoroethoxy ), a C _1-7 alkanoyl group optionally substituted by a halogen atom (e.g., acetyl, trifluoroacetyl), a C _1-7 alkanoyloxy group optionally substituted by a halogen atom (e.g., acetoxy, trifluoro acetoxy), a C _1-6 alkylsulfonyloxy group optionally substituted by a halogen atom (e.g., methanesulfonyloxy, trifluoromethanesulfonyloxy), a halogen atom, a nitro group, a cyano group and a C _1-6 alkyl group an arylsulfonyloxy group optionally substituted by a group selected from the group (e.g., benzenesulfonyloxy, 4-fluorobenzenesulfonyloxy, 2-nitrobenzenesulfonyloxy, p-toluenesulfonyloxy), C _1-8 alkoxy- carbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), C _6-10 aryloxy-carbonyl group optionally substituted by a halogen atom (eg, pentafluorophenoxy-carbonyl), tri-C _1-6 alkyl silyl group (e.g., trimethylsilyl, triethylsilyl, triisopropylsilyl), or C _1-6 alkylsulfonyl group, C _1-7 alkanoyl group, C _7-11 aroyl group, C _7-14 aralkyl-carbonyl group, C _{1 -6} an alkoxy-carbonyl group, a C _7-14 aralkyloxy-carbonyl group and an amino group substituted by a group selected from the group consisting of a C _6-10 arylsulfonyl group;
n is an integer from 0 to 2;
m is an integer of 0 to 2; and n R ¹ and m R ² are each independently absent or present in meta and/or para positions relative to the substituted styryl group. has a repeating unit,
Compound (II).

[Compound II-B']
n R ¹ in the formula (II) are each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _1-6 alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxy carbonyl), a C _6-10 aryloxy-carbonyl group optionally substituted by a halogen atom (e.g. pentafluorophenoxy-carbonyl), or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropyl Cyril);
m R ² are each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl, butyl, pentyl, trifluoromethyl), C _1-6 alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, heptyloxycarbonyl), substituted by halogen atoms a C _6-10 aryloxy-carbonyl group (e.g. pentafluorophenoxy-carbonyl), or a tri-C _1-4 alkylsilyl group (e.g. trimethylsilyl, triethylsilyl, triisopropylsilyl) which may be optionally
n is 0 or 1;
m is 0 or 1; and n R ¹ and m R ² are each independently absent or present at the meta-position or para-position relative to the substituted styryl group. having
Compound (II).

Preferable specific examples of compound (II) include the following formula:

It is a cyclic substituted poly(diphenylacetylene) (compound (II)) having a repeating unit represented by.

Among compounds (II), the following formula (II'):

[In the formula,
R ^1' and R ^2' each independently represent a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted Alkylsulfanyl group, optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted It represents an alkoxy-carbonyl group, an optionally substituted C _6-10 aryloxy-carbonyl group (eg pentafluorophenoxy-carbonyl), an optionally substituted carbamoyl group or a substituted amino group. ]
A cyclic substituted poly(diphenylacetylene) (compound (II')) or a salt thereof having a repeating unit represented by is a novel compound.

Suitable compounds (II') include the following compounds.
[Compound II′-A]
R ^1' and R ^2' in the formula (II') are each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl , butyl, pentyl, trifluoromethyl), C _1-6 alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl , heptyloxycarbonyl) or a tri-C _1-4 alkylsilyl group (eg, trimethylsilyl, triethylsilyl, triisopropylsilyl).

[Compound II'-B]
R ^1' and R ^2' in the formula (II') are each independently a halogen atom, a C _1-6 alkyl group optionally substituted by a halogen atom (e.g., methyl, ethyl, propyl, isopropyl , butyl, pentyl, trifluoromethyl), C _1-6 alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy), C _1-8 alkoxy-carbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl , heptyloxycarbonyl), a C _6-10 aryloxy-carbonyl group optionally substituted by a halogen atom (e.g., pentafluorophenoxy-carbonyl), or a tri-C _1-4 alkylsilyl group (e.g., trimethylsilyl, triethylsilyl , triisopropylsilyl).

