JPH0285231A - Nuclear substituted salicylic acid and salt thereof and production of same salt - Google Patents

Abstract

NEW MATERIAL:A nuclear substituted salicylic acid expressed by formula I (R1 and R2 are 1-10C alkyl; R3 and R4 are H or 1-4C alkyl) and salts thereof. EXAMPLE:3-(alpha,alpha-Dimethylbenzyl)-6-methylsalicylic acid. USE:Useful as a germicide, stabilizer for high polymers or developer for recording materials, excellent in solubility in organic solvents or high polymer compounds, capable of forming completely transparent compositions when transparency is required therefor and especially exhibiting stability to heat and light. PREPARATION:Sodium or potassium salt of a nuclear substituted phenol expressed by formula II is reacted with gaseous carbon dioxide in an organic solvent at 120-200 deg.C to afford the compound expressed by formula I. Furthermore, the compound expressed by formula II is synthesized by reacting a compound expressed by formula III with a compound expressed by formula IV (R5 and R6 are H or 1-9C alkyl).

Description

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

The novel nuclear-substituted salicylic acid and its salts have good solubility in water, organic solvents, or organic polymer compounds (and are suitable for use as bactericides, stabilizers for polymer compounds, or color developers for recording materials).

[Conventional technology]

Nuclear substituted salicylic acid and its salts have high bactericidal activity and are used as bactericidal agents. (Unexamined Japanese Patent Publication No. 62-1532
No. 45) 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. 5,611,2955) Polyvalent metal salts of nuclear-substituted salicylic acid, especially zinc salts, are used as color developers for recording materials. (Unexamined Japanese Patent Publication No. 48-989
No. 14, No. 62-25086 and No. 63-18672
No. 9) [Objective 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 polymeric compounds, and which is suitable as a bactericidal agent, a stabilizer for polymeric compounds, or a color developer for recording materials. An object of the present invention is to provide specific nuclear-substituted salicylic acids and salts thereof.

[Structure of the invention]

According to the present invention, -Form (1) (In -Form [1], R3 and R2 have 1 to 10 carbon atoms.
represents an alkyl group, and R3 and R4 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ) Novel nuclear-substituted salicylic acids and salts thereof are provided. These are characterized by extremely high solubility in water, organic solvents, or organic polymer compounds.

A highly water-soluble bactericide is most preferred since it can be formulated or applied using water as a medium. - Since the alkali metal salt, amine salt, or ammonium salt of the nuclear-substituted salicylic acid represented by the formula (1) is easily dissolved in water, a highly concentrated aqueous solution can be prepared. In addition, it does not exhibit any photoallergenic properties particularly to the skin.

Various metal compounds are used as stabilizers for halogen-containing polymer compounds, but when transparency is particularly required for the polymer composition, metal compounds that have good solubility in the polymer compound are selected. - The polyvalent metal salt of nuclear-substituted salicylic acid represented by the formula (1) has good solubility in polymeric compounds, forms a completely transparent composition, and has excellent stability, especially in resistance to heat and light.

The color development reaction of a color developer for recording materials is generally carried out in a low polar organic medium, and solubility in the medium is the most important characteristic of the color developer.

- Polyvalent metal salts of nuclear-substituted salicylic acid represented by formula (1), especially zinc salts, dissolve well in organic solvents with relatively low polarity and have excellent color developing action as color developers. There is.

Their solubility is closely related to the structure of general formula (1). In General 2 (1), R and R2 represent an alkyl group having 1 to 10 carbon atoms, specifically a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group , heptyl group, octyl group, nonyl group or decyl group. R1 and R2
If it is a hydrogen atom, better solubility, which is the object of the present invention, cannot be obtained than when it is an alkyl group. Further, an asymmetric structure in which R1 and R2 are not the same is preferable because better solubility can be obtained. R3 and R4 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and specific examples of the alkyl group include a methyl group, ethyl group, isopropyl group, sec-butyl group, or tertiary-butyl group, but R5 The structural influence on solubility is small compared to R2 and R2. The 6-position of the nuclear-substituted salicylic acid represented by general 2 (1) is a methyl group, and this is the most characteristic feature of the structure of the present invention.
The contribution of the methyl group at the 6-position to solubility is extremely significant, as is the contribution of the bulky substituent at the 3-position.

Specific examples of the nuclear-substituted salicylic acid represented by general formula CI) include 3-(α,α-dimethylbenzyl)-6-methylsalicylic acid, 3-(α,α-dimethylbenzyl)-5
, 6-dimethylsalicylic acid, 3-(α,α-dimethylhensyl)-5-isopropyl-6-methylsalicylic acid,
3-(α.

