JP4406550B2 - Method for producing arylamine - Google Patents

Description

  The present invention provides a method for producing an arylamine, particularly a triarylamine or diarylamine, useful as a positive charge transport material in an organic semiconductor element, or an intermediate thereof, with high purity and low cost.

The present invention falls within the category of reactions classified as Ullmann condensation reactions when synthesizing arylamine compounds.
The Ullmann condensation reaction is a method of synthesizing an arylamine by reacting an aromatic amine with an aromatic halogen compound, preferably an aromatic iodide compound, in the presence of a base and a copper catalyst. Discovered by Ullmann (see Non-Patent Document 1). This reaction generally takes a long reaction time, and usually requires a high temperature of 200 ° C. or higher to achieve a practical arylation rate. Therefore, decomposition of the raw material, oxidation of the product, disproportionation, A large amount of by-products are generated by the quantification reaction or the like.

  These by-products are different from the target compound in ionization potential and electron density distribution in the frontier orbitals, leading to a decrease in the electrical characteristics of the organic semiconductor device, so that the arylamine compound used is required to have a very high purity. For example, regarding the influence of impurities on the mobility of a hole transport material, it has been reported that the hole mobility is lowered by the addition of an impurity having a small ionization potential (see Non-Patent Documents 2 to 4). In order to obtain high mobility, it is pointed out that impurities form hole traps, and at least impurities with a small ionization potential by-produced by oxidation or dimerization of the product are not included as much as possible. It becomes the condition of. In addition, it has been reported that arylamine derivatives exhibit high mobility when the electron density distribution of the frontier orbitals in neutral and cation radical states is small (see Non-Patent Document 5), and the polarity generated by oxidation The presence of a coloring impurity having a group causes a decrease in electrical characteristics. For this reason, it is necessary to eliminate these by-products in the materials for electronic materials as much as possible, but their separation and purification is very difficult, and they must be repeatedly purified by recrystallization or column chromatography, resulting in high costs. There was a problem.

  In the Ullmann reaction, a method for suppressing a by-product that adversely affects electrical characteristics has been reported. For example, a method of synthesizing a styryl compound and an arylamine compound by reacting a halogenated aromatic compound with a large excess of an aromatic amine compound (see Patent Document 1 and Patent Document 2), a halogenated aromatic compound and an aromatic amine When synthesizing an arylamine compound having a fluorene skeleton by reacting with a compound, a method of reducing the amount of copper catalyst used to suppress by-products (see Patent Document 3), halogenated aromatic compounds and aromatics A method of suppressing a by-product by using an inert gas atmosphere and an inorganic sulfite together when a triarylamine derivative is synthesized by reacting an amine compound with a copper powder catalyst and a base (see Patent Document 4) In each case, by-products are suppressed, but coloring impurities, oxides, decomposition products, etc. are still produced, and the materials for electronic materials are used. Or had to be highly purified for use as intermediates.

  In order to produce a high purity arylamine compound, it is preferable to react at a lower temperature. An aromatic amine compound and an iodinated aromatic compound are mixed in an aromatic solvent, a copper catalyst, potassium hydroxide, and a tertiary amine. A method for producing a triarylamine compound that reacts at 120 to 150 ° C. in the presence of the compound has been proposed (see Patent Documents 6 to 9). However, in these methods, the reaction proceeds efficiently even at low temperatures, but the yield and purity are not satisfactory, and the above problems cannot be solved.

  As another method for synthesizing an arylamine compound at a low temperature, a chlorinated aromatic compound or a brominated aromatic compound and an aromatic amine compound in an aromatic solvent in the presence of a palladium catalyst, a phosphine compound, and a base, Although a method of reacting at ~ 140 ° C (see Patent Documents 11 to 15 and Non-Patent Documents 5 to 10) has been proposed, a palladium compound is very expensive and is difficult to separate and recover after the reaction. The production method is not particularly advantageous, and the yield and purity are not satisfactory.

JP-A-9-258465 JP-A-11-282180 JP 2000-178237 A JP 2000-239235 A JP-A-9-323958 JP-A-9-323959 JP-A-10-212267 JP 10-212268 A JP-A-10-212269 JP 10-312073 A JP-A-10-139742 JP-A-10-195031 JP 10-310561 A Japanese Patent Laid-Open No. 11-5769 JP 2002-275130 etc. “Hemiche Berichte”, 1920, 36 p. 2382 “The Journal of Applied Physics”, 1972, 43, p. 5033 “Physical Review Letters”, 1976, 37, p. 1360 “The Journal of Physical Chemistry”, 1984, 88, p. 4714f Journal of Electrophotographic Society, 1990, 29, 4 p. 366 “Angevante Chemie International English Ed.”, Vol. 37, 1998, p. 2046 “Journal of The American Chemical Society”, 1998, 120, p. 9722 “The Journal of Organic Chemistry”, 1996, 61 p. 1133 “Tetrahedron Letters”, 1995, Vol. 36, No. 21, p. 3609

  The present invention can synthesize very high purity arylamines, particularly triarylamines or diarylamines, by suppressing impurities that adversely affect electrical properties when synthesizing arylamine compounds in the Ullmann reaction. The present invention provides a method for producing a material suitable for use as an intermediate or an intermediate thereof at low cost.