Preferable specific examples of compound (II') include the following formula:

It is a cyclic substituted poly(diphenylacetylene) (compound (II')) having a repeating unit represented by

In the production method of the present invention, the compounding ratio of the tetravalent tungsten halide, the cocatalyst having reducing ability, and the optionally substituted triarylphosphine (the compounding ratio of the catalyst system) is 1 part of the tetravalent tungsten halide. Per mol, the promoter having reducing ability is 1.0 to 5.0 mol (preferably 1.0 to 4.0 mol, more preferably 1.0 to 3.0 mol), The optionally substituted triarylphosphine is 0.05 to 1.0 mol (preferably 0.1 to 0.5 mol, more preferably 0.1 to 0.2 mol).

The amount of compound (I) added in the production method of the present invention can be arbitrarily set according to the molecular weight of the desired compound (II) (or compound (II')) (polymer). The molar ratio of compound (I) (monomer) to 1 mol of tetravalent tungsten halide ([monomer]/[tungsten halide]) is 10 to 2,000, preferably 50 to 1,000.

As the solvent used in the production method of the present invention, any solvent can be used without particular limitation as long as it can dissolve the raw materials and is inert to the reaction. For example, ethers such as ethyl tert-butyl ether and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene and xylene; hydrogen halides such as dichloromethane and chloroform; N,N-dimethylformamide, N,N-dimethylacetamide and the like. These amides can be used singly or in combination of two or more. Among them, toluene is preferred.

In the production method of the present invention, suitable reaction conditions can be appropriately selected depending on the type of the tetravalent tungsten halide to be used, the co-catalyst having reducing ability, the triarylphosphine that may be substituted, and the solvent to be used. The reaction (polymerization reaction) is preferably carried out for 2 to 48 hours (preferably 12 to 24 hours) at the reflux temperature of the solvent used in a sealed tube (closed pressure resistant tube) under an inert gas atmosphere.

The concentration of compound (I) (monomer) in the reaction solution of the polymerization reaction can be appropriately optimized depending on the solubility of compound (I) in the reaction solvent, and is not particularly limited, but is usually 0.1M to 2M. .0M, preferably between 0.1M and 1.0M.

After completion of the polymerization reaction, the desired compound (II) (or compound (II')) can be obtained by pouring an excessive amount of poor solvent (e.g., methanol) into the reaction solution to perform precipitation or the like. can.

Compound (II) (or compound (II')) or a salt thereof obtained by the production method of the present invention has a number average molecular weight (M _n ) of 1,000 to 500,000, preferably 10,000 to 300,000, and a gel. The molecular weight distribution (M _w /M _n ) measured by permeation chromatography is about 1.5 to 7 (preferably 1.5 to 4).

The production method of the present invention produces substituted poly(diphenylacetylene)s having various functional groups with high yield while controlling the molecular weight in a wide molecular weight range from several thousand to several hundred thousand by simple operation. It is possible to Further, the substituted poly(diphenylacetylene)s obtained by the production method of the present invention are excellent in thermal stability, and therefore are extremely useful as raw materials for various functional polymer materials.

Hereinafter, the present invention will be described in more detail based on Examples and Test Examples, but the present invention is not limited by Examples and Test Examples, and can be changed without departing from the scope of the present invention. good too. Also, the reagents and starting compounds used in the present invention are commercially available unless otherwise specified.

Tungsten tetrachloride (Sigma-Aldrich, manufactured by Tokyo Chemical Industry Co., Ltd. (TCI)), tetraphenyltin (manufactured by Tokyo Chemical Industry Co., Ltd. (TCI)), and tetrabutyltin, which are reagents and starting compounds used in the following examples (manufactured by Kanto Chemical Co., Ltd.), triphenylphosphine (manufactured by Nacalai Tesque Co., Ltd.), compound (I-5) (manufactured by Tokyo Chemical Industry Co., Ltd. (TCI)), compound (I-6) (Tokyo Chemical Industry Co., Ltd. ( TCI) and toluene (dehydrated) (Kanto Kagaku Co., Ltd.) were used as commercially available products.

