JPS5941980B2 - Method for producing hydrazinoalkanesulfonic acid derivatives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing hydrazinoalkanesulfonic acid or hydrazinoalkanesulfonic acid (hereinafter collectively referred to as hydrazinoalkanesulfonic acid) derivatives represented by the general formula (■) or (V).

The hydrazinoalkanesulfonic acid derivatives of the present invention can be used as useful intermediates in heterocycle synthesis, and in particular,
It is a very important compound in the production of pyrazole rings such as 5-pyrazolones, 3,5-pyrazolodiones, pyrazologiazolones, pyrazoloquinolines, pyrazolobenzimidazoles, and pyrazolopyridines. In particular, the hydrazinoalkanesulfonic acids of the present invention (general formula (■)
When R1 is a hydrogen atom), it can be used as a magenta color forming agent (coupler) for silver halide photographic light-sensitive materials, and also as a sensitizing dye (for example, methine dye) and dye (for example, for filters) for silver halide photographic light-sensitive materials. It is an extremely useful compound as a raw material for 1-sulfoalkane-5-pyrazolones, which are raw materials for dyes for anti-irradiation and antihalation).

Alternatively, the azo dyes comprising the pyrazolones mentioned above are used as dyes for dyeing or printing natural or regenerated cellulose fibers, natural or synthetic polyamide or polyurethane fibers. Furthermore, in general formula (■), R1
Substituted hydrazinoalkanesulfonic acids consisting of an acyl group are also used as N-sulfoalkane-sulfonic acids, which are raw materials for sensitizing dyes and dyes for silver halide photographic light-sensitive materials (for example, dyes for filters, anti-irradiation, and anti-halation dyes). It is a very useful compound as a raw material for 3,5-pyrazolidiones.

In addition, the above-mentioned pyrazolone derivatives are also important in pharmaceutical applications, particularly as diuretics, salt stimulants, antihypertensive agents,
It is used as a hyperthrombotic agent, hypopyretic agent, analgesic agent, and anti-inflammatory agent. Two methods are known as conventional methods for producing hydrazinomonoalkanesulfonic acids represented by the general formula () or (V).

One is the method described in West German Patent No. 696776, in which 2-bromoethanesulfonic acid sodium salt is treated with an alkali to produce vinylsulfonic acid sodium salt, and hydrazine is added to this to produce 2-hydrazinoethanesulfone. This is a method of obtaining sodium chloride.

The other one is West German Patent No. 1287589 and “All
ll. Chem-1972.118, hydrazinoalkanesulfonic acids are obtained by reacting hydrazine with 4- to 5-membered sultones (for example, γ
- γ-hydrazinopropanesulfonic acid is obtained by reacting propane sultone with hydrazine hydrate at room temperature. ) method. However, in the latter method, the highly reactive sultones that react with hydrazine are limited to 4- to 5-membered rings.

Furthermore, these highly reactive sultones pose a serious problem in terms of chemical safety, and special consideration is required when handling them to reduce their impact on the human body. In the former method, a compound having a vinyl group is produced through an elimination reaction of a halogen acid by the action of an alkali, and the compound is reacted with hydrazines.

That is, in the method described in West German Patent No. 696776, when 2-halogen 7-substituted ethanesulfonic acid sodium salt (A) is treated in an aqueous solution containing an alkali (equimolar amount) as shown in the following formula, hydrogen halide is easily generated. By elimination, vinylsulfonic acid sodium salt (B) is quantitatively produced, and by adding hydrazine hydrate to this compound (B), the desired sodium 2-hydrazinoethanesulfonate (
This is a method to obtain C). In this method, monosulfoalkyl forms of hydrazines can be obtained, but the reaction conditions must be made strongly alkaline than PHLO, and a vinyl compound is produced, so if you raise the temperature to make the reaction proceed faster, it will polymerize. If this method is used, the reaction must be allowed to proceed for a long time at about room temperature.

Also, ``MethOdenderOrganische''
nChemie” (VOllO/2, P5~P7O(1
967)), when attempting to alkylate hydrated hydrazine or N-monosubstituted hydrazine by reacting an alkyl halide in a neutral region, N-N-dialkylated product or N-N・N It was said that the /-trialkylated product was mainly produced and that it was almost impossible to obtain the monoalkylated product.