式（Ｉ）および（ＩＩ）中、
Ｑは塩素原子、臭素原子またはヨウ素原子を表す。
Ｘは−Ｃ（Ｒ１５）（Ｒ１６）−、酸素原子、硫黄原子、−Ｎ（Ｒ１７）−、シクロアルキレン基、アリーレン基、フリレン基、チエニレン基、ピリジレン基、−Ｎ＝Ｎ−、または−Ｃ（Ｒ１５）＝Ｃ（Ｒ１６）−を表す。ｎ２は０〜３の整数を表し、ｎ２が０の場合には単結合を表す。ｎ２が２以上の場合にはＸは同じでも異なっていてもよい。
Ｒ１〜Ｒ１６は各々独立して水素原子、アルキル基、アルケニル基、アリール基、アルコキシ基、アリールオキシ基、ジメチルアミノ基、Ｎ−エチル−Ｎ−フェニルアミノ基、ジフェニルアミノ基、Ｎ−フェニル−Ｎ−ナフチルアミノ基、ニトロ基、またはハロゲン原子を表す。
Ｒ１７はアルキル基、アルケニル基、アリール基、アルコキシ基、アリールオキシ基、ジメチルアミノ基、Ｎ−エチル−Ｎ−フェニルアミノ基、ジフェニルアミノ基、Ｎ−フェニル−Ｎ−ナフチルアミノ基、ニトロ基、またはハロゲン原子を表す。
Ｒ１〜Ｒ５もしくはＲ６〜Ｒ１７における２つの基によって更に飽和環、シクロペンテン環、シクロヘキセン環、シクロオクテン環、または、芳香環を形成してもよい。
Ｒ６〜Ｒ１７において、炭素数１〜１０のアルキレン基、３〜１０員のシクロアルキレ
ン基、６〜１０員のアリーレン基、フリレン基、チエニレン基、またはピリジレン基を介
して式（ＩＩ）で表わされる構造をもう１つ有していてもよい。
Ｒ１〜Ｒ１７におけるアルキル基、アルケニル基、アリール基、アルコキシ基、アリールオキシ基、ジメチルアミノ基、Ｎ−エチル−Ｎ−フェニルアミノ基、ジフェニルアミノ基、およびＮ−フェニル−Ｎ−ナフチルアミノ基は、更にアルキル基、単環式または二〜四環式アリール基、アルコキシ基、アリールオキシ基、ニトロ基、またはハロゲン原子から選択される置換基を有していてもよい。

式（ＩＩＩ）および（ＩＶ）中、
Ｙは−Ｃ（Ｒ３４）（Ｒ３５）−、酸素原子、硫黄原子、シクロアルキレン基、アリーレン基、フリレン基、チエニレン基、ピリジレン基、−Ｎ＝Ｎ−、または−Ｃ（Ｒ３４）＝Ｃ（Ｒ３５）−を表す。
ｎ４は０〜３の整数を表し、ｎ４が０の場合は単結合を表す。ｎ４が２以上の場合はＹは同じでも異なっても良い。
Ｒ１８〜Ｒ３５は水素原子、アルキル基、アルケニル基、アリール基、アルコキシ基、アリールオキシ基、またはニトロ基を表す。
また、Ｒ１８〜Ｒ２３もしくはＲ２４〜Ｒ３５において２つの基によって飽和環、シクロペンテン環、シクロヘキセン環、シクロオクテン環、または、芳香環、または複素環を形成してもよい。
Ｒ２４〜Ｒ３５において、炭素数１〜１０のアルキレン基、３〜１０員のシクロアルキ
レン基、６〜１０員のアリーレン基、フリレン基、チエニレン基、またはピリジレン基を
介して式（ＩＶ）で表される構造をもう１つ有していてもよい。
Ｒ１８〜Ｒ３５におけるアルキル基、アルケニル基、アリール基、アルコキシ基、およびアリールオキシ基は、更にアルキル基、アルケニル基、単環式または二〜四環式アリール基、アルコキシ基、アリールオキシ基、ニトロ基、から選択される置換基を有していてもよい。
（２）
前記の減圧度が７０〜１０ｋＰａであることを特徴とする上記（１）に記載のアリールアミンの製造方法。
（３）
不活性ガスを導入しながら反応させることを特徴とする上記（１）または（２）に記載のアリールアミンの製造方法。 That is, the above object is achieved by the following configuration.
(1)
A process for producing an arylamine, comprising reacting an aromatic amine compound and an aromatic halogen compound under reduced pressure of 80 kPa or less in the presence of a copper catalyst and a base,
The copper catalyst is copper powder, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, copper iodide, cuprous oxide, cupric oxide, copper sulfate, copper nitrate, At least one selected from copper carbonate or cupric hydroxide,
The base is at least one selected from alkali metal hydroxides, alkali metal carbonates, alkali metal phosphates or alkali metal alkoxides;
The aromatic halogen compound is a compound represented by the following general formula (I) or (II):
A method for producing an arylamine, wherein the aromatic amine compound is a compound represented by the following general formula (III) or (IV).