% indicates mol/mol % for yields, otherwise indicates weight % unless otherwise specified. Further, room temperature indicates a temperature of 15 to 30° C. unless otherwise specified.
¹ H- and ¹³ C-NMR spectra were measured using JEOL JNM-ECA 500 with deuterated chloroform as a solvent. Data for ¹ H-NMR are given in terms of chemical shift (δ ppm), multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, quint = quintet, m = multiplet, dd = double doublet, dt = Reported as double triplet, brs = broad singlet), coupling constant (Hz), integral and assignment. The infrared spectrum was measured using a Fourier transform infrared spectrophotometer IR-4700 manufactured by JASCO Corporation. The average molecular weight and molecular weight distribution were determined by gel permeation chromatography (high-performance liquid chromatography pump PU-4180 manufactured by JASCO Corporation, UV-visible detector MD-4010 manufactured by JASCO Corporation, column oven CO-4060 manufactured by JASCO Corporation, Shodex Column KF-805L) was calculated in terms of polystyrene. Using an atomic force microscope (AFM) Cypher (registered trademark) manufactured by Asylum Research, a sample coated on a highly oriented pyrolytic graphite substrate was measured.

[Example 1]
In an argon atmosphere, tungsten tetrachloride (WCl ₄ ) (32.7 mg, 0.1 mmol), tetraphenyltin (42.6 mg, 0.1 mmol), and triphenylphosphine (2.3 mg, 0.01 mmol) were placed in a 15 mL pressure-resistant tube. ) and formula (I-1):

After adding toluene (2 mL) to a mixture of the compound represented by (compound (I-1); monomer) (925 mg, 2.0 mmol), the pressure tube was sealed and the mixture was stirred for one day while heating at 110°C. The resulting reaction mixture was poured into an excess amount of methanol, and the resulting precipitate dissolved in tetrahydrofuran (20 ml) was poured into an excess amount of methanol/tetrahydrofuran mixed solution (3/1, v/v) to precipitate. Obtained. This precipitate is washed with a methanol/tetrahydrofuran mixed solution (4/1, v/v) and dried under reduced pressure to obtain formula (II-1):

A polymer (compound (II-1)) having a repeating unit represented by (801 mg, yield calculated from the yield of the polymer with respect to the charged amount of monomer: 87%) was obtained as a yellow solid. The number average molecular weight (M _n ) and the molecular weight distribution (M _w /M _n ) estimated from gel permeation chromatography of the resulting compound (II-1) were M _n of 124,000 and M _w / _Mn was 1.92.
¹ H NMR (500 MHz, CDCl ₃ , 20° C.): δ 7.0-7.3 (br, 4H), 6.4-6.7 (br, 2H), 5.8-6.2 (br, 2H), 4.0-4.4 (br-d, 4H), 1.6-1.9 (br, 4H), 1.2-1.5 (br, 16H), 0.8-0.95 (br, 6H);
¹³ C NMR (126 MHz, CDCl ₃ , 20° C.): δ 165.6, 146.5, 146.4, 130.6, 128.9, 128.4, 127.0, 65.4, 31.9, 29.2, 28.7, 26.0, 22.7, 14.2;
IR (KBr, cm ^-1 ): 2929, 1722, 1275, 1107.

Compound (II-1) was coated on a highly oriented pyrolytic graphite substrate and measured using an atomic force microscope (AFM) (Cypher (registered trademark)) manufactured by Asylum Research Inc. Image and partial enlargement The image is shown in FIG.
According to FIG. 1, compound (II-1) was confirmed to have a cyclic structure.
As shown in FIG. 1, cyclic compounds (II-1) of various sizes were observed, suggesting that in the polymerization reaction of diphenylacetylenes using a low-valent tungsten catalyst, the polymerization proceeds via a ring expansion polymerization mechanism. It is assumed that the reaction proceeds to give a cyclic polymer.

[Examples 2-3]
Tetrabutyltin ( ⁿ Bu ₄ Sn) and bis(trimethylsilyl)cyclohexa-1,4-diene (BTCD) instead of tetraphenyltin as promoters; see J. Am. Chem. Soc. 2009, 131, 5370-5371 ) was used, the polymerization reaction of compound (I-1) was carried out under the same reaction conditions as in Example 1. Table 1 below shows the yield, number average molecular weight (M _n ) and molecular weight distribution (M _w /M _n ) of compound (II-1) obtained in Examples 1 to 3.

[Examples 4-5]
The amount of tungsten tetrachloride (WCl ₄ ) used was changed from 0.1 mmol (5 mol% relative to the monomer) to 0.2 mmol (10 mol% relative to the monomer) or 1.1 mmol (55 mol% relative to the monomer). The polymerization reaction of compound (I-1) was carried out under the same reaction conditions as in Example 1, except that the amounts of tetraphenyltin and triphenylphosphine used were changed accordingly. Table 2 below shows the number average molecular weight (M _n ) and molecular weight distribution (M _w /M _n ) of compound (II-1) obtained in Examples 1 and 4 and 5.

