JP2511127B2 - Nuclear substituted salicylic acid and its salts - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel nucleus-substituted salicylic acid and a salt thereof. The novel nucleus-substituted salicylic acid and its salts have good solubility in water, organic solvents or organic polymer compounds, and are fungicides,
It is suitable for application as a stabilizer for polymer compounds or a developer for recording materials.

[Conventional technology]

Nuclear-substituted salicylic acid and salts thereof have a high bactericidal activity and are used as bactericides (Japanese Patent Laid-Open No. 62-153245).
issue). A polyvalent metal salt of a nuclear-substituted salicylic acid is used as a stabilizer for a halogen-containing polymer compound such as polyvinyl chloride (JP-A-56-112855). A polyvalent metal salt of a nuclear-substituted salicylic acid, particularly a zinc salt, is used as a developer for recording materials (Japanese Patent Application Laid-Open Nos. 48-98914 and 62-250).
Nos. 86 and 63-186729).

[Object of the Invention]

The object of the present invention is a specific nucleus-substituted salicylic acid which has particularly good solubility in water, an organic solvent or an organic polymer compound and is suitable for application as a germicide, a stabilizer for polymer compounds, or a developer for recording materials. And its salt.

[Structure of Invention]

According to the present invention, general formula [I] (In the formula, R ₁ and R ₂ represent a tert-butyl group, a tert-aryamyl group, a tert-hexyl group, a tert-aryoctyl group, an α, α-dialkylbenzyl group or a nucleus-substituted α, α-dialkylbenzyl group. The present invention provides a novel nucleus-substituted salicylic acid and a salt thereof. These are characterized by having extremely high solubility in water, organic solvents or organic polymer compounds.

A water-soluble bactericide is most preferable because it can be easily formulated or applied using water as a medium. The alkali metal salt, amine salt or ammonium salt of the nuclear-substituted salicylic acid represented by the general formula [I] is easily dissolved in water, so that a high-concentration aqueous solution can be prepared. In addition, since they are not photoallergenic to the skin, they are safe and suitable for use as a bactericide in a wide range.

Various metal compounds are used as a stabilizer for the halogen-containing polymer compound. Particularly, when transparency is required for the polymer composition, a metal compound having good solubility in the polymer compound is used. To be elected. The polyvalent metal salt of a nuclear-substituted salicylic acid represented by the general formula [I] has good solubility in a polymer compound, forms a completely transparent composition, and has excellent stability especially against heat and light. give.

Since the color development reaction of a color developer for a recording material is generally performed in a relatively polar organic medium, solubility in the medium is the most important of the necessary properties of the color developer. it can. The polyvalent metal salt of the nucleus-substituted salicylic acid represented by the general formula [I], particularly the zinc salt, is well dissolved in an organic solvent having a small polarity and has a large color developing action. It has advantages such as excellent color density and developing speed.

These solubilities are closely related to the structure of the general formula [I]. In the general formula [I], R ₁ and R ₂ are tert-butyl groups,
A tert-aryamyl group, a tert-hexyl group, a tert-aryoctyl group, an α, α-dialkylbenzyl group or a nucleus-substituted α, α-dialkylbenzyl group, all of which are bulky and The solubility of the substituted salicylic acid and its salt in an organic solvent or an organic polymer compound is increased. However, the effect is not enough,
Good solubility, which is the target of the present invention, cannot be obtained.
The 6-position of the nucleus-substituted salicylic acid represented by the general formula [I] is a methyl group, which is the most characteristic of the structure of the present invention, and its contribution to solubility is due to the bulkiness of R ₁ and R _2. It is surprising, coupled with the group. in this way,
The nuclear-substituted salicylic acid having good solubility intended by the present invention is 6
By having the position of the methyl group and the 3 and 5 positions of bulky groups R ₁ and R _2, shaped, the invention is not configure.