In formulas (I) and (II)
Q represents a chlorine atom, a bromine atom or an iodine atom.
X is -C (R15) (R16)-, oxygen atom, sulfur atom, -N (R17)-, cycloalkylene group, arylene group, furylene group, thienylene group, pyridylene group, -N = N-, or -C. (R15) = C (R16)-is represented. n2 represents an integer of 0 to 3, and when n2 is 0, it represents a single bond. When n2 is 2 or more, X may be the same or different.
R1 to R16 are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, dimethylamino group, N-ethyl-N-phenylamino group, diphenylamino group, N-phenyl-N. -Represents a naphthylamino group , a nitro group, or a halogen atom.
R17 is an alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, dimethylamino group, N-ethyl-N-phenylamino group, diphenylamino group, N-phenyl-N-naphthylamino group , nitro group, or Represents a halogen atom.
A saturated ring, a cyclopentene ring, a cyclohexene ring, a cyclooctene ring, or an aromatic ring may be further formed by two groups in R1 to R5 or R6 to R17 .
R6 to R17 are represented by the formula (II) via an alkylene group having 1 to 10 carbon atoms, a 3 to 10 membered cycloalkylene group, a 6 to 10 membered arylene group, a furylene group, a thienylene group, or a pyridylene group. You may have another structure .
The alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, dimethylamino group, N-ethyl-N-phenylamino group, diphenylamino group, and N-phenyl-N-naphthylamino group in R1 to R17 are: Further, it may have a substituent selected from an alkyl group, a monocyclic or bicyclic to tetracyclic aryl group, an alkoxy group, an aryloxy group, a nitro group, or a halogen atom.

In formulas (III) and (IV),
Y is -C (R34) (R35)-, oxygen atom, sulfur atom, cycloalkylene group, arylene group, furylene group, thienylene group, pyridylene group, -N = N-, or -C (R34) = C (R35 )-.
n4 represents an integer of 0 to 3, and when n4 is 0, it represents a single bond. When n4 is 2 or more, Y may be the same or different.
R18 to R35 each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, or a nitro group.
In addition, a saturated ring, a cyclopentene ring, a cyclohexene ring, a cyclooctene ring, an aromatic ring, or a heterocyclic ring may be formed by two groups in R18 to R23 or R24 to R35 .
R24 to R35 are represented by the formula (IV) via an alkylene group having 1 to 10 carbon atoms, a 3 to 10 membered cycloalkylene group, a 6 to 10 membered arylene group, a furylene group, a thienylene group, or a pyridylene group. Another structure may be included .
The alkyl group, alkenyl group, aryl group, alkoxy group and aryloxy group in R18 to R35 are further an alkyl group, alkenyl group, monocyclic or bicyclic to tetracyclic aryl group, alkoxy group, aryloxy group, nitro group And may have a substituent selected from
(2)
Said pressure reduction degree is 70-10kPa, The manufacturing method of the arylamine as described in said (1) characterized by the above-mentioned.
(3)
The method for producing an arylamine according to the above (1) or (2), wherein the reaction is carried out while introducing an inert gas.

  According to the present invention, an arylamine, particularly a triarylamine or diarylamine compound useful as an electronic material or an intermediate thereof can be produced at a low cost by an extremely easy operation, and has high practicality. .

The present invention will be described in further detail.
In addition, although this invention has a structure as described in a claim, it described below also for reference below.
The present invention provides an arylamine, particularly a group of triarylamines or diarylamines useful as a material for electronic materials or intermediates thereof, in the presence of a copper catalyst and a base using an Ullmann condensation reaction. In this production method, the reaction is carried out under a reduced pressure of less than 1 atm. In the production method of the present invention, by-products such as coloring oxidation products, decomposition products, and dimerization products can be suppressed to a very high degree as compared with the conventionally proposed arylamine synthesis methods, and high purity. Arylamine compounds can be prepared. The arylamine compound synthesized here is not colored and contains almost no impurities having polar groups or low ionization potentials that cause a decrease in electrical properties, so it can be used as a material for electronic materials or an intermediate thereof with extremely easy purification. Can be used.

  In the present invention, the degree of reduced pressure during the reaction is usually 80 kPa or less, although an impurity suppressing effect can be obtained even if the pressure is reduced slightly. In order to obtain a higher impurity suppressing effect, the degree of reduced pressure is preferably higher, and an appropriate reduced pressure state is selected depending on the raw materials used. In the case of solventless reaction, the degree of vacuum is usually selected so that the raw materials used are not removed from the reaction system at the reaction temperature, but the reaction is carried out while returning the raw materials distilled from the reaction system at a high degree of vacuum. Is also possible. When a reaction solvent is used, the degree of vacuum at which the reaction solvent is not distilled off is selected, or the degree of vacuum at which the reaction is performed while refluxing the solvent is selected.

  It is preferable that the degree of vacuum is not excessively high in order to capture raw materials distilled during the reaction, and the degree of vacuum during the reaction is preferably 5 kPa or more. A preferable range of the degree of vacuum during the reaction is 70 to 10 kPa, and more preferably 60 to 10 kPa. It is preferable that the degree of vacuum is in the above range because a sufficient impurity suppression effect can be obtained with relatively easy equipment and low cost, and the used raw material distilled during the reaction can be easily captured.

