JP2961875B2 - Method for producing benzodifuranone compound - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a benzodifuranone compound. More specifically, the present invention relates to a method for producing a benzodifuranone compound useful for dyeing or printing a hydrophobic fiber material such as polyester fiber to a reddish hue.

<Background Art> Examples of benzodifuranone compounds useful for dyeing or printing hydrophobic fiber materials include various compounds described in JP-B-61-54058, JP-B-1-36859, and JP-A-1-258677. Compounds are described. As a method for producing these benzodifuranone compounds, in addition to the methods described in each of the above publications, a method using mandelic acids as a raw material is described in JP-A-60-178889, and a method using phenylglyoxylic acids in Europe is described. It is known as described in Japanese Patent No. 252406.

<Problems to be Solved by the Invention> However, according to the above-mentioned known methods, it is difficult to produce a high-purity benzodifuranone compound in a high yield, and it is difficult to supply a raw material and recover a solvent. There is a problem. For these reasons, development of a method for industrially advantageously producing a benzodifuranone compound is desired.

<Means for Solving the Problems> The present inventors have conducted intensive studies to find an industrially advantageous method for producing a benzodifuranone compound, and as a result, have completed the present invention.

The present invention provides the following general formula (I): In the formula, R ¹ and R ² are each independently a naphthyl group or a nitrile group, a halogen atom, an alkyl group, an alkoxy group,
Phenyl group, alkoxyphenyl group, phenoxy group, hydroxy group, cyano group, carboxylic acid group, carboxylic acid ester group, carbamoyl group, sulfonic acid group, sulfonyl chloride group, sulfonic acid ester group, sulfamoyl group,
Mercapto group, alkylthio group, phenylthio group, amino group, alkylamino group, acylamino group, phosphonic acid group, phosphonic acid ester group, alkylsulfonyl group, phenylsulfonyl group, aldehyde group, azo group or the following formula (1) or (2) ), (In the formula, R ³ represents a methylene group, or a linear or branched C _2-6 alkylene group which may be substituted with a hydroxyl group, an alkoxy group or an alkylcarbonyloxy group, and X ¹
Is -O -, - S -, - SO -, - SO 2 -, (In the formula, R ⁵ represents a hydrogen atom or an alkyl group.) Or Wherein R ⁵ represents a divalent group or a direct bond represented by the above formula, and X ² represents —O— or Wherein R ⁵ represents the same meaning as above, and T and U each independently represent a hydrogen atom or an alkyl group;
Represents an integer of 0 or 1 to 3, and Q represents an optionally substituted 5, 6 or 7-membered saturated or unsaturated heterocyclic residue. R ⁴ represents an alkyl group, X ³ represents —O— or —S—, and X ⁴ represents —O— or Wherein R ⁵ represents the same meaning as above, V and W each independently represent a hydrogen atom or an alkyl group,
Represents an integer of 1 to 3, n represents 0 or 1, and m + n is at least 2. A phenyl group which may be substituted with a group represented by the formula: In the method for producing a benzodifuranone compound represented by the formula: (Wherein, R ¹ represents the same meaning as described above) and a benzofuran compound represented by the following general formula (II)
I), [Wherein, R ² represents the above-mentioned meaning, and L represents -COR ⁶ , -CO ₂ R ⁷
Or -SO ₂ R ⁸ (wherein,. To represent each R ^6, R ⁷ and R ⁸ are independently an alkyl or phenyl group) represent a group represented by the. A method for producing a benzodifuranone compound represented by the above general formula (I), which comprises reacting the compound with an acetonitrile compound represented by the formula:

In the present invention, the expression “alkyl” or “alkoxy” in the substituents represented by the alkyl group, alkoxy group, alkoxyphenyl group, alkylthio group and alkylsulfonyl group means alkyl or alkoxy having 1 to 4 carbon atoms, respectively. These may be further substituted with groups such as a halogen atom, an alkoxy group, a phenyl group, an alkoxyphenyl group, a phenoxy group, a hydroxy group and a cyano group.

The alkylamino group in the present invention refers to a group having 1 to 4 carbon atoms.
Which may be further substituted with a halogen atom, a phenyl group, an alkoxyphenyl group, a phenoxy group, a hydroxy group, a cyano group, or the like.

In the present invention, the phenyl group may be substituted with a substituent such as a halogen atom and a nitro group.

