JPS6014017B2 - Method for producing anilines for intermediates of color developing agents for color photography - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing anilines for use as intermediates in color developing materials for color photography, which have a group containing an alkylene oxide divalent group in the N-position. Anilines having a group containing an alkylene oxide divalent group at the N-position are important compounds as intermediates for dyes, pigments, medicines, agricultural chemicals, etc. For example, they are useful intermediates for compounds useful as diazo components in the synthesis of many azo dyes. Also known as body etc. Furthermore, this compound is well known as an intermediate for coloring agents for copying paper and for compounds that are extremely important as color photographic color development agents. Many methods have been proposed for producing anilines having a group containing an alkylene oxide divalent group at the N-position, but the current situation is that each method has its advantages and disadvantages. Among them, at present, for example, Journal of the American Chemical Society, No. 7 Kagamito, pages 3100 to 3125, JP-A No. 47-1
It is said that the first step in the methods described in JP-A No. 1534, JP-A-47-11535, and Toku-Kekki JP-A-50-131526 is the most excellent. In this method, N-monoalkyl-m-
Using toluidine as a starting material, the hydrogen at the N-position of the compound is substituted with a substituted alkyl group, in particular with a group having an alkylene oxide divalent group, such as a 2-(2-ethoxyethoxy)ethyl group, and then nitrated. This is a method for producing 4-amino-N-alkyl-N-substituted alkylaniline by subsequent reduction, using a substituted alkyl halide, especially an alkyl halide containing an alkylene oxide divalent group, such as 2-(2-ethoxyshetoxy)ethyl bromide. The first step is to replace the hydrogen at the N-position of N-monoalkyl-m-toluidine with a substituted alkyl group, particularly with a group containing an alkylene oxide divalent group, such as a 2-(2-ethoxyshetoxy)ethyl group. That is. The substituted alkyl halide in the above first step, especially the alkyl halide containing an alkylene oxide divalent group, such as 2-(2-ethoxyethoxy)ethyl bromide, is generally a substituted alkyl halide containing an alcoholic OH group such as diethylene glycol monoethyl ether, etc. It is considered best to obtain the compound by reacting the compound with a phosphorus halide such as phosphorus tribromide. However, in order to obtain a substituted alkyl halide using this phosphorus halide, the yield of the substituted alkyl halide is extremely poor, at most 10 to 30%, and the phosphorus halide is harmful and dangerous in production and must be handled with great care. In short, it is a harmful substance that is undesirable in terms of pollution, and for this reason, it has the disadvantage that sufficient consideration and countermeasures must be taken for post-treatment after the completion of the reaction, and it is also disadvantageous in terms of price. be. Furthermore, the reaction of this substituted alkyl halide, especially an alkyl halide containing an alkylene oxide divalent group, with an aniline such as m-toluidine can cause the target group containing an alkylene oxide divalent group to be transferred to the N-position. It takes a long time of several days to obtain the anilines having the same properties, and the yield is still low, which is a major disadvantage, and those skilled in the art are still not satisfied with the results. Therefore, the conventional method for producing anilines having groups containing alkylene oxide-valent groups has many drawbacks in terms of yield, reaction rate, raw material availability, pollution, post-treatment, etc., and improvements are strongly needed. This is a demand in this industry. Therefore, the object of the present invention is to overcome the unsatisfactories of the conventional state of the art as described above, and to provide anilines 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 purpose of the present invention is to provide a novel method for producing anilines having a group containing an alkylene oxide divalent group at the N-position, which is industrially advantageous in terms of yield, reaction rate, raw material availability, pollution, etc. We are here to provide you with a method. The purpose of the present invention is to solve the following problems: Mochiko Sho 14-473 (Japanese Patent No. 134085), Tokuseki Sho 47-11534, Tsubaki Kaisho 47-115.
