TW200906816A - Method of producing 3-aminothiophene - Google Patents

Abstract

A method of producing 3-aminothiophene represented by Formula (4) comprises: hydrolyzing a derivative of 3-aminothiophene-2-carboxylic acid ester represented by Formula (1) to produce a metal salt of 3-aminothiophene-2-carboxylic acid represented by Formula (2); performing decarboxylation of the metal salt represented by Formula (2) under acidic conditions to produce a salt of 3-aminothiophene and an acid represented by Formula (3); and neutralizing the salt represented by Formula (3), wherein the decarboxylation is performed without isolating the metal salt represented by Formula (2) or the 3-aminothiophene-2-carboxilic acid represented by Formula (5) that is obtained by neutralizing the metal salt. According to the method of the invention, decomposition of the intermediates given in each step and of the product can be suppressed and the yield can be improved, thereby producing 3-aminothiophene that is useful as an intermediate of a pesticide in a cost-efficient industrial process. In the formulae, R represents an alkyl group of 1 to 12 carbon atoms or a phenyl group, M represents an alkali metal or an alkaline earth metal, and HX represents an acid.

Description

200906816 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing 3-aminothiophene. [Prior Art] Unexamined-Japanese-Patent No. 9-235282 (European Patent Publication No. 0737682A1) describes a 2-alkyl-3-aminothiophene derivative and a process for producing the same. Various methods are known for the method for producing the useful intermediate 3 - aminothiophene of the above compound. For example, Japanese Patent Publication No. Sho 44-12895 discloses that 3-(hydroxyimino)tetrahydrothiophene is synthesized by reacting tetrahydroσ-seceno-3-ketone with hydroxylamine, and aromatic treatment is carried out by acid treatment. To synthesize 3-aminothiophene (Reaction formula 1).

Η2νοη BaC03 EtOH *

?H

HCI ........... EtOH

NH2, Journal of Heterocyclic Chemistry, 10(6), 1067 - 1068 (1973), '5-loaded with 3-β 〇 e e 甲 amide amide amide 3 3 3 3 3 3 3 3 Amine stimuli method (Reaction formula 2).

2. However, it is difficult to ensure the safety of chemical engineering from the viewpoint of physicochemical properties or reaction control of raw materials or intermediates, and there are problems in industrialization. Japanese Patent Publication No. Hei. No. Hei 28980 discloses a method for producing 3-aminothiophene by deprotecting 3-bromothiophene to 3-oxophthalimide (Reaction Scheme 3). . Reaction formula 3

Phthalic imine imine endophyrin Cu^O

Tetraethylcne-pcntaminc

Therefore, the method described in this document is undesirable in industrialization because it produces large waste or copper waste due to phthalimide.

In Synthetic Communications, 25 (23), 3729-3734 (1995), a 3-amino thiophene-2-carboxylate derivative obtained as a starting point from a cheaper trader's conversion to a 3-amine by hydrolysis reaction After the thiophene-2-carboxylic acid derivative is subjected to decarboxylation with oxalic anhydride to obtain a 3-aminothiophene derivative (reaction formula: $.

Si type 4

1) NaOH aq. 2) Concentrated HCI (PH=5)

(〇〇2% 'PrOH

2 [wherein R represents a substitutable alkyl group] is 6^/〉= can be produced in an industrialized form, but due to the yield of 3-amino porphin, therefore, from the economic point of view, it is not People are satisfied. Also, the middle door = ^ base light - 2-carboxylic acid is prone to decarbonation, porphin. The product 3-amino group is inclined, and it is known that if the operation method is not small... = ΐίίΐΪ:: Therefore, the method is due to the unstable intermediate or production: easy to produce low or uneven productivity yak, in industrialized stable production There will be problems. Li Wei, a method of using a 3-aminothiophene-2-carboxylate touch as a raw material and I埏3 - a cosmetic thiophene, although described in the number of w〇2〇〇5—〇4〇ΐι〇号^ and 200906816 US Pat. No. 6,492,383, Tetrahedron Letters, 46, 109-112 (2005), but the yield of 3-amino-based π-phene is 29 - 56%, which is not satisfactory. Bi〇organic &