α-dimethylbenzyl)-5-sec-butyl-6-methylsalicylic acid, 3-(α,α,4-trimethylmethylhensyl)-6-methylsalicylic acid, 3-(α,α-dimethyl-4-isopropylhensyl) -6-methylsalicylic acid, 3-(α-methyl-α-ethylbenzyl)-6
-Methylsalicylic acid, 3-(α,4-dimethyl-α-ethylbenzyl)-6-methylsalicylic acid, 3-(α,2
Dimethyl-α-ethylbenzyl)-6-methylsalicylic acid, 3-(α-methyl-α-ethyl-4-tert-butylbenzyl)-6-methylsalicyl IW, 3-(α-
Methyl-α-propylbenzyl)-6-methylsalicylic acid, 3-(α-methyl α-isopropylbenzyl)-6
-Methylsalicylic acid, 3-(α-methyl-α-butylbenzyl)-6-methylsalicylic acid, 3-(α-methylα
-isobutylbenzyl)-6-methylsalicylic acid, 3-
(α-methyl-α-hexylbenzyl) = 6-methylsalicylic acid, 3-(α-methyl-α-octylbenzyl)-
6-Methylsalicylic acid, 3-(α-methyl-α-decylhensyl)-6methylsalicylic acid, 3-(α-ethyl-
α-propylbenzyl)-6-methylsalicylic acid, 3(
α-ethyl-α-pentylbenzyl)-6-methylsalicylic acid, 3-(α-ethyl-α-hebutylbenzyl)-
6-Methylsalicylic acid, 3-(α-ethyl-α-nonylbenzyl)-6-methylsalicylic acid, 3-(α-propyl-α-butylbenzyl)-6-methylsalicylic acid, 3
-(α-propyl-α-hexylbenzyl)-6-methylsalicylic acid, 3-(α-propyl-α-octylbenzyl)-6-methylsalicylic acid or 3-(α-phthyl-α-pentylbenzyl)-6- Examples include methylsalicylic acid. These nuclear-substituted salicylic acids represented by the -form [I] are represented by the general formula (II) R3 (-format (II), where R+, Rz, R3 and R4 are respectively the same as defined in the -i formula N). ) can be obtained as its sodium or potassium salt by reacting the sodium or potassium salt of the nuclear-substituted phenol with carbon dioxide (Kolgeschmidt reaction). −
format〔! ] and - Form (II) sodium salt or potassium salt both dissolve well in various organic solvents as intended by the present invention, so it is preferable to carry out the series of operations in an organic solvent.The reaction temperature is 120°C. A range of 0.degree. C. to 200.degree. C. is preferred.

The nuclear-substituted phenol represented by the general formula (II) is the phenol represented by the general formula (In) (-form (I[[), where R3 is the same as the definition of R1 in the general formula (1)). General formula (IV) (-format (
In IV), R1 and R4 are the same as the definitions of R1 and R4 in form (1), respectively, and R7 and R6 represent a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. ) is obtained by addition reaction with a styrene derivative represented by the following in the presence of a catalyst. - Specific examples of phenols represented by form (III) include metacresol, 3,4
-xylenol, 3-methyl-4-isopropylphenol or 3-methyl-4-sec-butylphenol, all of which are easily available industrially or can be easily derived by simple processing.

Specific examples of styrene derivatives represented by the format (IV) include α-methylstyrene, α,3-dimethylstyrene, α,4-dimethylstyrene, α-methyl-3-isopropylstyrene, α-methyl-4-isopropyl Styrene, α, β-dimethylstyrene, α-ethylstyrene, α
, β, 2-trimethylstyrene, 2-methyl-α-ethylstyrene, α, β, 4-trimethylstyrene, 4-methyl-α-ethylstyrene, α, β-dimethyl-4-kushabutylstyrene, α-ethyl -4 sheabutylstyrene, α, β, β-trimethylstyrene, α-isopropylstyrene, α-methyl-β-ethylstyrene,
α-propylstyrene, α-methyl-β-propylstyrene, α-butylstyrene, α-methyl-β-isopropylstyrene, α-isobutylstyrene, α, β-diethylstyrene, α-propyl-β-methylstyrene, α
-Methyl-β-pentylstyrene, α-hexylstyrene, α-ethyl-β-butylstyrene, α-pentyl-
β-methylstyrene, α, β-dipropylstyrene, α
-butyl-β-ethylstyrene, α-methyl-β-hebutylstyrene, α-octylstyrene, α-ethyl-β
-hexylstyrene, α-hebutyl-β-methylstyrene, α-propyl-β-pentylstyrene, α-hexyl-β-ethylstyrene, α,β-dibutylstyrene,
α-pentyl-β-propylstyrene, α-methyl-β
-nonylstyrene, α-decylstyrene, α-ethyl-
β-octylstyrene, α-nonyl-β-methylstyrene, α-propyl-β-hebutylstyrene, α-octyl-β-ethylstyrene, α-butyl-β-hexylstyrene or α-hebutyl-β- Examples include propyl. Specific examples of catalysts for the addition reaction include sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, boron trifluoride, or aluminum salts of phenols. 2
It is carried out at a temperature of 50°C.

