WO2001025205A1 - Nouveaux derives pyridiniques - Google Patents

Nouveaux derives pyridiniques Download PDF

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Publication number
WO2001025205A1
WO2001025205A1 PCT/JP2000/006733 JP0006733W WO0125205A1 WO 2001025205 A1 WO2001025205 A1 WO 2001025205A1 JP 0006733 W JP0006733 W JP 0006733W WO 0125205 A1 WO0125205 A1 WO 0125205A1
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group
alkyl
pyridyl
pyridyl group
methyl
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PCT/JP2000/006733
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English (en)
Japanese (ja)
Inventor
Taichi Shintou
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Sankio Chemical Co., Ltd.
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Priority to AU74483/00A priority Critical patent/AU7448300A/en
Publication of WO2001025205A1 publication Critical patent/WO2001025205A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl

Definitions

  • the present invention relates to a novel pyridine derivative that is an important intermediate in the fields of pharmaceuticals, pesticides, ligands, liquid crystals, surfactants, electrophotography, and organic electroluminescence. ⁇ Background technology>
  • pyridine derivatives have received attention over a wide range of fields.
  • pyrimidine derivatives have high affinity for endothelin receptors as endothelin antagonists (Japanese Patent Application Laid-Open Nos. 9-1162449, 10-194972, No. 11-92458) is disclosed.
  • the affinity of the receptor is insufficient, and there is an eager need to create an endocerin antagonist having a stronger receptor affinity.
  • WO 9852922 is disclosed.
  • dendrimer-type polynuclear metal complexes contained in dendrimer-type compounds have a new property as a polynuclear metal complex if the interaction between subunits is strong. Is being actively conducted.
  • One of them is a multinuclear complex using a ruthenium (II) polypyridine complex with photo-redox activity as a subunit and a virazine with electron interaction between skeletons as a bridging ligand (Chemistry and Industry, (7), 890 (1999), J. Am. Chem. Soc., 120, 5480 (1998)) and reported their electrochemical properties.
  • Such a dendrimer-type polynuclear metal complex is likely to be used in the artificial conversion process of solar energy, and is very promising. It is also expected to be useful as a ligand for various reaction catalysts. For example, as described in GB 2328686, Journal of Synthetic Organic Chemistry, ⁇ (9), 78 (1998), the use of a metal copper catalyst in a U11ma ⁇ -like reaction promotes reactivity. It is expected to work as an agent.
  • An object of the present invention is to provide a novel pyridine derivative as a substance or an intermediate useful in the fields of pharmaceuticals, pesticides, ligands, liquid crystals, surfactants, electrophotography, organic electroluminescence, and optical materials. is there. ⁇ Disclosure of Invention>
  • a 1 is a 2_pyridyl group, a virazinyl group, a 4-pyrimidyl group, a 3-alkyl-2-pyridyl group, a 4-alkyl-12-pyridyl group, a 5-alkyl-2-pyridyl group, 6-alkyl-2-pyridyl group, 2-pyridyl group substituted with one alkyl group and one phenyl group, 2-pyridyl group substituted with two alkyl groups, 2-substituted with three alkyl groups Represents a pyridyl group, a 2-pyridyl group substituted with two phenyl groups, and a virazinyl group substituted with one to three alkyl groups.
  • a 2 and A 3 may be the same or different and represent an alkyl group or an aryl group. A 2 and A 3 may combine with each other to form a ring.
  • a 1 is a 2-pyridyl group and A 2 and A 3 are simultaneously methyl groups
  • a 1 is a 2-pyridyl group and A 2 and A 3 are bonded to each other to form a cyclohexane ring;
  • a 1 is a 2-pyridyl group substituted with a methyl group at the 5 and 6 positions, and A 2 and A 3 are the same.
  • a 2 and A 3 are the same.
  • the alkyl group has 1 to 4 carbon atoms
  • the aryl group is a phenyl group or a naphthyl group. Lysine derivatives.
  • B 1 is a 2-pyridyl group, a 3-alkyl-12-pyridyl group, a 4-alkyl-2-pyridyl group, a 3-phenyl-12-pyridyl group, a 4-phenyl-2-pyridyl group, and two A 2-pyridyl group substituted with an alkyl group, a 2-pyridyl group substituted with one alkyl group and one phenyl group, a virazinyl group, and a virazinyl group substituted with 1 to 3 alkyl groups.
  • One of B2 and B3 represents a hydrogen atom, and the other represents an alkyl group or an aryl group.
  • B 1 is a 2-pyridyl group
  • B 2 represents an alkyl group (having 2 or more carbon atoms)
  • B 3 represents a hydrogen atom
  • B 1 is a virazinyl group
  • B 2 represents a hydrogen atom
  • B 3 represents an alkyl group.
  • B 1 is a 4-methyl-2-pyridyl group
  • the alkyl group has 1 to 4 carbon atoms
  • the aryl group is a phenyl group or a naphthyl group.
  • Pyridine derivative is a 2-pyridyl group
  • the alkyl group has 1 to 4 carbon atoms
  • the aryl group is a phenyl
  • C 1 is a 3-alkyl ( ⁇ prime number 2 or more) 1-2-pyridyl group, a 4-alkyl (carbon number 2 or more) — 2-pyridyl group, 2-pyridyl group substituted with two alkyl groups (The total number of carbon atoms in two alkyl groups is 3 or more), a 2-pyridyl group substituted with three alkyl groups, and a virazinyl group substituted with one to three alkyl groups.
  • D 1 is a 2-pyridyl group substituted with one alkyl group and one phenyl group, or 3,4-diphenyl-2-pyridyl group, 3,5-diphenyl-one Represents a pyridyl group or a 4,5-diphenyl-1-pyridyl group.
  • 2-pyridyl in which D 1 is substituted with one alkyl group and one phenyl group When the 6-position of the 2-pyridyl group is substituted with a methyl group, the phenyl group is substituted at the 3- or 5-position of the 2-pyridyl group.
  • examples of the alkyl group include a linear or branched alkyl group having 1 to 18 carbon atoms, preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group.
