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  • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
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Definitions

• the present invention relates to a novel heterocyclic compound and heterocyclic polymer (macromolecule).
• Conjugated polymers having as a repeating unit a structure containing a 5-membered heterocyclic ring are important as organic electronic materials.
• HT structure polymers having a high proportion of head to tail structure (hereinafter, referred to as “HT regioregular”) in which the orientation of the bonds of a repeating unit are constant (hereinafter, referred to as “HT regioregular”) are called “HT regioregular polymer”.
• HT regioregular polymers are known to have high electric conductivity since flatness is higher and conjugation length is longer as compared with regiorandom polymers having a small proportion of HT structure.
• a HT regioregular polythiophene in which the orientation of a repeating unit is fixed at the bond position of a side chain substituent (Polymer Journal, vol. 6, p. 65 (2004)).
• HT regioregular polymers having as a repeating unit a 5-membered ring of asymmetric ring structure are scarcely known.
• a HT regioregular oligomer of oxazole is suggested (JP-A No. 2005-223238).
• a compound with which a HT regioregular polymer can be synthesized having a high proportion of a HT structure having as a repeating unit a 5-membered ring of asymmetric ring structure.
• the present invention has an object of providing a compound with which a HT regioregular polymer can be synthesized having as a repeating unit a 5-membered ring of asymmetric ring structure and having a high proportion of HT structure.
• the present inventors have intensively studied to accomplish the above-described object and resultantly found a novel heterocyclic compound, and finally have completed the present inventions.
• the present invention provides a heterocyclic compound of the following general formula (I):
• the present invention provides, secondly, a method of producing the above-described heterocyclic compound comprising a step of halogenating a compound of the following general formula (III):
• the present invention provides a polymer having a repeating unit of the following formula (IV):
• the present invention further provides a method of producing the above-described polymer comprising condensing a heterocyclic compound of the following formula (V):
• the heterocyclic compound of the present invention is represented by the above-described general formula (I).
• X and Y are preferably a halogen atom selected from among a chlorine atom, a bromine atom or an iodine atom.
• X and Y are different, and the combination of X and Y is preferably, in no particular order, a combination of a chlorine atom and a bromine atom, a combination of a chlorine atom and an iodine atom, or a combination of a bromine atom and an iodine atom, and more specifically, when represented by (X, Y), further preferably (chlorine atom, bromine atom), (chlorine atom, iodine atom) or (bromine atom, iodine atom).
• the monovalent aliphatic hydrocarbon group represented by R 1 includes alicyclic hydrocarbon groups, and has a carbon number of preferably 2 to 16, more preferably 2 to 12, further preferably 2 to 8.
• Examples of the monovalent aliphatic hydrocarbon group represented by R 1 include alkyl groups, alkenyl groups, alkynyl groups and the like.
• alkyl group examples include an ethyl group, a n-propyl group, an isopropyl group, a cyclopropyl group, a n-butyl group, an isobutyl group, a t-butyl group, a cyclobutyl group, a pentyl group, an isopentyl group, a neopentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a methylcyclohexyl group, a menthyl group, a pinanyl group, a bicycloheptyl group (namely, a norbornyl group), an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group and the like.
• alkenyl group examples include a vinyl group, a n-propenyl group, an isopropenyl group, a cyclopropenyl group, a n-butylenyl group, an isobutylenyl group, a t-butylenyl group, a cyclobutylenyl group, a pentenyl group, an isopentenyl group, a neopentenyl group, a cyclopentenyl group, a hexenyl group, a cyclohexenyl group, a methylcyclohexenyl group, a cyclohexenyl group, a cyclohexadienyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group and the like.