Specific examples of the nucleus-substituted salicylic acid represented by the general formula [I] include 3,5-ditertiarybutyl-6-methylsalicylic acid, 3-tertiarybutyl-5-tertiaryamyl-6-methylsalicylic acid, 3- Tertiary butyl-5
-Tert-hexyl-6-methylsalicylic acid, 3-tert-butyl-5-tert-aryoctyl-6-methylsalicylic acid, 3-tert-butyl-5- (α, α-dimethylbenzyl) -6-methylsalicylic acid, 3 -Tert-butyl-5- (α, α, 3-trimethylbenzyl)-
6-Methylsalicylic acid, 3-tert-butyl-5-
(Α, α, 4-Trimethylbenzyl) -6-methylsalicylic acid, 3-tert-butyl-5- (α-methyl-α-
Ethylbenzyl) -6-methylsalicylic acid, 3-tertiaryamyl-5-tertiarybutyl-6-methylsalicylic acid, 3,5-ditertiaryamyl-6-methylsalicylic acid, 3-tertiaryhexyl-5-tertiarybutyl −
6-methylsalicylic acid, 3,5-ditertiary hexyl-
6-methylsalicylic acid, 3-tertiaryoctyl-5-
Tertiarybutyl-6-methylsalicylic acid, 3,5-ditertiaryoctyl-6-methylsalicylic acid, 3- (α,
α-Dimethylbenzyl) -5-tert-butyl-6-
Examples thereof include methylsalicylic acid and 3,5-di (α, α-dimethylbenzyl) -6-methylsalicylic acid, but from the viewpoint of easy industrial implementation, 3,5-ditertiarybutyl-6-methylsalicylic acid, 3-tert-butyl-5-
(Α, α-Dimethylbenzyl) -6-methylsalicylic acid, 3,5-ditertiaryamyl-6-methylsalicylic acid, 3-tertiaryoctyl-5-tertiarybutyl-
6-Methylsalicylic acid or 3- (α, α-dimethylbenzyl) -5-tertiarybutyl-6-methylsalicylic acid is selected and more preferred for the purposes of the present invention.

The nucleus-substituted salicylic acid represented by the general formula [I] is represented by the general formula [II] (In the formula, R ₁ and R ₂ are the same as defined in the general formula [I], respectively). Reaction of sodium or potassium salt of nuclear-substituted phenol with carbon dioxide (Kolbeschmitt reaction)
Can be obtained as its sodium or potassium salt. Since both the sodium salt and the potassium salt of the general formula [I] and the general formula [II] dissolve well in various organic solvents as the object of the present invention, a series of operations are preferably performed in the organic solvent. The reaction temperature is preferably in the range of 120 ° C to 200 ° C.

The nuclear-substituted phenol represented by the general formula [II] can be obtained by subjecting metacresol to a nuclear substitution reaction. As a reagent for introducing a substituent, isobutylene, tert-butyl chloride, tert-butanol, 2-methyl-1-butene, 2-methyl-2-butene, 2-methyl-
1-pentene, 2-methyl-2-pentene, 2-ethyl-1-hexene, diisobutylene, α-methylstyrene, α, 3-dimethylstyrene, α, 4-dimethylstyrene, α-ethylstyrene, α, β -Dimethylstyrene,
Examples include α-methyl-β-propylstyrene and α, β-diethylstyrene. As a catalyst for introducing a substituent, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, secondary butylbenzenesulfonic acid, heteropolyacid, boron trifluoride, aluminum chloride, zinc chloride, etc. Are preferred. When R ₁ and R _{2 of the} general formula [I] or the general formula [II] are the same, the substituents are introduced into metacresol all at once with one reagent. When R ₁ and R ₂ are different, R ₁ is introduced first, followed by R ₂ .

As described above, the nucleus-substituted salicylic acid of the present invention is produced as its sodium salt or potassium salt. In order to obtain free nucleus-substituted salicylic acid, an acid such as dilute sulfuric acid or dilute hydrochloric acid may be added to an aqueous solution of the sodium salt or potassium salt for acid precipitation. Further, it can be purified by recrystallization with an organic solvent. These are generally insoluble in water but are well soluble in organic solvents and are therefore used as oil-soluble fungicides in cutting oils and the like.