In addition to providing a new and useful method for producing anilines having a group containing a known alkylene oxide divalent group at the N-position as described in Publications No. 35 and Mochiseki No. 50-131526, etc., A new and useful compound represented by the following general formula [V-] which is an intermediate of a compound which is extremely useful as a color developing material for color photography as described in No. 17246 of 1988, even compared to the above-mentioned known anilines. The aim is to provide a manufacturing method. General formula [V] (wherein R represents a substituted or unsubstituted alkyl group, R2, R3, R4, R5 and R6 each represent a hydrogen atom, a halogen atom or an alkyl group, and R8 and R9 each represent a hydrogen atom, a halogen atom or an alkyl group) represents a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, R and o represent a substituted or unsubstituted phenyl group or an alkyl group having 1 to 6 carbon atoms,
p and q are integers greater than or equal to 0, and the sum of p and q is 3
That's all. ) A new compound in which R4 is an N ratio group can be obtained using the compound [V] represented by the above general formula as a starting material. When used as a developing agent, compared to known similar compounds, it has greater solubility in color developing solutions, has higher developing performance, can provide good images with no color turbidity, and is generally easy to use as a developing agent. It has the advantage that benzyl alcohol, which is contained in the developer as an agent and is harmful to environmental health, can be extremely reduced or removed. As a result of various studies regarding the above-mentioned object, the present inventors have discovered that the following general formula [m It has been found that the above object can be effectively achieved in a method for producing anilines having a group containing an alkylene oxide divalent group represented by the general formula [W] at the N-position. General Formula [1] In the formula, R represents a substituted or unsubstituted alkyl group. Here, the alkyl group refers to a straight chain or branched group such as a methyl group, an ethyl group, an isopropyl group, a butyl group, an rt-butyl group, a hexyl group, a ten-octyl group, a dodecyl group, a 2-ethylhexyl group, a cyclohexyl group, etc. Preferred is an alkyl group having 1 to 20 carbon atoms, and a substituted alkyl group refers to a substituted alkyl group in which one or more hydrogen atoms of the above alkyl group are substituted with, for example, a hydroxy group, a di- or monoalkylamino group, a di- or monoaryl group. Amino group, di- or mo/aralkylamido group, alkyloxy group, aryloxy group, aralkyloxy group, alkylamido group, arylamide group, aralkylamide group, carbamyl group, alkylsulfonamide group, arylsulfonamide group, aralkyl Sulfonamide group, cyano group, halogen atom, (for example, chlorine atom, bromine atom, fluorine atom, the same applies hereinafter) aralkyl group such as penzyl group, phenacyl group, carbamoyl group,
Mono- or dialkylcarbamoyl group, mono- or diarylcarbamoyl group, alkylthio group, arylthio group,
Substituents such as aralkylthio group, aryloxy group, aralkyloxy group (the term alkyl, aryl, or aralkyl in these exemplary substituents has the same meaning as the above alkyl group or the following aryl group or aralkyl group).
It was replaced with . In the formula, R2, R3, R4, R
5 and R6 are each a hydrogen atom, a halogen atom, or an alkyl group. This alkyl group may have a substituent for the alkyl group represented by R above or a phenyl group. The compound represented by the above-mentioned general formula [1] can be obtained by a conventional method. That is, is obtained by reducing the corresponding nitro compound by a conventional method. Further, a substituted or unsubstituted alkyl group can be introduced into the N-position from this aniline compound by a conventional method. Note that many of the compounds represented by the general formula [1] are commercially available. The present invention relates to a compound represented by the above general formula [1] and the following general formula

It is characterized by reacting with a compound represented by [0]. general formula

[0] R? -S03-(R80)n-(R90)m-R,. In the formula, R7 represents an alkyl group or an aryl group. Alkyl groups include, for example, methyl, ethyl, propyl,
A linear or branched alkyl group having 1 to 6 carbon atoms is more preferable, such as a butyl group or an isobutyl group. The alkyl group may have a substituent for the alkyl group in the general formula [1] described above. The aryl group is an aromatic group such as a phenyl group or a Q- or 8-naphthyl group, and these may have a substituent for the aryl group in the general formula [1] described above. Particularly preferred is a group represented by R, . , R,2 and R,3 are each a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, a butyl group, etc. For example, phenyl group, p-tolyl group, m-tolyl group, p-ethylphenyl group, p-propylphenyl group, p
Preferred groups include -isopropylphenyl group and 2,4-dimethylphenyl group. In the formula, R8 and R9 are each a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms. As a substituent for the alkylene group having 1 to 6 carbon atoms,
Alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, nonyl group, aralkyl group such as benzyl group, aryl group such as phenyl group, naphthyl group, methoxy group, ethoxy group, benzyloxy group, an alkyloxy group such as an octyloxy group, an aryloxy group such as a phenoxy group, an aralkyloxy group, and a halogen atom, and these substituents may be further substituted with a halogen atom or other group. Furthermore, in the formula, n and m are each an integer of 0 or more, and the sum of n and m is 1-5. Furthermore, in the formula, R and o represent a substituted or unsubstituted alkyl group or phenyl group. The alkyl group herein refers to a straight or branched alkyl group having 1 to 6 carbon atoms. Further, the substituent for substituting one or more hydrogens in the alkyl group is the same as the substituent for the alkyl group in R of the general formula [1]. General formula above

The compound represented by [0] is, for example, organic synthesis (0r scale to S skin thesis).
)Collective (Colle) published by Wiley
It can be obtained by the so-called pyridine method described in Vol. 1, p. 366 of Vol. The present invention provides a compound represented by the above general formula [1] and a compound represented by the above general formula [1].

