JPH10316690A - Aniline derivative having silicon substituent at ortho position and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound containing a silicon substituent at the ortho position and industrially useful as a raw material for synthesizing dyestuffs, medicines, etc. SOLUTION: A compound of formula I (R<1> -R<3> are each a 1-10c monovalent hydrocarbon; R<4> is H, a silicon-containing group of the formula: R<1> R<2> R<3> Si, a 1-10C monovalent hydrocarbon), e.g. 2-(trimethylsilyl) aniline. The compound of formula I is obtained e.g. by reacting a halogenated compound of formula II (X is a halogen) with an alkali(ne earth) metal as such or an organic metal compound (e.g. a Grignard reagent) obtained therefrom usually at -100 to 100 deg.C for 30 min to 50 hr, and subsequently removing the R<1> R<2> R<3> Si group and M bound to the nitrogen atom of the obtained compound of formula III by a solvolysis reaction. In the solvolysis reaction, a protonic solvent such as water or an alcohol is effectively used. The reaction is preferably carried out in a neutral or basic condition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel compound useful as a raw material for organic synthesis, an aniline derivative having a silicon substituent at the ortho position, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Aniline is an industrially important compound that is widely used as a raw material for synthesizing dyes, pharmaceuticals, fungicides, metal complex ligands and the like. In addition, many derivatives having various substituents on the benzene ring have been synthesized so far, and if these derivatives are used as a raw material for synthesis, it is possible to change variously the physical properties of the obtained compound.

[0003] Silicon can be used as the substituent, and aniline derivatives having a trimethylsilyl group at the para-position are known. However, when the substituent is introduced, the aniline derivative is most likely to be changed at the ortho-position. An aniline derivative having a silicon substituent is not known. As a method for synthesizing such an aniline derivative having a silicon substituent at the ortho position, an aniline compound having a substituent (protecting group) at the amino group and a silicon substituent at the ortho position is synthesized, and then the amino group is substituted. A method of removing the group (protecting group) can be considered. Examples of such an aniline compound having a substituent (protecting group) in the amino group and a silicon substituent in the ortho position include, for example, European Patent Publication No. 538231. The publication describes a synthesis example of a phenylcarbamate having a trimethylsilyl group at the ortho position. However, it is known that the silicon substituent bonded to the benzene ring is easily cleaved by an electrophile such as a proton. Therefore, it is difficult to use amine protecting groups such as carbamates and amides used for orthotrithiolation, which generally require deprotection by hydrolysis under strong acidic conditions. Further, in the same document, description of the synthesis of phenyl isocyanate having a trimethylsilyl group at the ortho position is also found. Although it is conceivable that an aniline derivative can be obtained by alkaline hydrolysis of this isocyanate, it is not the best method because the number of steps is large and isocyanates are generally toxic.

As described above, aniline derivatives having a silicon substituent at the ortho-position are industrially useful, but are not known at all at present, and have a substituent (protecting group) on the above-mentioned known amino group. Since it is difficult to synthesize from an aniline compound having a silicon substituent at the ortho position, its development and construction of a simple production method have been expected.

Accordingly, an object of the present invention is to provide an aniline derivative having a silicon substituent at the ortho position which is industrially useful as a raw material for synthesizing dyes and pharmaceuticals, and to provide a simple method for producing the aniline derivative. .

[0006]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, have found that a silicon substituent at the ortho position represented by the following general formula (1): Have been found. Further, as a production method thereof, a simple substance of an alkali metal or an alkaline earth metal, or an organometallic compound obtained therefrom is allowed to act on a halogen compound represented by the following general formula (2) to obtain a compound represented by the following general formula (3) After converting into the compound represented by the formula, a method was found in which R ¹ R ² R ³ Si— and M bonded to the nitrogen atom were removed by solvolysis.

[0007]

Embedded image (Wherein, R ¹ , R ² , and R ³ may be the same or different and are each selected from a monovalent hydrocarbon group having 1 to 10 carbon atoms. R ⁴ is a hydrogen atom, R ¹ R ² R It is a silicon-containing group represented by ³ Si- or a monovalent hydrocarbon group having 1 to 10 carbon atoms.)

