JP6501689B2 - Process for producing di- and triarylmethane dyes - Google Patents

Description

  The present invention relates to a process for the preparation of diaryl and triarylmethane dyes.

  Heretofore, when producing synthetic dyes of diaryl and triarylmethane compounds by oxidizing from leuco compounds industrially, heavy metals such as lead oxide and dichromate have been used as oxidation catalysts.

  And when manufacturing a diaryl and triarylmethane dye, the method of adding and manufacturing various oxidation catalysts and also the adjuvant is examined.

  For example, Patent Document 1 discloses a method of producing a triarylmethane dye from a leuco acid compound by supplying air or oxygen under pressure using a benzoquinone having a substituent, a vanadium catalyst, and a molybdate catalyst. Is disclosed.

  Further, in Patent Document 2, in order to produce a triarylmethane dye from a leuco acid compound, hydrogen peroxide or the like is used as an oxidizing agent, and heavy metal ions such as iron, tetraaza [14] annulene, porphyrin, and the like as an oxygen transfer catalyst. Methods using complexes with inclusion compounds such as phthalocyanines are disclosed.

Japanese Examined Patent Publication No. 2-30344 Unexamined-Japanese-Patent No. 6-25544

  However, oxidation catalysts for lead oxide and dichromate that have been used in the industry in the past are highly harmful, and when mixed with soil or groundwater, they affect the ecosystem and thus have an adverse effect on the human body. Management of the waste solution But it was expensive. On the other hand, lead and hexavalent chromium are mentioned in the RoHS directive which defines the use restriction of specified harmful substances in electronic and electrical devices. Lead and chromium remain in the produced diaryl and triarylmethane dyes, and it is at present very difficult technically and economically to make a product that complies with the RoHS regulations.

  Moreover, in the manufacturing method described in Patent Document 1, oxygen contained in air is used as the oxidizing agent, and in order to improve the reaction efficiency, the reaction is performed under pressure from atmospheric pressure, and the manufacturing is performed. It was not preferable from the fact that pressure-resistant reaction kettles, safety devices, etc. had to be introduced into the equipment and the cost as well as safety increased. Also, it is disclosed that the reaction can be carried out even at atmospheric pressure, but the reaction efficiency is lowered and it takes longer reaction time, which is not preferable. Absent.

  Furthermore, although the metal complex is used as an oxygen transfer catalyst in the manufacturing method described in Patent Document 2, since the metal complex is a compound in which a plurality of π electrons are delocalized such as containing an aromatic group, the manufacturing is performed. There is a problem that the metal complex must be removed by high affinity with the selected diaryl and triarylmethane dyes and precise purification.

  Therefore, the present invention can comply with the RoHS directive without using lead and hexavalent chromium, and the reaction can proceed even under atmospheric pressure, and can be manufactured without passing through a precise purification process. An object of the present invention is to provide a process for producing novel diaryl and triarylmethane dyes.

〔式中、Ｒ_１，Ｒ_２，Ｒ_３，Ｒ_４は相互に独立しており、水素原子、Ｃ_１〜Ｃ_８のアルキル基、フェニル基又はＣ_１〜Ｃ_８のアルキル基を有するフェニル基であり、Ｒ_５，Ｒ_６は、水素原子又はＣ_１〜Ｃ_８のアルキル基であり、Ｘは水素原子又はスルホン酸基、カルボン酸基、水酸基若しくはＣ_１〜Ｃ_８のアルキル基で置換されていてもよいフェニル基若しくはナフチル基である〕であらわされるロイコ化合物を用いて、
１価又は２価の銅化合物と、ヘテロポリ酸の存在下において、
過酸化水素、有機ヒドロペルオキシ化合物、ペルカルボン酸から選ばれる少なくとも１つの酸化剤により酸化させることを特徴とする

