JPH11199549A - Production of arylamine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject high-purity compound such as a triarylamine useful as a material for electronic materials or its intermediate at a low cost by reacting an aromatic amine with an aromatic halide in the presence of a copper-containing catalyst and a cyclic nitrogen-containing compound in a specific solvent. SOLUTION: (A) An aromatic amine such as diphenylamine is reacted with (B) an aromatic halide such as m-iodotoluene in the presence of (D) a copper- containing catalyst such as copper sulfate and (E) a cyclic nitrogen-containing compound such as picolinic acid in (C) a solvent having 8.0-9.0 eV ionization potential such as terpinolene. The reaction is usually carried out preferably in a nitrogen stream preferably at 200-210 deg.C for 1.5-3 hr by usually using 250-450 mL component C based on 1 mol component A, preferably using 0.001-0.005 mol component D based on 1 mol component B and preferably using 0.5-2.0 mol component E based on 1 mol component D. Thereby, the objective compound such as 3-methyltriphenylamine is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a material for electronic materials,
Alternatively, the present invention relates to a method for producing an arylamine, particularly a triarylamine or diarylamine, useful as an intermediate thereof, with high purity and low cost.

[0002]

BACKGROUND OF THE INVENTION The reaction of the present invention is included in the category of reactions classified as Ullmann condensation reaction. The Ullmann condensation reaction is a reaction for coupling an aromatic amine with an aromatic halogen compound, preferably an aromatic iodide compound in the presence of a base and a copper catalyst. Ullmann (Chem.
Ber. , 36 , 2382 (1902)). Conventionally, as a solvent in this reaction, an aromatic compound having an ionization potential of 9.1 eV or more, such as alkylbenzene, halogenobenzene, or nitrobenzene, or a saturated aliphatic hydrocarbon compound such as decane or tridecane has been used. As means for accelerating the reaction, cyclic nitrogen-containing compounds such as pyridines and quinolines are used as reaction solvents (for example, Tetrahedro).
n Lett. , 4531 (1965), Tetrah
edron Lett. 679 (1966)).

[0003]

However, the former reaction using an aromatic compound or a saturated aliphatic hydrocarbon compound as a solvent generally has a long reaction time and requires a practical aryl acceleration. Has a drawback that by-products are generated due to oxidation of a substituent, a dimerization reaction of a product, and the like because a considerably high temperature is required. Further, the latter method using a cyclic nitrogen-containing compound still does not solve the problem of formation of by-products. In addition, it is very difficult to separate and purify this by-product, and if it is used as a material for electronic materials or as an intermediate thereof, it is difficult to purify it with high purity, and the yield is reduced. was there. An object of the present invention is to provide a novel method for producing high-purity arylamines, particularly triarylamines or diarylamines, without the above-mentioned problems at low cost.

[0004]

The above objects of the present invention are as follows.
(1) An arylamine comprising reacting an aromatic amine with an aromatic halide in a solvent having an ionization potential of 8.0 to 9.0 eV in the presence of a copper-containing catalyst and a cyclic nitrogen-containing compound. The method for producing an arylamine according to (1), wherein the cyclic nitrogen-containing compound is a compound represented by the following general formula (1), (2) or (3). Achieved by

[0005]

