JPS6014018B2 - Method for producing 4-aminoanilines having a group containing an alkylene oxide divalent group at the N-position - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for producing 4-aminoanilines having a group containing an alkylene oxide divalent group at the N-position, and more specifically to anilines having a group containing an alkylene oxide divalent group at the N-position. The present invention relates to a new and useful method for producing 4-aminoanilines corresponding to 4-aminoanilines. N.N-disubstituted-4-aminoanilines, especially those having a group containing an alkylene oxide divalent group at the N-position, are extremely important compounds as color developing agents for color photography. In recent years, the use of color photography has rapidly progressed, and the demand for color development tools has also increased rapidly. For this reason, there is a need in the art to realize a useful production method for N·N-disubstituted-4-aminoanilines, which are extremely useful as color developing agents, especially those having a group containing an alkylene oxide divalent group at the N-position. There is a strong demand for this. This compound is also useful as a raw material for color formers for copying paper, and as a raw material for synthesizing many azo dyes. Therefore, there is a wide demand in the industrial community for a more advantageous method for producing the above-mentioned N·N-di-4-aminoanilines. Although several proposals have been made so far regarding methods for producing N.N-di-4-aminophanilines, none of them are satisfactory. The most common of these methods is m
The method involves replacing the hydrogen at the N-position of an aniline such as -tolydine, and introducing an amino group into the 4-position using the N.N-disubstituted aniline as a starting material. Several proposals have been made so far regarding this method of introducing amino acids. One method is to directly nitrate the 4-position and then reduce it to obtain a 4-aminoaniline compound. However, in this method, the 2-position in addition to the 43-position is nitrated, making it difficult to selectively produce only the 4-aminoaniline compound, and the yield is inevitably low. The second is, for example, the Journal of American Chemical Society.
Can3ChemicalS ratio) Volume 73, No. 31
Pages 00 to 3125 (1951), Mochiseki Sho 47-11 Wipeki Publication, Sho 50-1185, Sho 50-1
31526, etc., in which substituted or unsubstituted aniline is diazotized, and the obtained diazonium compound is used as a starting material for the above-mentioned N.N-dipupil-converted aniline and 4.
Coupling is carried out at this position to form an azo dye, which is then hydrogenated using a palladium-carbon catalyst, a Raney nickel catalyst, etc., to produce the corresponding 4-aminoaniline compound.This method still has a satisfactory yield. In addition, in order to obtain a high yield in this method, 2,5-dichloroaniline must be used as the raw material for the diazonium compound due to its high reactivity. is optimal, and 2,5-dichloroaniline is exclusively used, but 2,5-dichloroaniline, which is eliminated when reducing the diazo dye to obtain the target aminoaniline compound, is the target product. However, since 2,5-dichloroaniline has very similar properties to the target 4-aminoanilines, it is extremely difficult to remove it, making it difficult to purify the target compound. This drawback results in the fatal drawback that, especially when the target compound is used as a color developing agent for color photography in a halogenated radiation color photographic light-sensitive material, significant fogging occurs in the light-sensitive material. This is because even a small amount of 2,5-dichloroaniline remaining during the purification process of the final product in this method causes significant capping of the halogenated emulsion. Aminoanilines combined with organic acids or inorganic acids to form salts can be used as color developing agents for color photography with improved solubility in developing solutions, and among these, preferred are particularly preferred for improved solubility. In the form of p-toluenesulfonate, it is difficult to completely remove 215-dichloraniline because it improves its solubility in developing solutions and also improves its solubility in a considerable variety of organic solvents.