This relates to obtaining a compound represented by the following general formula [m] or [W] by reacting the compound represented by [0] with the compound represented by [0]. General formula [m] General formula [W] In both formulas, R,, R2, R3, R4, R5, R6, R8,
R9 and R,. Each of the above general formulas [1],

[0] represents the same group as the corresponding group, and n and m are the same as in the above general formula [B]. The method of the present invention includes:
Aniline amount and general formula expressed by general formula [1]

This is a method of reacting with a sulfonic acid ester represented by [0] to obtain an aniline having a group containing an alkylene oxide divalent group represented by the general formula [m] or [W] at the N-position. More detailed and more preferred reaction conditions are as follows. In order to obtain the compound represented by the general formula [m], a compound represented by the general formula [1] having at least one hydrogen atom at the N-position is used as a starting material; It is preferable to charge 1 to 5 moles, particularly preferably 1 to 3 moles, of the compound represented by the general formula [1] per 1 mole of the compound represented by the formula [1]. In order to obtain a compound represented by general formula [N], a compound represented by general formula [1] having two hydrogen atoms at the N-position is used as a starting material. ] per mole of the compound represented by the general formula [1]
2 to 6 moles of the compound represented by
It is preferable to charge between 4 mol and 4 mol. The reaction solvent in the above reaction may be carried out without a solvent, or if necessary, a solvent having a boiling point of 5,000 or higher can be used. Any solvent having a boiling point can be used as long as it does not adversely affect the above reaction. In addition, a deoxidizer such as an inorganic base such as anhydrous soda carbonate, sodium bicarbonate, fertile soda, fertile potassium, or an organic base such as pyridine or triethylamine may be added to the reaction system. may be a water-containing system. The reaction temperature is preferably 50 qo or higher, but 90 to 190 qo
qo is preferred, and a temperature range of 140 to 170 oo is particularly effective. The reaction time to obtain the desired yield may be several hours or less. This required reaction time is determined by the above-mentioned
-1/10 compared to the method of written competition published in No. 131526
The value is around 0, and the yield is still higher in the method of the present invention than in the above-mentioned method, which requires a reaction time of around 10 times. The method of the present invention greatly exceeds the conventional state of the art in terms of yield, reaction rate, ease of obtaining raw materials, pollution in obtaining raw materials, yield of raw material production, problems in production, etc. However, the reaction rate and yield of the process of the present invention are surprisingly high compared to the prior art. Next, the general formula [m] or [W] obtained according to the method of the present invention
Specific examples of the compound represented by are listed, and at the same time, the measured mass vector M and the calculated molecular weight M are attached for identification of the compound, but the technical scope of the present invention is not limited in any way by these specific examples. It's not a thing. Exemplary compound '1'N-methyl-N-(2-methoxyethyl)-aniline (2} N-ethyl-N-(2-methoxyethyl)
-3-Methylaniline [31 N-propyl-N-(2
-ethoxyethyl)-3-methylaniline '41 N-isobutyl-N-(2-methoxyethyl)-3-ethylaniline '51 N-ethyl-N-(2-methoxyethyl)-3-methylsulfonamide aniline '61 N-ethyl-N-(2- phenoxyethyl)-3-methylaniline (7) N-ethyl-N-[2-(2-chloroethoxy)ethyl]-3-methylaniline [8) N-ethyl-N-(2-methoxyethyl)-3-dodecylaniline {91 N-trifluoro. Methyl-N-[2-(2-methoxyethoxy)ethyl]
-Aniline 00 N-ethyl-N-[2-(2-methoxyethoxy)ethyl]-aniline (11)N-ethyl-
N-[2-(2-methoxyethoxy)ethyl]-3-methylaniline (12) N-ethyl-N-[2-(2-methoxyethoxy)ethyl]-3-methylaniline (13
)N-ethyl-N-[2-(2-bropoxyethoxy)
Ethyl]-3-methylaniline (1 core N-propyl-
N-[2-(2-methoxyethoxy)ethyl)-3-chloroaniline (15)N-ethyl-N-[2-(2-propoxyethoxy)ethyl)-3-(2-hydroxy)
Ethylaniline (16) N-butyl-N-[2-(2-ethoxyethoxy)ethyl]-13-(2-methoxy)ethylaniline (17) N-ethyl-N-[2-(2-methoxyethoxy)ethyl]-3 -Methylsulfonamidoethylaniline (18) N-ethyl-N- {2-[2
-(2-methoxyethoxy)ethoxy]ethyl}-aniline (1kalp N-methyl-N-{2-[2-(2-ethoxyethoxy)ethoxy]ethyl}-aniline (20)