〔式中、Ｒ_１，Ｒ_２，Ｒ_３，Ｒ_４は相互に独立しており、水素原子、Ｃ_１〜Ｃ_８のアルキル基、フェニル基又はＣ_１〜Ｃ_８のアルキル基を有するフェニル基であり、Ｒ_５，Ｒ_６は、水素原子又はＣ_１〜Ｃ_８のアルキル基であり、Ｘは水素原子又はスルホン酸基、カルボン酸基、水酸基若しくはＣ_１〜Ｃ_８のアルキル基で置換されていてもよいフェニル基若しくはナフチル基である〕であらわされるジ−及びトリアリールメタン染料の製造方法である。 [1] That is, the present invention is

[Wherein, R ₁ , R ₂ , R ₃ and R ₄ are independent of each other, and have a hydrogen atom, a C _{1 to} C ₈ alkyl group, a phenyl group or a C _{1 to} C ₈ alkyl group] R ₅ and R _{6 each} is a hydrogen atom or a C _{1 to} C ₈ alkyl group, and X is a hydrogen atom or a sulfonic acid group, a carboxylic acid group, a hydroxyl group or a C _{1 to} C ₈ alkyl group Leuco compounds represented by the following formula:
In the presence of a monovalent or divalent copper compound and a heteropoly acid,
It is characterized in that it is oxidized by at least one oxidizing agent selected from hydrogen peroxide, organic hydroperoxy compounds and percarboxylic acids.

[Wherein, R ₁ , R ₂ , R ₃ and R ₄ are independent of each other, and have a hydrogen atom, a C _{1 to} C ₈ alkyl group, a phenyl group or a C _{1 to} C ₈ alkyl group] R ₅ and R _{6 each} is a hydrogen atom or a C _{1 to} C ₈ alkyl group, and X is a hydrogen atom or a sulfonic acid group, a carboxylic acid group, a hydroxyl group or a C _{1 to} C ₈ alkyl group A phenyl group or a naphthyl group which may be optionally substituted] is a method for producing a di- and triarylmethane dye represented by the formula:

  [2] And, the copper compound is at least one selected from copper acetate, copper sulfate, copper carbonate, copper hydroxide, copper chloride, copper nitrate, copper oxide, and the like. Are methods for the preparation of di- and triarylmethane dyes.

  [3] And, the heteropoly acid is at least one selected from silicotungstic acid, phosphotungstic acid, phosphomolybdic acid, lintungstomolybdic acid, and phosphovanadomolybdic acid. It is a manufacturing method of the di- and triaryl methane dye as described in [2].

  According to the present invention, it is possible to comply with the RoHS directive without using lead and hexavalent chromium, the reaction proceeds under atmospheric pressure, and further, it can be manufactured without passing through a precise purification process. .

  BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the method for producing the di- and triarylmethane dyes according to the present invention will be described in detail below. Note that although the embodiments described below are specific examples preferable for practicing the present invention, various technical limitations have been made, but the present invention is intended to particularly limit the invention in the following description. It is not limited to this form unless otherwise specified. Further, a notation expressing a numerical range includes an upper limit and a lower limit.