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In the formula, N represents a nitrogen atom or an N-oxide (N → O), and Y represents an atomic group necessary for a component containing Y to form a 5- or 6-membered ring. R1 is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an aralkyloxy group,
Hydroxy group, oxo group, hydroperoxy group, carboxyl group, formyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, carbamoyl group, carboxyloxy group, acyloxy group, arylcarbonyloxy group, aralkylcarbonyl Oxy group, hydroxyalkyl group,
Carboxyalkyl group, acylalkyl group, nitro group,
Hydroxyamino group, alkylamino group, acylamino group, carboxylamino group, arylamino group, aralkylamino group, imino group, alkylimino group, hydroxyimino group, aldoxime group, cyano group, cyanate group, isocyanate group, thiocyanate group, Isothiocyanate group, mercapto group, furyl group, furfuryl group,
Represents a furoyl group, a thienyl group, a thenyl group, a thenoyl group, a pyridyl group, or a quinolyl group. R2 is Hammett's σm
Represents a substituent from -0.34 to 0.71 and? P represents a substituent from -0.84 to 0.73. k and m each represent an integer of 1 to 3. Each of the plurality of R1 or R2 may be the same or different.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail. The present invention relates to the production of arylamines, particularly a group of triarylamines or diarylamines useful as materials for electronic materials or intermediates thereof, by the Ullmann condensation reaction, with an ionization potential of 8.0 to 9.0 eV, preferably 8.5. ~
By using a cyclic nitrogen-containing compound as a catalyst and a cocatalyst containing a copper element in a reaction solvent of 9.0 eV, the reaction can be completed in a short time, and the desired compound can be obtained with high purity and low cost. .

As the reaction solvent usable in the present invention, any solvent having an ionization potential of 8.0 to 9.0 eV can be used, and terpenes are particularly preferable. Terpenes are compounds generally used widely as raw materials for medicines and perfumes. Here, terpenes include ocimene, myrcene, α-terpinene, β-terpinene, γ-
Terpinene, terpinolene, (+)-α-pherandrene, (−)-β-pherandrene, (−)-1-p-menthen, (+)-3-p-menthen, dipentene,
Monoterpene compounds such as (+)-limonene, (+)-sabinene, (+)-α-pinene, (+)-β-pinene, (−)-β-cadinene, (−)-β-caryophyllene, (−)-Β-santalen, (−)-α-sedren,
(+)-Β-selinene, (−)-β-bisabolene, α-
Sesquiterpene compounds such as humulene,
In particular, terpinenes, terpinolene, and ferrandrene are effective.

Further, geraniol, (+)-citronellol, nerol, (+)-linalool, cis-citral, trans-citral, (+)-citronellal,
(+)-Isomenthol, (+)-cis-carbeol, (+)-trans-carbeol, (-)-carbomenthol, (+)-dihydrocarbeol, (+)-α
-Terpineol, trans-β-terpineol, γ-
Terpineol, (+)-1-p-menthen-4-ol, (−)-menthol, trans-1,4-terpin, c
is-1,8-terpine, (+)-trans-sobrelol, (−)-isopulegone, (+)-isomentone, carbenone, (+)-carbontanacetone, (−)-carbomentone, (+)-carvone, ( -)-Dihydrocarbon, (-)-piperitone, (+)-pulegone, (-)-
Monoterpenes such as menthone, diosphenol and α-tsujon, sesquiterpenes such as farnesol and (+)-nerolidol are also included.

In the present invention, the ionization potential is a value representing the first ionization potential obtained by photoelectron spectroscopy, and is a photoelectron spectrum method obtained from the kinetic energy distribution of photoelectrons generated by photoionization. Can be measured by a vacuum ultraviolet absorption method or the like determined from the measurement of When a reaction solvent having an ionization potential lower than 8.0 eV is used, the reaction solvent, the raw material, and the product may react with each other.
When a higher reaction solvent is used, the progress of the reaction is slow, and the by-product of impurities increases, making purification difficult, and the intended purpose cannot be achieved. In the present invention, the reaction solvent is usually from 250 to 4 based on 1 mole of the aromatic amine as the raw material.
Used at a rate of 50 ml.

The catalyst containing copper element used in the present invention is not particularly limited, and a catalyst usually used in Ullmann condensation reaction can be used.
Cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, copper iodide, cuprous oxide, cupric oxide, copper acetate, copper sulfate, copper nitrate, copper carbonate, hydroxide Cupric or the like, preferably cupric bromide,
Copper iodide and copper sulfate are exemplified. In the production method of the present invention, the use amount of the catalyst containing the copper element is preferably 0.0005 to 1 mol of the aromatic halide.
0.01 mol is preferred, and more preferably 0.001 to
0.005 mol.