Many of the styrene derivatives represented by general formula (IV) cannot be easily obtained on an industrial scale.

Although many methods are known for producing the styrene derivatives used for the purpose of the present invention, the following two methods are industrially economical and practicable.

One of them is a method using the Grignard reaction, which is shown by the following chemical formula.

or (In the above chemical formula, the definitions of R3, R4, R5, and R6 are the same as the definitions in the general formula (rV), and X represents a halogen atom.) Each of these reactions is based on the experience of ordinary synthetic reactions. It can be easily implemented according to the following. Another method is to utilize an autoxidation reaction, which is represented by the following chemical formula.

+lI□o + 12 (In the above chemical formula, the definitions of R1, R4, R5, and R6 are the same as in the general formula (rV).) These reactions are also easy to carry out according to conventional methods. . The final step in both of the above two methods is a dehydration step of the tertiary alcohol, and the position of the pro-I-one that is eliminated along with the hydroxyl group is not necessarily constant, generally giving many isomers.

For example, when methylethyl phenyl carbinol is dehydrated using iodine as a catalyst, a mixture of two geometric isomers, α-ethylstyrene and α,β-dimethylstyrene, is obtained with a small amount.

Similarly, dehydration of ethylpropylphenyl carbinol yields a mixture of approximately equal amounts of α,β-diethylstyrene and α-propyl-β-methylstyrene, each of which contains two geometric isomers. However, there is no need to distinguish between these isomers for the purposes of this invention, since mixtures of these isomers give a single product when added to phenols. Using these two synthetic means, all sutyrene derivatives of the form (IV) can be prepared. The basic raw materials used in the first method include chlorobenzene, bromobenzene, 2-chlorotoluene, 4-chlorotoluene, 4-chloroethylbenzene,
-chlorotert-butylbenzene, ethyl bromide, isopropyl chloride, butyl chloride, isobutyl chloride, sec-butyl chloride, acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, or acetophenone. The basic raw materials used in the second method include cumene, cymene, sec-butylbenzene, 4-methyl sec-butylbenzene,
-tert-butyl secondary butylbenzene, secondary hexylbenzene, secondary octylbenzene,
Examples include secondary decylbenzene and secondary dodecylbenzene.

The novel nuclear-substituted salicylic acid, which is the object of the present invention, is produced as its sodium salt or potassium salt by the method described above.

To obtain nuclear-substituted salicylic acid, dilute sulfuric acid or an acid such as dilute hydrochloric acid is added to the aqueous solution of the above sodium salt or potassium salt for acid precipitation, and if necessary, purification by recrystallization in an organic solvent is also possible. Free nuclear substituted salicylic acid is obtained.

These are generally insoluble in water but dissolve well in organic solvents, so they are used as oil-soluble antifungal agents 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, dimethylamine, trimethylamine, and ethylamine.1. Examples include diethylamine, triethylamine, ethanolamine, jetanolamine, triethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, dimethylaminoethanol, diethylaminoethanol, and morpholine. These water-soluble nuclear-substituted narichlates have uses as water-soluble bactericides or fungicides.

Polyvalent metal salts of nuclear-substituted salicylic acid are poorly soluble or insoluble in water, but are well soluble in organic solvents. These are prepared as water-insoluble salts 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, calcium, iron, cobalt, nickel, zinc, strontium, cadmium, tin, barium, or lead, with calcium or zinc being most preferred. Water-soluble polyvalent metal salts refer to water-soluble polyvalent metal salts such as magnesium sulfate, aluminum sulfate, calcium chloride, zinc sulfate, or lead acetate;
Contains hydrochloride, nitrate or acetate. Polyvalent metal salts of nuclear-substituted salicylic acids, especially the magnesium, calcium, zinc, iron, rontium, cadmium, tin, barium or lead salts, are used as transparency stabilizers for chlorine-containing polymeric compounds. Polyvalent metal salts of nuclear-substituted salicylic acids, especially aluminum, cobalt, nickel or zinc salts, are also used as color developers for recording materials.

[Embodiments of the invention]

In order to further clarify the present invention, the present invention will be described below with reference to Examples and Comparative Examples.

In the examples, products were identified by nuclear magnetic resonance absorption spectroscopy. Note that the JR23 used is JNM-PMX60S+ manufactured by JEOL Ltd. The solvent is D
MSO-d5 was used, and the sample concentration was 5%. Unless otherwise specified, tetramethylsilane was used as a reference.

Example 1-1 432 g (4 mol) of metacresol and 5 mol of trifluoromethanesulfonic acid were placed in a hard glass four-eye flask with an internal volume of 2,000 millilindres equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser. Prepare grams. While slightly cooling the flask, 236 g (2 moles) of α-methylstyrene was added dropwise from the dropping funnel over a period of about 3 hours so that the temperature of the contents reached about 20°C. After dropping, add 300 grams of toluene and 300 grams of boiling water to the flask, stir vigorously, transfer the contents to a grammar load, let stand, and remove the lower aqueous layer.