From the above, there were many difficulties in producing monosulfoalkylated hydrazine derivatives as represented by the general formula () or (V).

Therefore, an object of the present invention is to provide a new method for producing hydrazinoalkanesulfonic acids or substituted hydrazinoalkanesulfonic acids using mild reaction conditions but at low cost.

The object of the present invention [ζ was achieved by the following manufacturing method.

That is, a chloroalkanesulfonate represented by the following general formula (1) (free form is also acceptable) and a hydrazine derivative represented by the general formula () or the general formula () are heated at PH5 to P
This was achieved by a method in which a hydrazinoalkanesulfonic acid derivative represented by general formula () or general formula (V) was obtained by reacting with H8 at a temperature of 50°C to 150°C.

(1) Cl-L-SO3M In the above general formulas (1), () and (V), L represents a divalent aliphatic group having 8 or less carbon atoms, and the carbon chain has no unsaturated bond, It may be interrupted with oxygen.

The above aliphatic groups include those substituted with various groups.

For example, it may be substituted with a hydroxy group, an alkoxy group having up to 3 carbon atoms (eg, a methoxy group, an ethoxy group), or the like. That is, the above aliphatic group includes an alkylene group (
For example, ethylene group, propylene group, 2-methylethylene group, butylene group, 3-methylpropylene group, 1-methyl-butylene group, hexylene group, etc.); alkyleneoxyalkylene group (for example, ethyleneoxyethylene group,
propyleneoxyethylene group) and substituted alkylene groups (e.g., 2-hydroxy-1,3-propylene group, 3
-hydroxy-1●4-butylene group, 3-methoxybenzene group, etc.).

R1 is a hydrogen atom or an acyl group derived from an aliphatic or aromatic carboxylic acid or sulfonic acid having 2 to 8 carbon atoms (e.g., acetyl group, propionyl group, benzoyl group, methanesulfonyl group, p-toluenesulfonyl group, etc.) ).

R2 and R3 may be the same or different, except when either one is a hydrogen atom, and R2 and R3 may be the same or different, and may be a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a n-propyl group, n-hexyl group, isopropyl group, etc.), a substituted alkyl group having a total number of carbon atoms of 8 or less [as a substituent, for example, a hydroxy group (e.g., 3-hydroxypropyl group, 4-hydroxybutyl group, etc.), an alkoxy group (e.g., 2-ethoxyethyl group, 2-propioxyethyl group, 3-methoxypropyl group, etc.), cyano group (
For example, 2-cyanoethyl group, 2-methyl-2-cyanoethyl group), alkoxycarbonyl group (for example, ethoxycarbonylmethyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonylpropyl group, 2-proboxycarbonylethyl group) ), or aryloxycarbonyl groups (e.g., phenoxycarbonylmethyl group, 2-(4-methylphenoxy)carbonylethyl group, etc.), phenyl group, substituted phenyl group [as a substituent, for example, a halogen atom (e.g. , chlorine atom, bromine atom, etc.), cyano group, hydroxy group, carboxy group, alkyl group having 1 to 3 carbon atoms (e.g. methyl group, ethyl group, etc.), alkoxy group having 1 to 3 carbon atoms (e.g. methoxy group) , ethoxy group, propioxy group, etc.), nitro group], or an aralkyl group having 7 to 8 carbon atoms (eg, benzyl group, phenethyl group, etc.). M represents a cation such as a hydrogen atom, an alkali metal (eg, sodium, potassium), an alkaline earth metal (eg, calcium), ammonium, or an organic base (eg, triethylamine, pyridine, piperidine, morpholine). A feature of the present invention is that a hydrazine derivative is monoalkylated using a chloroalkanesulfonate represented by the general formula (1).

When bromoalkanesulfonate is used instead of chloroalkanesulfonate, the above 1"MethOde
As concluded in derOrganischenChemie'5, polysubstituted products such as lydialkylhydrazine and trialkylhydrazine are formed, so the yield of monoalkyl-substituted hydrazine is extremely low.

In the present invention, since monoalkyl-substituted hydrazine is mainly produced, the yield is extremely high. It must be said that this was completely unexpected based on known knowledge. In the present invention, the solvent in which the compound represented by the general formula (1) is reacted with the general formula () or the substituted hydrazine represented by the general formula () may be water, and if necessary, a water-soluble organic solvent may be coexisting. .