[0008]

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are the same as R 1 in the formula (1))
^It represents the same as ¹ , R ² , R ³ , and R ⁴ . X represents a halogen atom. )

[0009]

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are the same as R 1 in the formula (1))
^It represents the same as ¹ , R ² , R ³ , and R ⁴ . M represents an alkali metal atom or an alkaline earth metal atom. n is a metal atom M
Is an integer of valence-1. )

Accordingly, the present invention provides an aniline derivative having a silicon substituent at the ortho position represented by the above general formula (1) and a halogen compound of the above general formula (2), wherein an alkali metal or an alkaline earth metal is added. After reacting with a simple substance or an organometallic compound obtained therefrom to convert to a compound represented by the above general formula (3), R ¹ R ² R ³ Si— and M bonded to a nitrogen atom are solvolyzed. A process for producing an aniline derivative having a silicon substituent at the ortho-position of the above formula (1), which is characterized by comprising:

Hereinafter, the present invention will be described in more detail.
The aniline derivative having a silicon substituent at the ortho position according to the present invention is represented by the following general formula (1).

[0012]

Embedded image

In the formula (1), R ¹ , R ² and R ³ may be the same or different from each other, and each has 1 to 1 carbon atoms.
0 is selected from monovalent hydrocarbon groups. R ¹ , R ² , and R ³ are methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n -Pentyl, isopentyl, 1-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, cyclopentyl, n-hexyl, texyl, cyclohexyl, n-heptyl, cycloheptyl, n -Octyl group, cyclooctyl group, n-nonyl group, n-decyl group, phenyl group, o-tolyl group, m-
Tolyl group, p-tolyl group, 2,6-dimethylphenyl group, 2,5-dimethylphenyl group, 2,4-dimethylphenyl group, 2,3-dimethylphenyl group, 3,4-dimethylphenyl group, 3, Examples include a 5-dimethylphenyl group, a mesityl group, a 1-naphthyl group, and a 2-naphthyl group. That is, the compound of formula (1) has a bulky silicon substituent at the ortho position of the amino group.

Specific examples of the silicon substituent represented by R ¹ R ² R ³ Si— include trimethylsilyl, ethyldimethylsilyl, n-propyldimethylsilyl, isopropyldimethylsilyl, and cyclopropyldimethylsilyl. , N-butyldimethylsilyl group, isobutyldimethylsilyl group, sec-butyldimethylsilyl group, te
rt-butyldimethylsilyl group, cyclobutyldimethylsilyl group, n-pentyldimethylsilyl group, isopentyldimethylsilyl group, (1-methylbutyl) dimethylsilyl group, (1-ethylpropyl) dimethylsilyl group,
(1,1-dimethylpropyl) dimethylsilyl group, cyclopentyldimethylsilyl group, n-hexyldimethylsilyl group, texyldimethylsilyl group, cyclohexyldimethylsilyl group, n-heptyldimethylsilyl group, cycloheptyldimethylsilyl group, n- Octyldimethylsilyl, cyclooctyldimethylsilyl, n-nonyldimethylsilyl, n-decyldimethylsilyl, diethylmethylsilyl, di-n-propylmethylsilyl, di-n-butylmethylsilyl, dicyclo Propylmethylsilyl group, triethylsilyl group, phenyldimethylsilyl group, o-tolyldimethylsilyl group, m-tolyldimethylsilyl group, p-tolyldimethylsilyl group, 2,
6-dimethylphenyldimethylsilyl group, 2,5-dimethylphenyldimethylsilyl group, 2,4-dimethylphenyldimethylsilyl group, 2,3-dimethylphenyldimethylsilyl group, 3,4-dimethylphenyldimethylsilyl group, 3, Examples thereof include a 5-dimethylphenyldimethylsilyl group, a mesityldimethylsilyl group, a 1-naphthyldimethylsilyl group, and a 2-naphthyldimethylsilyl group.

R ^{4 in the} formula (1) is a substituent on the benzene ring, and is a hydrogen atom, a silicon-containing group represented by R ¹ R ² R ³ Si—, or a monovalent hydrocarbon having 1 to 10 carbon atoms. Selected from among the groups. Examples of the monovalent hydrocarbon group include the same as those exemplified above. R ⁴ is particularly preferably a hydrogen atom or R ¹ R ² R ³ Si—.