Further, in the present invention, it is preferable to introduce an inert gas during the reaction, because the formation of by-products is prevented. For example, nitrogen, helium, neon, argon, krypton, xenon, or the like can be used as the inert gas, but among these, inexpensive nitrogen gas is preferable. When introducing the inert gas, it is preferable to perform the reaction under reduced pressure while introducing the inert gas after sufficiently replacing the inside of the reaction system with the inert gas at room temperature. Substitution with an inert gas in the reaction system is usually performed by repeatedly reducing the pressure in the reaction system to 8 kPa or less, more preferably 4 kPa or less, and even more preferably 2 kPa or less, and then returning to normal pressure with an inert gas. It is more preferable to react while introducing the inert gas from the lower part of the reactor.
It is preferable to carry out the reaction at a residual oxygen in the reactor of 5% or less, preferably 1% or less, more preferably 0.1% or less.

  The aromatic halogen compound used in the present invention is preferably a compound represented by the following general formula (A).

In formula (A),
Q represents a chlorine atom, a bromine atom or an iodine atom.
n1 represents the integer of 0-5.
When there are a plurality of Ras, each is independently a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, disubstituted amino group, nitro group, heterocyclic residue, halogen atom or -L1. Represents a group represented by -Rb. L1 represents a divalent linking group. Rb represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a disubstituted amino group, a nitro group, a heterocyclic residue, or a halogen atom.
The groups represented by Ra, Rb and L1 may each have a substituent.
A plurality of Ras may form a ring.

  The aromatic halogen compound represented by the formula (A) is more preferably a compound represented by the following general formula (I) or (II).

In formulas (I) and (II),
Q represents a chlorine atom, a bromine atom or an iodine atom.
X represents a divalent linking group, and when n2 is 2 or more, X may be the same or different. X is preferably -C (R15) (R16)-, an oxygen atom, a sulfur atom, -N (R17)-, a cycloalkylene group, an arylene group, a divalent heterocyclic residue, -N = N-, or- C (R15) = C (R16)-, more preferably a 3-10 membered cycloalkylene group, a 6-10 membered monocyclic or bicyclic arylene group, a furylene group, a thienylene group, a pyridylene group. is there.
n2 represents an integer of 0 to 3, and when n2 is 0, it represents a single bond.
R1 to R17 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a disubstituted amino group, a nitro group, a heterocyclic residue, or a halogen atom.
A ring may be further formed by two groups in R1 to R5 or R6 to R17.

  R6 to R17 may have another structure represented by the formula (II) through a divalent linking group. In this case, in the structure represented by a plurality of formulas (II), the connecting sites may be the same or different.

  In the general formulas (I) and (II), R1 to R17 are specifically hydrogen atoms; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, Linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms such as pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl; vinyl, Allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, o Linear, branched, or cyclic C2-C20 alkenyl groups such as tadecenyl, nonadecenyl, icocenyl, hexadienyl, dodecatrienyl, etc .; ethynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, cyclooctynyl, cyclononynyl, cyclodecynyl, etc. A linear, branched or cyclic alkynyl group having 2 to 20 carbon atoms; a monocyclic or di- to tetracyclic aryl group such as phenyl, naphthyl, phenanthryl, anthryl; methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyl C1-C20 alkoxy groups such as oxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, octadecyloxy; aryloxy groups such as phenoxy, naphthyloxy; dimethylamino, N- Di-substituted amino groups such as til-N-phenylamino, diphenylamino, N-phenyl-N-naphthylamino; nitro groups; heterocyclic residues such as furyl, thienyl, pyridyl; fluorine atoms, chlorine atoms, bromine atoms, iodine Represents a halogen atom such as an atom. Preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a disubstituted amino group, a nitro group, a heterocyclic residue, and a halogen atom, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, and a nitro group. is there. Examples of the divalent linking group include an alkylene group (preferably having 1 to 10 carbon atoms), a cycloalkylene group (preferably 3 to 10 members), an arylene group (preferably 6 to 10 members), and a divalent heterocycle. A residue is mentioned preferably, Among these, a cycloalkylene group, an arylene group, a furylene group, a thienylene group, and a pyridylene group are particularly preferable.

  In the general formulas (A), (I), and (II), Ra, Rb, L1, R1 to R17 may further have a substituent and are not particularly limited as long as they do not participate in the reaction. Specifically, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl; vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, Alkenyl groups such as dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icocenyl, hexadienyl, dodecatrienyl, etc .; ethynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, cyclooctyl, cyclodecyl Groups: monocyclic or di- to tetracyclic aryl groups such as phenyl, naphthyl, phenanthryl, anthryl, etc .; methoxy, ethoxy, Alkoxy groups such as poxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy; aryloxy groups such as phenoxy, naphthyloxy; dimethylamino, N-ethyl-N-phenylamino, diphenylamino, N -Disubstituted amino groups such as phenyl-N-naphthylamino; nitro groups; heterocyclic residues such as furyl, thienyl, pyridyl; halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom and the like. Preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, a disubstituted amino group, a nitro group, a heterocyclic residue, and a halogen atom, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, and a nitro group. is there.