• alkynyl group examples include an acetyl group, a n-propynyl group, a isopropynyl group, a cyclopropynyl group, a n-butylynyl group, an isobutylynyl group, a t-butylynyl group, a cyclobutylynyl group, a pentynyl group, an isopentynyl group, a neopentynyl group, a cyclopentynyl group, a hexynyl group, a cyclohexynyl group, a methylcyclohexynyl group, a cyclohexynyl group, an octynyl group a nonynyl group, a decynyl group, an undecynyl group, a dodecynyl group and the like, preferably al
• a part of or all of hydrogen atoms in the monovalent aliphatic hydrocarbon group represented by R 1 may be substituted by substituent(s).
• the above-described substituent includes a halogen atom, a nitrogen atom, a sulfur atom, phosphorus atom such as a halogen atom, an amino group, a nitro group, a sulfonyl group, a phosphonyl group, a thiol group, an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyloxy group having 1 to 20 carbon atoms, an alkylcarbonyl group having 1 to 20 carbon atoms, an aldehyde group and the like.
• alkyl group a methyl group is mentioned in addition to the examples of the above-described alkyl group.
• alkoxy group include a methoxy group, an ethoxy group, a n-propyloxy group, an isopropyloxy group, a cyclopropyloxy group, a n-butyloxy group, an isobutyloxy group, a t-butyloxy group, a cyclobutyloxy group, a pentyloxy group, an isopentyloxy group, a neopentyloxy group, a cyclopentyloxy group, a hexyloxy group, a cyclohexyloxy group, a methylcyclohexyloxy group, a cyclohexenyloxy group, a cyclohexadienyloxy group, a menthyloxy group, a pinanyloxy group, a bicyclo
• aryl group examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.
• aralkyl group examples include a 1-phenylethyl group, a 2-phenylethyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a benzyl group, a xylyl group, a mesityl group, a cumyl group and the like.
• alkyloxycarbonyl group an alkylcarbonyloxy group and an alkylcarbonyl group, groups obtained by binding an oxycarbonyl group, carbonyloxy group and carbonyl group, respectively, to the above-described alkyl groups (including a methyl group) are mentioned.
• one of A 1 and A 2 represents —S—, —O—, —Se— or Te—, while the other represents —N ⁇ , —P ⁇ or —Si(R 2 ) ⁇ , wherein R 2 represents a hydrogen atom, an optionally substituted monovalent hydrocarbon group, a halogen atom, an amino group or a carbonyl group.
• Examples of the combination of A 1 and A 2 include, in no particular order, a combination of —S— and —N ⁇ , a combination of —O— and —N ⁇ , a combination of —Se— and —N ⁇ , a combination of —S— and —P ⁇ , a combination of —O— and —P ⁇ , a combination of —Se— and —P ⁇ , a combination of —S— and —Si(R 2 ) ⁇ , a combination of —O— and —Si(R 2 ) ⁇ , a combination of —Se— and —Si(R 2 ) ⁇ , and the like, and more specifically, when represented by (A 1 , A 2 ), include preferably (—S—, —N ⁇ ), (—O—, —N ⁇ ), (—Se—, —N ⁇ ), (—S—, —P ⁇ ), (—O—, —P ⁇ ), (—Se—, —P ⁇ ), (—S—,
• R 2 As the optionally substituted monovalent hydrocarbon group represented by R 2 in the above-described general formula (I), a methyl group is mentioned in addition to those explained and shown in the above-described paragraph of the monovalent aliphatic hydrocarbon group.
• R 2 represent preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, further preferably a hydrogen atom.
• a part of or all of hydrogen atoms in the optionally substituted monovalent hydrocarbon group represented by R 2 may be substituted by substituent(s).
• the substituent includes a halogen atoms, an amino group, a nitro group, a sulfonyl group, a phosphonyl group, a thiol group, an alkoxy group having 1 to 20 carbon atoms, an aralkyloxy group having 1 to 20 carbon atoms, an aryloxy group having 1 to 20 carbon atoms, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyloxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyloxy group having 1 to 20 carbon atoms, an alkylcarbonyl group having 1 to 20 carbon atoms, an aldehyde group and the like.