The 4-aminoanilines obtained by this method cannot be advantageously used as a color developer, and obtaining the target compound useful as a color developer involves great difficulty in purification. is not an advantageous method for producing 4-aminoaniline having a group containing an alkylene oxide divalent group at the N-position, and the yield is still unsatisfactory. Therefore, alkylene oxide 2
As a method for producing 4-aminoaniline having a group containing a valent group at the N-position, 4-amino-N.N-dialkyl m
Practical in the production of m-toludine, etc., for example, the method described in the Journal of the American Chemical Society, in which N.N-dialkyl-m-toludine is nitrated and then reduced to obtain the desired product, is considered suitable. In the nitrosation of N.N-disubstituted anilines, 4
Since the nitroso group is selectively introduced into the position, there is no drawback like the first method mentioned above, and there is no difficulty in purification like the second method and the resulting adverse effects when used as a color developing agent. This is because it is unthinkable. However, when this method is applied to the production of anilines having a group containing an alkylene oxide divalent group at the N-position to obtain 4-aminoaniline having an alkylene oxide divalent group at the N-position, the yield is extremely low. Post-processing is also difficult, and the current situation is that it is not yet possible to advantageously produce 4-aminoanilines, which are extremely useful as color developers, using this method. Therefore, the object of the present invention is to overcome the unsatisfactories of the conventional state of the art and to provide 4-aminoanilines having a group containing an alkylene oxide divalent group at the N-position, which greatly improves the drawbacks in all aspects. The object of the present invention is to provide a new and advantageous manufacturing method. In other words, the object of the present invention is to produce 4-aminoaniline having a group containing an alkylene oxide divalent group at the N-position, which is novel and industrially advantageous in terms of yield, reaction rate, post-treatment, purification of the target product, etc. The aim is to provide manufacturing methods of the following types. Another object of the present invention is to improve the above-mentioned nitrosation method, which has been considered disadvantageous in the past, and to improve the inherent advantages of the 4-position substitution and the high purity and ease of purification of the target product. The object of the present invention is to provide a novel method for producing 4-aminoanilines having a group containing an alkylene oxide divalent group at the N-position, which takes advantage of the above properties and achieves dramatic improvements in yield, reaction rate, etc. Other objects of the present invention are Japanese Patent Publication No. 14-473 (Japanese Patent No. 134085), Japanese Unexamined Patent Publication No. 11534-1982, No. 11535-1973, and Japanese Unexamined Patent Publication No. 50-13
Known alkylene oxide 2 described in Publication No. 1526 etc.
The present invention provides a new and useful method for producing 4-aminoanilines having a group containing a valent group at the N-position, and also provides a new and useful color developing agent for color photography in comparison with the above-mentioned known 4-aminoanilines. The following general formula [m
It is an object of the present invention to provide a new and useful method for producing a compound represented by the following formula. General formula [m] (In the formula, R2 represents a hydrogen atom or an alkyl group optionally substituted with a halogen atom, and R3, R4, and R5 each represent a hydrogen atom, a halogen atom, an unsubstituted alkyl group, an alkyl group, and a halogen atom. group, or an acylamido group, R6
and R7 each represent an alkylene group having 1 to 6 carbon atoms which may be substituted with a halogen atom, and R8 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom. where p and q are 0
or more, and the sum of p and q is 1 to 5. ) The novel compound represented by the above general formula [m], as described in Hakama-gao No. 50-17246, has a higher dissolution rate into a color developer than known similar compounds, especially when used as a color developer. It has high properties and developing performance.
It has the advantage that it is possible to obtain good images without color turbidity, and that benzyl alcohol, which is generally contained in developers as a development aid and is harmful to environmental health, can be extremely reduced or removed. As a result of various studies for the above purpose, the present inventors (i) reacted a compound represented by the following general formula [1] with an alkali salt of nitrous acid in an aqueous inorganic acid solution, and (ii) reduced the reaction product. and/or the step (ii) is carried out in the presence of an organic solvent that is compatible with water.

Alkylene oxide 2 represented by [0]
It has been found that the above object can be effectively achieved in a method for producing 4-aminoanilines having a group containing a valent group at the N-position. The method according to the present invention greatly surpasses the conventional state of the art in terms of production problems such as yield, post-treatment, purity, etc. By carrying out the reaction in the presence of a solvent that is compatible with the general formula, the reaction rate and yield are dramatically increased.