Next, the method for producing the compound of the formula (1) of the present invention will be described in detail. First, a halogen compound of the following general formula (2) is added to a simple substance of an alkali metal or an alkaline earth metal, or an alkali metal or an alkali metal. Step A of converting an organometallic compound obtained from an earth metal, for example, an organolithium reagent or a Grignard reagent into a compound represented by the following general formula (3), and a nitrogen atom of the compound of the formula (3) B) removing R ¹ R ² R ³ Si— and M bonded to the compound by solvolysis.

[0017]

Embedded image (In the formula, R ¹ , R ² , R ³ , and R ⁴ represent the same as described above.)
X represents a halogen atom, and M represents an alkali metal or an alkaline earth metal. n is an integer of the valence of the metal atom M minus one. )

Here, in the step A, examples of the halogen atom of X include chlorine, bromine, fluorine and iodine. Examples of M include Li, Na, K, and Mg.

As described above, the compound of the formula (3) may be a simple compound of an alkali metal or an alkaline earth metal, or an organic compound represented by an organic lithium reagent or a Grignard reagent, in addition to the halogen compound represented by the formula (2). It can be obtained by allowing a metal reagent to act, but the reaction temperature at this time is usually -100 ° C to 100 ° C, and the reaction time is 30 minutes to 50 hours, and varies depending on the type of metal or metal reagent used. . As a reaction solvent, an ether solvent represented by tetrahydrofuran or diethyl ether, or a mixed solvent of a hydrocarbon solvent represented by hexane, toluene, xylene and the like and an ether solvent can be used.

In the step B, as a solvent used for solvolysis, a protic solvent such as water, a lower alcohol such as methanol or ethanol, or a mixed solvent of water and a lower alcohol is effectively used. The compound of 3) can be converted to the compound of formula (1) by solvolysis using the above-mentioned protic solvent such as water or alcohol. Since the compound of the formula (3) is sensitive to moisture and air and is difficult to isolate, the above-mentioned protic solvent is added to the reaction mixture in the previous step. When the reaction mixture is acidified, the decomposition reaction is accelerated, but the carbon-silicon bond is broken. Therefore, this reaction is preferably performed under neutral or basic conditions. The reaction temperature is usually from 0 to 100 ° C., and the reaction time is from 30 minutes to 10 hours. However, depending on the type of R ¹ , R ² and R ³ , long-time heating may be required.

This solvolysis reaction can be carried out in two steps successively. That is, if the solvolysis is performed under milder conditions, the aniline derivative represented by the following general formula (4) can be isolated. Thereafter, the compound of the formula (1) is obtained by reacting the compound of the formula (4) with a protic solvent under neutral or basic conditions.

[0022]

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are the same as R 1 in the formula (1))
^It represents the same as ¹ , R ² , R ³ , and R ⁴ . )

[0023]

The aniline derivative of the present invention is useful as a raw material for synthesizing dyes and pharmaceuticals, and according to the production method of the present invention, this aniline derivative can be produced efficiently.

[0024]

The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Example 1 Synthesis of 2- (trimethylsilyl) aniline using tert-butyllithium A 500-ml three-necked glass flask equipped with a dropping funnel, a thermometer, and a stirrer was replaced with nitrogen, and 2-bromobis (trimethylsilyl) was added. ) 31.6 g (0.10 mol) of aniline
And 200 ml of tetrahydrofuran. -70 ° C in a dry ice-acetone bath while stirring the contents
And cooled. From a dropping funnel, 118 ml (0.20 mol) of a 1.7 M tert-butyllithium pentane solution was added dropwise at -70 to -61 ° C for 1 hour. The mixture was stirred at −55 ° C. or lower for 4 hours, and the temperature was gradually raised to room temperature. 3.2 g (0.10 mol) of methanol was added to the reaction mixture, and the mixture was stirred at room temperature for 30 minutes, and then the solvent was distilled off with a rotary evaporator. 100 ml of hexane was added to the concentrated solution, and the precipitated salt was removed by filtration. The salt was washed with 100 ml of hexane, and the washing and the filtrate were combined, concentrated by a rotary evaporator, and then distilled under reduced pressure. 21.3 g of a colorless transparent fraction having a boiling point of 72 ° C. at 4 mmHg were obtained. Mass spectrum (E
I, m / z 237 (M ⁺ ), 222 ([M-Me] ⁺ ),
73 (Me ₃ Si ⁺ )), it was confirmed that this liquid was N, 2-bis (trimethylsilyl) aniline.