In Medicinal Chemistry Letters, 14, 21-24 (2004), in Experiment 2, methyl 3-aminothiophene-2-carboxylate was used as a raw material to obtain 3-aminothiophene in 85% yield, but not The detailed experimental method is described in U.S. Patent No. 6,492,383, the disclosure of which is incorporated herein by reference. That is to say, the 3-aminothiophene-2-carboxylate derivative has been used as a raw material, and the ester hydrolysis reaction is carried out to carry out the decarboxylation reaction, and in the method for producing the 3-aminothiophene, it is not known Industrial production perspective, a method that can be manufactured in high yield and stable. SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) The purpose of A month is to provide a 3-aminoamine which is useful as a pesticide intermediate, and which can be industrially obtained, 3-aminothiophene-2-carboxylic acid can be industrially priced. And the 3-amino group is stably produced. Sai. - In order to solve the above problems, "Mingren, etc." is an effort to develop a method for producing 3-amino stimuli by using 3-amino-based snails as a raw material. Condensation _ 3 - amine phenanthrene - 2 - lin and «, product; 聿, solution method 'by application in the manufacturing method, can be used as a workable ^ 为 is a pesticide intermediate useful for 3-amino porphin The method of the present invention is the following <1> to <8>. A method for producing a 3-amino porphin of the formula (4), which comprises: hydrolyzing a quinone-2-yl-acetic acid derivative of the formula (2) to produce a metal salt of a quinone-2-carboxylic acid To produce a salt which is formed by the decarboxylation reaction of the metal salt represented by the above formula (7); and characterized in that: 200906816 The metal salt or the metal salt of the above-mentioned metal salt is isolated: the aforementioned decarboxylation reaction , which does not represent the 3__ represented by the formula (5) obtained by the sum of the general formula (2)

NhL

(1

, 0 : 2)

NH^ HX

OM

P, s OH (5) (3) (4) The base of the base of the 'M' or the formula [wherein 'R represents a carbon number 1, a soil metal, and HX represents an acid]. The system is a salt formed by adding a solution of the aqueous solution of the salt and the organic solvent to the acid. The 3-amino group t ^ group represented by the formula (3) is obtained. &lt;5&gt; The method of &lt;4&gt; wherein, in the above formula (1), R is a methyl group or a method of 'M m1 ^ to <5 &gt; The method of any one of the above-mentioned general formula (2), wherein the method of the above formula (3), (the effect of the invention), is the method of any one of the above formula (2). Manufacture ==彳==Solution 2 =, and as a pesticide intermediate, it can be applied to industrial methods by applying it as a 2~Wei derivative in the month as the original 200906816 material. Useful as 3-aminothiophene. [Embodiment] (Best Mode for Carrying Out the Invention) The present invention will be described in detail below. Benjamin 3 - Amine. The method for producing a thiophene (Reaction formula 5) is a method for producing a 3-aminothiophene group represented by the formula (7) by hydrolyzing a derivative of the 3-amino quinone-2-carboxylic acid s represented by the formula (1). a metal salt of a carboxylic acid, which is subjected to a decarboxylation reaction of the metal salt under acidic conditions to produce a salt of 3-aminothiophene represented by the formula (3), and is produced by neutralizing the salt f. (4) A 3-aminothiophene which is characterized in that, in the above decarboxylation reaction, a metal salt of 3-aminothiophene-2-carboxylic acid represented by the formula (2) or a metal salt is not contained therein. And the obtained 3-aminothiophene-2-carboxylic acid represented by the formula (5) is isolated. Reaction formula (3)