1] In the formula, R represents a group represented by -(R60)m-(R70). Here, R6 and R7 represent a straight chain alkylene group having 1 to 6 carbon atoms which may be substituted with a halogen atom. Further, R8 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom. m and n are each an integer of 0 or more, and the sum of m and n is an integer of 1 to 5. In the general formula [1], R2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or a group represented by R above. Furthermore, in the formula, R3, R4 and R5 are each a hydrogen atom,
It represents a halogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, an alkoxy group, or an acylamido group. When R4 or R5 is an alkyl group having 1 to 6 carbon atoms, it is extremely useful as a color developer. The compound represented by the general formula [1] can be produced by reacting a halide with an aniline by the method described in the above-mentioned Journal of American Chemical Society, etc.; By using the reaction between an acid ester and an aniline, production can be more advantageous in terms of yield, reaction rate, availability of raw materials, and production of starting materials. Compounds that can be industrially advantageously produced using the present invention, that is, compounds that have a group containing an alkylene oxide divalent group and are particularly useful as color developing agents, have the following general formula:

Represented by [0]. In the general formula [b], R,, R2, R3, R4 and R5 each represent the same group as the corresponding group in the above general formula [1]. The production method according to the present invention includes: (i) reacting an aniline represented by the above general formula [1) with an alkali salt of nitrous acid in an aqueous inorganic acid solution; (ii) then reducing the reaction product; And the steps (il and/or (ii) are carried out to bring about the presence of an organic solvent that is compatible with water, and the above general formula

[0]
A group containing an alkylene oxide divalent group represented by N-
4-aminoanilines having the same position are obtained,
More detailed and more preferable manufacturing conditions are as follows. The first step of the manufacturing method according to the present invention is the above-mentioned one-wave method [1]
This is a step of nitrosating the 4-position of anilines represented by This nitrosation reaction is carried out in an aqueous solution by the action of an inorganic acid and an alkali salt of nitric acid, and at this time, the 4-position of the aniline is selectively nitrosated. Particularly preferred inorganic acids include hydrochloric acid and sulfuric acid. However, nitric acid cannot be advantageously used in the present invention due to its strong oxidizing action. In addition, the amount of inorganic acid to be added may be 1 mol or more per 1 mol of the compound represented by the above general formula [1]. It may be appropriately determined in consideration of the required amount of , the required amount for salt formation of the target compound described below, etc., and may be added to the reaction system in advance, or the required amount may be added at the time of need. The alkali salt of nitrous acid is an alkali metal salt of nitrite such as sodium or potassium, and the amount added to the inorganic acid aqueous solution is in excess of 1 mole per 1 mole of the compound represented by the above-mentioned formula [1]. It is preferable to add This first step is preferably carried out at 10° C. or lower under ice cooling. The reaction is 5
It will be completed in 2 to 4 hours at 1 to 0. The present invention is characterized in that the first step of nitrosation described above and/or the second step of reduction described below are carried out in the presence of an organic solvent that is compatible with water. In the present invention, an organic solvent compatible with the water may be added to the inorganic acid aqueous solution in advance. Here, the organic solvent that is compatible with water is not necessarily limited to those that dissolve in water in any proportion; any compound that is compatible with water may be used, but preferred compounds include, for example, methanol, ethanol, Lower alcohols such as propanol and butanol, lower cyclic alkyl alcohols such as cyclohexanol, lower alkylene glycols such as ethylene glycol, diethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Its lower alkyl ethers, acetone,
Examples include lower alkyl ketones such as methyl ethyl ketone, lower alkyl fatty acids such as acetic acid, lower alkyl amides such as dimethylformamide, and lower alkyl sulfoxides such as dimethyl sulfoxide.