  Moreover, you may form a ring further by two groups in several Ra, R1-R5, or R6-R17. Specifically, saturated rings such as cyclobutane, cyclopentane, and cyclohexane; partially saturated rings such as cyclopentene, cyclohexene, and cyclooctene; aromatic rings such as benzene and naphthalene; pyrrolidine, pyridine, pyran, oxolane, thiolane, oxane, thiane, and the like A heterocycle is mentioned. A saturated ring and an aromatic ring are preferable.

  The cycloalkylene group in X of the general formula (II) specifically represents cyclopentylene, cyclohexylene, cycloheptylene and the like. The arylene group specifically represents phenylene, naphthylene, anthrylene, phenanthrylene, pyrenylene and the like.

  Q represents a chlorine atom, a bromine atom or an iodine atom, preferably a bromine atom or an iodine atom.

  The aromatic amine compound used in the present invention is preferably a compound represented by the following general formula (B).

In formula (B),
n3 represents an integer of 0 to 5.
When there are a plurality of Rc, each independently represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, disubstituted amino group, nitro group, heterocyclic residue, halogen atom or -L2. Represents a group represented by -Re; Rd represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a disubstituted amino group, a nitro group, a heterocyclic residue, a halogen atom or a group represented by -L2-Re. Represent. L2 represents a divalent linking group. Re represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a disubstituted amino group, a nitro group, a heterocyclic residue, or a halogen atom.
The groups represented by Rc, Rd, Re, and L2 may each have a substituent.
A plurality of Rc may further form a ring.

  The aromatic amine compound used in the present invention is more preferably a compound represented by the following general formula (III) or (IV).

In formulas (III) and (IV),
Y represents a divalent linking group. When n4 is 2 or more, Y may be the same or different. Y is preferably -C (R34) (R35)-, oxygen atom, sulfur atom , cycloalkylene group, arylene group, divalent heterocyclic residue, -N = N-, or -C (R34) = C ( R35)-, more preferably a 3 to 10-membered cycloalkylene group, a 6 to 10-membered monocyclic or bicyclic arylene group, a furylene group, a thienylene group, and a pyridylene group.
n4 represents an integer of 0 to 3, and when n4 is 0, it represents a single bond.
R18 to R35 each represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a nitro group, a heterocyclic residue, or a halogen atom.
Moreover, you may form a saturated ring, an unsaturated ring, and a heterocyclic ring by two groups in R18-R23 or R24- R35 .
R24 to R35 may have another structure represented by the formula (IV) through a divalent linking group. In this case, in the structure represented by a plurality of formulas (IV), both of the connecting sites may be the same or different.

In the general formulas (III) and (IV), R18 to R35 are specifically hydrogen atoms; methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, Linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms such as pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl; vinyl, Allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl Linear, branched, or cyclic C2-C20 alkenyl groups such as octadecenyl, nonadecenyl, icocenyl, hexadienyl, dodecatrienyl, etc .; ethynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, cyclooctynyl, cyclononynyl, cyclodecynyl, etc. A linear, branched or cyclic alkynyl group having 2 to 20 carbon atoms; a monocyclic or bicyclic aryl group such as phenyl or naphthyl; methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyl C1-C20 alkoxy groups such as oxy, nonyloxy, decyloxy, dodecyloxy, octadecyloxy; aryloxy groups such as phenoxy, naphthyloxy; amino groups; methylamino, n-hexylamino, phenoxy It represents furyl, thienyl, a heterocyclic residue such as pyridyl; arylamino, dimethylamino, N- ethyl -N- phenylamino, diphenylamino, N- phenyl--N--substituted amino groups such naphthylamino; nitro group. Preferred are a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an amino group, a substituted amino group, a nitro group, a heterocyclic residue, and a halogen atom, and more preferred are a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, amino Group, a substituted amino group.

In the general formulas (B), (III), and (IV), Rc, Rd, Re, L2, and R18 to R35 may further have a substituent and are not particularly limited as long as they do not participate in the reaction. Specifically, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl; vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, Alkenyl groups such as dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icocenyl, hexadienyl, dodecatrienyl, etc .; ethynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, cyclooctyl, cyclodecyl Groups; monocyclic or di- to tetracyclic aryl groups such as phenyl, naphthyl, phenanthrene and anthracene; methoxy, ethoxy, Roxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy and other alkoxy groups; phenoxy, naphthyloxy and other aryloxy groups; amino groups; methylamino, n-hexylamino, phenylamino, dimethylamino N-ethyl-N-phenylamino, diphenylamino, substituted amino groups such as N-phenyl-N-naphthylamino; nitro groups; heterocyclic residues such as furyl, thienyl, pyridyl and the like. Preferred are a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an amino group, a substituted amino group, a nitro group, and a heterocyclic residue, and more preferred are a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an amino group, and a substituent. It is an amino group. Examples of the divalent linking group include an alkylene group (preferably having 1 to 10 carbon atoms), a cycloalkylene group (preferably 3 to 10 members), an arylene group (preferably 6 to 10 members), and a divalent heterocycle. Residues are preferred, and among them, a cycloalkylene group, an arylene group, a furylene group, a thienylene group, and a pyridylene group are particularly preferred.

