Process for producing N-(hetero)arylazoles

Patent metadata

Field	Value
Publication number	US-9233922-B2
Application number	US-201214342570-A
Country	US
Kind code	B2
Filing date	Aug 31, 2012
Priority date	Sep 2, 2011
Publication date	Jan 12, 2016
Grant date	Jan 12, 2016

Abstract

The present invention provides a process for effectively producing an N-(hetero)arylazole with high yield, which is useful as a medical or agrochemical product, an organic photoconductor material, an organic electroluminescent element material, or the like. The present invention relates to a process for producing an N-(hetero)arylazole, which includes reacting a (hetero)aryl (pseudo)halide with an NH-azole in the presence of: a catalyst including a palladium compound and a coordination compound; and a basic magnesium compound.

First claim

The invention claimed is:

1. A process for producing an N-arylazole or N-heteroarylazole, which comprises reacting a compound represented by the following general formula (5) with an azole in the presence of: a catalyst comprising a palladium compound and a monophosphine represented by the following general formula (1); a Grignard reagent represented by the following general formula (6′); and at least one solvent selected from the group consisting of a aliphatic hydrocarbon, an aromatic hydrocarbon and an ether, at a temperature range of 10° C. to 200° C.
(Het)Ar—X n   (5)

wherein (Het)Ar represents an aromatic ring group or a heteroaromatic ring group, in which at least one hydrogen atom on the aromatic ring group or heteroaromatic ring group may be substituted by at least one group selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an aliphatic heterocyclic group, a heteroaryl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a heteroaryloxy group, an acyl group, an alkylthio group, an arylthio group, an aralkylthio group, a heteroarylthio group, an amino group, a phosphino group, a silyl group, a boryl group, a cyano group and a fluoro group, X represents a group selected from the group consisting of a chloro group, a bromo group and a p-toluenesulfonyloxy group, a subscript n of X represents the number of the substituent X into (Het)Ar, and is an integer of from 1 to 3,

wherein P represents a phosphorus atom, R 1 and R 2 each independently represents a tertiary alkyl group, and R 3 represents a group selected from the group consisting of an alkyl group, alkenyl group, an aryl group, an aralkyl group, a pyrrolyl group, a pyrazolyl group, an indolyl group and a ferrocenyl group, in which at least one hydrogen atom on the aryl group, aralkyl group, pyrrolyl group, pyrazolyl group, indolyl group or ferrocenyl group may be substituted by a group selected from the group consisting of an alkyl group, an aryl group, an alkoxy group and an dialkylamino group,
R 12 —Mg—X′  (6′)

wherein Mg represents a magnesium atom; X′ represents a group selected from the group consisting of a chloro group, a bromo group and an iodo group, and R 12 represents a group selected from the group consisting of an alkyl group, an alkenyl group, an aryl group and aralkyl group, in which at least one hydrogen atom on the alkenyl group, aryl group or aralkyl group may be substituted by an alkyl group,
wherein the azole is selected from the group consisting of 1H-pyrrole, indole, carbazole, benzocarbazoles, dibenzocarbazoles, indolocarbazoles, biindoles and bicarbazoles, in which at least one hydrogen atom on a carbon atom of 1H-pyrrole, indole, carbazole, benzocarbazoles, dibenzocarbazoles, indolocarbazoles, biindoles or bicarbazoles may be substituted by at least one group selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an aliphatic heterocyclic group, a heteroaryl group, an alkoxy group, an aryloxy group, an aralkyloxy group, a heteroaryloxy group, an acyl group, an alkylthio group, an arylthio group, an aralkylthio group, a heteroarylthio group, an amino group, a phosphino group, a silyl group, a boryl group, a cyano group and a fluoro group
wherein an amount of the palladium compound is 0.0001 equivalents or more and less than 0.01 equivalents in terms of palladium atom per the amount of the azole used.

2. The process according to claim 1 , wherein the palladium compound is selected from the group consisting of bis(dibenzylideneacetone)palladium(0), tris(dibenzylideneacetone)dipalladium(0), tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct, palladium(II) chloride, palladium(II) bromide, dichlorobis(acetonitrile)palladium(II), dichlorobis(benzonitrile)palladium(II), dichloro(1,5-cyclooctadiene)palladium(II), palladium(II) acetate, allylpalladium(II) chloride dimer, methallylpalladium(II) chloride dimer, crotylpallaldium(II) chloride dimer, and cinnamylpalladium(II) chloride dimer, and an amount of the palladium compound is 0.0001 equivalents or more and less than 0.01 equivalents in terms of palladium atom per the amount of the azole used.