The benzofuran compound represented by the general formula (II) is
The aforementioned JP-A-60-178889, European Patent No. 2524
It is a known compound described in, for example, Japanese Patent Publication No. 06-2006. Usually, hydroquinone and the following general formula (IV), (Wherein, R ¹ has the above-mentioned meaning.) Can be easily obtained by a reaction with a glycolic acid compound represented by the formula: This reaction is preferably performed by Britrzzcki
And in a mixture of acetic acid and sulfuric acid according to the method of Flateau [Ber., 30 , 124 (1897)].

The acetonitrile compound represented by the general formula (III) includes, for example, an aldehyde compound represented by the following general formula (V) and R ² —CHO (V) (wherein R ² has the above-mentioned meaning); An acid represented by the following general formula (VI) L-Hal (VI) (wherein L has the above-mentioned meaning and Hal represents a halogen atom) with a metal cyanide such as potassium cyanide or sodium cyanide. It can be easily obtained by reacting in the presence of a halide.

In the general formula (VI), examples of the group represented by L include alkylcarbonyl such as acetyl, ethylcarbonyl, n- or i-propylcarbonyl, n-, i- or t-butylcarbonyl, benzoyl, o-, m Phenylcarbonyl, such as-or p-methylbenzoyl, o-, m- or p-methoxybenzoyl, o-, m- or p-nitrobenzoyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl,
Alkoxycarbonyl such as n-, i- or t-butoxycarbonyl, phenoxycarbonyl such as benzeneoxycarbonyl, p-methylbenzeneoxycarbonyl, p-nitrobenzeneoxycarbonyl, methanesulfonyl, ethanesulfonyl, n- or i-propanesulfonyl And phenylsulfonyl such as alkanesulfonyl such as n- or i-butanesulfonyl, benzenesulfonyl, p-methylbenzenesulfonyl and 4-methyl-2-nitrobenzenesulfonyl.

The reaction between the benzofuran compound represented by the general formula (II) and the acetonitrile compound represented by the general formula (III)
The reaction can be carried out using a stoichiometric amount of each compound and in the absence or preferably in the presence of a solvent, preferably at a temperature of 30 to 180 ° C, more preferably 50 to 120 ° C.

Solvents that can be used in the reaction include hydrocarbons,
Halogenated hydrocarbons (e.g. benzene, toluene, xylene, mesitylene, mono-, di- and trichlorobenzene, bromobenzene, chlornaphthalene, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2 -Tetrachloroethane, trichloroethylene, tetrachloroethylene, dichloromethane, chloroform, carbon tetrachloride,
Bromoform and low boiling petroleum fractions), nitrohydrocarbons (eg, nitrobenzene, nitrotoluene and nitromethane), ketones (eg, methyl isobutyl ketone and sulfolane), lower alkanecarboxylic acids and their anhydrides (eg, formic acid, acetic acid, propionic acid, and acetic anhydride) And the like.

Among these, aromatic hydrocarbons or halogenated hydrocarbons, especially toluene, monochlorobenzene, dichlorobenzene, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, Preferred are trichloroethylene, dichloromethane and chloroform.

This reaction can be advantageously performed in the presence of an acidic catalyst.

Examples of the acidic catalyst include unsubstituted or substituted benzenesulfonic acid (for example, benzenesulfonic acid, p-toluenesulfonic acid, benzene-m-disulfonic acid), alkanesulfonic acid (for example, methanesulfonic acid), and halogenated lower alkanecarboxylic acid (for example, tricarboxylic acid). Fluoroacetic acid), Lewis acids (eg, titanium tetrachloride, aluminum chloride, stannous and stannic chlorides, ferrous and ferric chlorides, zinc chloride and boron trifluoride) and mineral acids (eg, sulfuric acid and hydrochloric acid). Is exemplified.

The amount of these catalysts to be used is arbitrary, but is preferably 0.5 mol or more, more preferably 0.8 to 2 mol, further preferably 0.9 to 1.5 mol, per 1 mol of the compound of the formula (II).

In this way, the benzofuran compound represented by the general formula (II) is reacted with the acetonitrile compound represented by the general formula (III), followed by an oxidation reaction.

This oxidation reaction is usually carried out in the presence of a solvent at 30 to 180 ° C.
Preferably, it can be carried out at a temperature of 40 to 100 ° C.