Moreover, you may form a ring further by two groups in several Rc, R18-R23, or R24- R35 . Specifically, saturated rings such as cyclobutane, cyclopentane and cyclohexane; partially saturated rings such as cyclopentene, cyclohexene and cyclooctene; aromatic rings such as benzene and naphthalene; pyrrolidine, pyrrole, piperidine, pyridine, morpholine, thiomorpholine, piperazine, Examples include heterocycles such as azacycloheptane, azacycloheptene, azacycloheptatriene, oxolane, thiolane, oxane, thiane. A saturated ring and an aromatic ring are preferable.

Specific examples of the cycloalkylene group represented by Y in the general formula (IV) include cyclopentylene, cyclohexylene, cycloheptylene and the like. The arylene group specifically represents phenylene, naphthylene, anthrylene, phenanthrylene, pyrenylene and the like.
The amount of the aromatic amine compound used varies depending on the individual reaction, such as the number of reaction sites of the aromatic amine compound and the aromatic halogen compound, the reaction temperature, and when the aromatic halogen compound is used as a substrate and solvent. It is 0.1-20 times mole normally with respect to 1 mol of halogen compounds, Preferably it is 0.3-10 times mole.

  The copper catalyst used in the present invention is not particularly limited, and a catalyst usually used in the Ullmann condensation reaction can be used. For example, copper powder, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, copper iodide, cuprous oxide, cupric oxide, copper sulfate, copper nitrate, copper carbonate, water Examples include cupric oxide, and copper chloride, copper bromide, and copper iodide are preferable. The amount of these copper catalysts used is usually 0.001 to 0.4 mol, preferably 0.005 to 0.3 mol, more preferably 0.01 to 0.2 mol, per mol of the aromatic halogen compound. is there.

  If necessary, a promoter such as lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide or the like can be added. When these promoters are added, the amount used is 0.001 to 0.4 mol, preferably 0.005 to 0.3 mol, more preferably 0.01 to 0 mol, per mol of the aromatic halogen compound. .2 moles.

Examples of the base used in the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and other alkali metal hydroxides, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, carbonate Alkali metal carbonates such as cesium, alkali metal phosphates such as trilithium phosphate, trisodium phosphate, tripotassium phosphate, sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium-tert-butoxide, sodium- Examples thereof include alkali metal alkoxides such as tert-butoxide and potassium-tert-butoxide. Among the above, the alkali metal alkoxide may be added to the reaction system as it is, or prepared from an alkali metal, an alkali metal hydride, an alkali metal hydroxide, etc. and an alcohol. Of these bases, alkali metal carbonates and alkali metal hydroxides are preferred.
These bases are used in an amount of 1.0 to 4.0 equivalents, preferably 1.1 to 3.0 equivalents, more preferably 1.2 to 2.0 equivalents, relative to the aromatic amine compound.

In the production method of the present invention, a reaction solvent may not be used, but an aromatic compound or an aliphatic compound can be used as a reaction solvent as necessary. Specific examples include the following solvents having a boiling point of 100 ° C. or higher at 1 atmosphere.
(I) Aromatic hydrocarbon compounds that may be halogenated: toluene, xylene, mesitylene, durene, ethylbenzene, diethylbenzene, isopropylbenzene, diisopropylbenzene, diphenylmethane, chlorobenzene, 1,2-dichlorobenzene, 1,2,4- Trichlorobenzene and the like.
(Ii) Hydrogenated aromatic hydrocarbon compounds in which the ring skeleton is partially hydrogenated, such as dihydro, tetrahydro, hexahydro, octahydro, decahydro, etc .: 1,4-dihydronaphthalene, 1,2,3, 4-tetrahydronaphthalene, 9,10-dihydroanthracene, 9,10-dihydrophenanthrene, 4,5,9,10-tetrahydropyrene, 1,2,3,6,7,8-hexahydropyrene, dodecahydrotriphenylene, etc. .
(Iii) saturated aliphatic compounds: octane, nonane, decane, undecane, dodecane, tridecane, 2-methyldodecane, 4-ethylundecane, tetradecane, pentadecane, 3,3-dimethyltridecane, hexadecane, heptadecane, 2-methyl- 4-ethyltetradecane and the like.
(Iv) Unsaturated aliphatic compounds: 2-heptin, 3-heptin, 2-octene, 3-nonene, 1-decyne, 1-undecene, 4-dodecene, 3,3-dimethyl-1-decene, 1,3 , 5-dodecatriene, 5-tridecene, 3-methyl-4-ethyl-2-decene, 1-dodecyne, 3-dodecene-1-yne, 1-tridecyne, 5,5-dimethyl-3-undecene-1- In, 5-ethynyl-1,3-dodecadiene and the like, ocimene, myrcene, squalene and the like.
(V) Saturated alicyclic compounds: dicyclohexyl, decahydronaphthalene, dodecahydrofluorene and the like.
(Vi) Unsaturated alicyclic compound: α-terpinene, β-terpinene, γ-terpinene, terpinolene, (+)-α-ferrandolene, (−)-β-ferrandolene, (−)-1-p- Menten, (+)-3-Mentene, Dipentene, (+)-Limonene, (+)-Sabinene, (+)-α-Pinene, (+)-β-Pinene, (-)-β-Cadinene, (- )-[Beta] -caryophyllene, (-)-[beta] -santalene, (-)-[alpha] -cedrene, (+)-[beta] -selinene, (-)-[beta] -bisabolene, [alpha] -humulene and the like.