Examples of organic solvents to be used include alcohols such as aliphatic alcohols having 1 to 5 carbon atoms (e.g., methanol,
Ethanol, n-propyl alcohol, IsO-propyl alcohol! Nitriles (e.g., acetonitrile, propionitrile, etc.) and amides (e.g., N-N-dimethylformamide, N-N-dimethylacetamide, etc.) are preferred.
is also preferable. In the present invention, the chloroalkanesulfonic acid represented by the general formula (1) and the hydrated hydrazine or substituted hydrazine are used in a molar ratio of 1. O vs. 1. O~10
．． O and preferably 1.0 to 1.0. O~5. It is O.

In the present invention, the temperature for carrying out this reaction is from 50°C to 150°C, preferably from 70°C to 120°C, since there is no risk of forming a polymer of the vinyl compound.
It is. Since the reaction can be carried out at such a high temperature, the method of the present invention requires 1/4 to 1/8 the time required to obtain the same amount of the target product as compared to known methods. In addition, in the present invention, since chloroalkanesulfonic acid is used as a starting material, a monosubstituted product can be obtained in high yield without passing through a vinyl compound, so it is not necessary to specially add an alkali agent to obtain a vinyl compound. do not have.

Therefore, the pH of the reaction system does not become high, and there is no need to take special precautions in the reaction apparatus or reaction operation. In the present invention, since hydrazines and chloroalkanesulfonic acids are directly reacted without using an alkaline agent, the pH value of the reaction system is determined by the properties of the aqueous solution of hydrazines, and is therefore at most 8. Furthermore, if the pH is too low, the reaction will slow down. Therefore, a suitable pH range is 5 to 8,
More preferably it is 7-8. Representative compounds of the chloroalkanesulfonic acids represented by the general formula (1) used as raw materials of the present invention are shown below. For example, 2-chloroethane-1-sulfonic acid sodium salt, 3-chloropropane-1-sulfonic acid sodium salt, 4-chlorobutane-
1-sulfonic acid, 2-chlorobutane-1-sulfonic acid,
6-chlorohexane-1-sulfonic acid, 2-chloro2-
Methyl-ethane-1-sulfonic acid, 1-chloropropane-2-sulfonic acid, 2-chlorohexane-1-sulfonic acid, 3-chloro-2-hydroxy-propane-1-sulfonic acid, 5-chloro-3-oxaheptane -1-sulfonic acid, 6-chloro-3-oxahexane-1-sulfonic acid, 5-chloro-3-methoxypentane-1-
Sulfonic acid sodium salt, sodium 3-hydroxy-4-crobutane-1-sulfonate.

The chloroalkanesulfonic acids represented by the general formula (1) are
nChemie [V01 9, P343-404 (1
955)]. were prepared using various synthetic methods described in .

Specifically, the method of monosulfonation of alkylene dichlorides or alkylene chlorobromides with sulfites is described in the so-called Stretzker reaction [for example, British Patent No. 760379 and "Bu11.Chim.Soc.
Be1ges'64, 409 (1955)], or a method of hydrolyzing chloroalkanesulfonyl chlorides obtained by various methods [for example, Ann. Chim5
, Σdan'', 23 (1949), and Industrial Chemistry Magazine, 5
9, 1028 (1956), etc.).

More specifically, 3-chloropropane-1-sulfonic acid sodium salt is described in Ann. Chim. -588, 71 (
It was synthesized according to the method described in (1954).

Production examples of sodium 4-chlorobutane-1-sulfonate and sodium 5-chloro-3-oxapentane-1-sulfonate are listed below.

Synthesis example 1 (5-chloro-3-oxapentane-1-
Synthesis of sodium sulfonate salt) 20 ml of an aqueous solution of 5 kg of sodium hydroxide was added to 100 ml of a 25% sodium vinyl sulfonate aqueous solution, and the mixture was cooled to below 10°C with ice water.

