JPS5899432A - Unsaturated fatty acid or its salt and fungicide containing the same - Google Patents

Abstract

NEW MATERIAL:An unsaturated fatty acid of the formula[A is CH3-CH2-CH2-, CH3-C(CH3)H-; M is H, Na, Zn; n is M's valency]or its salt. EXAMPLE:2,7-Dimethyl-4-octenoic acid. USE:Fungicide: it has low toxicity and low irritating properties, shows a wide antibiotic activity against various kinds of microorganisms, especially shows excellent antibactericidal effect against gram-negative bacteria. it is used for food, cosmetics, medicines, paints and other purposes. PREPARATION:For example, 2,7-dimethyl-4-octenoic acid (M is H in the formula) and 2-methyl-4-nonenoic acid are prepared by hydroxylating 2,7-dimethyl-1,4- octadiene and 2-methyl-1,4-nonadiene resulting from altenate copolymerization of propylene with butadiene, followed by oxidation of the product.

Description

[Detailed description of the invention] M is H, Na or Zn and n is the valence of M)
The present invention relates to a novel unsaturated fatty acid represented by the formula or a salt thereof, and an antibacterial agent containing the same as an active ingredient.

Foods, cosmetics, pharmaceuticals, paints, etc. are easily contaminated by microorganisms, and the damage caused by such contamination is enormous. Conventionally, various microbial contamination inhibitors for these products have been developed and used. For example, organic metals such as organic mercury and organic tin, aromatic phenols, and the like have been used as anti-pollution agents, but they are highly toxic and have a high tendency to accumulate residue, which has become a social problem.

On the other hand, fatty acids such as sorbic acid, undecylenic acid, and 2-ethylhexylic acid, or their sodium salts and zinc salts are used as low-toxicity and hypoallergenic microbial contamination preventive agents, but these are effective against Durum-negative bacteria. For example, Ps
eudomonas aeruginosa (Pseudomonas aeruginosa)
, has low antibacterial activity against.

The present invention provides a new and useful antibacterial agent with low toxicity and low irritation that overcomes the drawbacks of the conventional products, and the antibacterial agent of the present invention is a new compound.

The compound of the present invention has low toxicity and low irritation, and has a wide range of antibacterial activity against various microorganisms, and particularly has excellent antibacterial activity against Guraro-negative bacteria.

Among the compounds of formula [1] of the present invention, 2, 7 in which M is H
-Simethyl-4-octenoic acid and 2-methyl-4-nonenoic acid are 2,7-dimethyl-1゜4- obtained by the method previously proposed by the present inventors, that is, by alternating copolymerization reaction of propylene and butadiene. Octadiene and 2
- Hydroxylation of methyl-1,4-nonadiene to 2
．． 7-dimethyl-4-octen-1-ol and 2-
After converting it into methyl-4-nonen-1-ol (Unexamined Japanese Patent Publication No.
6-108721) and further oxidize it.

2.7-cymethyl! , 4-octadiene and 2-methyl-1,4-nonadiene can be hydroxylated by hydroboration reaction using diporane followed by oxidative hydrolysis, or by hydroalumination/reaction using trialkylaluminium. This is done by oxidative hydrolysis after drying.

In addition, 2,7-dimethyl-4-octen-1-ol and 2-methyl-4-nonen-1-ol can be oxidized using air, oxygen, nitric acid, permanganate, chromate, organic peroxide, Oxidation can also be carried out by a general oxidation method using an oxidizing agent such as persulfuric acid or hydrogen peroxide, but it is not sufficient in terms of selectivity and yield. Oxidation methods that yield metal salts are preferred. It is preferable to carry out the reaction between the alcohol and the caustic alkali in a hydrogen atmosphere in order to increase selectivity and yield. During this reaction, Mn, Co,
Oxides such as Ni, Ag, Pt, Hg, and Zn are used as catalysts. Since the product obtained here is an alkali metal salt of a carboxylic acid, hydrolysis is necessary to obtain the free carboxylic acid, and this hydrolysis can be carried out by a conventional method. This hydrolysis is also useful as a purification step to increase product purity.