In the present invention, one of the above-mentioned solvents may be used alone, or a mixture of two or more may be used. The amount of these organic solvents added is not limited, but is 1'loo by weight per inorganic acid aqueous solution.
It is preferable to add from 4 times to 4 times. In the present invention, after the above-mentioned first step is substantially completed, a second step of reducing the generated nitrosate is performed, either by isolating the generated nitrosate or without isolating it. . Various known methods can be used for this reduction step. For example, a catalytic reduction method using a conventional metal hydrogenation catalyst, a reduction method using nascent hydrogen in an acidic solution of metals such as zinc, tin, iron, etc. (in this case, the produced nitrosate is isolated) Any method can be used in the present invention, such as adding the above-mentioned metal as it is to the reaction system after the first step has been completed, or a reduction method using various metal salts such as stannous chloride. Note that the water-compatible organic solvent mentioned above can be added in this step without being added in the first step, or added in this step after being added in the first step. Good too. The compound represented by the monopronged formula m] thus obtained may be isolated after neutralizing the acid present in the reaction system. Also, as mentioned above, the general formula [m
The compound represented by can be advantageously used as a color developing agent in the form of an inorganic acid or an organic acid salt.
The above first and/or second steps may be performed under conditions of excess inorganic acid and isolated in the form of an inorganic acid salt. Furthermore, after the completion of the second step, an organic or inorganic acid such as hydrochloric acid, sulfuric acid, oxalic acid, phosphoric acid, alkylbenzenesulfonic acid, benzenesulfonic acid, alkylsulfonic acid, naphthalene disulfonic acid, etc. is mixed into the reaction system. It may be reacted with a compound represented by the general formula [0) to precipitate the corresponding 4-aminoaniline in the form of a salt. Next, specific examples of the compound represented by the general formula [D] obtained according to the method of the present invention are listed, and at the same time, the measured value of the mass vector M+ and the calculated molecular weight M measured for the identification of the compound are attached.
The technical scope of the present invention is not limited in any way by these specific examples. The present invention will be explained below with reference to Examples, but the present invention is not limited by these in any way. Example 1 Method for producing exemplified compound '1' and its salts N-ethyl-N-(2 -methoxyethyl)-3-methylaniline 2
5 mols (0.13 mol) of the aniline was added, and while maintaining the temperature below 5° C., an aqueous solution prepared by dissolving 9.1 mols of sodium nitrite in a small amount of water was added dropwise to nitrosate the 4-position of the aniline. Next, 8 volumes of methanol were added, approximately 5 minutes of iron powder was added to reduce the mixture, and the oily component obtained at this time was extracted with ethyl acid. The residue was dried and further concentrated under reduced pressure to obtain the target exemplary compound '1}25 (yield: 92%). The structure of this product was confirmed by mass spectrometry spectrum M1208 (calculated value 208). Furthermore, in order to form the salt, a calculated amount of p-toluenesulfonic acid was added and reacted to obtain white powdery crystals. The melting point was 229-3ro. The yield after salt formation was 83%. Reference Example 1 Exemplary compound '11 was produced under the same conditions as in Example 1 except that methanol was not added in the pre-reduction step using iron-hydrochloric acid. The yield of the target product identified by mass spectrometry was about 10%. It can be seen that a surprising increase in yield can be achieved using the method according to the invention. Reference Example 2 An exemplary compound synthesized by the method of the present invention by performing wedge exposure on Sakura Color Paper (manufactured by Konishiroku Photo Industry Co., Ltd.) through a blue filter.