Add another 300 grams of boiling water and repeat the washing process three times. The oil layer was transferred to a vacuum distillation device with an internal volume of 1,000 ml, and fractionally distilled at 120°C at approximately 1 torr.
Collect 402 grams of nearby fraction. It was confirmed by gas chromatography that it was a single substance, and the infrared absorption spectrum and nuclear magnetic resonance absorption spectrum (reference Cf14) (Figure 1) showed that it was 2-(α, α
-dimethylbenzyl)-5-methylphenol.

Example 1-2 The sample obtained in Example 1-1 was placed in a four-eye flask made of hard glass with an internal volume of 1,000 ml and equipped with a stirrer, a thermometer, a gas inlet, and a reflux condenser that can separate water. 339 grams (1,5 moles) of 2-(α,α-dimethylhensyl)-5-methylphenol, 250 grams of diethylene glycol dimethyl ether, 150 grams of toluene and 120 grams of 50 percent aqueous sodium hydroxide solution.
gram (1.5 mol). Stir the contents while slowly blowing nitrogen gas through the gas inlet.

The flask is heated to remove the water that azeotropically distills off with the toluene to complete the dehydration. Transfer the entire contents of the flask to a stainless steel autoclave with an internal volume of 1 OOO ml, and maintain the temperature at 175°C and carbon dioxide gas pressure at 20°C.
kg/clIt for about 3 hours. After cooling the autoclave to 90°C, the pressure is removed and the contents are taken out. The contents are a completely fluid homogeneous liquid. Internal volume5.
2. Add water to OOO milliliter beaker. Add OOO grams and transfer the contents of the autoclave to it at about 80℃.
Heat until. After removing the upper oil layer, add 3 more toluene.
00 milliliters/torr is added to extract unreacted substances.

After removing the toluene layer, add 350 ml of 5N dilute sulfuric acid and stir vigorously. Crystals of the target substance precipitate, which are collected by filtration and recrystallized from 1,000 ml of toluene.

The pure white crystals obtained weigh approximately 315 grams.

Its melting point is 193°C, and its acid value is 206.3 (theoretical value; 20
7.55), and since the data of infrared absorption spectrum and nuclear magnetic resonance absorption spectrum (Figure 2) and liquid chromatography indicate that it is a single substance, this is 3-(α, α- It was confirmed to be dimethylhensyl)-6-methylsalicylic acid.

Example 2 3,4-xylenol and α-
2-(α,α-dimethylbenzyl)-4,5-dimethylphenol is obtained from methylstyrene. Subsequently, in the same manner as in Example 1-2, 2(α,α-dimethylpencyl)-4,5-dimethylphenol was converted to 3-(α,α-dimethylpencyl)-4,5-dimethylphenol.
α-dimethylbenzyl)5,6-dimethylsalicylic acid is obtained. It has a melting point of 212°C and an acid value of 197.0 (
Theoretical value: 197.31) and the nuclear magnetic resonance absorption spectrum are shown in FIG.

Example 3-1 97.3 grams of powdered magnesium is charged into a hard glass five-loaf flask with an internal volume of 2.000 milliliters, equipped with a stirrer, a thermometer, a reflux condenser, a gas inlet, and a water dropping funnel. . Blow dry nitrogen gas through the gas inlet to completely dry the inside of the flask. Add 800 milliliters of anhydrous tetrahydrofuran to the flask through a column of drying molecular sieves.

While stirring the contents, drop 495 grams of chlorobenzene from the dropping funnel. Since it generates a lot of heat during the process, the cooling of the flask and the dropping rate are adjusted so that the temperature of the contents does not exceed 50°C. Magnesium is completely dissolved by keeping the inside of the flask at 40° C. for about 10 hours after the completion of the dropwise addition. When the magnesium is completely dissolved, the temperature inside the flask is lowered to 10° C. and 288 g of anhydrous methyl ethyl ketone is added dropwise from the dropping funnel. After finishing dropping, keep at 10°C for about 2 hours. 2,000 ml of water in a beaker with an internal volume of 5,000 ml
gram and 300 grams of acetic acid and add the contents of the flask to this with vigorous stirring. Stir thoroughly, then transfer to a separating funnel and remove the aqueous layer. 50 more water
The washing operation is carried out three times with 0 grams each. Transfer the oil layer to a hard glass three-necked flask with an internal volume of 1,000 ml and equipped with a stirrer, thermometer and vacuum distillation port.
Low boiling components up to 80° C. are removed in a Torr vacuum. The vacuum distillation port is replaced with a reflux condenser with a water separator, 0.5 g of iodine is added to the flask, and the flask is heated. As water is produced during decomposition, the contents are boiled little by little so that the water is removed from the water separator. When the decomposition is completed, the temperature of the contents of the flask is lowered, and 200 ml of a 0.1N aqueous sodium carbonate solution is added to wash the flask. The oil layer has a diameter of 30 mm and a filling height of 500 mm.
Internal volume with millimeter packed tower 1. Transfer to an OOO ml vacuum distiller and collect fractions from 90°C to 108°C at 45 torr. Approximately 420 grams of clear colorless liquid are obtained. By gas chromatography,
This is confirmed to be a mixture of approximately 6 percent alpha-ethylstyrene and 94 percent alpha, beta-dimethylstyrene.