Among the compounds of formula CI'3 of the present invention, 2 in which M is Na
, sodium 7-dimethyl-4-octenoate and 2-
Sodium methyl-4-nonenoate can be easily obtained by bringing 27-dimethyl-4-octenoic acid and 2-methyl-4-nonenoic acid into contact with an aqueous solution of sodium hydroxide at a temperature around room temperature.

The present invention (among the compounds of formula 13, 2, 7 in which M is Zn)
-zinc cymethyl-4-octenoate and 2-methyl-4
Zinc nonenoate can be easily obtained by bringing 2,7-dimethyl-, sodium 1-octenoate, and sodium 2-methyl-4-nonenoate into contact with an aqueous solution of zinc chloride at a temperature around room temperature.

As the antibacterial agent of the present invention, the compounds of the present invention represented by formula 13 may be used alone or in combination with two or more thereof, or may be used in combination with appropriate adjuvants.

EXAMPLES The present invention will be described in more detail with reference to Examples below, but these are merely for illustrative purposes and the present invention should not be construed as being limited by these.

Example 12.7-Dimethyl-4-octenoic acid 2,7-dimethyl-4-octenoic acid synthesized in Reference Example 1 was placed in a stainless steel autoclave with a capacity of 100 ml equipped with a stirring device.
1-all 15.6i, caustic soda 484? , activated carbon 0.8? , 0.79 i of zinc oxide, and 0.09 i of water were added, and after replacing the air in the autoclave with hydrogen gas, the autoclave was heated to 300 C with stirring. Hydrogen gas generated by the reaction was discharged to the outside of the autoclave, and the internal pressure of the autoclave was constantly maintained at 2Q Ky/m 2 . 300t
The reaction was completed in about 3 hours after the autoclave was heated to .

Add an aqueous sulfuric acid solution with a concentration of 30% by weight to the contents taken out from the autoclave to make it acidic, wash the oil layer with water, and then
2.7 is a colorless, transparent and slightly viscous liquid obtained by distillation under reduced pressure.
-Simethyl-4-octenoic acid 14y- was obtained.

Infrared absorption (IR) spectrum 3100-360ocrn Carboxyl group stretching vibration (medium intensity) 2950 cm Methyl group stretching vibration
(〃 Strong) 1720// Carbonyl group stretching vibration (〃〃) 956 〃 Trans double bond out-of-plane bending vibration (〃〃) The TR spectrum of the product is shown in FIG.

Example 2 Sodium 2,7-dimethyl-4-octenoate In a beaker of 500++J, add 4% sodium hydroxide. and 200ml of water was added to dissolve it. Next, 19.5% of 2,7-dimethyl-4-octenoic acid synthesized in the same manner as in Example 1 was gradually added to the car with stirring, and about 3.
The reaction was allowed to proceed for 0 minutes at room temperature.

After extracting and removing unreacted 2,7-dimethyl-4-octenoic acid with ether, the water in the aqueous layer was removed under reduced pressure.
After drying, 19.454 sodium 2,7-dimethyl-4-octenoate was obtained as a white powder.

Infrared absorption (IR) spectrum 2960crn Methyl group stretching vibration (intensity
Strong) 2930 // Methylene group stretching vibration (/
///) 1550 // Carboxylic acid ion antisymmetric stretching vibration (// //) 1460 // Methylene group bending vibration (// middle) 1410 //
Carboxylic acid ion symmetrical stretching vibration (strong) 1375//
Figure 2 shows the TR spectrum of the methyl group bending vibration (medium) 965//) lance C-H bending vibration (strong) product.

Example 3 2.7-dimethyl-4-octenoic acid zinc 500
2,7-dimethyl-4 obtained in Example 2 in a beaker of m1
- Add 10y of sodium octenoate, and add 20y of water (IJ
was added and dissolved. In the beaker, under stirring, add 3 parts of zinc chloride.
．． 5f! - was dissolved in 50 cc of water was gradually added, and the mixture was allowed to react at room temperature for 30 minutes.

The precipitated zinc 2,7-dimethyl-4-octenoate was separated by filtration, washed with water, and dried under reduced pressure to obtain colorless, transparent, semi-solid zinc 2,7-dimethyl-4-octenoate. I got IJ.