• alkoxy group examples include a methoxy group, an ethoxy group, a n-propyloxy group, an isopropyloxy group, a cyclopropyloxy group, a n-butyloxy group, an isobutyloxy group, a t-butyloxy group, a cyclobutyloxy group, a pentyloxy group, an isopentyloxy group, a neopentyloxy group, a cyclopentyloxy group, a hexyloxy group, a cyclohexyloxy group, a methylcyclohexyloxy group, a cyclohexenyloxy group, a cyclohexadienyloxy group, a menthyloxy group, a pinanyloxy group, a bicycloheptyloxy group (namely, a norbornyloxy group), an octyloxy group, a nonyl
• aralkyloxy group examples include a 1-phenylethoxy group, a 2-phenylethyloxy group, a 2-methylphenyloxy group, a 3-methylphenyloxy group, a 4-methylphenyloxy group, a benzyloxy group and the like.
• aryloxy group examples include a phenyloxy group, a xylyloxy group, a mesityloxy group, a cumyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group and the like.
• alkyl group examples include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a cyclopropyl group, a n-butyl group, an isobutyl group, a t-butyl group, a cyclobutyl group, a pentyl group, an isopentyl group, a neopentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a methylcyclohexyl group, a cyclohexenyl group, a cyclohexadienyl group, a menthyl group, a pinanyl group, a bicycloheptyl group (namely, a norbornyl group), an octyl group, a nonyl group, a decyl group, an undecyl group and a dode
• aralkyl group examples include a 1-phenylethyl group, a 2-phenylethyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a benzyl group and the like.
• aryl group examples include a phenyl group, a xylyl group, a mesityl group, a cumyl group, a 1-naphthyl group, a 2-naphthyl group and the like.
• alkyloxycarbonyl group an alkylcarbonyloxy group and an alkylcarbonyl group, groups obtained by binding an oxycarbonyl group, a carbonyloxy group and a carbonyl group, respectively, to the above-described alkyl groups are mentioned.
• heterocyclic compounds of the present invention of the above-described general formula (I) in which X and Y are different each other and represent a chlorine atom, a bromine atom or an iodine atom, and one of A 1 and A 2 is —S— or —O—, while the other is —N ⁇ .
• heterocyclic compound of the present invention those represented by the following structural formulae are mentioned.
• heterocyclic compound of the present invention may be synthesized by any methods, and it is preferable that the heterocyclic compound is synthesized from a heterocyclic compound of the following general formula (II):
• R 1 , A 1 , A 2 , and two parallel lines composed of solid lines and dashed lines have the same meanings as described above, by a method including the following first step and/or second step, preferably a method including the following first step and second step, from the standpoint of purity thereof and synthesis efficiency.
• the two-stage reaction will be illustrated in detail below.
• the first step is a step of releasing an amino group from an amine compound of the above-described general formula (II) and adding a halogen atom, to synthesize a compound of the above-described general formula (III).
• the second step is a step of halogenating a compound of the above-described general formula (III).
• the halogenation is preferably carried out with halogen gas and/or N-halogenosuccinimide.
• the use amount of the alkyl nitrite is usually 1 to 2 mol, preferably 1 to 1.3 mol with respect to 1 mol of the above-described amine compound.
• the use amount of the hydrogen halide or metal halide is usually 1 to 5 mol, preferably 1 to 3 mol with respect to 1 mol of the above-described amine compound.
• compound in the second step, thus obtained compound can be halogenated with halogen gas (for example, chlorine gas and the like) and/or N-halogenosuccinimide (for example, N-bromosuccinimide and the like) to synthesize an intended thiazole compound.
• halogen gas for example, chlorine gas and the like
• N-halogenosuccinimide for example, N-bromosuccinimide and the like
• the total use amount of the above-described halogen gas and N-halogenosuccinimide is usually 1 to 10 mol, preferably 1 to 1 mol with respect to 1 mol of the above-described compound.