11, or a developer solution containing exemplified compound [1] synthesized according to the description in Tokokukan Sho 47-11534, and then treated with a bleach-fix solution and a stabilizer to produce color. A sample with an image was prepared. [Processing process] 3100 Processing time Color development 3 minutes 3 steps Sand bleach fixing 1 minute 3M stage water washing
2 minute stabilization
-1 minute [Color photographic developer] Penzyl alcohol 50' Sodium hexametaphosphate 3.00 t Inorganic sodium sulfite
1.85 Sodium bromide
1.40 Potassium bromide
0.50 ta shelf sand (Na280710 day 20)
39.10 exemplified compound {1'
Finish by adding 312 t water and PHIO. with sodium hydroxide. Adjusted to 3. The yellow color density of this sample was measured using a PD-7R densitometer (manufactured by Konishiroku Photo Industry Co., Ltd.), and the photographic performance obtained is shown in Table 1. Note that the sensitivity is 1 when using developer solution ■ containing exemplified compound '1' obtained by the present invention.
Relative values are shown as 00. As is clear from Table 1, the developing agent obtained by the present invention is superior in both sensitivity and fog compared to the diazotization method. Example 2 Starting material N-ethyl-N-(2-ethoxyethyl)-
The p-toluenesulfonic acid salt of Exemplified Compound (1) having a mass spectrometry spectrum of M+228 was prepared under the same conditions as in Example 1, except that 3-methoxyaniline 27 was used. The yield was 83%. Separately, Tokugatsu Sho 47-11534
In accordance with the instructions in the publication, p-toluenesulfonate of Exemplary Compound (1) was produced by a method using a diazonium compound, but the yield was 1%. It can be seen that the yield can be improved by using the production method according to the present invention. Example 3 Method for producing exemplified compound ■ and its salts To a solution of 17 parts of concentrated hydrochloric acid and 15 parts of water, add 5 parts of N-ethyl-N-{2-(2-methoxyethoxy)ethyl}-13-methylaniline under ice cooling. (0.021 mol) was added, and 5 methanol was added to make a homogeneous solution. While keeping this at 5°C or below, an aqueous solution of 1.9 mol of sodium nitrite dissolved in a small amount of water was added dropwise to make a homogeneous solution. It became. Next, about 6 hours of zinc powder was added to reduce the mixture, and then an appropriate amount of a 10% aqueous sodium carbonate solution was added at 10° C. or lower to neutralize it. The oily component obtained at this time is extracted with ethyl acid, and this extract is dried by adding trinitrate, and further concentrated under reduced pressure to obtain the target exemplary compound [8] 4.8 min (yield: 92%). Obtained. The structure of this product was confirmed by mass spectrometry spectrum M+238 (calculated value 238). Furthermore, in order to form the salt, a calculated amount of p-toluenesulfonic acid was added and reacted, and ethyl ether was gradually added to obtain white powdery crystals. Melting point 124-12 is 0 Example 4 Synthesis of exemplified compound side and its salt To a solution prepared by adding 15 parts of water to 16 parts of concentrated hydrochloric acid, N-ethyl-N-[2-(2-methoxyethoxy)] was added under ice-cooling. ethyl〕
Add 3-methylaniline (0.022 mol) and add 5 mol of methanol to make a homogeneous solution. While keeping this at around 5°C, add 1.8 mol of sodium nitrite to a small amount of water. It was added dropwise for nitrosation. Next, after reducing by adding about 5 hours of tin, 20% caustic soda
An appropriate amount of an aqueous solution was added at 10q0 or less to neutralize. The oily component obtained at this time is extracted with ethyl acetate, and this extract is dried and concentrated to obtain the target exemplary compound '9}5.
．． Three samples were obtained (yield 94%). The structure of this product was confirmed by mass spectrometry spectrum M1252 (calculated value 252). Furthermore, in order to form the salt, a solution of a calculated amount of p-toluenesulfonic acid dissolved in a small amount of methyl alcohol was added and reacted, and then ethyl acid acid was gradually added to obtain white powdery crystals. (Yield 85% based on the exemplified compound side) The melting point was 184-180. Reference example
The p-toluenesulfonic acid salt of 3 exemplified compounds [9} was produced by a method using a diazonium compound according to the description in JP-A-50-131526. The yield was 59% based on N-ethyl-N-[2-(2-methoxy)ethoxy]ethyl-3-methylaniline as the starting material. It can be seen that improved yields are realized when using the present invention. Example 5 Synthesis of Exemplified Compound (12) and its Salt A solution of concentrated hydrochloric acid 17 and 15 ml of water was added with N- under ice cooling.
