WO2019078040A1 - Composé, corps lié de celui-ci, et matériau semi-conducteur organique - Google Patents

Composé, corps lié de celui-ci, et matériau semi-conducteur organique Download PDF

Info

Publication number
WO2019078040A1
WO2019078040A1 PCT/JP2018/037394 JP2018037394W WO2019078040A1 WO 2019078040 A1 WO2019078040 A1 WO 2019078040A1 JP 2018037394 W JP2018037394 W JP 2018037394W WO 2019078040 A1 WO2019078040 A1 WO 2019078040A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
linking
compound
moiety
Prior art date
Application number
PCT/JP2018/037394
Other languages
English (en)
Japanese (ja)
Inventor
俊輔 丹波
家　裕隆
安蘇　芳雄
一剛 萩谷
光 田中
Original Assignee
国立大学法人大阪大学
東洋紡株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国立大学法人大阪大学, 東洋紡株式会社 filed Critical 国立大学法人大阪大学
Priority to JP2019549210A priority Critical patent/JP7320784B2/ja
Publication of WO2019078040A1 publication Critical patent/WO2019078040A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00

Definitions

  • the present invention relates to tetrazolopyridine compounds.
  • tetrazolopyridine compounds which can be used for organic semiconductors.
  • Tetrazolopyridine compounds are known as pharmaceutical intermediates.
  • a tetrazolopyridine compound having a glycidyl group is synthesized using 6-chloronicotinic acid chloride as a raw material.
  • Non-Patent Document 1 proposes a tetrazolopyridine compound having various substituents.
  • the effect of using the above-mentioned compounds for the organic semiconductor material has not been known.
  • the heat stability may not be sufficient.
  • Patent Document 2 an aromatic ring which may be substituted or a halogen atom is bonded to a tetrazolopyridine moiety, and a hydrogen atom, an aliphatic hydrocarbon group or an alicyclic hydrocarbon. It is a compound to which a functional group selected from the group consisting of groups may be bonded. Since this compound can be used to raise the HOMO level while keeping the LUMO level low, this compound is useful as an organic semiconductor material.
  • a tetrazolopyridine compound having a specific functional group or a combination thereof can maintain the LUMO level low and is useful as an organic semiconductor material. I found that.
  • R 1 represents a hydrogen atom or a group forming a conjugated ⁇ electron system with the tetrazolopyridine moiety of the formula (1), and the group has a linking part or a linking part It may have a good organic group. When it has two or more R ⁇ 1 >, they may be same or different.
  • a 1 represents at least one selected from the group consisting of —CN, malononitrile, —CF 3 , —CHO, —COOR a , —SO 2 R a , and —SO 2 —OR a .
  • R a represents a linking moiety or an organic group which may have a linking moiety.
  • a 1 's they may be the same or different.
  • m is an integer of 0 to 3
  • n is an integer of 1 to 4.
  • m + n is 4.
  • a plurality of compounds represented by the formula (1) may be bound to each other at the aforementioned linking portion to form a bound substance, and the linking portions form a direct bond.
  • the group constituting the conjugated ⁇ electron system is a group consisting of —C ⁇ C—R b , —CR b CRCR b 2 , and an aromatic ring which may be substituted (wherein R b is a hydrogen atom, And a linking portion or an organic group which may have a linking portion, and in the case of having a plurality of R b , they may be the same or different, and the aromatic ring is a group R c
  • at least one selected from the group consisting of a linking portion, or an organic group which may have a linking portion is preferable.
  • the present invention also includes a method for producing a compound represented by the following formula (1) or a conjugate thereof, in which an azide compound is reacted with a compound represented by the following formula (2) or a conjugate thereof in the presence of a base.
  • the compound represented by following formula (1) or its coupling material can also be manufactured by making an azide compound react, after halogenating the compound or its coupling material represented by following formula (2).
  • R 1 represents a hydrogen atom or a group forming a conjugated ⁇ electron system with the tetrazolopyridine moiety of the formula (1), and the group has a linking part or a linking part It may have a good organic group. When it has two or more R ⁇ 1 >, they may be same or different.
  • a 1 represents at least one selected from the group consisting of —CN, malononitrile, —CF 3 , —CHO, —COOR a , —SO 2 R a , and —SO 2 —OR a .
  • R a represents a linking moiety or an organic group which may have a linking moiety.
  • m is an integer of 0 to 3
  • n is an integer of 1 to 4.
  • m + n is 4.
  • a plurality of compounds represented by the formula (2) may be bonded to each other at the linking portion to form a bond, and the linking portions directly bond to each other.
  • R 1 , A 1 , m and n are as defined above.
  • the group constituting the conjugated ⁇ electron system is a group consisting of —C ⁇ C—R b , —CR b CRCR b 2 , and an aromatic ring which may be substituted (wherein R b is a hydrogen atom, And a linking portion or an organic group which may have a linking portion, and in the case of having a plurality of R b , they may be the same or different, and the aromatic ring is a group R c
  • at least one selected from the group consisting of a linking portion, or an organic group which may have a linking portion is preferable.