Chlorethylhydrin 16.1 in this? A solution prepared by dissolving 30 m of acetonitrile was added dropwise under stirring, and then 20 m
Stir at ~25°C for 10 hours. After neutralizing the reaction mixture with several drops of concentrated hydrochloric acid to a pH of 6, the solvent was concentrated under reduced pressure. 150 ml of 90% ethanol aqueous solution was added to the residue and dissolved under reflux, and undissolved materials were separated while hot. 1 part acetone to the sap
50 ml was added and cooled to below 10°C with ice water cooling. The precipitated crystals were collected, washed with isopropanol, and dried. Yield: 27.5 kg Recrystallized from a 90% aqueous ethanol solution to obtain white crystals with a melting point of 300°C or higher. C4H8Cl04sN
Calculated value as a: C; 22.82%, H;, 3.83
%, Cl; 16.83% Synthesis Example 2 (Synthesis of 4-chlorobutane-1-sulfonic acid sodium salt) [゜゛Bu11
Chin Soc Belges-64, 408 (1
955)] 1,4-butane dichloride (95.32 ml) was mixed with 350 ml of ethanol and 15 ml of water.
Dissolve in 0 ml of mixed solution and add 5 ml of copper powder to this solution. The mixture was added to 300 ml of an aqueous solution of sodium sulfite 63 (!) and stirred under reflux for 10 hours.

The reaction mixture dissolved and the pH of the solution was 6. After the reaction solution was filtered, the solvent was concentrated under reduced pressure. 90 for residue
% ethanol aqueous solution (350 WLI) was added and dissolved under reflux, and undissolved materials were separated while hot. ▲Add 300ml of acetone to the liquid
was added and cooled to below 10°C in ice water. The precipitated crystals were collected, washed with isopropanol, and dried. Yield: 73.5 kg Recrystallized from a 90% aqueous ethanol solution to obtain white crystals with a melting point of 300°C or higher.

Specific examples of substituted hydrazines represented by the general formula (■) are listed below.

Hydrazine hydrate, acetyl hydrazide, propionyl hydrazide, benzoyl hydrazide, methanesulfonyl hydrazide, p-toluenesulfonyl hydrazide More specifically, acetyl hydrazide was produced by the method described in 191.

Specific examples of the hydrazine derivatives represented by the general formula (■) are listed below.

Ethylidene hydrazine, propylidene hydrazine, 2-
Ethoxyethylidenehydrazine, butylidenehydrazine, 3-cyanopyropylidenehydrazine, 4-hydroxybutylidenehydrazine, allylidenehydrazine, benzylidenehydrazine, 4-nitrobenzylidenehydrazine, (methyl-phenyl-methylene)hydrazine, [methyl (4'- methylphenyl)-methylene]hydrazine More specifically, arylidenehydrazine is prepared according to Ber. ,
↓The method described in J1 3034, and benzylidenehydrazine, is described in Ber. , 49, 1906 and [methyl-phenyl-methylene]hydrazine, the method described in Beilstein Organiehe Chemie
．． It was produced by the method described in '7, 279.

Specific examples of the hydrazinoalkanesulfonic acids represented by the general formulas (■) and (V) are listed below.

2-hydrazinoethane-1-sulfonic acid 3-hydrazinopropane-1-sulfonic acid 4-hydrazinobutane-1-sulfonic acid 3-hydrazino-2-hydroxypropane-1-sulfonic acid 6-hydrazinohexane-1-sulfonic acid 1- hydrazinopropane-2-sulfonic acid 5-hydrazino-3-
Oxaheptane-1-sulfonic acid 6-hydrazino-3
-oxahexane-1 sulfonic acid 5-hydrazino-3
-methoxypentane-1-monosulfonic acid 4-hydrazino-3-hydroxybutane-1-monosulfonic acid 3-(N-
benzylidenehydrazino)propane-1-sulfonic acid 5
-(N/-benzylidenehydrazino)-3-oxoheptane-1-sulfonic acid 3-(N'-acetylhydrazino)propane-1-sulfonic acid 5-(N/-acetylhydrazino)-3-oxa monopentane-acesulfonic acid 3
-[N7-(methyl-phenylmethylene)hydrazino]
Propane-1-sulfonic acid 4-[N'-(dimethyl-methylene)hydrazino]bumen-1-sulfonic acid example
1 (Synthesis of 2-hydrazinoethane-1-sulfonic acid) 2-
Sodium chloroethanesulfonate 16.6? and water 30
ml of hydrazine hydrate heated to a temperature of 90°C. was added dropwise to the solution while stirring, and the mixture was further stirred at 90° C. for 3 hours.