Example 3-2 432 grams (4 moles) of metacresol and 5 grams of trifluoromethanesulfonic acid were placed in a four-hole hard glass flask with an internal volume of 2.000 milliliters equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser. Prepare. While cooling the flask, the temperature of the contents was adjusted to 15 °C, and the α obtained in Example 3-1 was added from the dropping funnel.
- 330 g (2.5 mol) of a mixture of ethylstyrene and α,β-dimethylstyrene are added dropwise over a period of about 4 hours.

One hour after the completion of the addition, add 30 g of boiling water containing 300 g of toluene and 2 g of sodium carbonate to the flask.
Add 0 grams and stir thoroughly.

Transfer this to a separatory funnel, remove the aqueous layer, and then
Repeat washing three times with 0g of boiling water. The oil layer is transferred to a vacuum distiller with an internal volume of 1.000 ml, and the fraction between 130°C and 135°C is collected at 1 torr. Approximately 550 g of a colorless, transparent, slightly viscous liquid is obtained. According to gas chromatography, this is a single component, and the hydroxy value is 231.9 (theoretical value; 233.4).Nuclear magnetic resonance absorption styrene (reference CC14) is as shown in Figure 4, and this is 2- It is confirmed that it is (α-methyl-α-ethylbenzyl)-5-methylphenol.

Example 3-3 2 obtained in Example 3-2 was placed in a 1.000 ml hard glass four-eye flask equipped with a stirrer, a thermometer, a gas inlet, and a reflux condenser that can separate water. 432 grams (1.8 moles) of -(α-methyl-α-ethylbenzyl)-5-methylphenol, 350 grams of toluene, and 144 grams (1.8 moles) of 50 percent aqueous sodium hydroxide solution are charged. Stir the contents while slowly blowing in nitrogen gas. Heat the flask to remove water azeotropic with toluene and complete dehydration. Transfer the contents of the flask to a stainless steel autoclave with an internal volume of 1.000 ml. Transfer the entire contents and react at 170°C and carbon dioxide gas pressure of 20kg/cJ for about 3 hours. Cool the autoclave to 90°C, then remove the pressure and open it. The contents are completely dissolved in toluene. Internal volume: 5. 2. Add water to a 000ml beaker.
000 grams and pour the autoclave contents onto it.

The mixture was heated to 80° C. while stirring, and left to stand to remove the upper notluene layer. Furthermore, unreacted substances are extracted with 500 milliliters of toluene. After completely removing the toluene layer, 400 ml of 5N dilute sulfur M was added while stirring vigorously. The target product is initially liberated as oil droplets, but as the stirring continues, crystals precipitate. If the crystals are filtered and recrystallized with 800 milliliters of toluene, about 400 grams of white crystals will be obtained. It has a melting point of 158°C and an acid value of 197.8 (theoretical value; 197.
31) And the nuclear magnetic resonance absorption spectrum is shown in FIG.

Furthermore, liquid chromatography confirmed that it was a single component, which was 3-(α-methyl-α-ethylbenzyl)=6-methylsalicylic acid.

Example 4-1 The methyl ethyl ketone in Example 3-1 was replaced with 400 grams of methyl isobutyl ketone, and the other conditions were exactly the same as in Example 3-1. The fraction from 120°C to 125°C was collected at 40 torr, and about 500 g of methyl isobutyl ketone was used. Grams of clear colorless liquid are obtained. This is determined by gas chromatography to give a 5% α
-Isobutylstyrene and 95% α-methyl-
It is confirmed that it is a mixture of β-isopropylstyrene.

Example 4-2 The mixture of α~ethylstyrene and α,β-dimethylstyrene of Example 3-2 was mixed with the mixture of α~isobutylstyrene and α-methyl=β~isopropylstyrene obtained in Example 4-1 400 About 600 grams of 2-(α-methyl-α-
Isobutylhensyl)-5-methylphenol is obtained. This has a hydroxyl value of 208.2 (theoretical value; 2
09.04), the nuclear magnetic resonance absorption spectrum (reference CC'A4) is shown in FIG.