The oxidation reaction can be advantageously performed in the presence of an oxidizing agent. Oxidizing agents include chloranil, bromoanil, thiosulfate, nitrite, hypochlorite, zincate, chlorate, perchlorate, persulfate, periodate, perborate, perborate Manganates, vanadates, dichromates, nitric acid, iodine, terachlorhydroquinone, lead dioxide, manganese dioxide, vanadium pentoxide, nitrobenzene, dicyanodichlorobenzoquinone, hydrogen peroxide and atmospheric oxygen are exemplified. They can be used alone or in combination of two or more. The amount of the oxidizing agent used is sufficient if it is a stoichiometric amount or more. In order to perform the oxidation reaction advantageously, it is preferable to use a mixture of two or more oxidizing agents. The kind of the oxidizing agent to be used in combination is arbitrary, but it is preferable to use a mixture of one kind selected from chloranil, bromanil and dicyanochlorobenzoquinone and nitrite. Among them, it is particularly preferable to use chloranil and sodium nitrite in combination.

After completion of the reaction, the desired benzodifuranone compound represented by the general formula (I) can be isolated from the reaction medium by a conventional method by adding a hydrophilic solvent such as a lower alkanol to the reaction mixture.

The obtained benzodifuranone compound is useful as a disperse dye for dyeing or printing hydrophobic fibers such as polyester fibers, triacetate fibers, diacetate fibers and polyamide fibers, especially polyester fibers.

Dyeing or printing is performed by a known method. For example, to a dye bath obtained by dispersing the obtained benzodifuranone compound in an aqueous medium by a usual method, after adding a pH adjuster, a dispersion leveling agent, and the like, if necessary, immersing the hydrophobic fiber, for example, In the case of polyester fibers, the dyeing is carried out by dyeing under pressure at 105 ° C. or higher, preferably at 110 to 140 ° C. for 30 to 60 minutes.

In addition, dyeing can be performed at a relatively high temperature, for example, in a boiling state of water, in the presence of a carrier such as o-phenylphenol or methylnaphthalene.

Furthermore, a dyeing method in which the dye dispersion is padded on a cloth and then steamed or heat-treated at 100 ° C. or higher is also possible.

On the other hand, printing can be performed by kneading a dye dispersion with an appropriate sizing agent, printing and drying this on a cloth, and then steaming or dry heat treatment.

According to the method of the present invention, a high-purity benzodifuranone compound can be produced in a high yield, and it is industrially advantageous, such as easy supply of raw materials and recovery of a solvent.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, "part" represents "part by weight" and "%" represents "% by weight".

Example 1. 1-benzoyloxy-1- (p-tetrahydrofurfuryloxyphenyl) -acetonitrile 3.37 parts, 5-hydroxy-2-oxo-8-phenyl-2,3-dihydrobenzofuran 2.26 parts, p-toluenesulfone 2.06 parts and 0.22 parts of acid are added to 33 parts of monochlorobenzene,
After keeping for 2 hours, add 2.46 parts of chloranil, 1 hour at 80 ° C
Kept. After cooling to room temperature, 30 parts of methanol was added, and the mixture was stirred under ice cooling for 1 hour. The purified crystals are separated, washed with 150 parts of methanol, further washed with 30 parts of water, and dried, and then the following formula (1) Was obtained in high yield and high purity.

Example 2. 1-ethoxycarbonyloxy-1- (p-tetrahydrofurfuryloxyphenyl) -acetonitrile 3.05
Part, 5-hydroxy-2-oxo-3-phenyl-2,3
-2.26 parts of dihydrobenzofuran, 2.06 parts of p-toluenesulfonic acid and 0.22 parts of water were added to 33 parts of monochlorobenzene and kept at 75 ° C for 4 hours, and 2.46 parts of chloranil were added.
It was kept at 75 ° C. for 1.5 hours. After cooling to room temperature, 35 parts of methanol was added, and the mixture was stirred for 1 hour under ice cooling. The formed crystals were separated, washed with 150 parts of methanol, further washed with 30 parts of water, and dried to obtain the compound of the formula (1) in high yield and high purity.

Example 3. 1-benzoyloxy-1- [p- (3-ethoxypropoxy) phenyl] -acetonitrile 3.40 parts, 5-hydroxy-2-oxo-3-phenyl-2,3-dihydrobenzofuran 2.26 parts, p- 2.06 parts of toluenesulfonic acid and 0.22 parts of water were added to 30 parts of monochlorobenzene, and the mixture was kept at 85 ° C. for 5 hours.
C. After cooling to room temperature, 30 parts of methanol was added, and the mixture was stirred under ice cooling for 1 hour. The generated crystals are separated, washed with 140 parts of methanol, further washed with 35 parts of water, and dried, and the following formula (2) Was obtained in high yield and high purity.