〔式中、Ｒ_１，Ｒ_２，Ｒ_３，Ｒ_４は相互に独立しており、水素原子、Ｃ_１〜Ｃ_８のアルキル基、フェニル基又はＣ_１〜Ｃ_８のアルキル基を有するフェニル基であり、Ｒ_５，Ｒ_６は、水素原子又はＣ_１〜Ｃ_８のアルキル基であり、Ｘは水素原子又はスルホン酸基、カルボン酸基、水酸基若しくはＣ_１〜Ｃ_８のアルキル基で置換されていてもよいフェニル基若しくはナフチル基である〕であらわされるロイコ化合物は、対応する酸化物の還元体であり、２個又は３個のアリール基を有するメタン化合物である。各置換基Ｒ_１，Ｒ_２，Ｒ_３，Ｒ_４は相互に独立しており、それぞれ水素原子、直鎖又は分岐鎖を有する炭素数１〜８のアルキル基、フェニル基や、直鎖又は分岐鎖を有する炭素数１〜８のアルキル基により置換されたフェニル基である。各置換基Ｒ_５，Ｒ_６は、水素原子や、直鎖又は分岐鎖を有する炭素数１〜８のアルキル基である。そして、Ｘが水素原子であるとロイコ化合物はジアリールメタン染料であり、Ｘがスルホン酸基、カルボン酸基、水酸基若しくは直鎖又は分岐鎖を有する炭素数１〜８のアルキル基で置換されていてもよいフェニル基、若しくはスルホン酸基、カルボン酸基、水酸基若しくは直鎖又は分岐鎖を有する炭素数１〜８のアルキル基で置換されていてもよいナフチル基であるとロイコ化合物はトアリールメタン染料である。ロイコ化合物としては、アシッドブルー１、アシッドブルー９、アシッドブルー３、キシレンシアノールＦＦなどの還元体が好ましい。 Used in the present invention

[Wherein, R ₁ , R ₂ , R ₃ and R ₄ are independent of each other, and have a hydrogen atom, a C _{1 to} C ₈ alkyl group, a phenyl group or a C _{1 to} C ₈ alkyl group] R ₅ and R _{6 each} is a hydrogen atom or a C _{1 to} C ₈ alkyl group, and X is a hydrogen atom or a sulfonic acid group, a carboxylic acid group, a hydroxyl group or a C _{1 to} C ₈ alkyl group The leuco compound represented by the phenyl group or the naphthyl group which may be substituted is a reductant of the corresponding oxide, and is a methane compound having two or three aryl groups. The substituents R ₁ , R ₂ , R ₃ and R ₄ are independent of each other, and each is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a phenyl group, or a linear or branched group. It is a phenyl group substituted by a C1-C8 alkyl group which has a chain. Each substituent R ₅ and R ₆ is a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms. And, when X is a hydrogen atom, the leuco compound is a diarylmethane dye, and X is substituted with a sulfonic acid group, a carboxylic acid group, a hydroxyl group, or a linear or branched alkyl group having 1 to 8 carbon atoms. The leuco compound is a triarylmethane dye as being a phenyl group or a sulfonic acid group, a carboxylic acid group, a hydroxyl group or a naphthyl group which may be substituted with a linear or branched alkyl group having 1 to 8 carbon atoms It is. As the leuco compound, reductants such as acid blue 1, acid blue 9, acid blue 3, and xylene cyanol FF are preferable.

  In addition, leuco compounds in which X is a sulfonic acid group, a phenyl group substituted with a carboxylic acid group, or a sulfonic acid group, or a naphthyl group substituted with a carboxylic acid group can also be used for production as it is. In order to improve the reactivity, it is preferable to treat with a basic compound such as sodium carbonate, sodium hydrogencarbonate or the like while stirring and to adjust in advance so that the pH becomes near neutral of 6-8.

  The monovalent or divalent copper compound used in the present invention is a catalyst to promote the oxidation reaction. As copper compounds, copper acetate (II), copper sulfate (II), copper carbonate (II), copper hydroxide (II), copper hydroxide (II), copper chloride (II), copper chloride (I), copper nitrate (II), copper oxide (copper II) Copper oxide (I) or the like is preferably used alone or in combination of two or more. The numbers I and II are valences of copper.

  The amount of the copper compound is preferably 0.005 to 0.4 mol, more preferably 0.01 to 0.3 mol, per 1 mol of the leuco compound. When the amount of the copper compound is in this range, the reaction from the leuco compound to the oxidized di- and triarylmethane dyes sufficiently proceeds.