N-ethyl-N-{2-[2-(2-methoxyethoxy)ethoxy]ethyl}-3-methylaniline (21)
N-ethyl-N-{2-[2-(2-ethoxyethoxy)ethoxy]ethyl}-3-methylani1''n (22)
N-ethyl-N- {2-[2-(2-methoxyethoxy)ethoxy]ethyl}-3-methylsulfonamidoethylani1''n○ (23) N-propyl-N- {2-[2- propoxyethoxy)ethoxy]ethyl}-3-propylani. Phosphorus (24) N dodecyl N-{2-[2-(2
-methoxyethoxy)ethoxy]ethyl}-aniline (
25) N-ethyl-N- {2-[2-(2-ethoxyethoxy)ethoxy]ethyl}-3-chloroaniline (
26) N-Methyl-N- {2-[2-(2-methoxyethoxy)ethoxy]ethyl}-3-(2-methoxyethyl)aniline (27) N-methyl-N-[2-{2
-[2-(2-methoxyethoxy)ethoxy]ethoxy}ethyl]-ani(28)N-ethyl-N-[2
- {2-[2-(2-methoxyethoxy)ethoxy]
Etquin}ethyl]-3-methylaniline (29)N-
Butyl-N-[2-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}ethyl]-3-methylsulfonamidoethylaniline (30) N-ethyl-N-K
2-[2-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}ethoxy]ethyl}-3-methylaniline (31)N-methyl-N-[2-[2-{2-[2
-(2-methoxyethoxy)ethoxy]ethoxy}ethoxy]ethyl》-3-aniline (32)N-ethyl-N
-K2-[2- {2-[2-(2-methoxyethoxy)ethoxy]ethoxy}ethoxy]ethyl}-3-propylaniline (33)N-N-bis-(2-methoxyethyl)-3-methylaniline 3 Heart N・Nbis-{2
-(2-methoxyethoxy)ethyl}-3-methylaniline (35) N.N-bis- {2-[2-(2-methoxyethoxy)ethoxy]ethyl}-aniline (36)
N-ethyl-N-(1-methyl-2-methoxyethyl)
-3-Methylaniline (37) N-ethyl-N-(1-butyl-2-butoxyethyl)-aniline (38) N-ethyl-N-[1-methyl-2-(1-methyl-2-methoxyethoxy)ethyl]-3- (2-methoxyethyl)aniline (39)N-methyl-N-[2-(1-methyl-2-methoxyethoxy)ethyl)-aniline (40
)N-ethyl-N-(1,1-dimethyl-2-ethoxyethyl)-3-methylaniline (41)N-methyl-N
-(1-ethyl-2-methyl-3-methoxypropyl)
-Aniline (42)N-ethyl-N-(1-isopropyl-2-methoxyethyl)-aniline (43)N-ethyl-N-(1-methyl-2-methoxyethyl)-3-(
methylsulfonamidoethyl)-aniline (4-core N-
Ethyl-N-(2-methoxyethyl)-2,5-dimethylaniline (45)N-ethyl-N-(1-methyl-2
-methoxyethyl)-2,3-dichloroaniline (46
)N-(2-hydroxyethyl)-N-[2-(2-methoxyethoxy)ethyl]-aniline (47)N-cyclohexyl-N-(2-methoxyethyl)-aniline (
48) N-(2-piveridinoethyl)-N-{2-[2
1(2-Methoxyethoxy)ethoxy]ethyl}-3-methylaniline J(49) N-(methylsulfonimidoethyl)-N-[2-(2-methoxyethoxy)ethyl]2-3-methylaniline (50) Nichi (
2-furylmethyl)-N-(2-methoxyethyl)-3
・5-dimethylaniline (51)N-dodecyl-N
-[2-(2-methoxyethoxy)ethyl]-aniline (52)N-ethyl-N-[2-(3-methoxypropoxy)ethyl]-3-methylaniline (53)N-(methylsulfonamidoethyl)-N-[ 2-{21 [2-
(2-methoxyethoxy)ethoxy]ethoxy}ethyl]-3-methylaniline (5-core N-ethyl-N-[2
-(2-bropoxyethoxy)ethoxy)ethyl-3-methylaniline (55)N-ethyl-N-{2-[2
1(2-Hydoxyethoxy)ethoxy]ethoxy}ethyl-3-methylaniline (56)N-ethyl-N-[1-methyl-2
1-(1-methyl-2-hydroxyethoxy)ethyl]aniline (57)N-(2-methoxyethyl)-3-methylaniline(58)N-[2-(2-methoxyethoxy)ethyl]-aniline(59)N- 21 {2-[2
1(2-Methoxyethoxy)ethoxy]ethoxy}ethyl]-3-methylaniline The above-mentioned compound obtained by the method of the present invention can be used as an intermediate for dyes, pigments, pharmaceuticals, agricultural chemicals, color formers for copying paper, etc. It is useful as an intermediate for color photography, but it is also extremely important as an intermediate for color photographic color development. The above general formula [m] or [
In order to convert the compound represented by the general formula [m] or [W
] must be converted into an N-group. There are various ways to do this. For example, R in the present invention
By using the method of the present invention using a compound represented by the general formula [1] in which 4 is a nitro group as a starting material, a compound represented by the general formula [m] or [W] having a nitro group at the 4-position is obtained. By only subsequent reduction, a compound useful as a color photographic color developer can be obtained. Also, general formula [
1], using an amine/group substituted with a protecting group as R4, the general formula [
By obtaining a compound represented by [m] or [W] and then removing the protective group, a compound useful as a color photographic color developing agent can be obtained. The protecting group includes, for example, an alkyl, aryl or aralkylsulfonyl group, an acyl group, an aryloyl group, an aralkylcarbonyl group, an alkyl, aryl or aralkyloxalyl group, an alkyl, aryl or aralkyloxalyloxy group, an alkyl, aryl or aralkyloxyoxalyl group. , an alkyl, aryl or aralkyloxalyloxy group, an alkyl, aryl or aralkyloxycarbonyloxy group, and the like. Using a compound represented by the general formula [1] having R4 other than an amino group substituted with a nitro group or a protecting group as a starting material, a compound represented by the general formula [m] is prepared by the method of the present invention.