Example 4-3 The 2-(α-methyl-α-ethylbenzyl)-5-methylphenol of Example 3-3 was converted to 2-(α-methyl-α-ethylbenzyl)-5-methylphenol obtained in Example 42.
-(α-Methyl-α-isobutylbenzyl)-5-methylphenol 482.4 In place of crumb, others are Example 3
Approximately 450 grams of white crystals are obtained in exactly the same manner as in -3. It has a melting point of 147°C and an acid value of 178.2 (theoretical value; 179.60), and the infrared absorption spectrum and nuclear magnetic resonance absorption spectrum (Figure 7) indicate that it is 3-(α-methyl-α- It is confirmed to be isobutylhensyl-6-methylsalicylic acid.

Example 5 A mixture of α-propylstyrene and α-methyl-β-ethylstyrene is obtained in the same manner as in Example 31, except that 334 grams of methylpropyl ketone is used instead of methyl ethyl ketone in Example 3-1. Next, Example 3-
2(α-methyl-α-propylbenzyl)-5-methylphenol is obtained in the same manner as in 2. This has a hydroxyl value of 220.1 (theoretical value; 221.2) and a nuclear magnetic resonance absorption spectrum (reference CCff 4) as shown in FIG. Furthermore, in the same manner as in Example 3-3, the melting point was 171°C, the acid value was 187.2 (theoretical value; 188.0
4) White crystals are obtained. From the infrared absorption spectrum and nuclear magnetic resonance absorption spectrum (Figure 9), this is 3-
It is confirmed that it is (α-methyl-α-propylbenzyl)-6-methylsalicylic acid.

Example 6 Internal volume with stirrer, thermometer, gas inlet and reflux condenser 5. 3.500 g of water in which 10 g of sodium laurate was dissolved in an OOO milliliter hard glass four-loaf flask, 500 g of secondary butylbenzene
00 grams, 10 milligrams of cobalt acetylacetate, and the pl+ of the system is 11 to 13 (The reason why the alkalinity is stronger than that in the synthesis reaction of hydroperoxide by normal autoxidation is that the target product of the synthesis is alcohol, not hydroperoxide. Sodium carbonate is added so that the result is . Bubble the contents with oxygen at 30°C to 40°C while stirring vigorously.

The contents are examined from time to time by liquid chromatography,
The reaction is continued until the conversion of secondary butylhenzene exceeds 70 percent.

In a hard glass beaker with an internal volume of 10,000 ml, 1,500 ml of 1N dilute sulfuric acid, 300 ml of a 10N aqueous sodium periosulfate solution, and 1 gram of potassium iodide were added, and the contents of the flask were gradually poured out while stirring vigorously. inject. Approximately 30 minutes after injection
Stir for a minute, then let stand and collect the oil layer. 1N sodium hydroxide water in the oil layer? W? Add 1lOOml of ff and stir vigorously for about 1 hour while boiling. Furthermore, let this stand still and the oil layer will be reduced to an internal volume of 1. Transfer to an OOO ml vacuum distiller and remove low-boiling components that bring the temperature of the pot to 90°C at 5 torr. Add 0.2 grams of iodine to the kettle and complete the decomposition reaction at atmospheric pressure while removing the water produced. If this is washed with alkali and then subjected to fractional distillation, 27 fractions from 88°C to 105°C will be obtained at 40 torr.
0 grams are obtained. It is identical to the product of Example 3-1 except that it contains 2.2 percent secondary butylbenzene and is a mixture of α-ethylstyrene and α,β-dimethylstyrene. And Example 3-2
, Subsequently, it is confirmed that 3-(α-methyl-α-ethylbenzyl)-6-methylsalicylic acid, which is exactly the same as that obtained in Example 3-3, can be obtained in the same manner as in Example 3-3. .

Example 7-1 2.73 ml of benzene was placed in a hard glass fifth flask with an internal volume of s, o o o ml, equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a gas inlet.
Charge 0 grams (35 moles) and 200 grams of a 30 percent aluminum chloride nitromethane solution. While slowly blowing dry hydrochloric acid gas through the gas inlet,
840 grams of 1-hexene (1
0 mol) was added dropwise over about 6 hours. After the addition is complete, the contents of the flask are heated to 50°C and kept for 2 hours. Add 500 ml of 0.2N hydrochloric acid to this and stir vigorously. Transfer this to a separatory funnel to remove the aqueous layer, and then
Wash with 0ml of boiling water until the water layer becomes neutral. Transfer the oil layer to an evaporator and heat from 110°C to 1°C at 38 Torr.
If the fraction up to 22°C is collected, 1.150 grams of a colorless and transparent liquid will be obtained. Gas chromatography shows that this is an isomeric mixture of secondary hexylbenzene consisting of approximately 60 percent α-methylpentylbenzene (hexyl-2-ylbenzene) and 40 percent α-ethylbutylbenzene (hexyl-3-ylbenzene). The matter is confirmed.