The heteropoly acid used in the present invention is a poly acid in which a hetero atom consisting of a P block element such as silicon, phosphorus or arsenic is inserted into an isopoly acid skeleton consisting of a metal such as tungsten, molybdenum or vanadium. Yes, it is a catalyst to promote the oxidation reaction. As a heteropoly acid, silicotungstic acid (H ₄ [SiW ₁₂ O ₄₀ ] .nH ₂ O; n is approximately 30), phosphotungstic acid (H ₃ [PW ₁₂ O ₄₀ ] .nH ₂ O; n is approximately 30), Phosphomolybdic acid (H ₃ [PMo ₁₂ O ₄₀ ] .nH ₂ O; n is approximately 30), lintungstomolybdic acid (H ₃ [PW _{12 -X} Mo _x O ₄₀ ] .nH ₂ O; x is greater than 0. less than 12, n is approximately 30), phosphovanadomolybdic acid _{(H 15-X [PV 12} -X Mo x O 40] · nH 2 O; x is greater than 6 less than 12, n is approximately 30) one from such Or it is preferable to use in combination of 2 or more types.

  The compounding amount of the heteropoly acid is preferably 0.005 to 0.3 mol, and more preferably 0.01 to 0.25 mol with respect to 1 mol of the leuco compound. When the compounding amount of the heteropoly acid is in this range, the reaction from the leuco compound to the oxidized di- and triarylmethane dyes sufficiently proceeds.

  In addition, the copper compound and the heteropoly acid must be used in combination since their reactivity is not sufficient if they are used alone. At this time, the compounding ratio of the copper compound and the heteropoly acid is preferably 100/1 to 1/10, more preferably 5/1 to 1/1, of the copper compound / heteropoly acid. When the mixing ratio of the copper compound and the heteropolyacid is in this range, the reaction from the leuco compound to the oxidized di- and triarylmethane dyes sufficiently proceeds.

  The oxidizing agent used in the present invention is a compound having an unstable and easily releasing oxygen atom in the molecule, and at least one compound selected from hydrogen peroxide, an organic hydroperoxy compound, and a percarboxylic acid. As the organic hydroperoxy compound, di-tert-butyl peroxide, dimethyldioxirane, acetone acetone, methyl ethyl ketone peroxide, hexamethylene triperoxide diamine, cumene hydroperoxide and the like are preferably used alone or in combination of two or more. As percarboxylic acid, it is preferable to use one or more in combination of peracetic acid, metachloroperbenzoic acid and the like.

  The compounding amount of the oxidizing agent is preferably a molar equivalent number or more of the number of moles of the leuco compound as the raw material, more preferably 2 to 20 equivalents relative to 1 mole of the leuco compound, relative to 1 mole of the leuco compound It is most preferable that it is 5 to 10 equivalents. When the blending amount of the oxidizing agent is in this range, it is possible to supply an oxygen atom which can sufficiently oxidize the leuco compound.

  As the reaction solvent, various solvents can be used according to the polarity of the raw material, and when the polarity of the leuco compound as the raw material is large, water, lower alcohols having 1 to 4 carbon atoms such as methanol and ethanol are used. When the polarity of the leuco compound as a raw material can be used, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, toluene or the like having smaller polarity than water or alcohol can be used. In addition, when the polarity of the reaction solvent is small, a phase transfer catalyst such as quaternary ammonium salt can also be used.

  Hereinafter, examples of the method for producing the di- and triarylmethane dyes according to the present invention will be more specifically described.

に示されるロイコ化合物１を用いた。ロイコ化合物１は、試薬など市販品として入手することができる化合物である。 As a leuco compound,

The leuco compound 1 shown in was used. The leuco compound 1 is a compound which can be obtained as a commercial product such as a reagent.

