JPH11130738A - Production of arylamine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject high purity compound, especially a triarylamine or diarylamine, in high yield, by reacting an aromatic amine with an aromatic halide in the presence of a specified catalyst in a specified solvent. SOLUTION: This compound is obtained by reacting (A) an aromatic amine with (B) an aromatic halide in the presence of (C) a catalyst containing copper element (e.g. copper sulfate), in 250-450 mL solvent having 8.0-9.0 eV ionization potential, preferably a terpene (e.g. terpinolene, based on one mole component A. The objective compound is such a compound as represented by formula I to formula III [R1 and R2 are each a substituent having -0.34 to 0.71 Hammett's σm and -0.84 to 0.78 Hammett's σp, or the like; (n) is 1-3; A is a group bound at any position of the aromatic ring of a compound represented by formula IV or formula V (R3 and R4 are each a substituent having -0.15 to 0.43 Hammett's σm and -0.32 to 0.54 Hammett's σp)].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention provides a method for producing an arylamine, particularly a triarylamine or a diarylamine, useful as a material for electronic materials or an intermediate thereof, with high purity and high yield.

[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, chlorobenzene, or nitrobenzene, or a saturated aliphatic hydrocarbon compound such as decane or tridecane has been used. However, in order to achieve a practical arylation rate in this reaction, a considerably high temperature is usually required, which has a disadvantage that by-product compounds are formed by oxidation of substituents or dimerization of products. is there. However, it is very difficult to separate and purify this by-product compound, and if it is attempted to purify it to the high purity required for use as a material for electronic materials or as an intermediate thereof, the yield is low, and the cost is high, and practicality is high. Did not.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a high-purity arylamine, particularly a triarylamine or diarylamine, which does not have the above-mentioned problems, in a high yield. is there.

[0004]

The above objects of the present invention are as follows.
(1) A method for producing 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 catalyst containing copper element, 2) The reaction solvent has an ionization potential of 8.0.
It is achieved by the method for producing an arylamine according to the above (1), which is a terpene of from 9.0 to 9.0 eV.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail. In the present invention, when an arylamine, particularly a group of triarylamines or diarylamines useful as materials for electronic materials or intermediates thereof, is produced by an Ullmann condensation reaction, the ionization potential is 8.0 to 9.0 eV, preferably 8.0.
By using a reaction solvent of 5 to 9.0 eV, a highly pure target compound is obtained in a high yield. Furthermore, it has been found that the effect is remarkable especially when terpenes are used as a reaction solvent.

As the above-mentioned reaction solvent which can be used in the present invention, any solvent having an ionization potential of 8.0 to 9.0 eV can be used, and terpene is particularly preferable. Terpenes are compounds that are commonly used 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-menten, (+)-3-p-menten, dipentene, (+)-
Limonene, (+)-sabinene, (+)-α pinene,
Monoterpene compounds such as (+)-β-pinene,
(−)-Β-kadinene, (−)-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, graniol, (+)-citronellol, nerol, (+)-linalool, cis-citral, trans-citral, (+) citronellal,
(+) Isomenthol, (+)-cis-carveol,
(+)-Trans-carveol, (-)-carbomenthol, (+)-dihydrocarbeol, (+)-α-terpineol, trans-β-terpineol, γ-terpineol, (+)-1-p-menten -4-ol,
(-)-Menthol, trans-1,4-terpine, cis
-1,8-terpine, (+)-trans-sobrelol,
(-)-Isopulegone, (+)-isomentone, carbenone, (+)-carbotanacetone, (-)-carbomentone, (+)-carvone, (-)-dihydrocarvone,
Monoterpenes such as (−)-piperitone, (+)-pulegone, (−)-menthone, diosphenol, α-tujon, sesquiterpenes such as farnesol and (+)-nerolidol are also included.

In the present invention, the ionization potential is a value representing a first ionization potential by photoelectron spectroscopy, and is a photoelectron spectrum method obtained from a kinetic energy distribution of photoelectrons generated by photoionization, and a series of emission or absorption spectra in a vacuum ultraviolet region. It can be measured by a vacuum ultraviolet absorption method or the like determined from the edge measurement. When a reaction solvent having an ionization potential lower than 8.0 eV is used , the reaction solvent, raw materials, and products may react with each other.
When a higher reaction solvent is used, purification by purification is difficult due to an increase in by-product impurities, and the intended purpose cannot be achieved. These reaction solvents are usually used in a ratio of 250 to 450 ml per 1 mol of the aromatic amine as a raw material. The catalyst used in the present invention is not particularly limited, and a catalyst generally used in an Ullmann condensation reaction can be used.For example, copper powder, copper sulfate, cuprous oxide,
Cupric oxide, cuprous chloride, cupric chloride, cupric acetate, cupric hydroxide, cuprous bromide, cupric bromide, copper iodide, etc., preferably copper sulfate, bromide Cupric. Although the reaction varies greatly depending on the raw materials used, it is usually 190 to 210.
C. for 6-12 hours.

As the arylamine produced in the present invention, for example, the following general formula (I), (II) or (II)
The triarylamine or diarylamine represented by I) can be mentioned.