This liquid was charged into a 100 ml three-necked glass flask equipped with a dropping funnel, a thermometer and a stirrer and purged with nitrogen, and 10 ml of methanol was added to the flask at 22 to 25 ° C. from the dropping funnel while stirring the contents. In minutes. After stirring for 1 hour at 20-25 ° C, the reaction mixture was distilled under reduced pressure. Boiling point 73 to 7 at 2.5 mmHg
13.8 g of a colorless transparent fraction at 5 ° C. was obtained. From the results of nuclear magnetic resonance spectrum, infrared absorption spectrum and mass spectrum, it was confirmed that this liquid was 2- (trimethylsilyl) aniline. The yield was 83.5%.

The ¹ H nuclear magnetic resonance spectrum (C
DCl ₃ solvent) in FIG. 1, ¹³ C nuclear magnetic resonance spectrum (CDCl ₃ solvent) in FIG. 2, also showing the infrared absorption spectrum (NaCl rock salt plate) in FIG. Mass spectrum (EI) m / z: 165 (M ⁺ ), 15
0 ([M-Me] ⁺ )

Example 2 2 using metallic magnesium
Synthesis of-(trimethylsilyl) aniline A 200 ml three-necked glass flask equipped with a dropping funnel, a thermometer, and a stirrer was purged with nitrogen, and 2.8 g of magnesium was added.
(0.116 mol) and 10 ml of tetrahydrofuran
Was charged. While stirring the contents, 2 drops from the dropping funnel.
-Bromobis (trimethylsilyl) aniline 36.6 g
(0.116 mol) in 25 ml of tetrahydrofuran was added dropwise at 5-10 ° C. for 1 hour. 10 ℃
At 20 to 25 ° C. for 40 hours. 30 g of hexane was added to the reaction mixture, and
2.9 g (0.116 mol) was added dropwise over 30 minutes while maintaining the temperature at 40 ° C. or lower. After stirring at room temperature for 30 minutes, the layers were separated, and the organic layer was distilled under reduced pressure. Boiling point 8 at 7 mmHg
12.2 g of a colorless and transparent fraction at 6 to 89 ° C. were obtained. From the results of nuclear magnetic resonance spectrum, infrared absorption spectrum and mass spectrum, it was confirmed that this liquid was 2- (trimethylsilyl) aniline. The yield was 63.6%.

Example 3 Synthesis of 2,6-bis (trimethylsilyl) aniline A 200-ml three-necked glass flask equipped with a dropping funnel, a thermometer, and a stirrer was purged with nitrogen to give 2,6-dibromo-aniline.
N, N-bis (trimethylsilyl) aniline 21.7 g
(0.055 mol) and 55 ml of tetrahydrofuran
Was charged. The contents were cooled to -70 ° C in a dry ice-acetone bath while stirring. Ter from the dropping funnel
t-butyllithium 1.64 M pentane solution 67 ml
(0.11 mol) was added dropwise at -70 to -62 ° C for 1.5 hours. After stirring at -70 ° C for 1 hour and raising the internal temperature to -30 ° C for 1 hour, 6.0 g (0.055 mol) of trimethylchlorosilane was added at -20 ° C from the dropping funnel. The reaction mixture was stirred for 1 hour while gradually raising the temperature to room temperature. According to GC-MS analysis, 2,6-dibromo-
N, N-bis (trimethylsilyl) aniline disappears,
2-bromo-N, N, 6-tris (trimethylsilyl)
It was found that aniline was formed. 50 g of a 10% aqueous ammonium chloride solution was added at room temperature, the layers were separated, and the organic layer was concentrated under reduced pressure to obtain 22.3 g of a brown concentrated solution.