に示されるトリアリールメタン２若しくはトリアリールメタン３、又はトリアリールメタン２及びトリアリールメタン３の混合物であるトリアリールメタン染料を得た。酸化銅（ＩＩ）は水に溶解しにくいので、塩析により容易にトリアリールメタン染料から分離することができる。 Example 1
Water, copper (II) oxide 4.77 mg (0.060 mmol), silicotungstic acid [H ₄ [SiW ₁₂ O ₄₀ ], 26 H _{2 in a} 10 ml two-necked flask, to a weight of 200 mg (0.30 mmol) of leuco compound 1 O) 99.31 mg (0.030 mmol) and 10.0 mL of water are mixed, 30% aqueous hydrogen peroxide (10 molar equivalents) is added while stirring, and the reaction solution is heated to 100 ° C. and stirred for 1 hour did. After the reaction, add sodium chloride,

A triarylmethane dye which is a mixture of triarylmethane 2 or triarylmethane 3 or triarylmethane 2 and triarylmethane 3 shown in the above is obtained. Since copper (II) oxide is poorly soluble in water, it can be easily separated from the triarylmethane dye by salting out.

  The reaction yield was determined using a calibration curve obtained by measuring an ultraviolet-visible spectrum of a triarylmethane dye comprising leuco acid 1 as a raw material and a salt of triarylmethane 2 as an objective substance. That is, using a solution obtained by diluting a triarylmethane dye consisting of a salt of triarylmethane 2 obtained by the reaction to a predetermined concentration, an ultraviolet-visible spectrometer (manufactured by Jasco Engineering, model number: V-560) is used. The reaction rate was determined by measuring the absorbance at and calculating the amount of formation of the triarylmethane dye consisting of the salt of triarylmethane 2 obtained by the reaction by back-calculating the concentration. As a result, the reaction yield was 75%.

Example 2
The reaction was performed in the same manner as in Example 1 except that 8.59 mg (0.060 mmol) of copper (I) oxide was used as the copper compound. The reaction yield of the triarylmethane dye consisting of the salt of triarylmethane 2 obtained by the reaction was 74%.

Example 3
The reaction was carried out in the same manner as in Example 1 except that 10.9 mg (0.060 mmol) of copper acetate (II) was used as the copper compound and the reaction time was 24 hours. The reaction yield of the triarylmethane dye consisting of the salt of triarylmethane 2 obtained by the reaction was 61%.

Example 4
The reaction was carried out in the same manner as in Example 1 except that 10.9 mg (0.060 mmol) of copper acetate (II) was used as the copper compound, and the reaction time was changed to 12 hours. The reaction yield of the triarylmethane dye consisting of the salt of triarylmethane 2 obtained by the reaction was 70%.

Example 5
The reaction was performed in the same manner as in Example 1 except that 10.9 mg (0.060 mmol) of copper acetate (II) was used as the copper compound. The reaction yield of the triarylmethane dye consisting of the salt of triarylmethane 2 obtained by the reaction was 60%.

Example 6
A reaction was performed in the same manner as in Example 1 except that 102.6 mg (0.030 mmol) of phosphotungstic acid [H ₃ [PW ₁₂ O ₄₀ ] · 30 H ₂ O] was used as the heteropoly acid. The reaction yield of the triarylmethane dye consisting of the salt of triarylmethane 2 obtained by the reaction was 62%.

Example 7
Copper (II) sulfate as a copper compound using 100 mg (0.15 mmol) of leuco compound 1 and 99.31 mg (0.030 mmol) of silicotungstic acid [H ₄ [SiW ₁₂ O ₄₀ ] .26H ₂ O] The reaction was performed in the same manner as in Example 1 except that 15.0 mg (0.060 mmol) was used, the reaction temperature was 60 ° C., and the reaction time was 24 hours. The reaction yield of the triarylmethane dye consisting of the salt of triarylmethane 2 obtained by the reaction was 25%.

Example 8
Using 71.0 mg (0.030 mmol) of phosphomolybdic acid [H ₃ [PMo ₁₂ O ₄₀ ] · 30 H ₂ O] as a heteropoly acid, 15.0 mg (0.060 mmol) of copper acetate (II) as a copper compound The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 60.degree. C. and the reaction time was 12 hours. The reaction yield of the triarylmethane dye consisting of the salt of triarylmethane 2 obtained by the reaction was 28%.