[0009]

Embedded image

In the formula, R1 and R2 are expressed as Hammett's σm−
A substituent from 0.34 to 0.71;
And represents a substituent from 4 to 0.78, R1 and R2 may be the same or different, and each may be substituted plurally. n shows the integer of 1-3. A represents a group bonded at an arbitrary position of the aromatic ring of the compound represented by the following general formula.

[0011]

Embedded image

In the formula, R3, R4, and R5 are substituents from -0.15 to 0.43 as Hammett's σm, and -0.
And represents a substituent from 32 to 0.54, which may be bonded at any position of the aromatic ring. Where Hammett's σm is-
Specific examples of the substituent from 0.34 to 0.71 include an alkyl, cycloalkyl, aryl, alkoxy, amino, nitro group, and a halogen atom. Specific examples of the substituent up to, for example, alkyl, alkoxy, amino,
Examples thereof include a nitro group and a halogen atom. Also, σ
Specific examples of the substituent for m as -0.15 to 0.43 include alkyl, cycloalkyl, aryl,
Alkoxy, etc., as σp of -0.32-
Specific examples of the substituent up to 0.54 include an alkyl, cycloalkyl, aryl, alkoxy, and halogen atom.

Formula (I), (II) or (II)
The following can be exemplified as specific examples of I).

[0014]

Embedded image

[0015]

Embedded image

[0016]

Embedded image

[0017]

Embedded image

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image

[0021]

Embedded image

In the present invention, the aromatic amine used for producing the arylamine, particularly the above-mentioned triarylamine or diarylamine, is the same as the above-mentioned general formula (I), (II) or (III) except for A. Amine obtained by the above method. As the aromatic halide, a halide of a compound corresponding to A in the above general formula (I), (II) or (III), usually iodide, is used. ~ 3 equivalents, preferably 1.1 ~
1.9 equivalents are used.

[0023]

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 (HPL).
C).

Example 1 Tri (4-methylphenyl)
Synthesis of Amine (I-1) Di (4-methylphenyl) amine 70.0 g (0.36
Mol), 100.0 g (0.46 mol) of p-iodotoluene, 70.0 g (0.50 mol) of potassium carbonate, 5.0 g (0.02 mol) of copper sulfate pentahydrate, terpinolene (ionization potential 8.98) 150 ml of the mixture was reacted at 200 to 210 ° C. for 6 hours under a nitrogen stream. After the reaction, 150 ml of toluene and 150 ml of water were added to carry out liquid separation. After distilling off toluene by concentration under reduced pressure, ethyl acetate 3
55 ml and methanol 2483 ml were added for crystallization, and the target compound (I-1) was obtained as white crude crystals.
9 g (94.5% yield) was obtained. Melting point 116-117 °
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 ml / min) was 99.5%. Elemental analysis value Calculated value (%) C: 87.72 H: 7.36 (as C ₂₁ H ₂₁ N) Actual value (%) C: 87.75 H: 7.34

Example 2 Synthesis of N, N, N ', N'-tetra (3-methylphenyl) -9,10-diaminophenanthrene (I-11) 9,10-di (3-methylanilino) phenanthrene 6
6.0 g (0.17 mol), m-iodotoluene 11
0.7 g (0.51 mol), 93.6 g of potassium carbonate
(0.68 mol), a mixture of 1.8 g (0.008 mol) of cupric bromide and 74 ml of α-terpinene in a nitrogen stream 2
The reaction was performed at 00 to 210 ° C for 10 hours. After the reaction, the reaction solvent was distilled off by concentration under reduced pressure, 45 ml of toluene, 666 ml of ethyl acetate, and 222 ml of water were added. After liquid separation, 708 ml of methanol was added for crystallization, and the target compound (I- 9) (94.1 g, yield 97.3)
%)Obtained. Melting point 223-224 ° C, HPLC content (column YMC-A-312, eluent methanol / tetrahydrofuran (abbreviated as THF)) (V / V = 99 /
1), detection UV: 254 nm, flow rate: 1.0 ml / min)
Was 99.6%. Elemental analysis value Calculated value (%) C: 88.69 H: 6.38 (as C ₄₂ H ₃₆ N ₂ ) Actual value (%) C: 88.72 H: 6.36

Examples 3 and 4, Comparative Examples 1 and 2 The same reaction as in Example 2 was carried out using the solvents shown in Table 1 below in place of α-terpinene used in Example 2, and the desired compound (I- 11) was synthesized. The same operation was performed except that the reaction solvent was changed, and the purity was evaluated by HPLC. Table 1 shows the results.

[0027]

[Table 1]

As is clear from Table 1, when a terpene compound is used as a reaction solvent as compared with a saturated aliphatic hydrocarbon compound or an aromatic compound which has been conventionally used as a reaction solvent, a higher purity target is obtained. The compound was obtained.

[0029]

As is apparent from the above examples, according to the present invention, arylamines, particularly triarylamines or diarylamines, which are useful as materials for electronic materials and intermediates thereof, are produced with high purity and high yield. can do.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C07B 61/00 300 C07B 61/00 300

Claims (2)

[Claims] 1. A process for producing 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 catalyst containing copper element. . 2. The reaction solvent has an ionization potential of 8.0 to 9.0.
The method for producing an arylamine according to claim 1, wherein the terpene is an eV.