The cyclic nitrogen-containing compound used as a co-catalyst in the present invention is preferably at least one of the compounds represented by the above general formulas (1), (2) and (3). The above general formulas (1), (2) and (3)
The 5-membered ring formed by the component containing Y in
Furan ring, thiophene ring, pyrrole ring, pyrazole ring,
Examples include an imidazole ring and the like, and examples of the 6-membered ring include a benzene ring, a cyclohexane ring, and a pyridine ring.

The alkyl group for R1 is methyl,
phenyl, naphthyl, etc. as an aryl group, benzyl, etc. as an aralkyl group, methoxy, ethoxy, etc., as an alkoxy group, phenoxy, naphthyloxy, etc., as an aryloxy group, benzyloxy, etc. as an aralkyloxy group. An acyl group such as acetyl and benzoyl; an alkoxycarbonyl group such as methoxycarbonyl and n-butoxycarbonyl; an aryloxycarbonyl group such as phenoxycarbonyl; an aralkyloxycarbonyl group such as benzyloxycarbonyl; and an acyloxy group such as acetyl. Oxy, benzoyloxy, etc .; arylcarbonyloxy groups such as phenylcarbonyloxy; aralkylcarbonyloxy groups such as benzylcarbonyloxy; Hydroxymethyl The group,
Hydroxyethyl and the like; carboxyalkyl groups such as carboxymethyl and carboxy-n-propyl; acylalkyl groups such as benzoylmethyl; alkylamino groups such as dimethylamino and ethylamino; acylamino groups such as acetylamino; arylamino; Examples of the group include phenylamino and the like, examples of the aralkylamino group include benzylamino and the like, and examples of the alkylimino group include methylimino and the like. Preferably, R1 is a carboxyl group, a carbamoyl group, a cyano group or a nitro group.

The Hammett's σm at R2 is −0.
Specific examples of the substituent from 34 to 0.71 include an alkyl group such as methyl and t-butyl, cyclopentyl,
Cycloalkyl groups such as cyclohexyl, phenyl, aryl groups such as naphthyl, methoxy, alkoxy groups such as ethoxy, amino, amino groups such as dimethylamino, nitro groups, or chlorine atoms, halogen atoms such as bromine atoms, and the like. Specific examples of the substituent from -0.84 to 0.73 as σp include alkyl groups such as methyl and t-butyl, alkoxy groups such as methoxy and ethoxy, amino,
Examples include an amino group such as dimethylamino, a nitro group, or a halogen atom such as a chlorine atom or a bromine atom.

Specific examples of the compounds represented by the general formulas (1), (2) and (3) include γ-picoline, 2,4-lutidine, 2,4,6-collidine, picolinic acid, quinolinic acid, 2-pyridylacetic acid, pyridine-2-aldoxime, pyridine-2-aldehyde, 2-pyridinemethanol, 2-pyridineethanol, 2-hydroxypyridine, 2-cyanopyridine, quinoline, quinaldine, 4-
Methylquinoline, 8-quinolinol, quinaldic acid,
2,2′-bipyridyl, 1,10-phenanthroline,
Imidazole, imidazole-5 (4) -acetic acid, 4,5
-Dicyanoimidazole, etc., and picolinic acid, quinolinic acid and 2,2′-bipyridyl are particularly effective.

The advantage of using a cyclic nitrogen-containing compound as a co-catalyst is that the reaction can be completed in a short time by selecting an optimum co-catalyst from the raw materials to be used. 0.1-6.0 to mole
Moles are preferred, more preferably 0.5 to 2.0 moles are used.

The reaction varies depending on the starting materials and the cocatalyst used, but is usually at 190 to 210 ° C. for 1 to 4 hours, preferably 2 to 4 hours.
The reaction is performed at 00 to 210 ° C. for 1.5 to 3 hours. In order to prevent the formation of by-products and to produce high-purity arylamine, the reaction is desirably performed in an inert gas atmosphere, particularly in a nitrogen stream. As the arylamine produced in the present invention, for example, a triarylamine or a diarylamine represented by the following general formula (I), (II) or (III) can be mentioned.

