JPH02204472A - Nucleus-substituted salicylic acid and salt thereof - Google Patents

Abstract

NEW MATERIAL:A nucleus-substituted salicylic acid of formula I (R1 is methyl or isopropyl; R2 is alpha,alpha-dialkylbenzyl or nucleus-substituted alpha,alpha-dialkylbenzyl) or a salt thereof. EXAMPLE:3,6-Dimethyl-5-(alpha,alpha-dimethylbenzyl)salicylic acid. USE:The acid has good solubility in water, organic solvents and organic polymeric compounds and is useful as a bactericide, a stabilizer for polymeric compounds or a developing agent for recording materials. PREPARATION:The sodium or potassium salt of a nucleus-substituted phenol of formula II is reacted with carbon dioxide in an organic solvent at 120-200 deg.C to provide the compound of formula I. The compound of formula II is synthesized by subjecting meta-cresol or 2,5-xylenol to a nucleus substitution reaction.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to novel nuclear-substituted salicylic acids and their salts.

The novel nuclear-substituted salicylic acids and their salts have good solubility in water, organic solvents, or organic polymer compounds, and are suitable for application as bactericides, stabilizers for polymer compounds, or color developers for recording materials.

[Conventional technology]

Salicylic acid and its salts have high bactericidal activity and are used as bactericidal agents. (Unexamined Japanese Patent Publication No. 62-15
No. 3245) Polyvalent metal salts of nuclear-substituted salicylic acid are used as stabilizers for halogen-containing polymeric compounds such as polyvinyl chloride. (Japanese Unexamined Patent Publication No. 56-112955) Polyvalent metal salts of nuclear-substituted salicylic acid, especially zinc salts, are used as color developers for recording materials. (Unexamined Japanese Patent Publication 1973-
No. 98914, No. 62-25086 and No. 63-28
No. 6729) [Object of the Invention] The object of the present invention is to provide a compound which has particularly good solubility in water, organic solvents or organic polymer compounds, and which can be used as a bactericidal agent, a stabilizer for polymer compounds, or a color developer for recording materials. An object of the present invention is to provide a specific nuclear-substituted salicylic acid and a salt thereof suitable for such applications.

[Structure of the invention]

According to the present invention, -.general
is α, α-dialkylbenzyl group or nuclear substituted α
, represents an α-dialkylpenzyl group. ) expressed as 71-
Provided are novel nuclear-substituted salicylic acids and salts thereof. These are characterized by extremely high solubility in water, organic solvents, or organic polymer compounds.

A highly water-soluble fungicide is most preferred because it can be easily formulated or applied using water as a medium. Alkali metal salts, amine salts, or ammonium salts of nuclear-substituted zarithi, rulic acid represented by the general formula C1) are easily dissolved in water, so a highly concentrated aqueous solution can be prepared. It is safe and does not cause any photoallergy to the skin.
Dust is suitable for use as a disinfectant over a wide range of areas.

Various metal compounds are used as stabilizers for halogen-containing polymer compounds, but especially when transparency is required for the polymer composition, metal compounds that have good solubility in the polymer compound are used. To be elected. The polyvalent metal salt of nuclear-substituted salicylic acid represented by the general formula CD is
- It has good solubility, forms completely transparent compositions, and provides excellent stability, especially against heat and minerals.

Since the color development reaction of a color developer for recording materials is generally carried out in an organic medium with relatively low polarity, solubility in the medium is the most important characteristic of the color developer. You can say that. Nuclear-substituted salicylic acid O polyvalent metal 4@ represented by general formula [I], especially zinc salt, dissolves well even in organic solvents with low polarity and has a strong color developing effect, so when applied as a color developer. 1. It has advantages such as 8 degrees of color development and speed of color development. ．． In the general formula [■], which is closely related to the structure of the mouth (7), R1 is a methyl group or an isoglycan, 1i2uα, α- Whether it is a dialkylbenzyl group or a nuclear-substituted +σ7α-dialkylpennol group, these groups are bulky and can be used in organic solvents or organic polymer compounds of nuclear-substituted thioleic acid and its salts, However, the young fruit alone is 1:j, which is still not as thick as the purpose of the present invention.
Good solubility cannot be obtained. The 6-position of the nuclear-substituted salicylic acid represented by the general formula [I] is a methyl group, and this is the most characteristic feature of the structure f of the present invention. Combined with the capstone group of R2, it ends. Such a trap 1 This invention f) 5 A machine with good solubility for the purpose is a chivalry, le I! ! 121. ! The present invention is formed by having a methyl group at the 6-position and bulky groups at the 3- and 5-positions R3 and R2.