The concentrated solution was added to 55 ml of tetrahydrofuran.
And charged to a 200 ml three-necked glass flask equipped with a dropping funnel, a thermometer, and a stirrer and purged with nitrogen.
While stirring the contents, dry ice in an acetone bath
Cooled to 70 ° C. From a dropping funnel, 67 ml of tert-butyllithium 1.64 M pentane solution (0.11 mol)
l) was added dropwise at -70 to -63 ° C for 1.5 hours. -7
After stirring at 0 ° C. for 30 minutes and raising the internal temperature to −35 to −30 ° C. for 2 hours, 56 g of 3.6% hydrochloric acid was added through a dropping funnel.
(0.055 mol) at 0 ° C. or lower. The reaction mixture was stirred for 30 minutes while gradually raising the temperature to room temperature.
The organic layer was separated and the organic layer was taken out and charged into another 200 ml three-necked glass flask equipped with a reflux condenser, a thermometer, and a stirrer and purged with nitrogen. 1.9 g (0.01 mol) of a 28% sodium methylate methanol solution and 10 g of methanol were added, and the mixture was stirred under heating and reflux for 4 hours. The resulting reaction mixture was distilled under reduced pressure to a boiling point of 93 mm at 3 mmHg.
9.4 g of a clear and colorless fraction at ~ 95 ° C were obtained. From the results of nuclear magnetic resonance spectrum, infrared absorption spectrum and mass spectrum, it was confirmed that this liquid was 2,6-bis (trimethylsilyl) aniline. The yield was 72%.

The ¹ H nuclear magnetic resonance spectrum (C
DCl ₃ solvent) in FIG. 4, ¹³ C nuclear magnetic resonance spectrum (CDCl ₃ solvent) in FIG. 5, also showing the infrared absorption spectrum (NaCl rock salt plate) in FIG. Mass spectrum (EI) m / z: 237 (M ^<+> ), 22
2 ([M-Me] ⁺ ), 206, 74

Example 4 Synthesis of 2- (triethylsilyl) aniline A 200-ml three-necked glass flask equipped with a dropping funnel, a thermometer, and a stirrer was replaced with nitrogen, and 2-bromobis (triethylsilyl) aniline. 0g (0.05mol)
And 50 ml of tetrahydrofuran. The contents were cooled to -66 ° C in a dry ice-acetone bath while stirring. From a dropping funnel, 61 ml (0.10 mol) of a tert-butyllithium 1.64M pentane solution was added dropwise at -66 to -57 ° C for 1.5 hours. The mixture was stirred at −64 ° C. for 30 minutes, and the temperature was increased to −30 to −25 ° C., and stirring was continued for 2 hours. Thereafter, the temperature was gradually raised to room temperature. To the reaction mixture was added 51 g (0.05 mol) of 3.6% hydrochloric acid in 2 parts.
The mixture was added at 0 ° C. or lower, liquid-separated, and the organic layer was taken out. Another 200 m of nitrogen-purged equipped with a reflux condenser, a thermometer, and a stirrer
of a three-necked glass flask. 2.9 g of 28% sodium methylate methanol solution (0.015 mol
l) and 20 g of methanol were added, and the mixture was stirred for 8 hours while heating under reflux. The obtained reaction mixture was distilled under reduced pressure, and
As a result, 8.5 g of a colorless transparent fraction having a boiling point of 80 to 81 ° C. was obtained. From the results of nuclear magnetic resonance spectrum, infrared absorption spectrum and mass spectrum, it was confirmed that this liquid was 2- (triethylsilyl) aniline. The yield was 82%.

The ¹ H nuclear magnetic resonance spectrum (C
DCl ₃ solvent) in FIG. 7, ¹³ C nuclear magnetic resonance spectrum (CDCl ₃ solvent) in FIG. 8, also illustrates an infrared absorption spectrum (NaCl rock salt plate) in FIG. Mass spectrum (EI) m / z: 207 (M ^<+> ), 17
8 ([M-Et] ⁺ ), 150, 122

Example 5 Synthesis of 2- (n-hexyldimethylsilyl) aniline A 200-ml three-necked glass flask equipped with a dropping funnel, a thermometer, and a stirrer was purged with nitrogen, and 2-bromobis (n-
Hexyldimethylsilyl) aniline 22.8 g (0.0
5 mol) and 50 ml of tetrahydrofuran. The contents were cooled to -65 ° C in a dry ice-acetone bath while stirring. From a dropping funnel, 61 ml of tert-butyllithium 1.64M pentane solution (0.10 M
mol) was added dropwise at -65 to -57 ° C for 1.5 hours.
The mixture was stirred at -67 to -64 ° C for 1 hour, the temperature was raised to -25 ° C, and the stirring was continued for 2 hours. Thereafter, the temperature was gradually raised to room temperature. 51% of 3.6% hydrochloric acid (0.05 mol) was added to the reaction mixture.
l) is added at 25 ° C or lower, and liquid separation is performed to take out an organic layer.
It was concentrated under reduced pressure. The concentrated solution was distilled under reduced pressure to obtain 9.8 g of a colorless transparent fraction having a boiling point of 93 ° C. at 1 mmHg. From the results of nuclear magnetic resonance spectrum, infrared absorption spectrum and mass spectrum, it was confirmed that this liquid was 2- (n-hexyldimethylsilyl) aniline. Yield 83
%Met.