Among the above solvents, alkylbenzenes such as toluene, xylene, diethylbenzene, and diisopropylbenzene, and terpenes such as α-terpinene, β-terpinene, γ-terpinene, ferrandrene, and terpinolene are preferable. When these solvents are used, the effect of suppressing the generation of impurities is improved, and a high yield and high purity arylamine can be produced.
These aromatic compounds and aliphatic compounds can be used as a solvent singly or in combination of two or more. When these reaction solvents are used, they are usually used in a proportion of 100 to 1000 ml with respect to 1 mol of the aromatic halogen compound as a raw material.

  The reaction temperature in this invention is the range of 80-280 degreeC. When the aromatic halide to be used is a chlorine compound or a bromine compound, the reaction time varies depending on the reaction conditions, but is usually about 1 to 12 hours. When the aromatic halide used is an iodine compound, the reaction proceeds very efficiently at a reaction temperature of 80 to 130 ° C., and the reaction time in this case varies depending on the raw material used and the organic salt to be added. About 1 to 3 hours.

  Specific examples of arylamines that can be synthesized in the present invention are shown below, but the present invention is not limited thereto.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to these. The purity was evaluated by high performance liquid chromatography (hereinafter abbreviated as HPLC).

Example 1
Synthesis of N, N′-diphenyl-N, N′-bis (3-methylphenyl)-(p-terphenyl) -4,4′-diamine (I-13) N- (3-methylphenyl) -N -Phenylamine 13.54 g (73.89 mmol), 4,4 ″ -diiodo-1,1 ′: 4 ′, 1 ″ -terphenyl 11.87 g (24.63 mmol), potassium carbonate 27.23 g (197 0.0 mmol) and copper sulfate pentahydrate 1.00 g (4.0 mmol) were mixed, and the reaction system was purged with nitrogen. Then, it reacted at 230-240 degreeC under reduced pressure of 50 kPa, introducing nitrogen, for 2 hours. After the reaction, 25 ml of toluene and 50 ml of water were added and separated, washed with water, and the organic layer was dried over anhydrous sodium sulfate. After the desiccant was filtered off, toluene was concentrated under reduced pressure and 28 ml of ethyl acetate was added. After cooling and crystallization, it was filtered off to obtain 13.7 g (yield 94.0%) of the target compound (I-13) as white crude crystals. . Mp 189-190 ° C. HPLC content (column: GL Science Inertsil ODS-3), eluent: acetonitrile / water (V / V = 80/20), detection UV: 300 nm, flow rate: 1.0 ml / min) was 99.2%. . The impurities are 0.011% oxidation product A having a polar group, 0% oxidation product B, 0.004% oxidation product C having a small ionization potential, and dimerization product D having a small ionization potential. Was 0.016% and dimerized product E was 0.009%.

Examples 2-5
The synthesis was performed in the same manner as in Example 1 except that the pressure in the reaction system of Example 1 was changed. The results are shown in Table 1.

Example 6
In Example 1, the synthesis was performed in the same manner as in Example 1 except that the degree of vacuum was 66.6 kPa and nitrogen was not introduced. The results are shown in Table 1.

Comparative Example 1
The synthesis was performed in the same manner as in Example 1 except that the decompression operation during the reaction was not performed in Example 1. The results are shown in Table 1.

Example 7
Synthesis of N, N, N ′, N′-tetra (3-methylphenyl) -9,10-diaminophenanthrene (Exemplary Compound I-32) 9,10-bis (3-methylanilino) phenanthrene 6.6 g (17. 0 mmol), 14.8 g (68.0 mmol) of m-iodotoluene, 3.82 g (68 mmol) of potassium hydroxide, 0.98 g (6.8 mmol) of cuprous bromide and 10 ml of terpinolene, and 80 kPa under a nitrogen stream. For 2 hours at 115 to 125 ° C. After the reaction, the reaction solvent was distilled off by concentration under reduced pressure, and 5 ml of toluene, 67 ml of ethyl acetate and 22 ml of water were added for liquid separation. 71 ml of methanol was added to the organic layer and cooled and crystallized to obtain 9.0 g (yield 93.0%) of the target compound (I-32) as pale yellow crude crystals. 223-224 ° C. The HPLC content (column: YMC-A-312, eluent: methanol / tetrahydrofuran (V / V = 99/1), detection UV: 254 nm, flow rate: 1.0 ml / min) was 99.6%. Further, the impurities include 0.006% oxidation product F having a polar group, 0.001% oxidation product G, 0.020% dimerization product H having a small ionization potential, and dimerization product I. Was 0.005%.

Comparative Example 2
The synthesis was performed in the same manner as in Example 7 except that the decompression operation was not performed in Example 7. The results are shown in Table 2.