Ethyl-N-(1-methyl-2-methoxyethyl)-3
- Add 5 ml of methylaniline (0.024 mol) and add 10 ml of ethanol to make a homogeneous solution. While keeping this at 5°C or lower, add dropwise an aqueous solution of 2 ml of sodium nitrite dissolved in a small amount of water. In addition, it was nitrosated. Next, approximately 5 hours of iron powder was added to reduce the mixture, and then an appropriate amount of a 10% aqueous sodium carbonate solution was added at a concentration of less than 100 mm to neutralize it. The oily component obtained at this time was extracted with ethyl acid, and this extract was dried by adding trinitrate, and then concentrated by distillation under reduced pressure to obtain the target exemplified compound (12) at 5.0 μl (yield: 93%). Obtained. The structure of this substance is shown in the mass spectrometry spectrum M1222 (
It was confirmed by the calculated value 222). Further, in order to form the salt, a calculated amount of p-toluenesulfonic acid was added and reacted, and ethyl ether was gradually added to obtain white powdery crystals. The melting point was 178-189q○.
Example 6 Synthesis of Exemplified Compound (29) and its Salt To a solution of 16 parts of concentrated hydrochloric acid and 15 parts of water was added N-ethyl-N-{2-[2-(2-methoxyethoxy)] under ice cooling. Ethoxy]ethyl}-3-methylaniline (0.018 mol) was added, and 15M methanol was added to this to make a homogeneous solution.While keeping this at around 5°C, 1.8 mol of sodium nitrite was added.
An aqueous solution of nitrate dissolved in a small amount of water was added dropwise to nitrosate. Next, about 5 minutes of iron powder was added to reduce the mixture, and then an appropriate amount of a 10% aqueous sodium carbonate solution was added at a concentration of 1,000 ml or less to neutralize it. The oily component obtained at this time was extracted with ethyl acid, and this extract was dried and concentrated to obtain the desired exemplary compound (29) 4.
．． 8 samples (yield 91%) were obtained. The structure of this product was confirmed by mass spectrometry spectrum M1296 (calculated value 296). Furthermore, in order to form the salt, a solution of a calculated amount of p-toluenesulfonic acid dissolved in a small amount of methyl alcohol was added and reacted, and then ethyl acid acid was gradually added to obtain white powdery crystals. . The melting point was 134-13 o. Reference Example 4 In Example 6, the exemplified compound (2 kalpas) was produced under the same conditions as in Example 6, except that methanol was not added before the nitrosation step with hydrochloric acid and sodium nitrite. Confirmed by mass spectrometry spectrum. The yield of the target product is 4
It was 5%. It can be seen that a surprising increase in yield can be achieved using the method according to the invention. Example 7 Synthesis of exemplified compound (3) and its salts To a solution of 85% concentrated hydrochloric acid and 80% water was added N-ethyl-N-{2-[2-(2-ethoxyethoxy)ethoxy] under ice cooling. ethyl}-3-methylaniline (0.1
Add 2 moles of sodium nitrite and add 80% of methanol to make a homogeneous solution.
．． Add dropwise an aqueous solution of 50ml dissolved in 20cc of water,
It was nitrosated. Next, 30 minutes of iron powder was added to reduce the mixture, and then an appropriate amount of a 10% aqueous sodium carbonate solution was added at 10° C. or lower to neutralize it. The oily component obtained at this time was extracted with ethyl chloride, and this extract was dried and concentrated to obtain the desired exemplary compound (30) 3.