Example 7-2 Is the secondary butylbenzene of Example 6 an example? 600 grams of secondary hexylbenzene obtained in Example 6 was replaced with 600 grams of secondary hexylbenzene obtained in Example 6, and 122
Approximately 350 grams of fraction from 127°C to 127°C are obtained. By gas chromatography, this is approximately 2% α-butylstyrene, 57% α-methyl-
A complex styrene derivative consisting of two geometric isomers of β-propylstyrene, 20 percent of two geometric isomers of α-propyl-β-methylstyrene and 20 percent of two geometric isomers of α,β-diethylstyrene. It is confirmed that it is a mixture.

Example 7-3 The mixture of α-ethylstyrene and α,β dimethylstyrene in Example 3-2 was replaced with 400 grams of the mixture of styrene derivatives obtained in Example 7-2, and the rest was as in Example 3-2. In exactly the same manner, 590 g of a fraction ranging from 150° C. to 160° C. at 1 torr is obtained. It was determined by gas chromatography that 60 percent of 2-(α-methyl-α-
butylbenzyl)-5-methylphenol and 40 percent of 2-(α-ethyl-α-propylbenzyl)-
It is confirmed that it is a mixture of 5-methylphenol.

Example 7-4 The mixture 402 obtained in Example 7-3 was placed in a fourth flask with an internal volume of i and ooo milliliter, equipped with a stirrer, a thermometer, a gas inlet, and a reflux condenser capable of separating water.
grams (1,5 mol), 350 grams of toluene and 50
120 grams of percent sodium hydroxide solution (1,
5 mol).

Stir the contents while slowly blowing nitrogen gas through the gas inlet. The flask is heated to remove the water that azeotropically distills off with the toluene to complete the dehydration. Transfer the entire contents of the flask to an autoclave with an internal volume of 1,000 ml, and heat at 175°C and carbon dioxide gas pressure of 20 kg.
/cut for about 3 hours. autoclave for 90
After cooling to ゛C, the pressure is removed and the contents are taken out. The contents are a completely fluid homogeneous liquid. Internal volume 10.
000ml flask of water, o o o
ml and transfer the autoclave contents to it. While stirring the flask, bring the contents to 80°C, then let it stand. Remove the upper oil layer and wash with 500 ml of toluene four times.

The aqueous phase contains some toluene, but liquid chromatography reveals only one peak.

After removing the toluene azeotropically with water and adding 400 grams of 20 percent dilute sulfuric acid, a light brown viscous liquid is liberated. Let it stand still to settle and separate it, then further 1,
Wash with 1,000 milliliters of boiling water. The oil layer was removed and dried at 80° C. under a vacuum of 1 Torr to yield 393 grams of a clear, viscous light brown liquid. It has an acid value of 176.8 (theoretical value; 179.60), and elemental analysis shows that carbon is 76.2% (theoretical value; 76.
89 percent) and 7.80 percent hydrogen (theoretical; 7.74 percent). Furthermore, when this was methyl esterified with methanol and examined by gas chromatography, the peak area of methyl 3-(α-methyl-α-butylhensyl)-6-methylsalicylate was 58.
1 percent, the peak area of methyl 3-(α-ethyl-α-propylbenzyl)-6-methylsalicylate is 39
．． 8% and the peak area of the unknown is 2.1%, which is about 60% 3-(α-methyl-α-butylbenzyl)-6-methylsalicylic acid and 40% 3-(α-ethyl-α -propylbenzyl)-6-methylsalicylic acid.

Example 8 270 grams (1 mol) of 3-(α,α-dimethylbenzyl)-6-methylsalicylic acid obtained in Example 1-2 was dissolved in 1,000 ml of a 1N aqueous sodium hydroxide solution. . This is about 22 percent 1 of sodium 3(α,α-dimethylbenzyl)-6-methylsalicylate.
2 volumes of water containing water at night.

Example 9 In the same manner as in Example 8, the sodium salts of the nuclear-substituted salicylic acids obtained in Examples 2, 33, 4-3, 5 and 7-4 are obtained.

Example 10 By replacing the aqueous sodium hydroxide solution in Examples 8 and 9 with triethanolamine or morpholine water, the corresponding triethanolamine or formoline salts of nuclear-substituted salicylic acids are obtained.

Example 11 Internal volume 2. OOO ml stainless steel beaker with 5 percent 1-sulphite fJ water? G?
(I prepared 1200 grams, stirred vigorously,
3-(α,α-dimethylhensyl) obtained in Example 8
-The total amount of sodium 6-methylsalicylate aqueous solution is about 20%
Infuse in minutes. After stirring for another 20 minutes, the precipitated 3-(
Filter the zinc α,α-dimethylbenzyl 6-methylsalicylate and wash with 1.00 ml of water. This is vacuum dried at 110°C to obtain 303 grams of white powder. This has a zinc content of 10.5% (theoretical value: 10.8%) and is confirmed to be the desired product.

Example 12 In the same manner as in Example 11, the target product in the form of pure white powder or pale brown resin was obtained from the nuclear-substituted sodium salicylate obtained in Example 9, and was confirmed by measuring the zinc content of each product.