[R represents a burnt group or a phenyl group of the slave number 1 to 12, and μ represents a metal test or a soil test ; (; genus, ΗΧ represents an acid] ^ The compound represented by the formula (1) is not limited to the following, R Representative examples are listed under the m2 base rW Hz 〇 (1). Alkyl groups having a carbon number of 1 to 12, for example, anthracenyl, ethyl, n-propyl, n-butyl, n-yl, n-hexyl, isopropyl, isobutyl a group, a second butyl group, a third butyl group, a neopentyl group, etc. R represents an alkyl group having 1 to 12 carbon atoms or a phenyl group, which may be substituted, in this case, a pyridyl group having a carbon number of 1:12 or a phenyl group. Examples of the substituent include an alkyl group such as a methyl group, an ethyl group, an isopropyl group or an isobutyl group; an alkenyl group such as a vinyl group or a propenyl group; an alkynyl group such as an ethynyl group or a propynyl group; Alkoxy group such as methoxy or ethoxy; trifluoromethoxy or methyl 200906816 oxy, etc. substituted alkoxy; alkylthio or ethylthio; alkyl strepto; , thiophene, carbazole, pyrrole, 1H-pyrazole, 3H-pyrazole, imidazole, oxazole, isothiazole, tetrahydrofuran, pyridine, etc.; halogen atom such as fluorine atom, gas atom, bromine atom or broken atom In the present invention, R has a carbon number of 1. The compound represented by the formula (2) is exemplified by an example of an alkali metal or an alkaline earth metal represented by M. Examples of the alkali metal, for example, lithium, are not limited to the following. Examples of the sodium and the final metal, for example, magnesium, calcium, barium, etc. In the present invention, M is preferably an alkali metal = HX' in the compound represented by the formula (3) or a decarbonation reaction (for example, Not limited to the following, representative examples, such as: hydrochloric acid:

Sulfuric acid, two, Gu and other inorganic acids, acetic acid, trifluoroacetic acid, cyanoacetin H 'oxalic acid, citric acid, phthalic acid, benzoic acid and other organic acids. In the present invention, hydrazine is preferably hydrochloric acid. The style is clear. The hydrolysis reaction of the compound represented by the formula (1) 'is not limited to the following, for example