Water and excess hydrazine hydrate were distilled off under reduced pressure, and the residue was dissolved in 30 me of water. In order to remove a small amount of hydrazine remaining, benzaldehyde was added while stirring at room temperature, and the mixture was crystallized as benzladine. Separate it by r, ▲
The liquid was concentrated, and methanol was added to precipitate crystals. The collected crystals were recrystallized from an 85% methanol aqueous solution to a melting point of 17.
10.8 white crystals with a temperature of 8-180°C were obtained. Comparative Example 1 60 mi of an aqueous solution in which 16.62 ml of sodium 2-chloroethanesulfonate and 4.0 ml of sodium hydroxide were dissolved! :
When the mixture was added to P and stirred at 45°C, it gradually became cloudy and became gel-like.

Even when hydrazine hydrate was added to this, almost no 2-hydrazinoethanesulfonic acid was obtained. Example 2 (Synthesis of 3-hydrazinopropane-1-sulfonic acid) 3
- Sodium chloropropane-1-sulfonate 187
An aqueous solution of 30 d of water was added dropwise to 30 ml of hydrazine hydrate heated to 90° C. with stirring, and the mixture was stirred at 90° C. for 3 hours.

Water and excess hydrazine hydrate were distilled off under reduced pressure, and the residue was dissolved in 50 ml of water. While stirring at room temperature, 25 grams of benzaldehyde was added to crystallize. The crystals were collected and thoroughly washed with ethyl acetate until the yellow color of the crystals disappeared. After steam distilling the crystals under hydrochloric acid acidity, the residual liquid was concentrated and crystallized by adding methanol to collect white crystals.

Recrystallized from 90% methanol aqueous solution, melting point 209.5℃
10.32 (yield 68%) of white crystals of 3-hydrazinopropane-1-sulfonic acid were obtained at ~210.5°C.

Comparative Example 2 (Synthesis of 3-hydrazinopropanesulfonic acid using 3-bromopropanesulfonic acid) 22.57 (0.1 mol) of sodium 3-bromofuropanesulfonate was added to 30 ml of water.
Hydrazine hydrate 25? (0.4 mol) was added dropwise over 1 hour with stirring, and the mixture was further stirred at that temperature for 2 hours.

Benzaldehyde 662 was added with stirring at room temperature, excess hydrazine was separated as yellow crystals of benzladine, and benzaldehyde 11f was further added to the aqueous solution to precipitate white-yellow crystals.

▲The crystals were collected, washed with acetonitrile and isopropanol, and then subjected to steam distillation under hydrochloric acid acidity. After carrying out steam distillation until the distillate no longer smells of benzaldehyde, the residual liquid was concentrated to dryness under reduced pressure.
% methanol aqueous solution (30 ml), white crystals 1.
5? (Yield 10%) was obtained. These crystals were recrystallized again from 90% methanol aqueous solution with a melting point of 209-209.5°C.
White crystals were obtained.

As is clear from Example 2 and Comparative Example 2, when hydrazine compound is reacted with 3-chloropropanesulfonic acid as in the present invention, the yield of the target product, 3-hydrazinopropane-1-1-sulfonic acid, is as follows. The yield was nearly 70%, far exceeding the 10% yield when using 3-bromopropanesulfonic acid.

Example 3 (Synthesis of 4-hydrazibutane-1-sulfonic acid) Sodium 4-chlorobutane-1-sulfonate 1
An aqueous solution of 9.4 ml of water and 35 ml of water was added dropwise to 30 y of hydrazine hydrate heated to 90° C. with stirring, and the mixture was stirred for 3 hours.

Water and excess hydrazine hydrate were distilled off under reduced pressure, and the residue was dissolved in water.
Dissolved in 0ml. 25 grams of benzaldehyde was added to cause crystallization, and the crystals were collected and thoroughly washed with ethyl acetate until the yellow color disappeared from the crystals. After steam distilling the crystals under hydrochloric acid acidity, the residual liquid was concentrated and methanol
Add 50ml, add a few drops of glacial acetic acid, and cool on ice for 5 minutes.
It was cooled to below ℃ to cause crystallization.