  • the present invention also encompasses an organic semiconductor material comprising the above-described compound or a combination thereof. Also included in the present invention is an organic electronic device comprising the organic semiconductor material.
  • the compound of the present invention or a conjugate thereof is a tetrazolopyridine compound having a specific functional group or a conjugate thereof, the LUMO level can be kept low and it is useful as an organic semiconductor material.
  • R 1 represents a hydrogen atom or a group forming a conjugated ⁇ electron system with the tetrazolopyridine moiety of formula (1), and the group has a linking part or a linking part] It may have a good organic group. When it has two or more R ⁇ 1 >, they may be same or different.
  • a 1 represents at least one selected from the group consisting of —CN, malononitrile, —CF 3 , —CHO, —COOR a , —SO 2 R a , and —SO 2 —OR a .
  • R a represents a linking moiety or an organic group which may have a linking moiety.
  • a 1 's When there are a plurality of A 1 's , they may be the same or different. m is an integer of 0 to 3, and n is an integer of 1 to 4. However, m + n is 4. A plurality of compounds represented by the formula (1) may be bound to each other at the aforementioned linking portion to form a bound substance, and the linking portions form a direct bond. ]
  • the compound represented by the formula (x) may be simply referred to as “the compound (x)”.
  • the above A 1 is a substituent that exhibits electron withdrawing property.
  • the above A 1 represents at least one member selected from the group consisting of -CN, malononitrile, -CF 3 , -CHO, -COOR a , -SO 2 R a , and -SO 2 -OR a , and -CN is preferred.
  • n is an integer of 1 to 4, preferably 1 or 2, and more preferably 1.
  • R a represents a linking moiety or an organic group which may have a linking moiety.
  • the linking portion R a and the organic group R a will be described later.
  • R 1 represents a hydrogen atom or a group forming a conjugated ⁇ electron system with the tetrazolopyridine moiety of the formula (1), and the group has a linking part or an organic group which may have a linking part It may be done. When it has two or more R ⁇ 1 >, they may be same or different.
  • m is an integer of 0 to 3, preferably 1 or 2, and more preferably 1.
  • the tetrazolopyridine moiety of the above formula (1) and the group constituting the conjugated ⁇ electron system are —C-C—R b , —CR b CRCR b 2 , and an optionally substituted aroma
  • At least one member selected from the group consisting of group rings is preferred, and more preferred is —C ⁇ C—R b or an aromatic ring which may be substituted.
  • R b represents a hydrogen atom, a linking moiety, or an organic group which may have a linking moiety. When they have a plurality of R b , they may be the same or different.
  • linking portion R b and the organic group R b will be described later.
  • aromatic ring an aromatic hydrocarbon ring or an aromatic heterocyclic ring is mentioned, for example.
  • Aromatic hydrocarbon ring As said aromatic hydrocarbon ring, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring etc. are mentioned, for example, A benzene ring is preferable.
  • Aromatic heterocycle examples of the above-mentioned aromatic heterocycle include nitrogen-containing aromatic heterocycles, sulfur-containing aromatic heterocycles, oxygen-containing aromatic heterocycles, etc. represented by the following formulae, and these include two or more hetero atoms. It may have as a ring-constituting atom, and the two or more hetero atoms may be the same or different.
  • a 5- or 6-membered monocyclic heterocyclic ring containing one or more hetero atoms is preferable, and a thiophene ring, a thiazole ring, a pyridine ring, a pyrrole ring, an imidazole ring, a furan ring, an oxazole ring and the like are more preferable.
  • the aromatic ring may be substituted, for example, substituted with a halogen atom.
  • a halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, Preferably it is a bromine atom or an iodine atom, More preferably, it is a bromine atom.
  • the number of halogen atoms substituted is preferably 1 or 2, and particularly preferably 1.
  • the aromatic ring may have a substituent other than a halogen atom.
  • substituent other than the halogen atom include an alkyl group, an alkoxy group, a halogenated alkyl group, -M x1 (L x1 ) kx and the like.
  • alkyl group Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 1-n-butylbutyl group, 1-n-propylpentyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 1-methylheptyl group, 2-methylheptyl group, 6-methyl Heptyl group, 2,4,4-trimethylpentyl group, 2,5-dimethylhexyl group, n-nonyl group, 1-n-propylhexyl group, 2-n-propylhexyl group, 1-ethylheptyl group, 2- Ethylheptyl
  • the carbon number of the alkyl group is preferably 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms.
  • alkoxy group examples include a group in which —O— is bonded to the above alkyl group.
  • the carbon number of the above alkoxy group is preferably 1 to 30 carbon atoms, more preferably 1 to 24 carbon atoms.
  • Halogenated alkyl group As said halogenated alkyl group, the group by which the hydrogen atom of the said alkyl group was substituted by halogen atoms (especially preferably a fluorine atom), such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, is mentioned.
  • the carbon number of the halogenated alkyl group is preferably 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 4 carbon atoms.