The base to be used for V f is not limited to the following, such as lithium hydroxide, hydroxide, potassium hydroxide, etc., metal hydroxide; sodium carbonate, carbonic acid, etc. Hydroxide, hydrogen peroxide, hydroxide of the genus genus, etc., may also be used, and the mixture of the two tests may be used for the purpose of the reaction, that is, it is not limited, and generally, it is expressed relative to the formula (1). The compound is L0~20 0 equivalent. The solvent used for the hydrazine reaction is not limited to the following, for example, an aprotic polar solvent such as water, methanol, an ether such as furfuryl alcohol or dimethylformamide, or the like: the weight of the compound of ίίΐΪ is more than 1 time. The weight below 40 times is preferably: --^ _ %, the reaction temperature and the reaction time can be varied widely. A glimpse of::: Do not limit 'to 〇 ~ _ is better:: crying order is not particularly limited, preferably (U ~ 5 〇 hours. Jiu Ying 200906816 in the above hydrolysis reaction, various conditions, that is, the type of alkali The conditions of the amount of use, the kind of the solvent, the amount thereof, the reaction temperature, and the reaction time may be appropriately selected and combined with each other. As described above, the conventional technique is based on the end of the hydrolysis reaction, and the product formula (5) is obtained. The 3-aminothiophene-2-carboxylic acid is isolated and subjected to a decarburization reaction of the second operation. In general, 3-aminothiophene-2-carboxylic acid is known to be susceptible to decarboxylation, and the product formula (4) The 3-aminothiophene is an unstable substance. Therefore, the yield reduction or unevenness is liable to occur in the isolation operation. On the other hand, the 3-amino porphin-2-carboxylic acid derivative As a result of the stability test, it is found that the compounds are stable if they are in the form of a salt. The 3-aminothiophene-2 obtained by the hydrolysis reaction of the 3__aminothiophene-2-carboxylate derivative represented by the formula (丨) a carboxylic acid which exists in the state of the salt represented by the formula (2) in the reaction liquid Therefore, by acidifying the reaction solution to a pH at which the decarboxylation reaction can be carried out and performing a decarboxylation reaction, the production of the carboxylic acid represented by the formula (5) obtained by neutralizing the reaction solution can be avoided. When the rate is lowered, the yield can be improved. Regarding the decarboxylation reaction of the 3-amino group β-phene-2 represented by the formula (5) or the formula (2), the tarenic acid or its metal salt, the reaction obtained by the above hydrolysis reaction is used. The method of the liquid is not limited to the following. The acid used in the reaction is not limited to the following, for example, inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, and samaric acid; acetic acid, tri-I acetic acid, and cyano group. Acetic acid, benzoic acid, oxalic acid, methyl (tetra) acid, p-toluene, benzene and other organic acids make a mixture of these acids. The amount of acid used in the reaction, as long as the purpose of the reaction proceeds, S raw materials, intermediates, products do not decompose That is, it is not limited to, the same as the formula (2), 3-amino porphin-2, or its metal salt, is a solvent used for the reaction, not limited to the following For example, this reaction, the field = the reaction liquid of the previous stage hydrolysis reaction as a raw material Therefore, the aprotic polar such as guanamine can be dissolved, or such a mixed solvent; class, 3 is added to ΜΙΒΚ (4-mercapto-2-pentane, etc., solvent, toluene, ^ family solvent, dichloroline (4) A solvent or the like, and a mixture of 10 200906816 is used, and it is not particularly limited to "normally, with respect to the weight of the 3-amino porphin-2-carboxylic acid represented by the formula (7) or the formula (2) or The weight of 丨 times more than 4 () times or less is better. Under the reaction conditions, '3-amino group. The stability test of the phenanthrene, it is found that the compound has the lowest stability in the linonic region near pH 4, in the thief 镰The sexual region is stable. When operating 3-wire porphin, 'the product is in a state of unstable and weak acidity as much as possible'. In the case of strong acidity or test operation, it is important to inhibit the unevenness of the yield. The moon brother stone disgusted Han should start reacting at the weak acidity around pm. The addition of an acid to the metal salt of 3-aminosuccin-2-pyrexate produced by strong alkaline hydrolysis is carried out, and the resulting 3-amino porphin is highly dangerous in an unstable, weakly acidic state. Therefore, it is preferable to add a hydrolysis reaction liquid to the acidic solution to prevent the risk of pH from being unstable, and it is preferable to contribute to the increase in the reaction yield. Specifically, Lu's decarburization of the metal salt of 3-amino-based phenanthrene-2-carboxylate represented by the general formula (7) is reversed, and the 3-amino fine phenophene-2 = ttr is represented by (2) The one-phase solution of the acidic aqueous solution and the organic solvent is preferably a salt of the formula (3), and the salt of the 3-aminothiophene and the acid is preferably used. The reaction temperature and reaction time of the decarboxylation reaction can be carried out in a broad manner. The reaction temperature is not particularly limited as long as the reaction proceeds, and the raw material = body, = is not decomposed, and is not particularly limited to -1 〇 〜1 〇〇. . Preferably, the production time is not particularly limited as long as the reaction of the purpose is carried out, preferably α丨~, sleeping back, and: U produces the general formula (), which is formed by the formation of the aminothiophene and the acid. Skin = time. The positive pH is alkaline, and the extraction formula (4) represents 3-aminothiophene to a :. Here, in the above-mentioned pH adjustment, a mixed solvent of an aqueous solution and an organic solvent which is adjusted by adding an alkaline aqueous solution to a reaction liquid containing a salt of a strongly acidic 3-amine compound is used. ; alkali acid 3-amine base salt reaction solution adjustment (the whole mouth: medium, two strong 11 200906816 pH adjustment of the base used, not limited to the lower hydrogen oxysaki, carbon coffee, potassium carbonate, etc. = secret clock , sodium hydroxide, the temperature of the whole time, as long as the product is not divided into the mixture of the test, the weight of the salt formed, in order to more than 40 times; acetaminophen. The above decarbonation reaction and post-treatment of the phenanthrene and acid Heavy gui. Class and its use, post-treatment test ^ ^ Reaction use of acid species, reaction temperature, reaction time and other mites and their combination. Tiller can be appropriately selected from each other and group 1 ^月: The base 嗟 之 solution, by appropriate choice of solvent, can be used directly, 乂I form the acid used alone, not citric acid, hydrobromic acid, sulfuric acid, acid, I, etc. I. Representative 1 for example: salt benzoic acid, 4-cyanobenzoic acid, 2-gas benzene 4 methyl acetate, fumaric acid, C Acid, oxalic acid, maleic acid, loaded / basic nail knocking, citric acid, tartaric acid, benzophenone, p-toluene, etc. organic; in the hospital, continued toluene 3 - aminothiophene derivatives, to 丨〇 Mohrs, and the formula (4): and the 3-amino group represented by the formula (4) == two at =: the temperature is -2 ° ~ boots is preferred, more preferably the second province ΐ ^ ^ 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验 试验