Since the alkali metal salt, amine salt or ammonium salt of the nuclear-substituted salicylic acid is water-soluble, the aqueous solution can be obtained by neutralizing free nuclear-substituted salicylic acid with alkali hydroxide, amine or ammonia in water as a medium. Preferred alkali hydroxides are lithium hydroxide, sodium hydroxide or potassium hydroxide, and preferred amines are methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, isopropanolamine, Examples thereof include diisopropanolamine, triisopropanolamine, dimethylaminoethanol, diethylaminoethanol, and morpholine. These water-soluble nucleus-substituted salicylates have applications as water-soluble fungicides or fungicides.

The polyvalent metal salt of the nuclear-substituted salicylic acid is hardly soluble or insoluble in water, but is well dissolved in an organic solvent or an organic polymer compound. These are prepared as a water-insoluble salt from an aqueous solution of a water-soluble salt of a nuclear-substituted salicylic acid and an aqueous solution of a water-soluble polyvalent metal salt by a metathesis method. At this time, if desired, heating or addition of an organic solvent can be performed. Preferred polyvalent metals are magnesium, aluminum,
Examples include calcium, iron, cobalt, nickel, zinc, strontium, cadmium, tin, barium or lead, and most preferably magnesium, calcium or zinc. Examples of the water-soluble polyvalent metal salt include magnesium sulfate, aluminum sulfate, calcium chloride, zinc sulfate, and lead acetate. Polyvalent metal salts of nuclear-substituted salicylic acids, particularly magnesium, calcium or zinc salts, are used as stabilizers for polymer compounds containing chlorine. At this time, those in which R ₁ and R _{2 in} the general formula [I] are different are preferable because they have better solubility. Further, a polyvalent metal salt of nuclei-substituted salicylic acid, particularly a zinc salt, is used as a developer for recording materials. At this time, when the total number of carbon atoms of R ₁ and R _{2 in} the general formula [I] is 9 or more, more preferably 12 or more, the recorded image has good resistance to humidity or water.

Example of Invention

Next, in order to further clarify the present invention, specific examples and reference examples will be described.

Example 1 A hard glass three-necked flask with an internal volume of 2,000 ml equipped with a stirrer, a thermometer, and a reflux condenser capable of separating and removing water was used to prepare 2,4-ditertiarybutyl-
330 g (1.5 mol) of 5-methylphenol, 1,000 g of diethylene glycol dimethyl ether, 1 toluene
00 grams and 50% sodium hydroxide aqueous solution 120
Charge gram. The flask is heated with stirring to remove water azeotropic with toluene. The contents of the dehydrated flask are transferred to a stainless steel autoclave with an internal volume of 2,000 ml. Carbon dioxide gas was injected under pressure of 20 kg / cm ² into the autoclave and reacted at 180 ° C for 3 hours.
When the autoclave is cooled and the temperature of the contents falls below 90 ° C, depressurize and transfer the contents to a beaker with an internal volume of 5,000 ml. Add 3,000 grams of boiling water and 500 grams of toluene and stir. This is left to stand and the oil layer that separates into the upper layer is removed. While stirring
170 ml of 10N dilute sulfuric acid is gradually added. Crystals will precipitate when cooled, so this is filtered and removed.
If recrystallized with 0 ml of toluene, white crystals 262
Grams are obtained. It has a melting point of 178 ° C and an acid value of 210.9.
(Theoretical value; 212.2) And the nuclear magnetic resonance absorption spectrum is as shown in Fig. 1, and it is confirmed that it is 3,5-ditertiarybutyl-6-methylsalicylic acid.