• a heterocyclic compound of the present invention and methylmagnesium chloride are stirred in the presence of a solvent, either a halogen atom X or Y in the above-described heterocyclic compound reacts selectively, and then, if a suitable catalyst (for example, 1,3-diphenylphosphinopropanenickel(II) chloride (Ni(dppp)Cl 2 ) and the like) is added to the reaction liquid, polymerization occurs to obtain a HT regular polymer. Utilizing the difference of such reactivity (selectivity), only one regioisomer based on the above-described heterocyclic compound as a substrate can be obtained selectively.
• a suitable catalyst for example, 1,3-diphenylphosphinopropanenickel(II) chloride (Ni(dppp)Cl 2 ) and the like
• the polymer of the present invention contains a repeating unit of the above-described formula (IV) and is characterized in that the above-described Conditions (A) and (B) are satisfied.
• Examples of the substituent represented by R 3 in the above-described formula (IV) include an optionally substituted hydrocarbon group, an optionally substituted alkoxy group, an optionally substituted di(hydrocarbyl)amino group, an optionally substituted hydrocarbylmercapto group, an optionally substituted hydrocarbylcarbonyl group, an optionally substituted hydrocarbyloxycarbonyl group, an optionally substituted di(hydrocarbyl)aminocarbonyl group, an optionally substituted hydrocarbyloxysulfonyl group and the like, preferably an optionally substituted hydrocarbon group, an optionally substituted alkoxy group, an optionally substituted di(hydrocarbyl)amino group, an optionally substituted hydrocarbylmercapto group, an optionally substituted hydrocarbylcarbonyl group and an optionally substituted hydrocarbyloxycarbonyl group, more preferably an optionally substituted hydrocarbon group, an optionally substituted alkoxy group and an optionally substituted di(hydr
• Examples of the hydrocarbon group represented by R 3 in the above-described formula (I) include alkyl groups having about 1 to 50 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a nonyl group, a dodecyl group, a pentadecyl group, an octadecyl group, a docosyl group and the like; cyclic saturated hydrocarbon groups having about 3 to 50 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclononyl group, a cyclododecyl group, a norbornyl group, an adamantyl group
• the hydrocarbon group represented by R 3 in the above-described formula (IV) preferably has 1 to 20 carbon atoms, more preferably has 2 to 18 carbon atoms, and further preferably has 3 to 13 carbon atoms.
• the alkoxy group, hydrocarbylmercapto group, hydrocarbylcarbonyl group, hydrocarbyloxycarbonyl group and hydrocarbylsulfonyl group represented by R 3 in the above-described formula (IV) are groups obtained by binding one of the above-described hydrocarbon groups to an oxy group, a mercapto group, a carbonyl group, an oxycarbonyl group and a sulfonyl group, respectively. These hydrocarbon groups are the same as explained and shown above.
• the di(hydrocarbyl)amino group and di(hydrocarbyl)aminocarbonyl group represented by R 3 in the above-described (IV) are groups obtained by substituting two hydrogen atoms in an amino group and an aminocarbonyl group (namely, —C( ⁇ O)—NH 2 ) by the above-described hydrocarbon group, respectively. These hydrocarbon groups are the same as explained and shown above.
• Part of or all of hydrogen atoms contained in the hydrocarbon group, alkoxy group, di(hydrocarbyl)amino group, hydrocarbylmercapto group, hydrocarbylcarbonyl group, hydrocarbyloxycarbonyl group, di(hydrocarbyl)aminocarbonyl group, hydrocarbyloxysulfonyl group and the like represented by R 3 in the above-described formula (IV) may be substituted by halogen atom(s), hydroxyl group(s), aldehyde group(s), amino group(s), nitro group(s), cyano group(s), hydroxycarbonyl group(s), alkoxy group(s), hydrocarbylmercapto group(s), hydrocarbylcarbonyl group(s), hydrocarbyloxycarbonyl group(s), hydrocarbylsulfonyl group(s) and the like.