The ¹ H nuclear magnetic resonance spectrum (C
The DCl ₃ solvent) FIG. 10, the ¹³ C nuclear magnetic resonance spectrum (CDCl ₃ solvent) in FIG. 11, also shown the infrared absorption spectrum (NaCl rock salt plate) Figure 12. Mass spectrum (EI) m / z: 235 (M ^<+> ), 22
0 ([M-Me] ⁺ ), 150 ([M-C ₆ H ₁₃ ] ⁺ )

[Brief description of the drawings]

FIG. 1 shows the ¹ H nuclear magnetic resonance spectrum of the compound obtained in Example 1 of the present invention.

FIG. 2 shows a ¹³ C nuclear magnetic resonance spectrum of the compound obtained in Example 1 of the present invention.

FIG. 3 shows the results of the compound obtained in Example 1 of the present invention. Infrared absorption
The spectrum is shown.

FIG. 4 shows a ¹ H nuclear magnetic resonance spectrum of the compound obtained in Example 3 of the present invention.

FIG. 5 shows a ¹³ C nuclear magnetic resonance spectrum of the compound obtained in Example 3 of the present invention.

FIG. 6 shows the results of the compound obtained in Example 3 of the present invention. Infrared absorption
The spectrum is shown.

FIG. 7 shows a ¹ H nuclear magnetic resonance spectrum of the compound obtained in Example 4 of the present invention.

FIG. 8 shows a ¹³ C nuclear magnetic resonance spectrum of the compound obtained in Example 4 of the present invention.

FIG. 9 shows the results of the compound obtained in Example 4 of the present invention. Infrared absorption
The spectrum is shown.

FIG. 10 shows a ¹ H nuclear magnetic resonance spectrum of the compound obtained in Example 5 of the present invention.

FIG. 11 shows a ¹³ C nuclear magnetic resonance spectrum of the compound obtained in Example 5 of the present invention.

FIG. 12 shows the results of the compound obtained in Example 5 of the present invention. Infrared absorption
2 shows a collection spectrum.

Claims (3)

[Claims] [Claim 1] The following general formula (1) (Wherein, R ¹ , R ² , and R ³ may be the same or different and are each selected from a monovalent hydrocarbon group having 1 to 10 carbon atoms. R ⁴ is a hydrogen atom, R ¹ R ² R An aniline derivative having a silicon substituent at the ortho position represented by ³ Si— or a silicon-containing group or a monovalent hydrocarbon group having 1 to 10 carbon atoms. 2. The aniline derivative having a silicon substituent at the ortho-position according to claim ^1, wherein in the formula (1), R ⁴ is a hydrogen atom or a silicon-containing group represented by R ¹ R ² R ³ Si—. . 3. The following general formula (2): (Wherein R ¹ , R ² , R ³ and R ⁴ are the same as R 1 in the formula (1))
^It represents the same as ¹ , R ² , R ³ , and R ⁴ . X represents a halogen atom. ) Is reacted with a simple substance of an alkali metal or an alkaline earth metal, or an organometallic compound obtained therefrom, to give a compound represented by the following general formula (3): (Wherein R ¹ , R ² , R ³ and R ⁴ are the same as R 1 in the formula (1))
^It represents the same as ¹ , R ² , R ³ , and R ⁴ . M represents an alkali metal atom or an alkaline earth metal atom. n is a metal atom M
Is an integer of valence-1. ^3. ) The compound of claim 1 or 2, wherein R ¹ R ² R ³ Si— and M bonded to the nitrogen atom are removed by solvolysis after conversion into the compound represented by the formula (1). A method for producing an aniline derivative having a group.