Or when a compound represented by [W] is obtained, the above Journal of American Society No. 72 Registration No. 3
The method described on pages 100 to 3125 may be used, but
More preferably, a method such as that described in Samurai Gan Sho 50-157315 can be used to obtain compounds useful as color photographic color developing agents in high yield and high reaction rate. In addition, anilines having a group containing an alkylene oxide divalent group at the N-position are produced by using an alkyl halide containing an alkylene oxide divalent group, which is described in Tokusekki No. 50-131526. Compared to the intermediates prepared by the method of the present invention, the sensitivity and fogging, especially the occurrence of capri, are low. Next, the present invention will be specifically explained with reference to examples.
This does not limit the embodiments of the present invention. Example 1 Method for producing exemplified compound (21) 1 Production of 2-methoxyethyl-p-toluenesulfonate Z acid ester B-methoxyethanol 22.8 min (0.
To a pyridine solution obtained by dissolving 3 moles of p-toluenesulfonyl chloride in 96 moles of pyridine, 62.7 moles of p-toluenesulfonyl chloride (0.33 moles) was gradually added and reacted while stirring at 20° C. or lower. After reacting this solution for 2 hours, it was poured into ice water containing hydrochloric acid to obtain an oily substance. This was extracted from ethyl acetate, washed with water, dehydrated, and concentrated. Next, vacuum distillation was carried out to obtain 52% of 2-methoxy-2-methyl-p-toluenesulfonic acid ester with a boiling point of 125 to 130°C/1 side Hg (yield 75%).
) was obtained. It can be seen that this yield is extremely high when compared with the production of substituted alkyl halides described in the above-mentioned Tokokukan Sho 47-11534.
20 Method for producing exemplified compound (1) Commercially available N-ethyl-m-toluidine 27 (0.2 mol) was added to the above p-toluenesulfonic acid ester 23 (0.1 mol) and heated at 140 to 150 qo for 2 hours. Made me react. Ethyl chloride was added to the reaction mixture for 3 extractions, 5% caustic soda aqueous solution was added to make it alkaline, the ethyl chloride extract was washed with water, dehydrated, concentrated, and distilled under reduced pressure to a boiling point of 91-9.
50/3 Yanagi Hg exemplified compound {2}17.6 times (yield 91%) was obtained. The structure of this substance was determined by mass spectroscopy (M+19
Confirmed by 3 calculations and 3 molecular weights (193). Example 2 Method for producing exemplified compound (11) 1 Production of (2-methoxyethoxy)ethyl-p-toluenesulfonic acid ester Obtained by adding pyridine 96 to diethylene glycol monomethyl ether 36 (0.3 mol) 20 qo in pyridine solution
Below, p-toluenesulfonyl is shown below. 62.7 moles (0.33 mol) of Ride was gradually added to react. After reacting this solution for 3 hours, it was poured into ice water containing hydrochloric acid to obtain a solid precipitate. The solid matter was filtered, washed with water, and dried to obtain a white solid of p-toluenesulfonic acid ester. The melting point is 25°C and the yield is 95.
%Met. This yield is the above Hakama Kaisho 50-13152
It can be seen that the yield is extremely high when compared with the production of substituted alkyl halides described in Publication No. 6. Incidentally, as described on page 4 of the same publication, the yield of 2-methoxytoxyethyl bromide using phosphorus tribromide is about 20%. 0 Preparation of Exemplified Compound (11) Add N-methyl-m to 40% aqueous sodium hydroxide solution 6'.
- Add and dissolve 10.5 moles (0.09 moles) of toluidine, and add 25 moles (0.09 moles) of the p-toluenesulfonic acid ester obtained in 1 above while stirring into the resulting solution. was added and reacted for 3 hours while heating to 110 qo. This reaction solution was poured into water, and the oily component in the resulting product was extracted with ethyl acetate. This extract was dried over E-nitrogen, concentrated under reduced pressure, and then distilled under reduced pressure. After distilling off N-methyl-m-toluidine, which has a low boiling point, the boiling point area is
Example Compound (11) (yield: 60%) was obtained.
The structure of this substance was determined by mass spectrometry (M+223, calculated molecular weight 2
23). Example 3 Method for producing exemplified compound (12) p-Toluenesulfonic acid ester was synthesized in the same manner as in Example 2. Next, this p-toluenesulfonic acid ester 29 (0.