• R 3 is an optionally substituted di(hydrocarbyl)amino group or an optionally substituted di(hydrocarbyl)aminocarbonyl group
• a part of or all of hydrogen atoms bonded to a nitrogen atom are preferably substituted by a monovalent alkoxy group from the standpoint of synthesis and solubility in an organic solvent of a polymer.
• the combination of A 1 and A 2 includes, in no particular order, preferably a combination of —S— and —N ⁇ , a combination of —O— and —N ⁇ , a combination of —Se— and —N ⁇ , a combination of —S— and —P ⁇ , a combination of —O— and —P ⁇ , a combination of —Se—and —P ⁇ , a combination of —S— and —Si(R 2 ) ⁇ , a combination of —O— and —Si(R 2 ) ⁇ , and a combination of —Se—and —Si(R 2 ) ⁇ , more preferably a combination of —S— and —N ⁇ , a combination of —O— and —N ⁇ , a combination of —Se—and —N ⁇ , a combination of —S— and —Si(R 2 ) ⁇ ,
• repeating units represented by the following structural formulae are preferable from the standpoint of synthesis of polymer.
• repeating units represented by the following structural formulae are more preferable from the standpoint of synthesis of polymer.
• the repeating unit contained in the polymer of the present invention may be only one repeating unit of the above-described formula (IV) (namely, homopolymer) or a combination of two or more repeating units of the above-described formula (IV) (namely, copolymer), and from the standpoint of synthesis of polymer, the number of the repeating unit of the above-described formula (IV) is preferably 3 or less, more preferably 2 or less, particularly preferably 1.
• the polymer of the present invention may contain also other repeating units, in addition to the repeating unit of the above-described formula (IV).
• the proportion of the total number of repeating units or the above-described formula (IV) with respect to the total number of all repeating units contained in the polymer is preferably 80% or more and less than 100%, from the standpoint of packing property between molecules, more preferably 85% or more and less than 100%, further preferably 90% or more and less than 100%, particularly preferably 94% or more and less than 100%.
• the number of repeating units of the above-described formula (IV) consecutively connected can be estimated by a matrix assisted laser desorption ionization mass analysis (MALDI-TOFMS) method.
• the polymer of the present invention has a structure in which 7 or more repeating units of the above-described formula (IV) are consecutively connected, and from the standpoint of solubility of the polymer in an organic solvent and easiness of purification thereof, a structure in which 7 to 10 6 repeating units are consecutively connected is preferable, a structure in which 7 to 10 5 repeating units are consecutively connected is more preferable, a structure in which 7 to 10 4 repeating units are consecutively connected is particularly preferable.
• the head to tail (HT) bond contained in the polymer of the present invention is defined as described below.
• a carbon atom directly bonded to A 1 and A 2 namely, a carbon atom represented by C* 1 in -A 1 -C* 1 -A 2 - part in the 5-membered ring
• head (H) the other carbon atom directly bonded to A 1
• a direct bond (H-T) connecting “head” in one heterocyclic ring and “tail” in the other heterocyclic ring is the head to tail (H-T) bond. Since a plurality (7 or more)
• the proportion of the total number of the direct bond forming the HT bond (hereinafter, referred to as “HT regioregularity”) with respect to the total number of direct bonds (specifically, H—H bond, T-T bond, H-T can be applied) between a plurality of repeating units contained in the polymer is 60% or more in the polymer of the present invention, and from the standpoint of sufficiently securing the flatness of the whole polymer molecule, it is preferably 80% or more, more preferably 90% or more, particularly preferably 95% or more. The upper limit thereof is 100%.
• the HT regioregularity is less than 60%, the flatness of the whole polymer molecule is poor to cause difficult flow of electricity.
• the HT regioregularity of the polymer of the present invention is obtained in the form of average value according to 1 H-NMR spectrum.
• it cannot be measured because of overlap of different signals in the 1 H-NMR spectrum depending on the kind of a substituent however, it can be obtained in the form of average value according to ultraviolet spectrum.