Example 2-1 In a four-necked flask made of hard glass and having an inner volume of 1,000 ml, equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, tert-butyl 2-tert-butyl-5-methylphenonor (492 g, 3 mol) ) And 10 grams of dehydrated paratoluene sulfonic acid. Cool the flask and keep it at about 30-35 ° C. While stirring vigorously, 319 g (2.7 mol) of α-methylstyrene is added dropwise over about 10 hours. After 10 hours from the completion of the dropping, 200 g of water is added, and the temperature is raised with stirring while boiling for about 1 hour. This is transferred to a separating funnel and the aqueous layer is removed. Furthermore,
Repeat the washing operation three times with 200 grams each of boiling water. Transfer this to a vacuum distillation unit with an internal volume of 1.000 ml
Approximately 610 grams of distillate from 153 ° C to 158 ° C is collected at 1.5 torr. It has a melting point of 92 ° C., a hydroxyl number of 199.1 (theoretical value; 198.7), and is 2-tert-butyl-4-
It is confirmed to be (α, α-dimethylbenzyl) -5-methylphenol.

Example 2-2 2-Tertiary flask obtained in Example 2-1 in a three-neck flask made of hard glass and having an inner volume of 2,000 ml equipped with a stirrer, a thermometer, and a reflux condenser capable of separating water. Butyl-4- (α, α-dimethylbenzyl) -5-
Charge 423 grams of methylphenol (1.5 moles), 800 grams of diethylene glycol dimethyl ether, 350 grams of toluene and 120 grams of 50 percent aqueous sodium hydroxide. The flask is heated with stirring to remove water azeotropic with toluene. The contents of the dehydrated flask are transferred to a stainless steel autoclave with an internal volume of 2,000 ml. Carbon dioxide in the autoclave
Press in at 20 kg / cm ² and react at 180 ° C for 3 hours. The autoclave is cooled, and when the temperature of the contents becomes 90 ° C or lower, the pressure is released and the contents are transferred to a flask having an internal volume of 10,000 ml. Add 5,000 ml of water to this and stir while warming to 85 ° C. After removing the upper oil layer, 170 ml of 10N dilute sulfuric acid is gradually added dropwise with stirring. An oil separates which crystallizes on cooling. Recrystallization from normal hexane gives 368 g of white crystals. It has a melting point of 172 ° C., an acid value of 172.2 (theoretical value; 171.9), and a nuclear magnetic resonance absorption spectrum as shown in FIG. 2, and 3-tertiarybutyl-5- (α, α-dimethylbenzyl) -6.
-Methylsalicylic acid is confirmed.

Example 3-1 A hard glass four-necked flask having an inner volume of 1,000 ml, equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, was charged with 378 g (3.5 mol) of metacresol and 5 g of xylenesulfonic acid. While stirring the contents vigorously, 420 g (3 mol) of 2-methyl-2-butene containing a small amount of 2-methyl-1-butene is added dropwise from a dropping funnel over about 10 hours. During the dropping, the temperature of the flask is raised by the heat of reaction, so the flask is cooled and the temperature is kept at 30 to 35 ° C. After 10 hours from the end of the dropping, 200 g of water is added and heated with stirring while boiling for about 1 hour. Transfer to a separatory funnel to remove the water layer, and then wash with 200 ml of hot water three times. This is transferred to a vacuum distillation system and 510 grams of distillate from 110 ° C to 120 ° C is obtained at 1 torr. It has a melting point of 64 ° C. and a hydroxyl number of 226.5 (theoretical value: 225.9), and is confirmed to be 2,4-ditersiariamyl-5-methylphenol.

Example 3-2 2,4-ditertiary mill obtained in Example 3-1
From 372 grams (1.5 moles) of 5-methylphenol, 278 grams of white crystals are obtained in exactly the same manner as in Example 1. It has a melting point of 125 ° C and an acid value of 193.0 (theoretical value; 191.9).
The nuclear magnetic resonance absorption spectrum is as shown in FIG. 3, and it is confirmed that it is 3,5-ditersialyamyl-6-methylsalicylic acid.

Example 4-1 From 540 g (5 mol) of metacresol and 336 g (3 mol) of diisobutylene, 590 g of a fraction from 100 ° C. to 105 ° C. at 1.5 torr was obtained in exactly the same manner as in Example 3-1. To be This is a colorless, transparent and slightly viscous liquid,
The hydroxyl number is 253.5 (theoretical value; 254.6). or,
Gas chromatography confirms that this is 2-tertiaryoctyl-5-methylphenol containing about 0.5 percent 3-methyl-4-tertiaryoctylphenol.