09 mol) and 2 times the mol of N-ethyl m-toluidine (
0.18 mol) was added thereto, and the mixture was reacted for 2 hours while heating to 140 to 150 oo. The reaction solution was extracted from ethyl acid, made alkaline with a 5% aqueous solution of caustic soda, washed with water, dried over bitter salt, concentrated under reduced pressure, and then distilled under reduced pressure. After recovering the low boiling point N-ethyl-m-tolesine, the boiling point was 115°C/0.
5 Exemplary compound of Yanagi Hg (1 core 17.0 minutes (yield 80%)
I got it. The structure of this product was confirmed by mass spectrometry (M+237, calculated molecular weight 237). On page 4 of the above-mentioned Tokukan Sho 50-1131526 publication, the production of exemplified compound (13) using 2-(2-methoxyshethoxy)ethylfuromide is described, but in this method the reaction takes 10 hours. However, the yield is still lower than that of the present invention, which shows that the method of the present invention is extremely superior. Example 4 Production method of exemplified compound (36) 1 Production of 1-methyl-2-methoxyethyl-p-toluenesulfonic acid ester 45% of propylene glycol-Q-monomethyl ether (0.5 mol) and 18% of pyridine
104.5 moles (0.55 mol) of p-toluenesulfonyl chloride was gradually added to the pyridine solution obtained by adding 0.0 mole of p-toluenesulfonyl chloride under a pressure of 20 °C or less for reaction. After reacting this solution for 3 hours, it was poured into ice water containing hydrochloric acid. The oily substance obtained at this time was extracted with ethyl acetate, and the extract was dried with sulfur and concentrated to obtain a pale yellow liquid. The yield at this time was 95%. (b) The p-toluenesulfonic acid ester 91 obtained in Production 1 of Exemplary Compound (36) (
0.37 mol) of N-ethyl-m-toluidine (0.8 mol) was added thereto, and the mixture was reacted for 2 hours while heating at 140 to 160°C. This reaction solution was extracted from ethyl acid and extracted with 5% caustic soda.
After making the extract alkaline with an aqueous solution and washing with water, the extract was dried over ramie, concentrated under reduced pressure, and then distilled under reduced pressure. After recovering the low boiling point N-ethyl-m-toludine, the boiling point is 76~78oo/
1 Willow Hg Exemplary Compound (46) 57.5 days (yield 75%)
) was obtained. The structure of this product was confirmed by mass spectrometry (M+207, calculated molecular weight 207). Example 5 Process for producing exemplified compound (20) 12-[2-methoxyethoxy)ethoxy] Production of ethyl p-toluenesulfonic acid ester Triethylene glycol monomethyl ether 49 (0.3 mol)
To the pyridine solution obtained by adding 96% of pyridine to
62.7 mol (0.33 motyl) of p-toluenesulfonyl chloride was gradually added to the reactant below ◯ to cause a reaction. After further reacting this solution for 3 hours, it was poured into ice water containing hydrochloric acid to obtain an oily substance. This was extracted using ethyl acetate. This extract was dried with trisnitrogen and concentrated under reduced pressure to obtain a colorless and transparent liquid. Yield was 95%. D Exemplary compound (p-toluenesulfonic acid ester 29 obtained in Production 1 of 200 (
0.09 mol) to 25 mol of N-ethyl toluidine (
0.18 mol) was added and reacted for 2 hours at 140 to 150 qo. This reaction solution was extracted from ethyl acid, and extracted with 5% caustic soda.
After making alkaline with an aqueous solution and washing with water, the extract was dried with sulfur and concentrated under reduced pressure, and then distilled under reduced pressure. After recovering the low boiling point N-ethyl-m-toluidine, the boiling point 115q0/
0.5 Hg of N-ethyl-N-{2-[2-(2-methoxyethoxy)ethoxy]ethyl}-3-methylaniline (yield: 80%) was obtained. The structure of this product was confirmed by mass spectrometry (M+281 calculated molecular weight 281). Example 6 Process for producing exemplified compound (21) 12-[2-methoxyethoxy)ethoxy] Production of ethyl-p-toluenesulfonic acid ester Triethylene glycol monoethyl ether 36 (0.2 mol)
To the pyridine solution obtained by adding 64% of pyridine to
42 moles (0.22 mol) of p-toluenesulfonyl chloride was gradually added to the mixture under a loss of pressure to cause a reaction. After further reacting this solution for 3 hours, it was poured into ice water containing hydrochloric acid to obtain an oily substance. This was extracted using ethyl acetate. This extract was dried over ramie and concentrated under reduced pressure to obtain a colorless and transparent liquid. The yield was 90%. B
The p-toluenesulfonic acid ester obtained in Production 1 of Exemplified Compound (21) 55 (
0.17 mol) was added with 48 mol of N-ethyl toluidine, and reacted at 140 to 150 qo for 2 to 3 hours. This reaction solution was extracted from ethyl acid, and extracted with 5% caustic soda.