• the polymer of the present invention may be synthesized by any methods, and it is preferable that the polymer is synthesized by a method containing condensing a heterocyclic compound of the above-described formula (V) from the standpoint of purity and synthesis efficiency thereof.
• the heterocyclic compound of the above-described formula (V) can be synthesized by the same method as the synthesis method of a heterocyclic compound of the formula (I) described above.
• X and/or Y in the heterocyclic compound reacts selectively when a heterocyclic compound of the above-described formula (V) and a suspension of activated zinc or a Grignard reagent (R 4 MgZ) are mixed in the presence of a solvent, then the polymerization reaction initiates by adding suitable catalyst to the mixture, and the polymer of the present invention can be obtained.
• the suspension of activated zinc to be used in the above-described polymerization reaction can be purchased from Aldrich, and it is obtained in the form of THF suspension by slowly adding dropwise a THF solution of zinc chloride into a tetrahydrofuran (THF) solution of lithium and effective amount of naphthalene, in an argon flow, as shown in J. Am. Chem. Soc. vol. 117, p. 242 (1995).
• THF tetrahydrofuran
• R 4 represents a hydrocarbon group.
• the hydrocarbon group represented by R 4 is the same as explained and shown for the hydrocarbon group represented by R 3 .
• Z represents a halogen atom, specifically, a chlorine atom, a bromine atom, an iodine atom or the like.
• Grignard reagent examples include CH 3 MgCl, CH 3 C(CH 3 ) 2 MgCl, CH 3 (CH 2 ) 3 MgCl, CH 3 MgBr, CH 3 C(CH 3 ) 2 MgBr, CH 3 (CH 2 ) 3 MgBr, CH 3 MgI, CH 3 C(CH 3 ) 2 MgI, CH 3 (CH 2 ) 3 MgI and the like, preferably CH 3 MgCl, CH 3 C(CH 3 ) 2 MgCl, CH 3 (CH 2 ) 3 MgCl, CH 3 MgBr, CH 3 C(CH 3 ) 2 MgBr and CH 3 (CH 2 ) 3 MgBr, further preferably CH 3 MgCl, CH 3 C(CH 3 ) 2 MgCl and CH 3 (CH 2 ) 3 MgCl.
• the Grignard reagent is preferable from the standpoint of easy handling.
• aprotic solvents and non-polar solvents which are hard to cause side reactions are preferable, and examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene and the like; linear and cyclic aliphatic hydrocarbons such as heptane, cyclohexane and the like; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, dichloromethane and the like; nitriles such as acetonitrile, benzonitrile and the like; ethers such as dioxane, THF, ethylene glycol dimethyl ether and the like; amides such as N,N-dimethylformamide, N-methylpyrrolidone and the like; nitro compounds such as nitromethane, nitrobenzene and the like.
• aromatic hydrocarbons such as benzene, toluene, xylene and the like
• linear and cyclic aliphatic hydrocarbons such as h
• X, Y, R 3 , A 1 and A 2 and solid lines and dashed lines represent the same meanings as described above, and M represents MgZ or Zn, and Z represents the same meaning as described above.
• Suitable catalysts to be used in the above-described polymerization reaction include copper complexes, palladium complexes, nickel complexes and the like containing ligands represented by the following formulae, among complexes described in Chem. Rev. 102, 1359 (2002).
• suitable catalysts to be used in the above-described polymerization reaction are Pd(PPh 2 Me) 2 , Pd(P(t-Bu) 3 ) 2 , Pd(PEt 3 ) 2 , Pd(PCy 3 ) 2 , Pd(dppb), Pd(dppe), Pd(dppp), Pd(BINAP) and the like.
• Ph represents phenyl
• Me represents methyl
• Et represents ethyl
• t-Bu represents tert-butyl
• Cy represents cyclohexyl
• dppb represents 1,4-bis(diphenylphosphino)butane
• dppe represents 1,2-bis(diphenylphosphino)ethane
• dppp represents 1,3-bis(diphenylphosphino)propane
• BINAP represents 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl.