  • an alkyl group having 1 to 4 carbon atoms such as a sec-butyl group and a tert-butyl group, and more preferably a methyl group and an ethyl group which can be induced to a carboxylic acid or an aldehyde.
  • examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. Preferred are a phenyl group and a naphthyl group, and particularly preferred is a phenyl group.
  • A2 and A3 may be the same or different, but preferably A2 and A3 are the same.
  • a 2 and A 3 may be bonded to each other to form a ring.
  • the ring formed is specifically a cycloalkane such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, etc., and preferably cyclohexane.
  • R in R Is R 2 and R 3 represents A to D, and has the same meaning as described above. Next, each step will be described.
  • the cyano heterocyclic compound represented by the general formula (II) is reacted with hydrazine to obtain an amidrazone compound represented by the general formula (III).
  • the amidrazone compound (III) can be obtained by the method described in Japanese Patent Application No. 11-167708 or a method analogous thereto.
  • cyano heterocyclic compound represented by the general formula (II) include the general formulas (II-11), (II-2) and 4-cyanovirimidine (II-3) shown below.
  • P 1 and P 2 represent a hydrogen atom, an alkyl group, an aryl group
  • Q represents a hydrogen atom, an alkyl group
  • n and m represent 1 to 3, and the total thereof is 3 or less.
  • Preferred examples are shown below, but the alkyl groups include straight-chain and branched ones.
  • 6-diphenyl-2-nitridinecarbonitrile 5,6-diphenyl-2-nitridinecarbonitrile, 3,4,5—trimethyl-1-2-pyridinepyridine, 3,4,6-trimethyl-2- Pyridinecarbonitrile, 3,5,6—Trimethyl-1-2—Pyridinecarbonitrile, 4,5,6—Trimethyl-12-pyridinecarbonitrile, 3-Ethyl-4-Methyl-2—Pyridinecarbonitrile, 3-E Thiruyl 5-methyl-2-pyridinecarbonitrile, 3-ethyl-16-methyl-2-pyridinepyridine, 4-ethyl-3-methyl-12-pyridinecarbonitrile, 4-ethylethyl-5- Methyl-2—pyridinecarbonitrile, 4-ethyl-6— Methyl-2-pyridinecarbonitrile, 5-ethyl-3-methyl-1-pyridinecarbonitrile,
  • 2-pyridinecarbonitrile 3-methyl-12-pyridine liponitrile, 4-methyl-12-pyridinecarbonitrile, 5-methyl-2-pyridinecarbonitrile, and 6-methyl1-2.
  • the above-mentioned cyano heterocyclic compound can be easily obtained as a commercial product.
  • 1,2,4-triazine compound represented by the general formula (V) is obtained by reacting the amidrazone compound (III) with the diketone compound represented by the general formula (IV).
  • 1,2,4-triazine compound (V) can be obtained by the method described in Japanese Patent Application No. 11-167308, Tetrahedron Lett., 3_9_, 8817, 8821, 8825 (1998), or a similar method. be able to.
  • Examples of the compound represented by the general formula (IV) include the following.
  • R 3 represents a compound represented by the general formula (IV) in which R 3 is the same alkyl group or aryl group.
  • R 2 and R 3 may be bonded to each other to form a ring.
  • the alkyl group includes an alkyl group having 1 to 4 carbon atoms
  • the aryl group includes a phenyl group and a 4-methylphenyl group.
  • 1,2-cyclohexanedione 2,3-butanedione, 3,4-hexanedione, benzyl, and 4,4'-dimethylbenzyl.
  • the alkyl group includes an alkyl group having 1 to 4 carbon atoms
  • the aryl group includes a phenyl group and a 4-methylphenyl group.
  • 2,3-pentanedione 2,3-heptanedione
  • 1-phenyl-1,2-propanedione 2,3-pentanedione, 2,3-heptanedione, and 1-phenyl-1,2-propanedione.
  • aqueous glyoxal examples thereof include aqueous glyoxal, glyoxal di (sodium hydrogen sulfite), 1,4-dioxane-2,3-diol which is an equivalent of glyoxal, and glyoxal trimeric dihydrate.
  • aqueous glyoxal solutions and 1,4-dioxane-1,2,3-diol, and more preferred are aqueous glyoxal solutions which are inexpensive and easy to obtain and handle.
  • Ketoaldehyde compound (when one of R 2 and R 3 is a hydrogen atom and the other is an alkyl group)
  • R 2 and R 3 represents a hydrogen atom and the other represents an alkyl group or an aryl group represented by the general formula (IV).
  • the alkyl group is an alkyl group having 1 to 4 carbon atoms
  • the aryl group is a phenyl group.
  • methyl glyoxal (pyruvic aldehyde), ethyl glyoxal, propyl glyoxal, isopropyl glycol glyoxal Butylglyoxal, t-butylglyoxal, isobutylglyoxal, sec-butylglyoxal, phenylglyoxal and the like.
  • Particularly preferred are methylglyoxal and phenylglyoxal.
  • the 1,2,4-triazine compound represented by the general formula (V) is reacted with 2,5-norbornadiene to obtain a 2,5,6-trisubstituted pyridine derivative represented by the general formula (I) .
  • the pyridine derivative represented by the general formula (I) can be obtained by the method described in Tetrahedron Lett., 39, 8817, 8821, 8825 (1998), or a method analogous thereto. Can be.
  • This application example was used as a catalyst (ligand) of a metal copper catalyst in the U11m anne reaction, as described in GB23288686.
  • the following substrates were used.
  • Example 1 The same operation as in Example 1 was carried out except that in Example 1, the cocatalyst shown in Table 3 below was used instead of 2- (5,6-diphenyl-2-pyridyl) pyridine (A-2), N, N, diphenyl N, N, di (3-methylphenyl) -1,1,4-phenylenediamine was synthesized, and the yield and purity by HP LC were evaluated. Comparative Examples 1-3
  • a novel compound by providing a novel compound, a pyridine derivative, particularly novel pharmaceuticals, agricultural chemicals, ligands, liquid crystals, liquid crystals, surfactants, electrophotography, and organic compounds having pyridine, virazine and pyrimidine nuclei are provided.
  • the route for acquiring elect-emission luminescence has been expanded, and it is very important for research and development in these research fields, as well as for industrial and practical applications.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