The mixture was made alkaline with an aqueous solution, washed with water, and the extract was dried over ramie and concentrated under reduced pressure, followed by distillation under reduced pressure. After recovering the low boiling point N-ethyl-m-toluidine, the boiling point 13 was 0/1.
37.5 hours of N-ethyl-N-{2-[2-(2-ethoxyethoxy)ethoxy]ethyl}-3-methylaniline (yield 75%) was obtained from 5 Yanagi Hg. The structure of this product was confirmed by mass spectrometry (M+295 calculated molecular weight 295). Example 7 Exemplary compound (5-core manufacturing method 1 2-[2-(2-propoxyethoxy)ethoxy]
Preparation of ethyl-p-toluenesulfonic acid ester Triethylene glycol monopropylene ester 5.8 hours (0.
To a pyridine solution obtained by adding 9.6 moles of pyridine to 0.3 moles of p-toluenesulfonyl chloride under a vacuum at 20 DEG C. or lower, 6.3 moles of p-toluenesulfonyl chloride (0.0 paper moles) was gradually added to react. After further reacting this solution for 3 hours, it was poured into ice water containing hydrochloric acid to obtain an oily substance. This was extracted using ethyl acetate. This extract was dried over ramie and concentrated under reduced pressure to obtain a colorless and transparent liquid. The yield was 85%. B
To 3.5 moles (0.01 mol) of p-toluenesulfonic acid ester obtained in Production 1 of Exemplary Compound (50), 2.7 moles (0.02 mol) of N-ethyl-toluidine was added, and 140 ~15
The reaction was allowed to proceed for 2 hours while heating to 0q0. The reaction product was extracted with ethyl acid acid, made alkaline with a 5% aqueous solution of caustic soda, washed with water, and the extract was dried over reed sulfur, concentrated under reduced pressure, and then distilled under reduced pressure. Low boiling point N
- After recovering ethyl-m-toludine, the boiling point is 135~
Exemplary compound (54) 23 times (yield 75%) was obtained at 140°C/1 day Hg. The structure of this substance was determined by mass spectroscopy (M+30
9 calculated molecular weight 309). Example 8 Method for producing exemplified compound (18) p-toluenesulfonic acid ester was synthesized in the same manner as in Example 5. Next, this p-toluenesulfonic acid ester was added for 3.2 hours (0
．． 11 moles) was added with 2.5 moles (0.02 moles) of N-ethylaniline, and the mixture was reacted for 2 hours while heating to 140 to 15,000 mol. This reaction product was extracted from ethyl acid and extracted with 5% caustic soda.
After making alkaline with an aqueous solution and washing with water, the extract was dried with trinitric nitrate, concentrated under reduced pressure, and then distilled under reduced pressure. After recovering N-ethylaniline with a low boiling point, 1.9 quarts (yield 72%) of exemplary compound (18) with a boiling point of 110 to 115 qo/2 side Hg was obtained. The structure of this product was confirmed by mass spectrometry (M+267 calculated molecular weight 267). Example 9 Exemplary Compound (Production Method of 2 Mothers Using tetraethylene glycol monomethyl ether,
p-toluenesulfonic acid ester was synthesized in the same manner as in Example 8. A colorless transparent liquid was obtained. The yield at this time was 70%. Next, using this p-toluenesulfonic acid ester, the exemplified compound (28) was obtained by reacting with N-ethyl-m-toluidine in the same manner as in Example 7. The boiling point is 140-145℃/1 Hg, and the yield is about 60%.
Met. The structure of this product was confirmed by mass spectrometry (M+325 calculated molecular weight 325). Example 10 The p-toluenesulfonic acid ester synthesized by the method of Example 2 was used as the exemplified compound (3$).
6.4 m-toluidine (0.06 mol) was added to 4 mol) and reacted for 3 hours while heating at 160 to 180°C. This reaction solution was extracted from ethyl nitrate, made alkaline with 5% caustic soda-aqueous solution, washed with water, the extract was dried over reed sulfur, concentrated under reduced pressure, and then distilled under reduced pressure.