[Examples 6 to 12]
As a monomer, instead of compound (I-1), the following formula:

Diphenylacetylene represented by (Compound (I-2) (Example 6), Compound (I-3) (Example 7), Compound (I-4) (Example 8), Compound (I-5) ( Example 9), compound (I-6) (Example 10), compound (I-7) (Example 11) or compound (I-8) (Example 12)), A polymerization reaction of diphenylacetylene was carried out under the same reaction conditions as in Example 1. Table 3 shows the structural formula, yield, number average molecular weight (M _n ) and molecular weight distribution (M _w /M _n ) of the repeating units of the obtained substituted poly(diphenylacetylene).

[Test example]
Using the compound (I-1) as a monomer, the production method of the present invention (Example 1) and the conventional method (the method described in Patent Document 1, the method described in Patent Document 2, and the method described in Non-Patent Document 4 Method) is shown in Table 4.

From the results in Table 4, the substituted poly(diphenylacetylene) (i.e., the compound (II-1 )) can be obtained with a high molecular weight (molecular weight of 20,000 or more, preferably 100,000 or more) and in a high yield.

According to the present invention, substituted poly(diphenylacetylene)s having various functional groups can be produced with high yield while controlling the molecular weight in a wide range of molecular weights from several thousand to several hundred thousand by a simple operation. be able to. In addition, according to the present invention, a cyclic substituted poly(diphenylacetylene) having a molecular weight controlled to some extent and a desired functional group and having excellent thermal stability, for which no effective synthesis method has been available so far, can be obtained. Since it can be obtained in good yield, it is extremely useful as a raw material synthesis method for various functional polymer materials.

Claims (8)

In the presence of a tetravalent tungsten halide, a cocatalyst having reducibility, and an optionally substituted triarylphosphine, formula (I):

[In the formula,
n R ¹ are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
m R ² are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
n represents an integer of 0-3, and m represents an integer of 0-3. ]
comprising the step of polymerizing a compound represented by formula (II):

[Each symbol in the formula has the same meaning as defined above. ]
A method for producing a substituted poly(diphenylacetylene) having repeating units represented by In the formula (I),
n R ¹ are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
m R ² are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkylsulfanyl optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted alkoxy- a carbonyl group, an optionally substituted carbamoyl group or a substituted amino group,
The manufacturing method according to claim 1, wherein n is an integer of 0-3 and m is an integer of 0-3. Co-catalysts with reducing ability include tetraphenyltin, tetra-n-butyltin, bis(trimethylsilyl)cyclohexa-1,4-diene, bis(trimethylsilyl)2-methylcyclohexa-1,4-diene, aluminum hydride reagent, boron 3. The method according to claim 1, wherein the reagent is selected from the group consisting of hydride reagents, silane reagents, organomagnesium reagents and organolithium reagents. The production method according to any one of claims 1 to 3, wherein the optionally substituted triarylphosphine is triphenylphosphine, tris(4-fluorophenyl)phosphine or tris(4-chlorophenyl)phosphine. The production method according to any one of claims 1 to 4, wherein the tetravalent tungsten halide is tungsten tetrachloride. The tetravalent tungsten halide is tungsten tetrachloride,
The cocatalyst having reducing ability is selected from the group consisting of tetraphenyltin, tetra-n-butyltin and bis(trimethylsilyl)cyclohexa-1,4-diene, and the optionally substituted triarylphosphine is triphenylphosphine The manufacturing method according to claim 1 or 2, wherein Formula (II'):

[In the formula,
R ^1' and R ^2' each independently represent a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted Alkylsulfanyl group, optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted It represents an alkoxy-carbonyl group, an optionally substituted aryloxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group. ]
A substituted poly(diphenylacetylene) having a repeating unit represented by or a salt thereof. R ^1' and R ^2' are each independently a halogen atom, a hydroxy group, a cyano group, a nitro group, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted Alkylsulfanyl group, optionally substituted acyl group, optionally substituted acyloxy group, optionally substituted alkylsulfonyloxy group, optionally substituted arylsulfonyloxy group, optionally substituted 8. The substituted poly(diphenylacetylene) or salt thereof according to claim 7, which is an alkoxy-carbonyl group, an optionally substituted carbamoyl group or a substituted amino group.

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