  • halogenated alkyl group examples include perfluoroalkyl groups such as trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group and nonafluorobutyl group, and the like, with trifluoromethyl group being particularly preferable.
  • M x1 represents a boron atom or a tin atom.
  • L x1 represents an alkyl group having 1 to 6 carbon atoms, -OH, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an aralkyloxy group having 7 to 10 carbon atoms; L x1 may form a ring with M x1 .
  • the carbon number of the alkyl group represented by L x1 is preferably 1 to 4.
  • Examples of the alkoxy group represented by L x1 include a group in which —O— is bonded to the alkyl group, and the alkoxy group preferably has 1 to 4 carbon atoms.
  • Examples of the aryloxy group represented by L x1 include a phenyloxy group and the like, and the aryloxy group preferably has 6 to 8 carbon atoms.
  • Examples of the aralkyloxy group represented by L x1 include a benzyloxy group and the like, and the aralkyloxy group preferably has 7 or 8 carbon atoms.
  • kx represents 2 or 3 depending on the type of M x1 . kx is 2 when M x1 is a boron atom, and 3 when M x1 is a tin atom.
  • examples of * -M x1 (L x1 ) kx include groups represented by the following formulae, and the like.
  • R x14 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. * Represents a bond.
  • examples of * -M x1 (L x1 ) kx include groups represented by the following formulae, and the like. In the formula, * represents a bond. Me is methyl and Bu is butyl.
  • the aromatic ring may further have, as a group R c , a linking portion, or an organic group which may have a linking portion.
  • the linking portion R c and the organic group R c will be described later.
  • the aromatic ring is preferably an aromatic ring represented by the following formulas (Ar1) to (Ar8).
  • R 2 represents a halogen atom, an alkyl group, an alkoxy group, a halogenated alkyl group, -M x1 (L x1 ) kx , or a group R c (that is, a connecting portion R c , Or an organic group R c ) optionally having a linking part.
  • R 3 represents a hydrogen atom or an alkyl group.
  • a fluorine atom a chlorine atom, a bromine atom, an iodine atom is mentioned, Preferably it is a bromine atom or an iodine atom.
  • Alkyl group of the R 2 an alkoxy group, a halogenated alkyl group, -M x1 (L x1) kx , and the alkyl groups of R 3, exemplified as the substituent which may be possessed by the aromatic ring It is the same as the alkyl group, the alkoxy group, the halogenated alkyl group, or -M x1 (L x1 ) kx .
  • the above R 2 is preferably an alkoxy group or a halogenated alkyl group.
  • At least one R 2 may be a halogen atom.
  • Each of p1, p2, p3 and p4 is preferably an integer of 0 to 2.
  • the formulas (Ar1) to (Ar4) are preferable, and the formulas (Ar1) to (Ar4) are more preferably the following formulas (Ar1-1) to (Ar4-2) preferable.
  • R 4 represents a halogen atom, an alkyl group, an alkoxy group, a halogenated alkyl group, or —M x1 (L x1 ) kx . When two or more R 4 are present, they may be the same or different.
  • X 2 represents a linking portion R c or an organic group R c which may have a linking portion.
  • p5 is an integer of 0 to 2
  • p6 is 0 or 1
  • p7 is an integer of 0 to 4
  • p8 is an integer of 0 to 3
  • p9 is an integer of 0 to 3
  • p10 is 0 to 2
  • the integer, p11 is an integer of 0 to 5, and p12 is an integer of 0 to 4. * Represents a bond. ]
  • the above X 2 is preferably bonded to the 5-position in the above formulas (Ar1-1) and (Ar2-1), and is preferably bonded to the 6-position in the above formula (Ar4-1) In the formula (Ar3-1), the 4-position is preferred.
  • halogen atom of R 4 an alkyl group, an alkoxy group, a halogenated alkyl group, or -M x1 (L x1 ) kx , a halogen atom, an alkyl group, an alkoxy group or a halogenated alkyl exemplified as the above R 2 It is the same as the group or -M x1 (L x1 ) kx, and is preferably a halogen atom, an alkoxy group or a halogenated alkyl group.
  • P5, p6, p7, p8, p9, p10, p11 and p12 are preferably 0 or 1.
  • R a , R b , R c , R 2 and X 2 may be a linking moiety or an organic group having a linking moiety.
  • the linking part forms a direct bond with the linking part of another compound represented by the formula (1) .
  • R a , R b , R c of the compound represented by one Formula (1) And R 2 or X 2 is a linking moiety
  • R a , R b , R c , R 2 or X 2 of the other compound represented by the formula (1) is an organic group having a linking moiety Is preferred.
  • the compound represented by Formula (1) has the organic group which has a connection part is demonstrated using a following formula.
  • a compound f represented by one formula (1) and a compound g represented by the other formula (1) are linked at a linking part h.
  • R 1 represents a group forming a conjugated ⁇ electron system with the tetrazolopyridine moiety i of the formula (1), and the group has an organic group R b having a linking part h There is.
  • R 1 represents a group forming a conjugated ⁇ electron system with the tetrazolopyridine moiety i of the formula (1), and the group has a linking part h.
  • the number of tetrazolopyridine moieties is not particularly limited as long as it is 2 or more, but preferably 2 to 10, more preferably 2 to 4, particularly preferably 2 It is.
  • organic group examples include (1) aliphatic hydrocarbon group or alicyclic hydrocarbon group, and (2) aromatic group.