• the regularity of the HT bond in a polymer obtained by the above-described polymerization reaction is believed to be determined depending on the generation selectivity of the above-described organometal compound and a difference in the reactivity thereof. Therefore, for obtaining a polymer having a sufficiently high proportion of the HT bond, it is preferable that at least one of
• the resultant reaction mixed liquid was poured into 100 ml of chloroform/hexane mixed liquid, and the precipitate was removed by filtration.
• the filtrate was washed with 100 ml of a 20 wt % hydrochloric acid aqueous solution three times, then, extracted with chloroform.
• the resultant red transparent liquid was identified as 2-bromo-4-hexyl-5-iodothiazole from the following data.
• HT regioregular polymer can be synthesized at high yield.
• the resultant reaction mixed liquid was poured into 100 ml of chloroform/hexane mixed liquid, and the precipitate was removed by filtration.
• the filtrate was washed with 100 ml of a 20 wt % hydrochloric acid aqueous solution three times, then, extracted with chloroform.
• the resultant red transparent liquid was identified as 2-chloro-4-hexyl-5-iodothiazole from the following data.
• 1,4-diphenyl-1,3-butadiene (reagent manufactured by Lancaster) was used as a matrix for MALDI mass analysis.
• the mixed solution of the matrix for MALDI mass analysis and the analysis subject sample substance was poured in an amount of 1.5 ⁇ l by a micropipetter and allowed to adhere onto a target for MALDI mass analysis, and the target was inserted into Reflex III type MALDI mass analysis apparatus manufactured by Bruker Daltonics K.K. Thereafter, measurement was performed in positive-ionization mode with laser shot 1000-times accumulation at an accelerating voltage of 27.5 kV.
• Powder X-ray analysis was carried out to find that the distance between main chain planes in the solid state of HT-PHTz was 3.60 ⁇ . This value is smaller than 3.80 ⁇ as an inter-planar distance of poly(3-hexylthiophene) having a HT bond proportion of over 98% which is a typical polymer manifesting easy flow of electricity (see, J. Am. Chem. Soc. 115, 4910 (1993)). Therefore, HT-PHTz is expected to show excellent packing between molecules, have near ⁇ orbital between molecules, and have high moving efficiency of charges.
• a solution of the HT-PHTz (the total concentration of all repeating units: 1 ⁇ 10 ⁇ 4 mol/L) and a solution of the RR-PHTz (the total concentration of all repeating units: 1 ⁇ 10 ⁇ 4 mol/L) were prepared, respectively, and UV absorption spectra thereof were observed by an ultraviolet visible spectrophotometer (trade name: V-530, manufactured by JASCO Corporation).
• the maximum absorption wavelength (vHT-PHTz) of the HT-PHTz solution was 499 nm
• the maximum absorption wavelength (vRR-PHTz) of the RR-PHTz solution was 453 nm.
• HT-PHTz has an absorption maximum at the longer wavelength side than RR-PHTz, and HT-PHTz has higher flatness, thus, shows good conjugation connection, the energy difference between HOMO level and LUMO level is smaller, and a light of weaker energy can be absorbed by HT-PHTz. Therefore, HT-PHTz is expected to show better packing between molecules, have nearer ⁇ orbital between molecules and show higher charge moving efficiency.
• the heterocyclic compound of the present invention can be used to synthesize a HT regioregular polymer having as a repeating unit a 5-membered ring of asymmetric ring structure. Usually, the HT regioregular polymer is obtained with high yield.
• the orientations of bonds between repeating units of the above-described formula (IV) are substantially controlled to a constant direction, thus, repulsion between atoms constituting side chains of adjacent repeating units is lowered, to increase flatness thereof.
• This polymer is guessed to show high mobility since the conjugation length increases and the packing property between molecules is improved because of such structural features.
• the polymer of the present invention has high HT selectivity, manifests excellent practical utility, and usually has sufficiently high molecular weight.
• the polymer of the present invention can be synthesized easily in a short process.

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