Example 8
Synthesis of 9-phenylcarbazole (Exemplary Compound II-1) 16.47 g (98.52 mmol) of carbazole, 31.0 g (197.04 mmol) of bromobenzene, 5.53 g (98.52 mmol) of potassium hydroxide, cuprous chloride 0.4 g (8.0 mmol) was mixed and reacted for 4 hours while returning bromobenzene distilled off at 115 to 125 ° C. under a reduced pressure of 33 kPa under a nitrogen stream. After the reaction, toluene (50 ml) and water (100 ml) were added, followed by liquid separation, washing with water, and drying the organic layer over anhydrous sodium sulfate. After the desiccant was filtered off, toluene was concentrated under reduced pressure and 352 ml of methanol was added and crystallized to obtain 22.7 g (yield 94.8%) of the desired compound (II-1) as white crude crystals. Melting point 96-97 ° C. HPLC content (column: ODS-80TM, eluent: acetonitrile / water (V / V = 65/35), buffer: triethylamine, acetic acid 0.1% each, detection UV: 254 nm, flow rate: 1.0 ml / min) Was 99.8%. The impurities contained were 0.008% for the dimerization product J having a small ionization potential and 0% for the dimerization product K.

Comparative Example 3
The synthesis was performed in the same manner as in Example 8 except that the decompression operation was not performed in Example 8. The results are shown in Table 3.

  From the results of Tables 1 to 3, when the reaction is carried out under reduced pressure, by-products with different electron density distributions and by-products with small ionization potentials that cause deterioration of electrical properties are highly suppressed, and extremely high purity. It can be seen that a novel arylamine can be synthesized. Moreover, it can be seen from Table 1 that the higher the degree of vacuum in the reaction system, the higher the effect of suppressing impurities, and the impurity suppression effect is closely related to the degree of vacuum in the reaction system.

Claims (3)

A process for producing an arylamine, comprising reacting an aromatic amine compound and an aromatic halogen compound under reduced pressure of 80 kPa or less in the presence of a copper catalyst and a base,
The copper catalyst is copper powder, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, copper iodide, cuprous oxide, cupric oxide, copper sulfate, copper nitrate, At least one selected from copper carbonate or cupric hydroxide,
The base is at least one selected from alkali metal hydroxides, alkali metal carbonates, alkali metal phosphates or alkali metal alkoxides;
The aromatic halogen compound is a compound represented by the following general formula (I) or (II):
A method for producing an arylamine, wherein the aromatic amine compound is a compound represented by the following general formula (III) or (IV).

In formulas (I) and (II)
Q represents a chlorine atom, a bromine atom or an iodine atom.
X is -C (R15) (R16)-, oxygen atom, sulfur atom, -N (R17)-, cycloalkylene group, arylene group, furylene group, thienylene group, pyridylene group, -N = N-, or -C. (R15) = C (R16)-is represented. n2 represents an integer of 0 to 3, and when n2 is 0, it represents a single bond. When n2 is 2 or more, X may be the same or different.
R1 to R16 are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, dimethylamino group, N-ethyl-N-phenylamino group, diphenylamino group, N-phenyl-N. -Represents a naphthylamino group , a nitro group, or a halogen atom.
R17 is an alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, dimethylamino group, N-ethyl-N-phenylamino group, diphenylamino group, N-phenyl-N-naphthylamino group , nitro group, or Represents a halogen atom.
A saturated ring, a cyclopentene ring, a cyclohexene ring, a cyclooctene ring, or an aromatic ring may be further formed by two groups in R1 to R5 or R6 to R17 .
R6 to R17 are represented by the formula (II) via an alkylene group having 1 to 10 carbon atoms, a 3 to 10 membered cycloalkylene group, a 6 to 10 membered arylene group, a furylene group, a thienylene group, or a pyridylene group. You may have another structure .
The alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, dimethylamino group, N-ethyl-N-phenylamino group, diphenylamino group, and N-phenyl-N-naphthylamino group in R1 to R17 are: Further, it may have a substituent selected from an alkyl group, a monocyclic or bicyclic to tetracyclic aryl group, an alkoxy group, an aryloxy group, a nitro group, or a halogen atom.

In formulas (III) and (IV),
Y is -C (R34) (R35)-, oxygen atom, sulfur atom, cycloalkylene group, arylene group, furylene group, thienylene group, pyridylene group, -N = N-, or -C (R34) = C (R35 )-.
n4 represents an integer of 0 to 3, and when n4 is 0, it represents a single bond. When n4 is 2 or more, Y may be the same or different.
R18 to R35 each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, or a nitro group.
In addition, a saturated ring, a cyclopentene ring, a cyclohexene ring, a cyclooctene ring, an aromatic ring, or a heterocyclic ring may be formed by two groups in R18 to R23 or R24 to R35 .
R24 to R35 are represented by the formula (IV) via an alkylene group having 1 to 10 carbon atoms, a 3 to 10 membered cycloalkylene group, a 6 to 10 membered arylene group, a furylene group, a thienylene group, or a pyridylene group. Another structure may be included .
The alkyl group, alkenyl group, aryl group, alkoxy group and aryloxy group in R18 to R35 are further an alkyl group, alkenyl group, monocyclic or bicyclic to tetracyclic aryl group, alkoxy group, aryloxy group, nitro group And may have a substituent selected from The method for producing an arylamine according to claim 1, wherein the degree of vacuum is 70 to 10 kPa .   The method for producing an arylamine according to claim 1 or 2, wherein the reaction is carried out while introducing an inert gas.