  • Aliphatic hydrocarbon group may be linear or branched.
  • the aliphatic hydrocarbon group may be any of an alkyl group or an unsaturated aliphatic hydrocarbon group such as an alkenyl group and an alkynyl group, and is preferably an alkyl group.
  • the carbon number of the aliphatic hydrocarbon group is preferably 1 to 24, and more preferably 1 to 20.
  • the alicyclic hydrocarbon group may be monocyclic or polycyclic.
  • the alicyclic hydrocarbon group may be any of a cycloalkyl group, or an unsaturated alicyclic hydrocarbon group such as a cycloalkenyl group and a cycloalkynyl group, and a cycloalkyl group is preferable.
  • the carbon number of the above-mentioned alicyclic hydrocarbon group is preferably 3 to 20, more preferably 3 to 14.
  • alicyclic hydrocarbon group examples include monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group and the like; bicyclohexyl And a polycyclic cycloalkyl group such as a bicycloheptyl group and a bicyclooctyl group.
  • Aromatic group may be the aromatic ring exemplified in the above R 1 but is preferably an acceptor unit, and examples thereof include the following formulas (Ar1-1k) to (Ar17- The structure represented by any of 1k) is mentioned.
  • * represents a bond.
  • one of * represents a bond as an organic group R a , R b , R c , R 2 or X 2
  • the other of * is the organic group R a , R b , R c , R 2 , Or a hydrogen atom or a linking portion of X 2 .
  • X represents a halogen atom.
  • Each R 3 independently represents a hydrogen atom or an alkyl group.
  • R 5 represents an alkyl group, an alkoxy group or a halogenated alkyl group. When two or more R 5 are present, they may be the same or different.
  • R 6 and R 7 each independently represent a hydrocarbon group having 8 to 30 carbon atoms.
  • n6 is 0 or 1
  • n7 is an integer of 0 to 3
  • n8 is an integer of 0 to 2
  • n9 is an integer of 0 to 4.
  • the halogen atom of X is the same as the halogen atom of R 2 above, preferably a bromine atom or an iodine atom, and more preferably a bromine atom.
  • the alkyl group of R 3, the alkyl group of R 5 , an alkoxy group, or a halogenated alkyl group is respectively the same as the alkyl group of R 2 , an alkoxy group, or a halogenated alkyl group.
  • the hydrocarbon group having 8 to 30 carbon atoms represented by R 6 and R 7 is preferably an alkyl group having 8 to 30 carbon atoms, and the alkyl group may be linear or branched. .
  • Examples of the alkyl group having 8 to 30 carbon atoms include n-octyl group, 1-n-butylbutyl group, 1-n-propylpentyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, and 4-ethylhexyl group.
  • An alkyl group having 8 carbon atoms such as ethylhexyl group, 1-methylheptyl group, 2-methylheptyl group, 6-methylheptyl group, 2,4,4-trimethylpentyl group, 2,5-dimethylhexyl group; n-nonyl Group, 1-n-propylhexyl group, 2-n-propylhexyl group, 1-ethylheptyl group, 2-ethylheptyl group, 1-methyloctyl group, 2-methyloctyl group, 6-methyloctyl group, 2, An alkyl group having 9 carbon atoms such as 3,3,4-tetramethylpentyl group and 3,5,5-trimethylhexyl group; n-decyl group, 1-n-pentyl penci Group, 1-n-butylhexyl group, 2-n-butylhexyl group, 1-n-propylheptyl group, 1-eth
  • an alkyl group having 8 to 20 carbon atoms is preferable, an alkyl group having 8 to 16 carbon atoms is more preferable, and a branched alkyl group having 8 to 16 carbon atoms is more preferable.
  • octyl, 2-ethylhexyl, 3,7-dimethyloctyl, 2-n-butyloctyl and 2-n-hexyldecyl groups are examples of these alkyl group having 8 to 20 carbon atoms.
  • R 1 and A 1 are the same as described above (but without the connecting portion), and m and n are the same as the above.
  • R 20 represents an acceptor unit represented by the above formulas (Ar1-1k) to (Ar17-1k), and m1 is 1 or 2. When there are a plurality of R 20 's , they may be the same or different.
  • the linking part is a compound (11) or (12) of the following formula (preferably a compound It is preferable to have a direct bond with the linking part of 11)).
  • R 1 and A 1 are the same as described above (but without the connecting portion), and m and n are the same as the above.
  • the aromatic ring And at least one selected from the group consisting of When two or more R 11 are present, they may be the same or different.
  • a 11 is at least one member selected from the group consisting of —COOR a1 , —SO 2 R a1 , and —SO 2 —OR a1 , and R a1 represents a linking moiety. If having a plurality of A 11, which may be different may be the same. ]
  • the R 1, A 1 may be attached to any position of the respective tetrazolo [1,5-a] pyridine 5-8 ring positions, but at least one of R 1 and A 1 (preferably at least R Preferably, 1 , more preferably both A 1 and R 1 ) are attached to the 5- and / or 8-position of the tetrazolopyridine ring.
  • the bonding position of the tetrazolopyridine ring is in accordance with the position indication shown in the following formula.
  • R 1 and A Configurations represented by the following formulas (1-1) to (1-12) in which at least one of 1 is bonded to the 5- and / or 8-position are preferred.
  • R 1 and A 1 are as defined above.
  • formulas (1-2), (1-3), (1-6), (1-7), (1-10) and (1-11) in which A 1 and R 1 are not adjacent to each other are preferable, More preferably, it is the formula (1-2), (1-3), (1-10), (1-11) in which R 1 is bonded at the 5- or 8-position, and still more preferably R 1 and A 1 Is a group represented by the formulas (1-3) and (1-10), which is bonded at the 5- and 8-positions, and particularly preferably a formula (1-10).