Example 4. 1-benzoyloxy-1- (p-tetrahydrofurfuryloxyphenyl) -acetonitrile 3.37 parts, 5-
2.26 parts of hydroxy-2-oxo-3-phenyl-2,8-dihydrobenzofuran, 2.06 parts of p-toluenesulfonic acid and 0.22 parts of water were added to 35 parts of monochlorobenzene, and 80 ° C.
, And a mixture of 0.24 part of chloranil and 0.62 part of sodium nitrite was added, and the mixture was kept at 80 ° C for 2 hours. After cooling to room temperature, 30 parts of methanol was added, and the mixture was stirred under ice cooling for 1 hour. The formed crystals were separated, washed with 100 parts of methanol, further washed with 30 parts of water, and dried to obtain a compound of formula (1) in high yield and high purity.

Example 5-19. The method of Example 1 was carried out at a temperature shown in Table 1 using a solvent shown in Table 1 in place of monochloroben as a solvent. Obtained in high purity.

Examples 20 to 35 When the method of Example 1 was performed using the oxidizing agents shown in Table 2 in place of chloranil, all of the methods represented by the formula (1)
Was obtained in high yield and high purity.

Examples 36 to 46 When the method of Example 1 was repeated using the acidic catalyst shown in Table 4 in place of p-toluenesulfonic acid and at the temperature shown in Table 4, all of the compounds of the formula (1) were obtained. Was obtained in high yield and high purity.

Examples 47 to 50 When the method of Example 1 was carried out using p-toluenesulfonic acid in the amounts shown in Table 5, all the compounds of the formula (1) were obtained in high yield and high purity.

Examples 51 to 55 When the method of Example 4 was used by mixing the weights of chloranil and sodium nitrite shown in Table 6 as oxidizing agents, the compounds of formula (1) were all obtained in high yield. ,
Obtained in high purity.

Examples 56-68 The method of Example 1 was repeated, except that 4-tetrahydrofurfuryloxymandenitrile benzoyl ester was replaced with tert.
When performed using the compound represented by the general formula in the table,
In each case, the compound of formula (1) was obtained in high yield and high purity.

Examples 69 to 82 According to the method of Example 1, the compound represented by the formula III-
The compound of formula a was reacted with 5-hydroxy-2-oxo-3-phenyl-2,3-dihydrobenzofuran to obtain the corresponding compound of formula Ia in high yield and high purity.

Examples 88 to 89 According to the method of Example 1, the compound represented by the formula III-
The compound b was reacted with 5-hydroxy-2-oxo-3-phenyl-2,3-dihydrobenzofuran to obtain the corresponding compound of formula Ib in high yield and high purity.

Reference Example 1 1.0 part of the compound represented by the formula (1) obtained in Example 1 was obtained by condensing naphthalenesulfonic acid and formaldehyde.
It was atomized and dispersed in an aqueous medium together with 0 parts. 10 parts of a tetron jersey (polyester cloth, manufactured by Teijin Limited) was immersed in a dye bath containing 0.6 part of a powder obtained by drying the dye dispersion, and dyed under pressure at 130 to 135 ° C. for 60 minutes. Then, stain the dyed product with 3 parts of sodium hydroxide and 3 parts of hydrosulfite.
Parts, a treatment solution consisting of 3 parts of betaine-type amphoteric surfactant and 3,000 parts of water was subjected to reduction washing treatment at 85 ° C. for 10 minutes, and when washed and dried, a clear red dyed product was obtained.
Sublimation and wet fastnesses were excellent.

Reference Example 2 To 1.3 parts of the compound represented by the formula (1) obtained in Example 1, 3.7 parts of ligninsulfonic acid was added and atomized and dispersed, and 35 parts of hot water and 60 parts of a half emulsion paste having the following composition were added thereto. The mixture was mixed to prepare a printing paste.