La présente invention concerne des composés représentés par la formule générale (A) dans laquelle A1 est 2-pyridyle, pyrazinyle, 4-pyrimidyle ou analogue, et A2 et A3 sont chacun indépendamment alkyle ou aryle, mais peuvent également être réunis en cycle sous la réserve que les cas (1) à (3) suivants sont exclus. Cas 1: A1 est 2-pyridyle et A2 et A3 sont méthyle. Cas 2: A1 est 2-pyridyle et A2 et A3 sont réunis en cycle cyclohexane. Cas 3: A1 est 5,6-diméthyl-2-pyridyle, et A2 et A2 sont l'un et l'autre méthyle.
PCT/JP2000/006733 1999-10-01 2000-09-28 Nouveaux derives pyridiniques WO2001025205A1 (fr)

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AU74483/00A AU7448300A (en) 1999-10-01 2000-09-28 Novel pyridine derivatives

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JP28175899A JP2001097950A (ja) 1999-10-01 1999-10-01 新規なピリジン誘導体
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
US20160264553A1 (en) * 2015-02-20 2016-09-15 Rigel Pharmaceuticals, Inc. GDF-8 Inhibitors

Families Citing this family (4)

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Publication number Priority date Publication date Assignee Title
TWI490215B (zh) * 2008-05-16 2015-07-01 Semiconductor Energy Lab 有機化合物，苯並唑衍生物，以及使用苯並唑衍生物之發光元件，發光裝置，和電子裝置
US9105852B2 (en) 2012-02-17 2015-08-11 Semiconductor Energy Laboratory Co., Ltd. Bipyridine compound, light-emitting element material, organic semiconductor material, light-emitting element, display module, lighting module, light-emitting device, lighting device, display device and electronic device
TWI633100B (zh) 2013-07-19 2018-08-21 半導體能源研究所股份有限公司 有機化合物、發光元件、顯示器模組、照明模組、發光裝置、顯示裝置、照明設備及電子裝置
JP2019019124A (ja) * 2017-07-19 2019-02-07 日本化薬株式会社 ピラジン化合物

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160264553A1 (en) * 2015-02-20 2016-09-15 Rigel Pharmaceuticals, Inc. GDF-8 Inhibitors
US9981944B2 (en) * 2015-02-20 2018-05-29 Rigel Pharmaceuticals, Inc GDF-8 inhibitors

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AU7448300A (en) 2001-05-10

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