  • Examples of the compound represented by the formula (1) for example, in the following ones can be exemplified (the following formula, E is expressed -CN, malononitrile, a -CF 3, or -CHO, preferably a -CN .D Represents an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and G represents a hydrocarbon group having 8 to 30 carbon atoms.
  • the compound represented by the following formula (1) according to the present invention or a bound product thereof is prepared by reacting an azide compound with (A) a compound represented by the following formula (2) or a bound product thereof in the presence of a base Or (B) after halogenating a compound represented by the following formula (2) or a combination thereof, the compound can be produced by reacting an azide compound.
  • step 1 The outline of the method for producing a compound represented by the following formula (1) according to the present invention shown in the above (A) or a combined product thereof is represented by the following scheme (step 1).
  • R 1 represents a hydrogen atom or a group forming a conjugated ⁇ electron system with the tetrazolopyridine moiety of formula (1), and the group has a linking part or a linking part] It may have a good organic group. When it has two or more R ⁇ 1 >, they may be same or different.
  • a 1 represents at least one selected from the group consisting of —CN, malononitrile, —CF 3 , —CHO, —COOR a , —SO 2 R a , and —SO 2 —OR a .
  • R a represents a linking moiety or an organic group which may have a linking moiety.
  • a 1 's When there are a plurality of A 1 's , they may be the same or different. m is an integer of 0 to 3, and n is an integer of 1 to 4. However, m + n is 4. A plurality of compounds represented by the formula (2) may be bonded to each other at the linking portion to form a bond, and the linking portions directly bond to each other.
  • R 1 , A 1 , m and n are as defined above.
  • the azide compound examples include diaryl phosphoryl azides such as diphenyl phosphoryl azide (DPPA) and bis (4-nitrophenyl) phosphoryl azide; trialkyl silyl azides such as trimethylsilyl azide (TMSA); organic azide compounds such as, and sodium Inorganic azide compounds such as azides are preferred.
  • the organic azide compound may be supported by a polymer. Among them, organic azide compounds are more preferable, and trialkylsilyl azides such as trimethylsilyl azide are particularly preferable.
  • the amount of the azide compound is preferably 0.5 mol or more and 10 mol or less, more preferably 1 mol or more and 8 mol or less, still more preferably 1 mol or more and 5 mol per 1 mol of the compound (2). It is below. When the amount of the azide compound is in this range, the yield and the reaction efficiency are good.
  • trialkylsilyl azide When trialkylsilyl azide is used as the azide compound, it is preferable to further allow a sulfonyl halide compound or a phosphoric acid halide compound to coexist.
  • sulfonyl halide compounds examples include sulfonyl chloride compounds and sulfonyl fluoride compounds. That is, alkylsulfonyl chloride compounds such as methanesulfonyl chloride, ethanesulfonyl chloride, propanesulfonyl chloride, isopropanesulfonyl chloride, butanesulfonyl chloride, pentanesulfonyl chloride, hexane sulfonyl chloride and the like; benzenesulfonyl chloride, 2-methylbenzenesulfonyl chloride, 3- Methylbenzenesulfonyl chloride, 4-methylbenzenesulfonyl chloride, 2-chlorobenzenesulfonyl chloride, 3-chlorobenzenesulfonyl chloride, 4-chlorobenzenesulfulfonyl chloride, 4-chloro
  • the amount of the sulfonyl halide compound is preferably 0.5 mol or more and 20 mol or less, more preferably 1 mol or more and 15 mol or less, still more preferably 1 mol or more, per 1 mol of the compound (2). It is preferably at most 1 mole, and more preferably at most 10 moles. When the amount of the sulfonyl halide compound is in this range, the yield and the reaction efficiency are good.
  • phosphoric acid halide compound examples include dialkylphosphoryl chloride compounds such as dimethyl phosphoryl chloride, diethyl phosphoryl chloride, dipropyl phosphoryl chloride, diisopropyl phosphoryl chloride, dibutyl phosphoryl chloride and the like; bis (2,2,2-trichloroethyl) phosphoryl chloride and the like Dihalogenated alkyl phosphoryl chloride compound; 2-chloro-2-oxo-1,3,2-dioxaphospholane; diphenyl phosphoryl chloride, bis (2-methylphenyl) phosphoryl chloride, bis (3-methylphenyl) phosphoryl chloride Bis (4-methylphenyl) phosphoryl chloride, bis (3,5-dimethylphenyl) phosphoryl chloride, bis (2-chlorophenyl) phosphoryl chloride, bis (3-chlorophenyl) phosphoryl chloride Le) phosphoryl chloride, bis (4-chlor
  • dihalogenated alkyl phosphoryl chloride compounds and diaryl phosphoryl chloride compounds are preferable, and bis (2,2,2-trichloroethyl) phosphoryl chloride and diphenyl phosphoryl chloride are more preferable.
  • the amount of the phosphoric acid halide compound is preferably 0.5 mol or more and 20 mol or less, more preferably 1 mol or more and 15 mol or less, still more preferably 1 mol or more, per 1 mol of the compound (2). It is 13 mol or less, preferably 1 to 10 mol. When the amount of the phosphoric acid halide compound is in this range, the yield and the reaction efficiency are good.