O / W emulsion 300 parts Maypro gum NP 12% paste 694 parts Sodium chlorate 4 parts Tartaric acid 2 parts Total 1,000 parts Tetron tropical (polyester cloth, manufactured by Teijin Limited) is printed with this printing paste and dried, and then dried. The mixture was steamed and fixed at 170 ° C. for 7 minutes using a high-temperature steamer having a high pressure, and then subjected to reduction cleaning, water washing, drying, and softness / antistatic treatment in the order of Example 90. The red dyed product thus obtained was excellent in light fastness, sublimation and wet fastness, and particularly excellent in washing fastness.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-60-178889 (JP, A) JP-A-61-127766 (JP, A) JP-A-56-122869 (JP, A) JP-A-2- 151663 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09B 57/00 CA (STN) REGISTRY (STN)

Claims (9)

(57) [Claims] 1. A compound represented by the following general formula (I) In the formula, R ¹ and R ² are each independently a naphthyl group or a nitro group, a halogen atom, an alkyl group, an alkoxy group, a phenyl group, an alkoxyphenyl group, a phenoxy group, a hydroxy group, a cyano group, a carboxylic acid group, and a carboxylic acid. Ester group, carbamoyl group, sulfonic acid group, sulfonyl chloride group, sulfonic acid ester group, sulfamoyl group, mercapto group, alkylthio group, phenylthio group, amino group, alkylamino group, acylamino group, phosphonic acid group, phosphonic acid ester group, Alkylsulfonyl group, phenylsulfonyl group, aldehyde group, azo group or the following formula (1) or (2) [Wherein, R ³ represents a methylene group, or a linear or branched C _2-6 alkylene group which may be substituted with a hydroxyl group, an alkoxy group or an alkylcarbonyloxy group, and X ¹ represents —O—, —S −, −SO−, −SO ₂ −, (In the formula, R ⁵ represents a hydrogen atom or an alkyl group.) Wherein R ⁵ represents the above-mentioned meaning or a direct bond, and X ² represents —O— or (R ⁵ in. Which the above meaning) represents, T and U each independently represent a hydrogen atom or an alkyl group, is 0 or an integer of 1 to 3, Q is optionally substituted 5, Represents a 6- or 7-membered saturated or unsaturated heterocyclic residue. R ⁴ represents an alkyl group, X ³ represents —O— or —S—, and X ⁴ represents —O— or (R ⁵ represents the above meaning), V and W each independently represent a hydrogen atom or an alkyl group, and m is 1 to
An integer of 3, n represents 0 or 1, and m + n is at least 2. Represents a phenyl group which may be substituted with a group represented by In the method for producing a benzodifuranone compound represented by the formula: (Wherein, R ¹ represents the above-mentioned meaning.) And a benzofuran compound represented by the following general formula (III) [Wherein, R ² represents the above-mentioned meaning, and L represents -COR ⁶ , -CO ₂ R ⁷ or -SO ₂ R ⁸ (wherein, R ⁶ , R ⁷ and R ⁸ each independently represent an alkyl or phenyl group. Represents a group represented by: A method for producing a benzodifuranone compound represented by the above general formula (I), which comprises reacting the compound with an acetonitrile compound represented by the formula (1) and then oxidizing the compound. 2. The method according to claim 1, wherein the benzofuran compound represented by the general formula (II) and the acetonitrile compound represented by the general formula (III) are reacted in the presence of an acidic catalyst. 3. The method according to claim 2, wherein the amount of the acidic catalyst used is 0.5 mol or more based on 1 mol of the benzofuran compound represented by the general formula (II). 4. The method according to claim 1, wherein the benzofuran compound represented by the general formula (II) and the acetonitrile compound represented by the general formula (III) are reacted in the presence of a solvent. Manufacturing method. 5. The acetonitrile compound represented by the general formula (III) is represented by the following general formula (V) R ² —CHO (V) (wherein R ² has the meaning described in claim 1). The aldehyde compound and the metal cyanide are represented by the following general formula (VI) L-Hal (VI) (where L has the meaning described in claim 1 and Hal represents a halogen atom). The method according to any one of claims 1 to 4, which is obtained by reacting in the presence of an acid halide. 6. The method according to claim 1, wherein the oxidation is performed using an oxidizing agent. 7. The oxidant is chloranil, bromanil, thiosulfate, nitrite, hypochlorite, chlorite, chlorate, perchlorate, persulfate, periodate, perboric acid Selected from salts, permanganates, vanadates, dichromates, nitric acid, iodine, tetrachlorohydroquinone, lead dioxide, manganese dioxide, vanadium pentoxide, nitrobenzene, dicyanodichlorobenzoquinone, hydrogen peroxide and atmospheric oxygen The method according to claim 6, wherein one or more kinds are used. 8. An oxidizing agent comprising chloranil, bromanil,
The method according to claim 7, wherein one of dicyanodichlorobenzoquinone and nitrite are mixed and used. 9. The method according to claim 8, wherein chloranil and sodium nitrite are used as a mixture as the oxidizing agent.