9000/1 side Hg of Exemplified Compound (33) 4.9 hours (yield 55%) was obtained. The structure of this substance was determined by mass spectroscopy (M12
Confirmed by 2Rokujusan molecular weight 223). Example 11 Method for producing exemplified compound (1) Method for producing 2-phenoxyethyl-p-toluenesulfonic acid ester 2-Phenoxyethanol 50 mg (0
．． To a pyridine solution obtained by adding 115 moles of pyridine to 36 moles), 76 moles of p-toluenesulfonyl chloride (0.4 moles) was gradually added under a pressure of 2,000 mol or less to cause a reaction. After further reacting this solution for 1 hour, it was poured into ice water containing hydrochloric acid to obtain a solid precipitate. It was filtered and dried to obtain white powdery crystals. This is mass spectrometry (M + calculated molecular weight 2
92) It was confirmed that the target substance was p-toluenesulfonic acid ester based on elemental analysis values. The yield at this time is 7
It was 8%. B. Method for producing exemplified compound (6) N-ethyl-m-toluidine (0.03 mol) 40
Add 12% caustic potassium aqueous solution and while vigorously praying, 1
The p-toluenesulfonic acid ester obtained in
0.03 mol) is added. The mixture was reacted for 3 hours at a reaction temperature of 110 to 120°C, poured into ice water, extracted with ethyl acetate, washed with water, dehydrated, and concentrated to obtain a solid product. The mixture was recrystallized from ether/alcohol to give Exemplary Compound 14.8 (yield: 63%) with a mp of 55 to 8°C. The structure of this substance was determined by mass spectroscopy (M1255 calculated molecular weight 25
5) was confirmed. Example 12 Exemplary compound (14)
Method for producing p-tresosulfonic acid ester was carried out in the same manner as in Example 2. Next, the exemplified compound (17) was obtained using this p-toluenesulfonic acid ester in the same manner as in Example 3 and using N-ethyl-3-chloroaniline as a raw material. Boiling point 12000/0.5-leg Hg (yield 69%) The structure of this product was determined by mass spectrometry (M+271 calculated molecular weight 271.5)
Confirmed by. Example 13 Process for producing exemplified compound {7- 1 Production of 2-(2-chloroethoxy)ethyl-p-toluenesulfonic acid ester Adding pyridine 76 to 3M (0.24 mol) of ethylene glycol monochloroethyl ether
To the pyridine solution obtained by adding 30% of p-toluenesulfonyl chloride (0.2%) was added 46% of p-toluenesulfonyl chloride (0.2
4 mol) was gradually added to react. After further reacting this solution for 3 hours, it was poured into ice water containing hydrochloric acid to obtain an oily substance. This was extracted using ethyl acetate. This extract was dried with trisnitrogen and concentrated under reduced pressure to obtain a colorless and transparent liquid. The yield was 81%. B
p-toluenesulfonic acid ester 11.2 obtained in Production 1 of Exemplified Compound '7-
(0.04 mol) and N-ethyl-m-toludine 10
．． The reaction solution was extracted from ethyl chloride, made alkali-based with a 5% aqueous solution of caustic soda, and after washing with water, the extract was washed with water. was dried with sulfur, concentrated under reduced pressure, and then distilled under reduced pressure.Boiling point: 115~
1170/1 Exemplary compound '7'51 of Hg (yield 5
3%). Examples A compound (referred to as compound A) obtained by reducing a compound having a nitro group at the para position to the amide/group of the exemplary compound Exemplary compound '1' described in No.-131526 was prepared. Sakura color paper (manufactured by Konishiroku Photo Industry Co., Ltd.) was then subjected to wedge exposure through a blue filter, and this was then exposed to a developer (1) containing the above-mentioned compound (1) synthesized by the method according to the present invention, or a developer (1996). 1131
A sample having a color image was prepared by processing with an exemplary compound {developer 'B containing 11} synthesized according to the description in No. 526, followed by processing with a bleach-fix solution and a stabilizer. [Processing process] 3100 Processing time Color development 3 minutes 3 minutes Bleach fixing 1 minute 3 light @Water 2 minutes stabilization 1 minute [Color photographic developer] Penzyl alcohol 5.0 ml Sodium hexametaphosphate 300 t Anhydrous sulfite Sodium 1.85 Sodium bromide 1.40 Potassium bromide
0.50 ta shelf sand (Na2&07
10 days 20) Add 39.10 ta compound style or exemplified compound {11 3.12 ta water and 1
Saw, 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. The sensitivity is expressed as a relative value, with the sensitivity when using a developer containing the compound (1) obtained according to the present invention as 100. Table 1 As can be seen from the above experimental examples, the color developing agent for color photography using the compound according to the present invention as an intermediate has lower sensitivity and fog than the color developing agent obtained by the known method. It can be seen that the results are excellent, and the occurrence of fogging is particularly low.

Claims (1)

[Claims] 1 General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents an alkyl group, R_2, R_3
, R_4, R_5 and R_6 each represent a hydrogen atom, a halogen atom or an alkyl group. ) and the general formula [II] R_7-SO_3-
(R_8O_1)_n-(R_9O)_m-R_1_0
(In the formula, R_7 represents an alkyl group or an aryl group, and R
_8 and R_9 each represent an alkylene group having 1 to 6 carbon atoms, n and m are each an integer of 0 or more, and the sum of n and m is 1 to 5, and R_1_0 is a phenyl group or a carbon atom Represents an alkyl group of numbers 1 to 6. ) General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, R_3, R_4, R_5 and R_6 are each represented by the general formula [III] I] is the same as in
R_8, R_9 and R_1_0 and n and m are each the same as in general formula [II]. ) or general formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_2, R_3, R_4, R_5 and R_6 are respectively the same as in general formula [I], R_8,
R_9 and R_1_0 and n and m are each the same as in general formula [II]. ) A method for producing anilines for intermediates of color developing agents for color photography, which have an alkylene oxide divalent group at the N-position.