  • Imidazole compounds such as N- methyl imidazole and imidazole; Lithium hydroxide, sodium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, sodium carbonate, potassium carbonate, cesium carbonate etc.
  • Alkaline metal salt compounds such as magnesium hydroxide, calcium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate and barium carbonate; lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, Sodium ethoxide, potassium ethoxide, lithium isopropoxide, sodium isopropoxide, potassium isopropoxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide Alkoxy alkali metal compounds such as hydroxide, lithium tert-amyl alkoxide, sodium tert-amyl alkoxide, potassium tert-amyl alkoxide; Hydrogenated metal compounds such as lithium hydride, sodium hydride and potassium hydride; trimethylamine, triethylamine, tripropyl Amine, diisopropylethylamine, tributylamine, tripentylamine, trihexylamine
  • Undec-7-tertiary amine such as ene; and the like.
  • imidazole compounds, alkali metal salt compounds and amines are preferable, N-methylimidazole, potassium carbonate, triethylamine and pyridine are more preferable, and potassium carbonate, triethylamine and pyridine are more preferable.
  • the amount of the base is preferably 0.5 mol or more and 10 mol or less, more preferably 1 mol or more and 8 mol or less, still more preferably 1 mol or more and 7 mol or less, per 1 mol of the compound (2). Particularly preferably, it is at least 1 mol and at most 5 mol.
  • reaction solvent it is preferable not to use a reaction solvent during the above reaction.
  • a reaction solvent it can be used in a range which does not affect the reaction, for example, ether solvents, aromatic solvents, ester solvents, hydrocarbon solvents, halogen solvents, ketone solvents, amide solvents and the like It can be used.
  • ether solvents examples include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydroflan, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, t-butyl methyl ether and dioxane.
  • aromatic solvents include benzene, toluene, xylene, mesitylene, chlorobenzene and dichlorobenzene.
  • ester solvents examples include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate and butyl acetate.
  • hydrocarbon solvent examples include pentane, hexane, cyclohexane and heptane.
  • halogen-based solvent examples include dichloromethane, chloroform, dichloroethane and dichloropropane.
  • ketone solvents examples include acetone, methyl ethyl ketone and methyl isobutyl ketone.
  • amide solvents include N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl 3,4,5,6-tetrahydro- (1H) -pyrimidine is mentioned.
  • nitrile solvents such as acetonitrile, sulfoxide solvents such as dimethylsulfoxide, and sulfone solvents such as sulfolane can be used.
  • the reaction temperature is preferably 0 ° C. or more and 200 ° C. or less, more preferably 30 ° C. or more and 180 ° C. or less, and still more preferably 40 ° C. or more and 150 ° C. or less from the viewpoint of enhancing the reaction yield.
  • the reaction temperature may be adjusted using microwaves.
  • R 1 and Configurations represented by the following formulas (2-1) to (2-12) in which at least one of A 1 is bonded to the 5- and / or 8-position are preferable.
  • R 1 and A 1 are as defined above.
  • formulas (2-2), (2-3), (2-6), (2-7), (2-10) and (2-11) in which A 1 and R 1 are not adjacent are preferable, More preferably, it is the formula (2-2), (2-3), (2-10), (2-11) in which R 1 is bonded at the 5- or 8-position, and still more preferably R 1 and A 1 Is a group represented by the formulas (2-3) and (2-10), which is bonded at the 5- and 8-positions, particularly preferably a formula (2-10).
  • the compound represented by the above formula (1) according to the present invention or a bound product thereof can also be produced by the method shown in the above (B).
  • the compound represented by the above formula (1) or a combination thereof can be produced without using the base shown in the above (A).
  • the halogenation can be carried out by various methods, for example, by contacting the compound represented by the above formula (2) or a combination thereof with a halogenation reagent.
  • a halogenation reagent examples include inorganic halides such as thionyl chloride, phosphorus pentachloride, phosphorus trichloride, and phosphoryl chloride; and oxalic acid halides such as oxalyl chloride and oxalyl bromide.
  • halogen solvents such as methylene chloride, dichloromethane, chloroform, dichloroethane, dichloropropane, etc., methyl acetate, ethyl acetate, propyl acetate, propyl acetate, isopropyl acetate, isopropyl acetate, ester solvents such as butyl acetate, pentane, hexane, cyclohexane, Hydrocarbon solvents such as heptane, aromatic solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazo It is preferable to use an amide solvent such as lidinone and 1,3-dimethyl 3,4,5,6-tetrahydro- (1H) -pyrimidine
  • the compound represented by the formula (1) or a conjugate thereof can be produced by reacting the azide compound shown in the above (A) with the compound obtained by halogenation or the conjugate thereof.
  • reaction initiator When reacting with the azide compound, it is preferable to add a reaction initiator.
  • the reaction initiator include sodium fluoride (NaF), potassium fluoride (KF), cesium fluoride (CsF), barium fluoride (BaF 2 ), zinc fluoride (ZnF 2 ), copper fluoride CuF 2 ), magnesium fluoride (MgF 2 ), tetramethylammonium fluoride (TMAF), tetrabutylammonium fluoride (TBAF), tris (dimethylamino) sulfonium difluorotrimethylsilicate (TASF) and the like can be used.