3. The process according to claim 2 , wherein the monophoshine represented by the general formula (1) is selected from the group consisting of tri-tert-butylphosphine, di-tert-butylmethylphosphine, di-tert-butylneopentylphosphine, 1-[2-(di-tert-butylphosphino)phenyl]-3,5-diphenyl-1H-pyrazole, 5-(di-tert-butylphosphino)-1′,3′,5′-triphenyl-1′H-[1,4′]bipyrazole, [4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine, (2-biphenyl)di-tert-butylphosphine, 2-di-tert-butylphosphino-2′,4′,6′-triisopropylbiphenyl, 2-di-tert-butylphosphino-2′-(N,N-dimethylamino)biphenyl, 2-(di-tert-butylphosphino)-3,6-dimethoxy-2′,4′,6′-triisopropyl-1,1′-biphenyl, 1,2,3,4,5-pentaphenyl-1′-(di-tert-butylphosphino)ferrocene, di(1-adamantyl)-n-butylphosphine, di(1-adamantyl)benzylphosphine, 2-(di-tert-butylphosphino)-1-phenylindole, 2-(di-tert-butylphosphino)-1-phenyl-1H-pyrrole, N-[2-di(1-adamantyl)phosphinophenyl]morpholine, di-tert-butyl(2,2-diphenyl-1-methylvinyl)phosphine, and di-tert-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine.

4. The process according to claim 3 , wherein the Grignard reagent represented by the general formula (6′) is selected from the group consisting of methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium bromide, n-propylmagnesium bromide, isopropylmagnesium chloride, isopropylmagnesium bromide, cyclopropylmagnesium bromide, n-butylmagnesium chloride, isobutylmagnesium bromide, sec-butylmagnesium bromide, tert-butylmagnesium chloride, n-pentylmagnesium bromide, cyclopentylmagnesium bromide, n-hexylmagnesium bromide, cyclohexylmagnesium bromide, n-heptylmagnesium bromide, n-octylmagnesium bromide, vinylmagnesium bromide, allylmagnesium chloride, allylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, phenylmagnesium iodide, o-tolylmagnesium bromide, m-tolylmagnesium bromide, p-tolylmagnesium bromide, (2,5-dimethylphenyl)magnesium bromide, benzylmagnesium chloride, and benzylmagnesium bromide.

5. The process according to claim 4 , wherein (Het)Ar in the compound represented by the general formula (5) represents a group selected from the group consisting of phenyl group, naphthyl group, anthryl group, phenanthrenyl group, pyrenyl group, perylenyl group, fluorenyl group, biphenyl group, binaphthyl group, bianthryl group, 9,9′-spirobi[9H-fluorene]-yl group, anthraquinolyl group, fluorenonyl group, furyl group, thienyl group, pyrrolyl group, pyridyl group, oxadiazolyl group, thiadiazolyl group, triazinyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, quinolyl group, acridinyl group, phenanthridinyl group, benzoquinolinyl group, isoquinolinyl group, and benzoisoquinolinyl group.

6. The process according to claim 5 , wherein a substituent that (Het)Ar in the compound represented by the general formula (5) may have and that the azole may have is selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkylthio group, an arylthio group, an amino group, a silyl group, a cyano group and a fluoro group.

Assignees

• Nakayama Yuji
• Kobayashi Tohru
• Takasago Perfumery Co Ltd

Inventors

• Nakayama Yuji
• Kobayashi Tohru

Classifications

• C07D401/04

  directly linked by a ring-member-to-ring-member bond · CPC title

• C07D409/04

  directly linked by a ring-member-to-ring-member bond · CPC title

• C07D209/60 Primary

  Naphtho [b] pyrroles; Hydrogenated naphtho [b] pyrroles · CPC title

• C07D401/14

  containing three or more hetero rings · CPC title

• C07D209/86

  with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system · CPC title