NaOH η2ο ο ,ΝΚ ς)丫 a HCI ^2〇. PhMe

vNH, HCI

NaOH

After PhWe S' PhMe ,, add 3-amino hydrazine H2%, 〇.2〇m〇1) at room temperature, dilute with water (51·_), and (=) make the reaction time ==98 Article, 3_g, insoluble matter from raw material inclusions: water = should, after the pit, add a K14S owe (9.77§) in the filter. In the obtained liquid state of the filtration, the reaction is finely transferred to a acidic impurity at 25 ° C, at 2 ° (ΓΑ f =, plus _, the reaction liquid is J from the Han should be J hours. The reaction liquid is cooled to 5 ° Below C, the liquid separation is carried out under the circumstance. The organic phase is added with ϊ SI: After separating the organic phase, toluene is added to the aqueous phase (just (10) and extracted. The organic phase to which the stroke is paid is separated from the previously separated organic The mixture was mixed to obtain a target benzene solution of 3 - month female thiophene (3 〇 l. 62 g, 3-amino porphin concentration: 6 〇 3 wt%, content: 18.19 g, yield: 96.56%). Example 2] 3-amino thiophene _2 - sulphuric acid 曱g is used as a raw material to synthesize an aminothiophene

NaOH h2o nh2 r U η .ONa HCI NH, HCI /Ti/ NaOH 〇_ Hs0, MIBK [0 j —— MIBK _ _ IVUBK solution 0 32% aqueous sodium hydroxide solution (64.13 g, 0.5 lmol) in water (204.50 g) After dilution, 3-aminothiophene-2-carboxylate (94.87%, 68. g, 0.41 brain 1) was added at room temperature to carry out the reaction at 70 ° C for 3 hours. After cooling the reaction mixture to 25 ° C, MIBK (267.08 g) was added. The temperature of the reaction liquid was maintained at 25 ° C under a nitrogen stream, and a 35% aqueous hydrochloric acid solution (98.09 g, 0.94 mol) was added dropwise. After the completion of the dropwise addition, the reaction solution became acidic 13 200906816 · , and it was allowed to react at 25 C for 5 hours. The reaction solution was cooled to below the well, and an aqueous solution of sodium hydroxide (68 74 g, 〇 55 m 〇 1) was added under a nitrogen atmosphere to make it standability. The organic phase was separated, and MIBK (267 12 g) was added to the aqueous phase, which was taken up under a nitrogen stream. The extracted organic phase was mixed with the previously separated organic phase to obtain a desired 3-amino group MIBK solution (556.4 Gg, 3 - silk age concentration: 6 J3 wt%, content: 37.47 g, yield: 92.15%) . [Example 3] Synthesis of 3-aminothiophene using methyl 3-aminothiophene-2-carboxylate as a raw material