4 of silicylic acid replaced with nucleus 1 represented by general formula [1]
Physical example! : [, then 3.6-cymethyl-5-(α
, α-somethyl A...i/f nor) salibulic acid, 3.
6-No, methyl-5-(also α, 3-to'I methylbennor)zalythyl isthmus, 3,6-cymethy, Ay-5-(α
, α,4-trimethylpemethyl)
-Tsumeburu 5-(σ-Mefruα-Echito・Be/Nor) Salicylic Acid, 3-・Ingro$ A-5-(α, α-
Methylbentrue 6-・Me2-fi・Jōsuchiru Gimata (
Bow: 3-Ingropil.

5-(α・-Methyl-α~ethylbenzyl)-6-methyl'? 3.6-dimethyl-5-(α, α
. . .Tumebulbennor)salicylic acid or 3. .Inglovir-5-(α,α-damethylpentyl)-6-methylsalicylic acid) are present, and these are also more preferred for the purposes of the present invention.

These general cuts r: The nuclear substituted salicylic branch represented by the formula is -
・Reaction of the sodium salt or potassium salt of a nuclear substituted phenol represented by the general formula [1]] (wherein R1 and R2 have the same definitions as in the general formula [I]) and carbon dioxide gas (Colpeci , Mituto's reaction)
It can be obtained as its sodium salt or potassium salt. Both the sodium salt or potassium salt of the general formula C1) and the general formula [■] dissolve well in an organic solvent, as is the object of the present invention, so it is preferable to carry out the series of operations in an organic solvent. The reaction temperature is 120℃ to 20℃
A range of 0°C is preferred.

The nuclear substituted phenol represented by the general formula (n) can be obtained by subjecting metacresol or 2,5-xylenol to a nuclear substitution reaction. Reagents for introducing substituents include propylene, α-methylstyrene, α,3-dimethylstyrene, α,4-trimethylstyrene, α-ethylstyrene, α,β-trimethylstyrene α-methyl-β Examples include -glopylstyrene and α,β-noethylstyrene. Catalysts for introducing substituents include sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, radical radical sulfonic acid, xylene sulfonic acid, secondary ligtylbenzenesulfonic acid, heteropolyacid, boron trifluoride, and aluminum chloride. Or acidic catalysts such as zinc chloride are preferred.

As described above, the nuclear-substituted salicyl powder of the present invention is produced as its sodium salt or potassium salt. In order to obtain free nuclear-substituted salicylic acid, an aqueous solution of the sodium or potassium salt may be acid-precipitated by adding an acid such as sulfuric acid or dilute hydrochloric acid. Furthermore, it can also be purified by recrystallization with an organic solvent.

These are generally insoluble in water but soluble in organic solvents, so they are used as oil-soluble fungicides in cutting oils and the like.

Since the alkali metal salt, amine salt, or ammonium salt of nuclear-substituted salicylic acid is water-soluble, an aqueous solution thereof can be obtained by neutralizing free nuclear-substituted salicylic acid with alkali hydroxide, amine, or ammonia in water as a medium. Preferred alkali hydroxides include lithium hydroxide, sodium hydroxide, and potassium hydroxide, and preferred amines include methylamine, trimethylamine, trimethylamine, ethylamine, trimethylamine, triethylamine, ethanolamine, noethanolamine, triethanolamine, and impronoamine. Arm nolamine, noisoglo 74'nolamine, triiso! Examples include lono-f-nolamine, trimethylaminoethanol, diethylaminoethanol, and morpholine. These water-soluble nuclear-substituted salicylates have uses as water-soluble fungicides and fungicides.