  • step 2 the compound (3) represented by the following formula (3)
  • step 3 The method (process 3) of substituting the halogen of the compound (4) which is an oxidation halide shown by following formula (4) by said A 1 is mentioned.
  • X represents a halogen atom.
  • R 1 , A 1 , m and n are as defined above.
  • Step 2 The compound (2) can be obtained by reacting the compound (3) with an oxidizing agent.
  • an oxidizing agent percarboxylic acid such as metachloroperbenzoic acid (mCPBA) can be used, for example.
  • the amount of the oxidizing agent is preferably 0.1 mol or more and 10 mol or less, more preferably 0.5 mol or more and 5 mol or less, per 1 mol of the compound (3).
  • halogen solvents such as dichloromethane, chloroform, dichloroethane, dichloropropane and the like are preferable.
  • the method for substituting the halogen atom X 1 of the compound (4) with the above A 1 is not particularly limited, and known conditions can be adopted.
  • the reaction temperature is preferably 0 ° C. or more and 250 ° C. or less, more preferably 30 ° C. or more and 230 ° C. or less, and still more preferably 40 ° C. or more and 200 ° C. or less from the viewpoint of enhancing the reaction yield.
  • the reaction temperature may be adjusted using microwaves.
  • the compound (1) of the present invention is useful as an organic semiconductor material because it can lower the LUMO level.
  • the tetrazolopyridine moiety is electron accepting and can be expected to function as an acceptor unit in the extended ⁇ conjugated system.
  • Organic semiconductor material of the present invention is useful for organic electronic devices because of its high electron acceptability.
  • organic electronic device an organic electroluminescent element, an organic thin-film transistor element, a photoelectric conversion element, a solar cell, a solar cell module etc. are mentioned, for example.
  • Example 4 The N-oxide (1.33 g, 6.6 mmol) obtained in Example 3 above is placed in an eggplant flask, POCl 3 (10.1 g, 66 mmol) is added, and then anhydrous DMF (0.5 ml, 6. 6 mmol) was added and stirred at 70 ° C. for 2 hours under a nitrogen atmosphere. After stirring for 2 hours, POCl 3 was concentrated, the concentrate was added dropwise to chloroform / water, neutralized with an aqueous Na 2 CO 3 solution, extracted with chloroform, and the solvent was concentrated.
  • N-oxide 32 mg, 0.05 mmol
  • DPPA 138 mg, 0.5 mmol
  • anhydrous pyridine 39.5 mg, 0.5 mmol
  • FET measurement The ozone treated silicon substrate was treated with hexamethyldisilazane (HMDS).
  • HMDS hexamethyldisilazane
  • a bottom gate-bottom contact type FET device was fabricated by spin-coating (1000 rpm, 1 minute) a solution in which target A was dissolved in chloroform so that the concentration of the target A was 1 mg / mL on the substrate surface after HMDS treatment. , FET measurements were made. The channel length was 5 ⁇ m.
  • the obtained FET device was annealed at 80 ° C. or 120 ° C. for 1 hour, and FET measurement was performed in the same manner. The results are shown in Table 1 below.
  • the compound of the present invention can maintain the LUMO level low and is useful as an organic semiconductor material.
  • the compounds of the present invention are useful as organic semiconductor materials because of their high electron acceptability.
  • the organic semiconductor material of the present invention is useful, for example, for organic electronic devices such as organic electroluminescent devices, organic thin film transistor devices, photoelectric conversion devices, solar cells, solar cell modules and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Electroluminescent Light Sources (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne un composé tétrazolopyridine qui est capable de maintenir un niveau bas de LUMO lorsque le composé tétrazolopyridine est utilisé en tant que matériau semi-conducteur organique. L'invention concerne également un composé représenté par la formule (1), ou un corps lié du composé. Dans la formule (1), R1 représente un atome d'hydrogène ou un groupe qui constitue un système π-électron conjugué avec une fraction tétrazolopyridine de formule (1), et le groupe peut avoir une fraction de liaison ou un groupe organique qui peut avoir une fraction de liaison ; dans les cas où il y a plusieurs fractions R1, les fractions R1 peuvent être identiques ou différentes les unes des autres ; A1 représente au moins un groupe choisi parmi -CN, un malononitrile,-CF3, -CHO, -COORa, -SO2Ra et -SO2-ORa, Ra représentant une fraction de liaison ou un groupe organique qui peut avoir une fraction de liaison ; dans les cas où il y a plusieurs fractions A1, les fractions A1 peuvent être identiques ou différentes les unes des autres ; m représente un nombre entier compris entre 0 et 3, et n représente un nombre entier compris entre 1 et 4, à condition que (m + n) soit 4. Selon l'invention, plusieurs composés représentés par la formule (1) peuvent former, de manière incidente, un corps lié du fait que les composés sont liés au niveau des fractions de liaison ; et les fractions de liaison forment une liaison directe.
PCT/JP2018/037394 2017-10-18 2018-10-05 Composé, corps lié de celui-ci, et matériau semi-conducteur organique WO2019078040A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2019549210A JP7320784B2 (ja) 2017-10-18 2018-10-05 化合物の結合物、及び有機半導体材料