[0018]

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In the formula, R3 and R4 are substituents from -0.34 to 0.71 as Hammett's σm, and -0.
84 to 0.73, and a plurality of R3 or R3
Each of 4 may be the same or different, and two of each of a plurality of R3 or R4 may be bonded to each other to form a ring. n represents an integer of 1 to 3, and p or q represents an integer of 1 to 4, respectively. A represents an n-valent group that forms a bond at an arbitrary position of the aromatic ring of the compound represented by the following general formula.

[0020]

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In the formula, R5, R6, and R7 each independently represent a substituent having a Hammett's σm of -0.15 to 0.43 and a σp of -0.32 to 0.54, It may be bonded at any position of the aromatic ring. r, s, and t each represent an integer of 1 to 5.

The ring formed by bonding two of R3 or R4 to each other is a cyclohexyl ring,
And a benzene ring. Here, specific examples of the substituent having a Hammett σm of −0.34 to 0.71 include alkyl groups such as methyl and t-butyl, cycloalkyl groups such as cyclopentyl and cyclohexyl, and alkenyl groups such as a vinyl group. Group, phenyl, aryl groups such as naphthyl, methoxy, alkoxy groups such as ethoxy, amino,
Examples thereof include an amino group such as dimethylamino, a nitro group, and a halogen atom such as a chlorine atom and a bromine atom. Specific examples of the substituent having? P of -0.84 to 0.73 include methyl, t- Examples include an alkyl group such as butyl, an alkenyl group such as a vinyl group, an alkoxy group such as methoxy and ethoxy, an amino group such as amino and dimethylamino, a nitro group, and a halogen atom such as a chlorine atom and a bromine atom. Specific examples of the substituent from -0.15 to 0.43 as σm include alkyl groups such as methyl and t-butyl, cycloalkyl groups such as cyclopentyl and cyclohexyl, aryl groups such as phenyl and naphthyl, methoxy, Alkoxy groups such as ethoxy and the like are mentioned. Specific examples of the substituent having a σp of -0.32 to 0.54 include alkyl groups such as methyl and t-butyl, cycloalkyl groups such as cyclopentyl and cyclohexyl, and phenyl. ,
Examples include an aryl group such as naphthyl, an alkoxy group such as methoxy and ethoxy, and a halogen atom such as a chlorine atom.

Specific examples represented by the general formulas (I), (II) and (III) include the following.

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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In the present invention, the aromatic amine used for producing the arylylamine, particularly the above-mentioned triarylamine or diarylamine, may be substituted for A in the above-mentioned general formula (I), (II) or (III). An amine having a hydrogen atom (here, n represents 1) may be mentioned. Further, as the aromatic halogen compound, a halide of a compound corresponding to A in the above general formula (I), (II) or (III), usually iodide, is used.
Usually, a halide is used in an amount of 0.3 to 4.0 equivalents, preferably 0.9 to 2.0 equivalents, based on the aromatic amine.

[0031]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The purity was evaluated by high performance liquid chromatography (HPLC
(Abbreviated).

Example 1 Synthesis of 3-methyltriphenylamine (I-1) Diphenylamine 20.3 g (0.12 mol), m-iodotoluene (0.12 mol), potassium carbonate 32.6
g (0.24 mol), 0.27 g of copper sulfate pentahydrate (0.
001 mol), 0.12 g of picolinic acid and 32 ml of terpinolene (ionization potential: 8.98 eV) were reacted at 200 to 210 ° C. for 1.5 hours under a nitrogen stream. After the reaction, 66 ml of toluene and 66 ml of water are added. After liquid separation, the toluene is concentrated under reduced pressure. 39 ml of ethyl acetate and 243 ml of methanol were added for crystallization, and 29.9 g (yield: 96.1%) of the target compound (I-1) was obtained as pale yellow crude crystals.
Obtained. Melting point 69-70 ° C HPLC content (column YMC-A-312, eluent
Methanol / tetrahydrofuran (abbreviated as THF) (V
/ V = 99/1), detection UV 300 nm, flow rate 1.0 m
1 / min) was 99.6% (purity). Elemental analysis value Calculated value (%) C: 87.99 H: 6.61 (as C ₁₉ H ₁₇ N) Observed value (%) C: 88.02 H: 6.59