NH Nam \ .ONa HCI .NHjHCI NaOH ,nh2 h2o ^ _ 0 Η,Ο, MIBK MIBK ΜOld K i

f Aqueous sodium hydroxide solution (77 50 g, 0 62 mol) was diluted with water (246 14 g), and 3~-aminothiophene-2-carboxylate (97 〇 6%, 8 〇〇 • 49 mol) was added at room temperature. 'The reaction was allowed to proceed for 3 hours at 70C. The reaction solution was cooled to 25. After that, add %!)ϋ2ΐ.468). Under a nitrogen stream, the temperature of the reaction solution was maintained at 25 ° C, and the raw = if night (118 qing, hi7 chest sputum was added dropwise. The filament was added dropwise, and the reaction solution became acid " &amp; 5 C for 5 hours. The reaction solution is cooled to a temperature of 5. 〇, and the liquid is separated under a nitrogen atmosphere. The organic phase towel is cooled by a person. The =2, = rr is obtained in a two-phase solution, under the genus:: production, alkali formation After separating the organic phase, the hydrazine is added to the aqueous phase (32 ι 4 for extraction. The extracted organic phase is separated before the amine-diamine' bis-zinc-3-amino thiophene mibk solution (7G5. 74g, March female, plugging knife degree. 6.62wt%, content: 46.72g, yield: %, 16%). -Amine Ιί Example 4] with 3~amine ° phene-2-carboxylic acid , as raw material synthesis 3 14 200906816

m!bk mm , after diluting 32% aqueous sodium hydroxide solution (73.75 g, 〇.59 mol) with water (85.23 g), adding 3-aminothiophene-2-carboxylic acid oxime ester at room temperature (97.〇l 〇/0,78.〇〇g, 〇.48m〇l), reacted at 6crc for 3 hours. After cooling the reaction mixture to 25 Torr: the insoluble material was removed by filtration and washed with water (25.11 g). The obtained filtrate was added dropwise to a two-phase solution of MIBK (328.73 g) and 36% aqueous hydrochloric acid (i〇8.36 g, 1.0 g) in a nitrogen stream. After the completion of the dropwise addition, the reaction was carried out. The liquid was in an acidic state and was allowed to stand at 2 rc for 2 hours. The reaction liquid was cooled to 5 T: or less, and a 32% aqueous sodium hydroxide solution (81.25 g, 0.65 mol) was added under a nitrogen atmosphere to make it alkaline. After the organic phase was separated, MlBK (312.12g) was added to the aqueous phase, and extraction was carried out under a nitrogen stream. The extracted organic phase was mixed with the previously separated organic phase to obtain a MIBK solution of the desired 3-aminothiophene (652.98 g, 3-amino group). Porphin concentration: 6.87 wt%, content: 44.86 g, yield: 94.25%) [Example 5] Synthesis of 3 -aminothiophene with 3-aminothiophene-2-carboxylate as raw material

Nh2 Γ 1 NaOH o HC[ NH.HCI _ NaOH HjO Hpt IVIIBK MIBK MIBK solution

Add 32% aqueous sodium hydroxide solution (T7.14g, 0.62mol) to water (86.92g) and then add 3 -aminothiophene-2-carboxylate (97.01%, 80.〇〇g) at room temperature. , 〇, 49m〇1), reacted at 6 ° C for 3 hours. After cooling the reaction mixture to 25 ° C, the insoluble material was removed by filtration and washed with water (25.61 g). The obtained filtrate was added dropwise to a solution of MIBK (310.43 g) and 36% aqueous hydrochloric acid (ll 〇.〇lg, l.〇9m〇i) 15 200906816 under a nitrogen stream at 25 C, and the acid was recorded. The pit reaction is right-handed; t is from day 4, day and night Q to below 5 C, and liquid separation is carried out under a nitrogen atmosphere. Yu Qiao = Tim, cooling to 25% of the hydrogen in the pit - Yu, dripping the aqueous phase under the mixing, so that the test. Will be organic