Comparative Example 1
The reaction was carried out in the same manner as in Example 1 except that the heteropoly acid was not used. The reaction yield of the triarylmethane dye consisting of the salt of triarylmethane 2 obtained by the reaction could not be detected.

Comparative Example 2
The reaction was performed in the same manner as in Example 1 except that the copper compound was not used. The reaction yield of the triarylmethane dye consisting of the salt of triarylmethane 2 obtained by the reaction was 15%.

Comparative Example 3
The reaction was carried out in the same manner as in Example 1 except that 4.88 mg (0.060 mmol) of zinc oxide was used as the copper compound. The reaction yield of the triarylmethane dye consisting of the salt of triarylmethane 2 obtained by the reaction was 11%.

Comparative Example 4
The reaction was carried out in the same manner as in Example 1 except that 200 mg (0.30 mmol) of leuco compound 1 was used, and 5.21 mg (0.060 mmol) of manganese (IV) dioxide was used as a substitute for the copper compound. The reaction yield of the triarylmethane dye consisting of the salt of triarylmethane 2 obtained by the reaction was 57%.

Comparative Example 5
The reaction was performed in the same manner as in Example 1 except that the copper compound was not used, the reaction temperature was 60 ° C., and the reaction time was 24 hours. The reaction yield of the triarylmethane dye consisting of the salt of triarylmethane 2 obtained by the reaction was 3%.

  The results are shown in Table 1.

  From the results in Table 1, when heteropoly acid and copper compound were used in combination as a catalyst, reaction yield was 60% or more at 100 ° C., and when only heteropoly acid was used, When only copper compounds were used, when metal catalysts other than heteropoly acid and copper compounds were used, the reaction yield was all less than 60% at a reaction temperature of 100 ° C., which was insufficient. The reaction yield tends to decrease as the reaction temperature is 60 ° C. as compared to the case of 100 ° C., but the reaction yield is found to be large as compared with the case where the copper compound is not used in combination at the same temperature. From these results, it was found that by using a heteropoly acid and a copper compound in combination, a triarylmethane dye consisting of a salt of triarylmethane 2 can be obtained with a yield applicable to actual production.

Claims (3)

[Wherein, R ₁ , R ₂ , R ₃ and R ₄ are independent of each other, and have a hydrogen atom, a C _{1 to} C ₈ alkyl group, a phenyl group or a C _{1 to} C ₈ alkyl group] R ₅ and R _{6 each} is a hydrogen atom or a C _{1 to} C ₈ alkyl group, and X is a hydrogen atom or a sulfonic acid group, a carboxylic acid group, a hydroxyl group or a C _{1 to} C ₈ alkyl group Leuco compounds represented by the following formula:
In the presence of a monovalent or divalent copper compound and a heteropoly acid,
It is characterized in that it is oxidized by at least one oxidizing agent selected from hydrogen peroxide, organic hydroperoxy compounds and percarboxylic acids.

[Wherein, R ₁ , R ₂ , R ₃ and R ₄ are independent of each other, and have a hydrogen atom, a C _{1 to} C ₈ alkyl group, a phenyl group or a C _{1 to} C ₈ alkyl group] R ₅ and R _{6 each} is a hydrogen atom or a C _{1 to} C ₈ alkyl group, and X is a hydrogen atom or a sulfonic acid group, a carboxylic acid group, a hydroxyl group or a C _{1 to} C ₈ alkyl group A method of producing a di- and triarylmethane dye represented by the following formula:   The di- and triaryl according to claim 1, wherein the copper compound is at least one selected from copper acetate, copper sulfate, copper carbonate, copper hydroxide, copper chloride, copper nitrate, and copper oxide. Method of producing methane dye.   3. The di-compound according to claim 1, wherein the heteropoly acid is at least one selected from silicotungstic acid, phosphotungstic acid, phosphomolybdic acid, lintungstomolybdic acid, and phosphovanadomolybdic acid. -And methods for producing triarylmethane dyes.