Example 4-2 Internal Volume with Reflux Cooler with Stirrer, Thermometer, Gas Inlet and Top Connected to Dry Ice Strap
A 1,000 ml hard glass four-necked flask is charged with 550 g (2.5 mol) of 2-tertiaryoctyl-5-methylphenol obtained in Example 4-1 and 5 g of secondary butylbenzenesulfonic acid. Blowing isobutylene through the gas blowing port while stirring. As the reaction exotherms, the flask is cooled so that the temperature of the contents is from 30 ° C to 45 ° C. The contents are sampled occasionally to follow the progress of the reaction by gas chromatography. Blow in isobutylene so that it takes about 20 hours to complete the reaction. When the desired reaction is completed, the blowing of isobutylene is stopped and the contents are washed with hot water. The content is a clear reddish brown viscous liquid with a hydroxyl number of 192.4 (theoretical value; 202.9).
The deviation of the hydroxyl value from the theoretical value is considered to be due to impurities such as a polymer of isobutylene. Also, it was confirmed by gas chromatography that this had a purity of 93%.
-Tertiaryoctyl-4-tertiarybutyl-5-methylphenol is confirmed. The melting point of the purified product which was purified separately was 72 ° C.

Example 4-3 60% of the product of Example 4-2 (1.5 mol) gives 341 grams of white crystals in the same manner as Example 2-2. It has a melting point of 165 ° C and an acid value of 176.4 (theoretical value; 1
75.1) and the nuclear magnetic resonance absorption spectrum is as shown in FIG. 4, and 3-tertiaryoctyl-5-tertiarybutyl-6-methylsalicylic acid, namely 3- (1,1,3,3-tetramethylbutyl)- It is confirmed to be 5-tert-butyl-6-methylsalicylic acid.

Example 5-1 In the same manner as in Example 3-1, from 540 g (5 mol) of meta-cresol and 354 g (3 mol) of α-methylstyrene, 618 g of a fraction from 105 ° C. to 115 ° C. at 1 Torr was obtained. can get. It is an almost colorless, very viscous liquid with a hydroxyl number of 245.9 (theoretical value; 247.9).
It was also found by gas chromatography that it contained 1.3% 3-methyl-4- (α, α-dimethylbenzyl) phenol 2- (α, α-dimethylbenzyl) -5-.
Confirmed to be methylphenol.

Example 5-2 From 565 g (2.5 mol) of 2- (α, α-dimethylbenzyl) -5-methylphenol obtained in Example 5-1, the same procedure as in Example 4-2 was carried out. A viscous liquid is obtained. It has a hydroxyl number of 187.2 (theoretical value; 198.7) and has a purity of 94% of 2- (α, α-dimethylbenzyl)-by gas chromatography.
It is confirmed to be 4-tert-butyl-5-methylphenol.

Example 5-3 White crystals were obtained from 2- (α, α-dimethylbenzyl) -4-tert-butyl-5-methylphenol obtained in Example 5-2 in exactly the same manner as in Example 4-3. 362 grams are obtained. It has a melting point of 181 ° C., an acid value of 170.2 (theoretical value; 171.9), and a nuclear magnetic resonance absorption spectrum is as shown in FIG.
-Tertiarybutyl-6-methylsalicylic acid is confirmed.

Example 6 3,5-ditertiarybutyl-6-obtained in Example 1
264 grams (1 mole) of methylsalicylic acid is dissolved in 700 grams of an aqueous solution containing 1 mole of sodium hydroxide. This is an aqueous solution containing about 30 percent sodium 3,5-ditertiarybutyl-6-methylsalicylate.

Example 7 Similar to Example 6, Example 2-2, Example 3-2,
From the nuclear-substituted salicylic acids obtained in Examples 4-3 and 5-3, their sodium salts can be obtained.

Example 8 Instead of the aqueous sodium hydroxide solution of Examples 6 and 7 with an aqueous solution of triethanolamine or morpholine,
The corresponding trisubstituted amine or morpholine salt of the nucleus-substituted salicylic acid is obtained.