The precipitated crystals were collected, thoroughly washed with ethanol, and dried to obtain 1565 grams of white crystals. Recrystallization from a 90% aqueous methanol solution gave white crystals with a melting point of 178-179°C.

Calculated values as C4Hl2N2O3S: C; 28.50%, H; 7.19%, N; 16
．． 65% analysis value: C; 28.53%, H; 7.08%,
N: 16.72% Example 4 (Synthesis of 6-hydrazino-3-oxopentane-1-sulfonic acid) An aqueous solution of 22,52 sodium 6-chloro-3oxopentanesulfonate and 50 ml of water was heated at a temperature of 100 ml. The mixture was added dropwise to hydrazine hydrate 307 heated to ~105°C while stirring, and the mixture was stirred for 3 hours.

Water and excess hydrazine hydrate were distilled off under reduced pressure, and the residue was dissolved in 100 WLI of water.

Benzaldehyde 25? The crystals were collected and thoroughly washed with ethyl acetate until the yellow color disappeared. The crystals were steam-distilled under acidic conditions with hydrochloric acid, the residual liquid was concentrated, and 100 ml of methanol was added to crystallize, and white crystals were collected. Recrystallize with 90% methanol aqueous solution,
White crystals with a melting point of 166-169°C 9.0? I got it.

Calculated values as C4Hl2N2O4S: C; 26.09%, H: 6.57%, N; 15
．． 21% analysis value: C; 26.13%, H; 6,56%,
N; 15.32% Example 5 (Synthesis of 3-(N'-acetylhydrazino)propane-1-sulfonic acid) Sodium 3-chloropropanesulfonate 18.0I? An aqueous solution of 30 ml of water and N-acetyl hydrazide 14,8? was added dropwise to a mixture of 30 ml of water and 30 ml of ethanol under reflux and stirring, and the mixture was stirred for 3 hours.

The reaction mixture was concentrated under reduced pressure, and 30 ml of water was added to the candy-like concentrated residue.
After adding and dissolving, 100 ml of ethyl acetate was added and shaken to separate the aqueous layer.

The mixture was concentrated under reduced pressure again, 100 ml of a 90% aqueous methanol solution and several drops of glacial acetic acid were added, and the mixture was cooled to 5° C. or lower with ice water to cause crystallization. Collect the precipitated crystals, wash with acetonitrile, dry and give 13.5? crystals were obtained. Recrystallization from methanol gave white crystals with a melting point of 183-186°C.

Calculated values as C5Hl2N2O4S: C; 30.61%, H; 6.17%, N; 14
．． 27% elemental analysis value: C; 30.57%, H; 6.18
%, N; 14.33%Example 6 (3-(N'-benzylidenehydrazino)propane-1
-Synthesis of sulfonic acid) Benzylidenehydrazine 18? was dissolved in 100 ml of 50% ethanol aqueous solution, and immediately 8
It was heated to 0-85°C.

Sodium 3-chloropropanesulfonate 18? water 3
A solution dissolved in 0 ml was added dropwise over 40 minutes while stirring, and then stirred as it was for 2 hours. The reaction mixture was concentrated under reduced pressure, and 30 ml of water was added to the residue to precipitate crystals. After washing the crystals with ethyl acetate, ▲ the collected crystals were further thoroughly washed with acetonitrile and dried to give pale white yellow crystals with 23.5
? I got it. Recrystallized from 80% methanol water, melting point 20
White crystals at 3°C were obtained.

as ClOHl4N2O3S

Claims (1)

[Claims] 1. A chloroalkanesulfonate represented by the general formula (I) and a hydrazine derivative represented by the general formula (II) or (III) are mixed at pH 5 to pH 8 and at 50°C to 15°C.
General formula (IV) characterized by being reacted at 0°C
Alternatively, a method for producing a hydrazinoalkanesulfonic acid derivative represented by general formula (V). (I) Cl-L-SO_3M (II) R^1-NH-NH_2 (III) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (IV) R^
1-NH-NH-L-SO_3M(V) ▲ Numerical formulas, chemical formulas, tables, etc. ). R^1 represents a hydrogen atom or an acyl group. R^2 and R^3 may be the same or different and are hydrogen atoms,
It represents an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group, or an aralkyl group. However, R^2 and R
^3 cannot become a hydrogen atom at the same time. M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, or an organic base cation. ]