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017202189 2017-10-18
JP2017-202189 2017-10-18

Publications (1)

Publication Number Publication Date
WO2019078040A1 true WO2019078040A1 (fr) 2019-04-25

Family

ID=66174509

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/037394 WO2019078040A1 (fr) 2017-10-18 2018-10-05 Composé, corps lié de celui-ci, et matériau semi-conducteur organique

Country Status (3)

Country Link
JP (1) JP7320784B2 (fr)
TW (1) TW201922743A (fr)
WO (1) WO2019078040A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021024675A1 (fr) * 2019-08-05 2021-02-11 国立大学法人大阪大学 Composé et son procédé de fabrication

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011518226A (ja) * 2008-04-22 2011-06-23 ジヤンセン・フアーマシユーチカ・ナームローゼ・フエンノートシヤツプ キノリン若しくはイソキノリン置換ｐ２ｘ７アンタゴニスト
WO2016143823A1 (fr) * 2015-03-10 2016-09-15 国立大学法人大阪大学 Composé et matériau semi-conducteur organique contenant celui-ci
WO2017155030A1 (fr) * 2016-03-09 2017-09-14 国立大学法人大阪大学 Composé et matériau semi-conducteur organique contenant celui-ci

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011518226A (ja) * 2008-04-22 2011-06-23 ジヤンセン・フアーマシユーチカ・ナームローゼ・フエンノートシヤツプ キノリン若しくはイソキノリン置換ｐ２ｘ７アンタゴニスト
WO2016143823A1 (fr) * 2015-03-10 2016-09-15 国立大学法人大阪大学 Composé et matériau semi-conducteur organique contenant celui-ci
WO2017155030A1 (fr) * 2016-03-09 2017-09-14 国立大学法人大阪大学 Composé et matériau semi-conducteur organique contenant celui-ci

Non-Patent Citations (12)

* Cited by examiner, † Cited by third party
Title
BATTERJEE, S. M., JOURNAL OF THE CHINESE CHEMICAL SOCIETY, vol. 52, 2005, pages 97 - 102 *
BERIONNI, G. ET AL., EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2011, pages 5104 - 5113 *
BOYER, J. H. ET AL., JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 82, 1960, pages 2218 - 2220 *
BOYER, J. H. ET AL.: "2,3-PSI-DINITROSOPYRIDINES", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 78, 1956, pages 423 - 425, XP002005129 *
DAWOOD, N. T. A. ET AL.: "SYNTHESIS OF SOME PYRIDONE DERIVATIVES", BOLLETTINO CHIMICO FARMACEUTICO, vol. 140, no. 3, 2001, pages 149 - 154, XP008054803 *
EMAN, H. A. ET AL., JOURNAL OF THE SERBIAN CHEMICAL SOCIETY, vol. 62, no. 7, 1997, pages 541 - 549 *
GOGOI, S. ET AL., SYNTHESIS, vol. 45, 2013, pages 219 - 224 *
LIU, S. ET AL.: "Conversion of Pyridine N -Oxides to Tetrazolopyridines", THE JOURNAL OF ORGANIC CHEMISTRY, vol. 79, no. 7, 2014, pages 3249 - 3254, XP055313089 *
PORTNOY, S., JOURNAL OF HETEROCYCLIC CHEMISTRY, vol. 7, 1970, pages 703 - 705 *
REISINGER, A. ET AL.: "1H-1,3-Diazepines, 5H-1,3-diazepines, 1,3-diazepinones, and 2,4-diazabicyclo[3.2.0]heptenes,", ORGANIC & BIOMOLECULAR CHEMISTRY, vol. 2, no. 8, 2004, pages 1227 - 1238, XP055597349, DOI: 10.1039/B317099C *
SHAH, H. C. ET AL., ARKIVOC, 2009, pages 76 - 87 *
ZHANG, Q. ET AL., ORGANIC & BIOMOLECULAR CHEMISTRY, vol. 10, 2012, pages 2847 - 2854 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021024675A1 (fr) * 2019-08-05 2021-02-11 国立大学法人大阪大学 Composé et son procédé de fabrication

Also Published As

Publication number Publication date
JP7320784B2 (ja) 2023-08-04
TW201922743A (zh) 2019-06-16
JPWO2019078040A1 (ja) 2021-01-21

Similar Documents

Publication Publication Date Title
JP6706822B2 (ja) 化合物、及びこれを含む有機半導体材料
JP6883806B2 (ja) 化合物、及びこれを含む有機半導体材料
KR101278079B1 (ko) 치환된 폴리티오펜 폴리머의 개선된 제조 방법
WO2018051979A1 (fr) Composé polymère et matériau semi-conducteur organique en comprenant
JPH1083821A (ja) 溶融塩型高分子電解質
JP7097573B2 (ja) 化合物、及びこれを含む有機半導体材料
US8299272B2 (en) Process for production of fused ring compound
WO2019078040A1 (fr) Composé, corps lié de celui-ci, et matériau semi-conducteur organique
JP6954456B2 (ja) スルファミン酸リチウムの製造方法及び新規スルファミン酸リチウム
JP5088918B2 (ja) イオン液体およびその製造方法、ならびに該イオン液体を含む電解コンデンサ
JP7308489B2 (ja) 化合物、化合物の前駆体、化合物を含む有機半導体材料、および有機半導体材料を含む有機電子デバイス
JP7179614B2 (ja) 含窒素複素環化合物の製造方法
JP7194392B2 (ja) 高分子化合物、高分子化合物を含む有機半導体材料、および有機半導体材料を含む有機電子デバイス
US20230121865A1 (en) Method for producing naphthylsilole, naphthylsilole containing heterocyclic group, and graphene nanoribbon containing heterocyclic group
KR20200139098A (ko) 만곡된 방향족화합물 및 이의 제조방법
JP7034776B2 (ja) 化合物の製造方法
WO2017094872A1 (fr) Absorbant d'ultraviolets
WO2023280638A1 (fr) Composé de vinyle thianthrenium, son procédé de préparation et son utilisation pour le transfert d'un groupe vinyle
WO2021024675A1 (fr) Composé et son procédé de fabrication
WO2016072366A1 (fr) Composé de butyrolactone et son procédé de production
JP2018162239A (ja) 芳香族化合物およびその製造方法
JP2002205967A (ja) アセナフチレン環を有する新規な架橋性化合物及びその合成中間体
JP2013075832A (ja) アルコキシチオフェン誘導体の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18867657

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019549210

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18867657

Country of ref document: EP

Kind code of ref document: A1