Four samples were obtained (yield 92%). The structure of this product was confirmed by mass spectrometry spectrum M+310 (calculated value 310). Furthermore, in order to form the salt, a calculated amount of a solution of p-toluenesulfonic acid dissolved in methanol was added thereto for reaction, and then ethyl acetate was gradually added to obtain white powdery crystals. The melting point was 140-1420. Example 8 Synthesis of Exemplified Compound (31) and Salts thereof N-ethyl-N-{2-[2-(2-propoxyethoxy)ethoxy)ethyl] was added to a solution of 21 parts of concentrated hydrochloric acid and 20 parts of water under ice cooling. }1-3-Methylaniline 9.3 hours (0.0
3 mol) was added, 25% of acetone was added to make a homogeneous solution, and while keeping this at around 5°C, an aqueous solution of 2.5% of sodium nitrite dissolved in a small amount of water was added dropwise to nitrosate. . Next, approximately 9 hours of iron powder was added to reduce the mixture, and then an appropriate amount of a 10% aqueous sodium carbonate solution was added at a concentration of 1 mm or less to neutralize it. The oily component obtained at this time was extracted with ethyl acetate, and this extract was dried and concentrated to obtain the desired exemplary compound (31) 9.
．． 02 (yield 93%) was obtained. The structure of this product was determined from the mass spectrometry spectrum M1324 (calculated value 324). Further, to form a salt, a calculated amount of a solution of p-toluenesulfonic acid dissolved in methanol was added and reacted, and ethyl acetate was gradually added to obtain white powdery crystals. The melting point was 136-138 CO. Example 9 Synthesis of Exemplified Compound (33) and Its Salt A solution of concentrated hydrochloric acid (21 parts) and water (20 parts) was added with N under ice cooling.
-Ethyl-N-{2-[2-(2-methoxyethoxy)
Ethoxy]ethyl}aniline 8.4 units (0.03 mol)
Add 25% of methanol to this to make a homogeneous solution.While keeping this at around 5℃, add 2.5% of sodium nitrite.
An aqueous solution of nitrate dissolved in a small amount of water was added dropwise to nitrosate. Next, approximately 90% of iron powder was added to reduce the mixture, and then an appropriate amount of a 10% sodium carbonate aqueous solution was added at a concentration of 1,000 ml or less to neutralize it. The oily component obtained at this time was extracted with ethyl chloride, and this extract was dried and concentrated to obtain the desired exemplary compound (33) 8.
．． One night (yield 95%) was obtained. The structure of this product was determined from the mass spectrometry spectrum M1282 (calculated value 282). Further, to form a salt, a calculated amount of a solution of p-toluenesulfonic acid dissolved in methanol was added and reacted, and ethyl acid acid was gradually added to obtain white powdery crystals. The melting point was 125-128°C. Example 10 Synthesis of Exemplified Compound (58) and its Salt After nitrosation and reduction in the same manner as in Example 8, the above aniline compound was obtained.

Claims (1)

[Claims] 1 General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 is the formula -(R_6O)m-(R_7O)n
-Ra (wherein R_6 and R_7 each represent an alkylene group having 1 to 6 carbon atoms which may be substituted with a halogen atom, and R_8 is a hydrogen atom or a carbon atom number 1 which may be substituted with a halogen atom) represents an alkyl group of 6 to 6, m and n are each an integer of 0 or more, and m
and the sum of n is an integer from 1 to 5. ), R_2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms optionally substituted with a halogen atom, or a group represented by R_1 above, R_3, R
_4 and R_5 each represent a hydrogen atom, a halogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, an alkoxy group, or an acylamido group. ] for the compound represented by (i
) React with an alkali salt of nitrous acid in an inorganic acid aqueous solution,
(ii) then reducing the reaction product and said (i
) and/or (ii) are carried out in the presence of an organic solvent that is compatible with water. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2, R_3, R_4 and R_5 are R_1, R_2, R_ in general formula [I], respectively.
3, represents the same group as R_4 and R_5. ] A group containing an alkylene oxide divalent group represented by N-
A method for producing 4-aminoanilines having the same position.