Infrared absorption (IR) spectrum 2960 crn Methyl group stretching vibration (intensity node) 2930〃 Methylene group stretching vibration (〃〃) 1
550// Carboxylic acid ion antisymmetric stretching vibration (〃
〃)1460// Methylene group bending vibration (〃
Medium) 1430// Carbo/acid ion symmetrical stretching vibration (// Strong) 1375// Methyl group bending vibration
(// Medium) 965〃Trans C-H bending vibration
(Strong) The IR spectrum of the product is shown in Figure 3.

Example 4 2-Methyl-4-nonenoic acid In Example 1, 2,7-dimethyl-4-octene-
2-methyl- synthesized in Reference Example 2 instead of 1-ol
The reaction was carried out under the same conditions except that 4-nonen-1-ol 16.0i was used to obtain 2-methyl-4-nonenoic acid 15i as a colorless, transparent and slightly viscous liquid.

IFt spectrum 3100-3600Crn-1 Carboxylic acid 0-H stretching vibration (medium intensity) 2960crn-1 Methyl group stretching vibration
(Strong) 2930 Methylene group stretching vibration
(〃〃)1720// Carbonyl group stretching vibration
(////) 1460 // Methylene group bending vibration (〃 Medium) 1375 // Methyl group bending vibration
(////)12401/ C-0 stretching vibration
(l) Strong) 965// l-Lance C-H
The TR spectrum of the bending vibration (////) product is shown in FIG.

Example 5 Synthesis of sodium 2-methyl-4-nonenoate In Example 2, 2,7-dimethyl-4-octenoic acid (19.5%) was replaced with 2, which was obtained in the same manner as in Example 4.
The reaction was carried out under the same conditions except that -methyl-4-nonenoic acid 18y- was used to obtain 17.9i of sodium 2-methyl-4-nonenoic acid in the form of a white powder.

TR spectrum 2960crn-1 methyl group stretching vibration (intensity node)
2930Crn-1 Methylene group stretching vibration (intensity node) 1560 〃 Carboxylic acid ion antisymmetric stretching vibration (
////)1460// Methylene radical bending vibration
(Medium) 1410 Carboxylic acid ion symmetrical stretching vibration (Strong) 1375 Methyl group bending vibration
(// Medium) 965/'l-Lance C-H bending vibration (Strong) The IFL spectrum of the product is shown in FIG.

Example 6 Synthesis of zinc 2-methyl-4-nonenoate Example 3
2-methyl-4-obtained in Example 5 in place of 1Of sodium 2,7-dimethyl-4-octenoate.
The reaction was carried out under the same conditions except that sodium nonenoate 107 was used to obtain 9.2 g of colorless and transparent semi-solid zinc 2-methyl-4-nonenoate.

IR spectrum 2960Crn-1 Methyl group stretching vibration 2930 Methylene group stretching vibration 1570/I Carboxylic acid ion reverse symmetric stretching vibration 14
60 〃 Methylene group bending vibration 1430 // Carboxylic acid ion symmetric stretching vibration 137
5crn-' Methyl group bending vibration 965//) Lance C
The IR spectrum of the -H bending vibration product is shown in FIG.

Example 7 2,7-dimethyl-4-octenoic acid according to the present invention, 2.
Various types of sodium 7-dimethyl-4-octenoate, zinc 2゜7-dimethyl-4-octenoate, 2-methyl-4-nonenoic acid, sodium 2-methyl-4-nonenoate and zinc 2-methyl-4-nonenoate. The minimum inhibitory concentration (MIC) against microorganisms is shown in Table 1, and for comparison, undecylenic acid, sodium decylenate, zinc undecylenate, casorylic acid, sodium caprylate, zinc casorylate, and n-p-oxybenzoate. Table 2 shows the MICs of the samples.

Test method: An ordinary agar medium was used as a bacterial medium, and a potato dextrose agar medium was used as a fungal medium. In the inoculating bacterial solution used to examine antibacterial properties, bacteria were cultured in a bouillon medium at 35C overnight.

However, Bacillus 5ubtilis ATC
For C6633, a spore suspension was used. For filamentous fungi, spores were sufficiently formed after inoculating and culturing potato dextrose agar slant medium, and the spores were suspended in a sterilized 0,005 qb sodium dioctyl succinate solution (approximately 10 per ml).

Furthermore, yeast was inoculated and cultured on a potato dextrose agar slant medium, allowed to sufficiently form bacterial cells, and suspended in sterile physiological saline (approximately 10 cells per ml).