Polyvalent metal salts of nuclear-substituted salicylic acids are soluble or insoluble in water, but are well soluble in organic solvents or organic polymer compounds. These are prepared as water-insoluble salts v4 by a metathesis method 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. At this time, heating or addition of an organic solvent can be carried out if desired. Preferred polyvalent metals include magnesium, aluminum,
Examples include calcium, iron, cobalt, dichloride, zinc, strontium, cadmium, tin, barium, and lead, but magnesilla is most preferred.

aluminum, calcium or zinc. Examples of water-soluble polyvalent metal salts include magnesium sulfate, aluminum sulfate, calcium chloride, zinc sulfate, and lead acetate. Polyvalent metal salts of nuclear-substituted salicylic acids, especially magnesium, calcium or zinc salts, are used as stabilizers for chlorine-containing polymeric compounds. Polyvalent metal salts of nuclear-substituted salicylic acids, especially zinc salts, are used as pigments for recording materials.

[Embodiments of the invention]

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

Example 1 2,5-xylenol 366y ram (3 mol) and Hino's radish were placed in a four-loaf flask made of Torr hard glass with an internal volume of 400 mm and equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser. Add 3 grams of ensulfonic acid.

If you heat the flask and the temperature of the contents reaches 75°C or higher, the contents will melt, so start stirring, maintain the temperature at 75°C to 80°C, and add about 295 grams (25 moles) of α-methylstyrene from the dropping funnel. Drop in 4 hours. One hour after the completion of the dropping, 200 ml of toluene and 200 ml of water were successively added from the dropping funnel.
The contents are heated to their boiling point. Transfer this to a separatory funnel 1 and remove the acidic water that separates into the lower layer. Furthermore, add 200 ml of boiling water and toluate to the separating funnel to perform a washing operation, and repeat this 3 times. The oil layer is transferred to a vacuum distillation apparatus to obtain about 520 grams of a fraction ranging from 145 DEG C. to 148 DEG C. in about 1 to-4. If this is recrystallized with toluene, the melting point is 64.
370 grams of white crystals are obtained. This has a hydroxyl value of 232 (theoretical value; 23λ45) and 2.5-
It is confirmed to be trimethyl-4-(α,α-dimethylpentyl)phenol.

Example 1-2 A stirrer, a thermometer, and a reflux condenser capable of separating and removing water (inner volume 1,000 ml J! 300 grams of the obtained 2,5-trimethyl-4-(α,α・-trimethylbenzyl)phenol (L25 mol χ sulfone 5
00 grams, 100 grams of toluene, and 140 grams of potassium hydroxide. Heat the flask while stirring to remove toluene and other azeotropic water. After the dehydration has been completed, the contents of the flask are transferred to an autoclave with an internal volume of 1,000 ml. Pressurely inject carbon dioxide gas into the autoclave at 20 kg/cn1" and heat it at 160℃ for 6 hours.
Allow time to react. Cool the autoclave, and when the temperature of the contents is below 90°C, remove the pressure (~) and transfer the contents to a 400 mm internal volume, Torr flask, and add 3.
000 milliliters of heat
Add hot water and 500 milliliters of toluene, stir, and let stand.

After the upper toluene layer is completely removed, 350 grams of 20,-9-7 dilute sulfuric acid is added. Filter and collect the free crystals, and then recrystallize with toluene to obtain white crystals 2.
20 grams are obtained. It has a melting point of 208°C, an oxidation value of 196.6 (theoretical value; 197°31), a nuclear magnetic resonance absorption spectrum as shown in Figure 1, and the desired 3
, 6-nomethyl-5-(α,α-trimethylpentyl)salicylic acid.

Example 2 Thymol (2-isof-ropyru-5) was prepared in the same manner as in Example 1.
-Methylphenol) 450 grams (3 moles) and 295 grams (25 moles) of α-methylstyrene with a melting point of 96
℃), hydroxyl number is 207.6 (theory 1 straight;
480 grams of white crystals of 209[5] were obtained.1.
This is 2-isopropyl-4-(α,α-trimethylbenol)-5-methylphenol.

Practical Example 2-2 Performed in the same manner as in Example 1-2 (+jl 2-yne 7'o pyl-4-(α,α-nomethimethine dilin-5-methylphenol obtained in +jl 2) 335.5 (L25 mol), the melting point is 174°C and the acid value is 179-1 (theoretical value; 17
9.60), 210 grams of white crystals were obtained whose nuclear magnetic resonance absorption spectrum is as shown in FIG. 2, which is 3-isopropyl-5-(α,α-dimethylpencyl)-6-methylsalicylic acid.