Example 13 Calcium salts of nuclear-substituted salicylic acid are obtained by the same treatment as in Examples 11 and 12, replacing the zinc sulfate with the same equivalent amount of calcium chloride, and are confirmed by measuring the respective calcium contents.

Comparative Example 1 Example 1-1 was continued in the same manner as Example 1-2 except that metacresol in Example 1-1 was replaced with para-cresol.
α,α-dimethylhensyl)-5=methylsalicylic acid is obtained. It has a melting point of 253°C and an acid value of 207.3.
(Theoretical value, 207.55), and a nuclear magnetic resonance absorption spectrum chart is shown in FIG.

Comparative Example 2 3-(α,α-dimethylhensyl) obtained in Comparative Example 1
Sodium, triethanolamine, morpholine, zinc and calcium salts are obtained from -5-methylsalicylic acid in the same manner as in Examples 8, 10, 11 and 13.

〔Effect of the invention〕

The nuclear-substituted salicylic acid and its salt of the present invention are characterized by poor 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. is large.

Table 1 shows the results of those tests. Regarding solubility, ◎ means 50% or more, ○ means 20% to 50%, △ means 2% to 20%, and ×
represents a solubility of 2% or less, and the transparency of PVC is determined by kneading 100 parts by weight of polyvinyl chloride with a degree of polymerization L300, 100 parts by weight of dioctyl phthalate, and 3 parts by weight of each nuclear substituted zinc salicylate at 220°C for 10 minutes. ■ is completely transparent, 0 is almost transparent, △ is slightly cloudy, and × is very cloudy. Spread it on the paper surface so that 0.7 grams per square meter is applied, let it dry, and then print using commercially available pressure-sensitive recording paper. O indicates strong color, Δ indicates slightly inferior, and × indicates no color development.

Part 1 table

[Brief explanation of drawings]

Figures 1 to 10 are all nuclear magnetic resonance absorption spectra charts, in which Figure 1 shows the nuclear-substituted phenol obtained in Example 1-1, Figure 2 shows the nuclear-substituted salicylic acid obtained in Example 1-2, Figure 3 shows the nuclear substituted salicylic acid obtained in Example 2,
Figure 4 shows the nuclear substituted phenol obtained in Example 32;
The figure shows the nuclear-substituted salicylic acid obtained in Example 3-3, Figure 6 shows the nuclear-substituted phenol obtained in Example 4-2, and Figure 7 shows the nuclear-substituted salicylic acid obtained in Example 4-3. Figure 8 shows the nuclear substituted phenol obtained in Example 5, and Figure 9 shows Example 5.
The nuclear-substituted salicylic acid obtained in FIG. 1O is the nuclear-substituted salicylic acid obtained in Comparative Example 1. Agent Patent Attorney Johei Yamashita

Claims (1)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[I
] (In the formula, R_1 and R_2 represent an alkyl group having 1 to 10 carbon atoms, and R_3 and R_4 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) A nuclear-substituted salicylic acid and its salt. (2) 3-(α,α-dimethylbenzyl)-6-methylsalicylic acid, 3-(α,α-dimethylbenzyl)-5,
6-dimethylsalicylic acid, 3-(α-methyl-α-ethylbenzyl)-6-methylsalicylic acid, 3-(α-methyl-α-propylbenzyl)-6-methylsalicylic acid,
3-(α-methyl-α-butylbenzyl)-6-methylsalicylic acid, 3-(α-ethyl-α-propylbenzyl)-6-methylsalicylic acid or 3-(α-methyl-α-
A nuclear-substituted salicylic acid selected from isobutylbenzyl-6-methylsalicylic acid and its salt. (3) The nuclear-substituted salicylate according to claim 1 or 2, wherein the salt is an alkali metal salt. (4) The nuclear-substituted salicylate according to claim 1 or 2, wherein the salt is an amine or ammonium salt. (5) The nuclear substituted salicylate according to claim 1 or 2, wherein the salt is a polyvalent metal salt. (6) General formula [II] ▲Mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[II] (In the formula, R_1 and R_2 represent an alkyl group having 1 to 10 carbon atoms, and R_3 and R_4 are A nuclear-substituted phenol represented by (representing a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). (7) General formula [II] ▲Mathematical formulas, chemical formulas, tables, etc.▼・・・・・・[II] (In the formula, R_1 and R_2 represent an alkyl group having 1 to 10 carbon atoms, and R_3 and R_4 are (represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) A general formula [I] created by reacting a sodium or potassium salt of a nuclear-substituted phenol represented by (representing a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) with carbon dioxide gas [I] ▲Mathematical formulas, chemical formulas, tables, etc. are available▼・・・・・・〔I
] (In the formula, R_1 and R_2 represent an alkyl group having 1 to 10 carbon atoms, and R_3 and R_4 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) Sodium or potassium salt of a nuclear-substituted salicylic acid represented by manufacturing method.