Hit ; ΐ ΐ ΐ ^ 310 310 310 310 310 310 310 310 310 310 310 310 310 310 310 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 47.3 〇 g, yield: 9735%) f 3 domain phenophene / Chen. [Example 6] Synthesis of 3-filament light benzoate ΝΗ λ

ΝβΟΗ HjO - d^,〇Na HO 1 NaOH 0 Η^Ο, ΜΙΘΚ HCI s MIBK 1 h〇!0 MIBK MIBK it® NH. ^ H〇S.

aJD (BOO.OOg &gt; 3 - dehydration under reduced pressure. Will be obtained: 4〇.〇9g &gt; 222.99mm〇l) , ^ Washed with MIBK (40.20g), and served in Jiemao leaflets. Filtration of the precipitated crystals, arbitrarily yellowish salt [Simplified illustration] None [Main component symbol description] Μ Μ*, 16

Claims (1)

200906816 - VII. Patent application scope: 'h A method for producing 3-aminothiophene represented by the formula (4), comprising: hydrolyzing a 3-amino n-phenate vinegar contact represented by the general formula (1) Producing a metal salt of '3-amino porphin-2-carboxylate acid of the formula (2), and decarbonation of gold (4) on the surface of the acid cake Tit to produce a general formula (3) a salt formed by 3-amino porphin and an acid; and a salt neutralized by the salt represented by the general formula (3); characterized in that the acid-removing reaction is not a metal salt represented by the general formula (7) or The metal salt is neutralized to the 3-amino group-derived carboxylic acid represented by the formula (5): Soil surface? ^ shows a green number or a phenyl group having a carbon number of 1 to 12, M represents a genus or a soil of a soil test, and HX represents an acid]. 2. If you apply for a patent scope! The production formula (4) represents the square value of the 3-amino porphin ' in the formula (3), wherein the 3-amino porphin is neutralized with the salt formed by the acid, and 3) An aqueous solution of 3-amine, phenanthrene and acid, which is added to a two-phase solution of an aqueous alkaline solution and an organic solvent, is used. The 3-amino-based oxime 魄Ια ’ ray represented by the production formula (4) of the invention of claim i or 2 is subjected to the 3-filament represented by the general formula (7). When the decarboxylation reaction of the gold of the phenanthroline-dicarboxylic acid is carried out, the aqueous solution of the metal salt of the 3-aminothiophene-2-carboxylate represented by the formula (2) is added to the two-phase system of the acidic aqueous solution and the organic solvent. The solution is made by the formula 3 (3) which represents the g meaning of the 3-amino singer and the acid. The method (such as the formula (4) of claim 1 of the invention, wherein the R is an alkyl group having 1 to 12 carbon atoms. In the formula (1), R is an alkyl group having 1 to 12 carbon atoms. The formula (4) of the fourth aspect of the invention represents the 3-aminothiophene group, wherein in the formula (1), R is a methyl group or an ethyl group. 17 200906816, 6. The scope of claim 1 A method of producing a 3-aminothiophene represented by the formula (4), wherein, in the formula (2), hydrazine is an alkali metal. 7. The production formula (4) of claim 6 is 3 a method of the aminothiophene, wherein in the formula (2), the hydrazine is sodium (Na). 8. The method for producing a 3-aminothiophene represented by the formula (4) according to the first aspect of the patent application, wherein In the general formula (3), HX is hydrochloric acid (HC1). 18 200906816 IV. Designation of representative drawings: (1) The representative figure of the case is: no drawing. (2) Simple description of the symbol of the representative figure: None 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 3