After accurately weighing a certain amount of the test reagent, the test solution is arbitrarily diluted with sterile deionized water or 50% ethyl alcohol solution, etc., and the concentration after addition is 12.5.25.50.100.200.
It was adjusted to 400.800.1600 ppm.

For the flat plate, add the test solution to 100ml of the medium after heat sterilization.
After adding the solution to a ratio of 1.0 ml, the mixture was thoroughly mixed, and 15 mJ of the solution was separated and solidified.

To measure the antibacterial activity, a loopful of the inoculum solution was applied to a plate at each concentration level, and after culturing at 35C for 24 hours for bacteria and 6 days at 30C for fungi (filamentous fungi, yeast), The presence or absence of growth is determined visually and the minimum inhibitory concentration (
MIC) was issued.

The strain used was 5taphylococcus aureus 653 as a bacterium.
8-p (Staphylococcus aureus), Bacillus 5u
btilis ATCC6633 (Bacillus subtilis), Esch
erichia coli 0-55 (E. coli) and Pseudomonas aeruginosa (
4 types of Pseudomonas aeruginosa), Aspergillus as a filamentous fungus
s niger (black aspergillus), Aspergillus
lus flavus, Fusarium mon
iliformeNAL-F-616, Penicil
lium citrinum.

Cladosporium cladosporioi
des% Trichoderma and Chaetom
Seven types of Saccharomyces globosum ATCC6205 and Saccharomyces cerevisiae
It is QC-2 (grape yeast).

Reference Example 1 2,7-dimethyl-4-octen-1-ol with nitrogen-substituted dropping funnel 2! trans-2 into 20 flasks of
, 7-dimethyl-1,4-octadiene 19oz and tetrahydrofuran 500m/! After cooling to 0-5C, add 200 ml of diborane in tetrahydrofuran solution (concentration 1 mol/g) from the dropping funnel while stirring.
was added dropwise over a period of 30 minutes. Furthermore, after stirring for 5 hours at a temperature of 0 to IOC, 100% of 3N sodium hydroxide solution was added.
iJ and 100 ml of 30% hydrogen peroxide solution were added to carry out oxidative hydrolysis.

The product was extracted with ether, treated in a conventional manner, and then distilled under reduced pressure to obtain 2,7-dimethyl-4-octen-1-ol (b, p = 68-7), which is a colorless and transparent liquid with a citrus aroma.
3C/2mmHg, n14=1.4.502) to 35
I got 7.

Reference Example 2 2-Methyl-4-nonen-1-ol 2 with nitrogen-substituted dropping funnel! In a ρ20 eggplant flask, 190 g of 2-methyl-1,4-nonadiene and 500 m of tetrahydrofuran! After cooling to a temperature of 0 to 5C, a solution of diborane in tetrahydrofuran (
2 oomg (concentration: 1 molar) was added dropwise over 30 minutes.

After further stirring for 5 hours at a temperature of 0 to 10C, 1100ml of 3N sodium hydroxide solution and 1100ml of 30% circulating hydrogen oxide solution were added.
00ml was added for oxidative hydrolysis.

The product was extracted with ether, treated in a conventional manner, and then distilled under reduced pressure to obtain 2-, which is a colorless and transparent liquid with a floral odor.
Methyl-4-nonen-1-ol (b, p = 70~
75 C/2mm+Hg, n14=1.4528
) was obtained by 36%.

[Brief explanation of the drawing]

FIG. 1 shows Example 1, FIG. 2 shows Example 2, FIG. 3 shows Example 3, FIG. 4 shows Example 4, FIG. 5 shows Example 5, and FIG. 6 shows Example 2. I Spectrum of each product of Example 6.

Claims (1)

[Scope of Claims] An unsaturated fatty acid or a salt thereof represented by: M is H, Na or Zn, and n is the valence of M. CH3 (2) The salt according to claim 1, wherein A is CH3-CI- (- and M is Zn. M is H, Na or Zn and n is the valence of M).
An antibacterial agent consisting of an unsaturated fatty acid or a salt thereof. The antibacterial agent according to claim 3, wherein CH3 (4) A is CH3-CH- and M is Zn. (5) The antibacterial agent according to claim 4, wherein the fungi to be controlled are Durum-negative bacteria.