Comparative Example 1 2-Methyl-4-(α,α-trimethylbenzyl)phenol was obtained from orthocresol and α-methylstyrene in the same manner as in Example 1, and then the melting point was determined in the same manner as in Example 1-2. is 180°C, and the acid value is 205.2 (theoretical).
07.55) 3-methyl-5.-(σ,α-nomethylmethidyl)salicylic acid is obtained.

Example 3 3,6- obtained in Example 1, Example 2 and Comparative Example 1
trimethyl-5-(α,α-trimethylbenzyl)salicylic acid, 3-isogropi#-5-(α,α-), methylpennorune-6·-methylsalicylic acid or 3-meb-ru5
...(α,α-dimethylbenzyl)salicylic acid is neutralized with a water sensitized sodium or morpholine water bath solution to obtain an aqueous solution of the respective sulfur and lithium salts or morpholine salts.

Example 4 400 g of a 25% zinc sulfate aqueous solution was placed in a 4,000 ml internal volume flask, and after stirring vigorously, each of the sodium salts obtained in Example 3 was added to 7% water with water. Inject the diluted solution. When the flask is heated to bring the temperature of the contents to 55°C to 65°C, the particles in the contents become coarse, so the flask is cooled again. If this is filtered, washed with water and dried, 3.
6-dumethyl-5-(α,α-trimethylpennol)t'
) powders of zinc fluorate, zinc 3-isopropyl-5-(α,α-dimethylbenzyl)-6-methylsalicylate, or zinc 3-methyl-5-(α,α-trimethylbenzyl)salicylic acid are obtained. This has a zinc content of 10° 1 mfli (theoretical value; 1α34) 10 mfli; 82
percentage).

〔Effect of the invention〕

The nuclear-substituted salicylic acid and its salt of the present invention are characterized by excellent solubility in water and organic compounds, and have utility value as a bactericidal agent, a stabilizer for polymeric compounds, or a color developer for recording paper. big.

Table 1 shows the test results. In terms of solubility, ◎ means 50 cents or more, 0 means 20 to 50 cents,
Δ stands for 5 to 20 cents, and X stands for solubility of less than 5 percent.
0 parts by weight and 3 parts by weight of nuclear substituted zinc salicylate at 220°C.
Knead for 10 minutes with ◎, completely transparent, O, almost transparent, Δ
It shows a slight turbidity and a lot of turbidity, and the color developing ability is determined by using a paint solution containing nuclear-substituted zinc salicylate made from VI4 with adhesive etc. added per square meter of nuclear-substituted zinc salicylate. After coating the paper surface with 0.7 g of paint and drying, print using commercially available pressure-sensitive recording paper.
indicates strong color, Δ indicates slightly inferior, and × indicates no color development.

[Brief explanation of the drawing]

1 and 2 are nuclear magnetic resonance absorption spectra charts, FIG. 1 shows each nuclear-substituted salicylic acid obtained in Example 1-2, and FIG. 2 shows each nuclear-substituted salicylic acid obtained in Example 2-2. All devices used are JNM-PMX60SI manufactured by JEOL Ltd.
CDCl2 was used as the solvent, and tetramethylsilane was used as the reference. Agent Patent Attorney Johei Yamashita

Claims (4)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, R_1 is a methyl group or isopropyl group, R_2
is α,α-dialkylbenzyl group or nuclear substituted α,
Indicates an α-dialkylbenzyl group. ) Nucleically substituted salicylic acid and its salts. (2) Nucleically substituted salicylic acid represented by the general formula [I] is 3,6-dimethyl-5-(α,α-dimethylbenzyl)
The nuclear substituted salicylic acid and its salt according to claim 1, which is an acid selected from salicylic acid or 3-isopropyl-5-(α,α-dimethylbenzyl-6-methylsalicylic acid). (3) The nuclear substituted salicylate according to claim 1 or 2, wherein the salt is a polyvalent metal salt. (4) The nuclear substituted salicylate according to claim 1 or 2, wherein the salt is a zinc salt.