Example 2 N, N'-diphenyl-N,
Synthesis of N′-di (3-methylphenyl) -1,4-phenylenediamine (I-3) N, N′-diphenyl-p-phenylenediamine
09 g (0.25 mol), m-iodotoluene 26.1
6 g (0.12 mol), 65.1 g of potassium carbonate (0.
47 mol), 0.54 g (0.002 mol) of copper sulfate pentahydrate, 0.25 g (0.002 mol) of picolinic acid, and 32 ml of terpinolene in a nitrogen stream at 200 to 210 mol.
The reaction was carried out at 3 ° C. for 3 hours. After the reaction, 66 ml of toluene and 66 ml of water are added. After liquid separation, the toluene is concentrated under reduced pressure. Ethyl acetate (39 ml) and IPA (253 ml) were added for crystallization, and the target compound (I-3) was obtained as pale yellow crude crystals.
2 g (95.0% yield) was obtained. 170-171 ° C
HPLC content (column YMC-A-002, eluent
Hexane / THF (95/5), detection UV 310m
1, flow rate 1.1 ml / min) is 99.4% (purity)
Met. Elemental analysis value Calculated value (%) C: 87.23 H: 6.41 (as C ₃₂ H ₂₈ N ₂ ) Actual value (%) C: 87.27 H: 6.43

Comparative Examples 1, 2, and 3 Using terpinolene used in Example 2 or a solvent shown in Table 1 below, the same reaction as in Example 2 was carried out to synthesize a target compound (I-3). The procedure was exactly the same except that the reaction solvent type and the presence or absence of the cocatalyst were changed, and the purity and yield were evaluated by HPLC. Table 1 shows the results.

[0035]

[Table 1]

As is clear from Table 1, when a reaction solvent having an ionization potential of 8.0 to 9.0 eV is used as compared with a saturated aliphatic hydrocarbon compound or an aromatic compound conventionally used as a reaction solvent. The reaction was remarkably accelerated by the addition of a cyclic nitrogen-containing compound, and a higher purity target compound was obtained.

[0037]

As is clear from the above Examples and Comparative Examples, the present invention produces arylamines, particularly triarylamines or diarylamines, useful as materials for electronic materials or intermediates thereof, with high purity and low cost. be able to.

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Claims (2)

[Claims] 1. An aryl, comprising reacting an aromatic amine with an aromatic halide in a solvent having an ionization potential of 8.0 to 9.0 eV in the presence of a copper-containing catalyst and a cyclic nitrogen-containing compound. Method for producing amine. 2. The cyclic nitrogen-containing compound is represented by the following general formula (1):
The method for producing an arylamine according to claim 1, which is a compound represented by (2) or (3). Embedded image In the formula, N represents a nitrogen atom or an N-oxide (N → O), and Y represents an atomic group necessary for a component containing Y to form a 5- or 6-membered ring. R1 is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group,
Aryloxy group, aralkyloxy group, hydroxy group, oxo group, hydroperoxy group, carboxyl group,
Formyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, carbamoyl group, carboxyloxy group, acyloxy group, arylcarbonyloxy group, aralkylcarbonyloxy group, hydroxyalkyl group, carboxyalkyl group, acylalkyl Group, nitro group, hydroxyamino group, alkylamino group, acylamino group, carboxylamino group, arylamino group, aralkylamino group, imino group, alkylimino group, hydroxyimino group, aldoxime group, cyano group, cyanate group, isocyanate Group, thiocyanate group, isothiocyanate group, mercapto group, furyl group, furfuryl group, furoyl group, thienyl group, thenyl group, tenoyl group, pyridyl group,
Or a quinolyl group. R2 is Hammett's σm −
A substituent from 0.34 to 0.71;
Represents a substituent from 4 to 0.73. k and m are each 1 to 3
Represents an integer. Each of the plurality of R1 or R2 may be the same or different.