Example 9 A beaker made of stainless steel having an inner volume of 2,000 ml was charged with 400 g of a 25% zinc sulfate aqueous solution, and the mixture obtained in Example 6 was vigorously stirred.
The entire aqueous solution of 5-ditertiarybutyl-6-methylsalicylate is injected in about 20 minutes. After stirring for another 20 minutes, the precipitated zinc 3,5-ditertiarybutyl-6-methylsalicylate is filtered and washed with 1,000 ml of water. This is vacuum dried at 110 ° C. to obtain 297 grams of white powder. It has a zinc content of 10.9 percent (theoretical value; 11.0 percent) and is confirmed to be zinc 3,5-ditertiarybutyl-6-methylsalicylate.

Example 10 A pure white powder was obtained from the nuclear-substituted sodium salicylate obtained in Example 7 in the same manner as in Example 9, and it was confirmed by the measurement of each zinc content that it was a target product.

Comparative Example 1 (Salt of 3,5-ditertiarybutylsalicylic acid) From 3,5-ditertiarybutylsalicylic acid, its sodium salt, morpholine salt and zinc salt were prepared in the same manner as in Example 6, Example 8 and Example 9. can get.

〔The invention's effect〕

The nuclear-substituted salicylic acid and salts thereof of the present invention are characterized by having excellent solubility in water and organic compounds,
It is highly useful as a disinfectant, a stabilizer for high molecular compounds or a developer for recording paper. Table 1 shows the test results. In terms of solubility, ◎ is 50% or more, ○ is 20
Represents a solubility of 5 to 20% and X represents a solubility of 5% or less. The transparency of PVC is 100 parts by weight of polyvinyl chloride having a polymerization degree of 1,300, 100 parts by weight of dioctyl phthalate and 3 parts by weight of a zinc-substituted zinc salicylate. 220
Kneaded at ℃ for 10 minutes, ◎ is completely transparent, ○ is almost transparent, △
X indicates a little turbidity and X indicates a lot of turbidity, and the color developing ability is such that a coating liquid containing a zinc-substituted zinc salicylate prepared by adding an adhesive or the like is coated with 0.7 g of a nuclear-substituted zinc salicylate per square meter. After coating and drying on the paper surface as described above, printing is performed using the upper paper of commercially available pressure-sensitive recording paper, ◎ is very dense and the color developing speed is large, ○ is rich,
Δ represents a little inferior, and x represents no color development.

[Brief description of drawings]

1 to 5 are all nuclear magnetic resonance absorption spectrum charts. FIG. 1 shows Example 1 and FIG. 2 shows Example 2-
2, FIG. 3 is for Example 3-2, FIG. 4 is for Example 4-3, and FIG. 5 is for each nucleus-substituted salicylic acid obtained in Example 5-3. DMSO-d6 was used as the solvent, and tetramethylsilane was used as the reference.

Claims (4)

(57) [Claims] 1. A general formula [I] (In the formula, R ₁ and R ₂ represent a tert-butyl group, a tert-aryamyl group, a tert-hexyl group, a tert-aryoctyl group, an α, α-dialkylbenzyl group or a nucleus-substituted α, α-dialkylbenzyl group. The nucleus-substituted salicylic acid and salts thereof represented by 2. An acid represented by the general formula [I] and a salt thereof are
3,5-ditertiarybutyl-6-methylsalicylic acid, 3
-Tertiarybutyl-5- (α, α-dimethylbenzyl) -6-methylsalicylic acid, 3,5-ditertiaryamyl-6-methylsalicylic acid, 3-tertiaryoctyl-
5-ditertiarybutyl-6-methylsalicylic acid and 3
The nucleus-substituted salicylic acid and a salt thereof according to claim 1, which is an acid selected from-(α, α-dimethylbenzyl) -5-ditertiarybutyl-6-methylsalicylic acid and a salt thereof. 3. The nucleus-substituted salicylate according to claim 1, wherein the salt is a polyvalent metal salt. 4. The nucleus-substituted salicylate according to claim 3, wherein the polyvalent metal salt is a zinc salt.