JPS6293203A - Polybasic acid amine salt disinfectant - Google Patents

Abstract

PURPOSE:To provide a disinfectant containing tetra-or pentacarboxylic acid amine salt as an active component, having low frothing tendency, low toxicity and low irritation, exhibiting strong antimicrobial activity against various bacteria, yeasts, etc., and usable in the field of food and medicine. CONSTITUTION:A tetra- or pentacarboxylic acid amine salt of formula (n and n' are 4-10; X is H or COOZ; Z is H, alkyl or substituted ammonium ion; at least one of Z is substituted ammonium ion) is used as an active component of the objective disinfectant. The compound of formula can be used in various uses e.g. in the form of an aqueous solution. Usually, it is used as an aqueous solution having a concentration of 0.0005-2.0wt%, preferably 0.01-1.0wt%. Since the pH of the aqueous solution decreases with increase of free carboxyl group, the pH of the compound itself can be controlled according to the use.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel polybasic acid amine salt type disinfectant, and more specifically, the present invention relates to a novel polybasic acid amine salt type disinfectant. is a hydrogen atom or COOZ, Z is a hydrogen atom, or an alkyl group, or a substituted ammonium ion, and at least one of Z is a substituted ammonium ion.) This invention relates to a disinfectant consisting of a salt such as a group alkanolamine.

Conventionally, tens of thousands of disinfectants are known, including chlorine compounds, phenol compounds, aldehydes, acids, esters, quaternary ammonium salts, antibiotics, etc., and are used in a wide variety of fields.

However, these are generally only effective against specific types of microorganisms, are more toxic or irritating, and are only soluble in certain solvents, making them inconvenient to use. .

The pentacarboxylic acid amine salt according to the present invention can be used in various solvents to obtain compounds with various structures, has a wide range of solubility for each compound, has low foaming properties, and is convenient to use. Although anionic, salts of alkylamines with appropriate chain lengths exhibit strong antibacterial activity against various bacteria and enzymes, and are low in toxicity and non-irritant.

Many fatty acids, ranging from short-chain to long-chain, have bactericidal and antifungal effects, although they are not extremely strong, and many of them are generally of low toxicity and are used in food and medicine. It is often used as salt, but its bactericidal power is often slightly reduced. For example, propionic acid is effective against black mold and other diseases;
．． 1~0. ■% is used. Sodium salts are used by adding 0.4% to flour. Also, sorbic acid is 50
is 10.50g/kg and is used in foods as acid and alkali metal salts. There are also examples of undecylenic acid being used to treat skin diseases.

The salt of the tetra or pentacarboxylic acid represented by the general formula (I), which is an active ingredient of the disinfectant of the present invention, can be produced by neutralizing the acid of the following general formula (II) by a conventional method. Examples of amines used for neutralization include aliphatic amines and aliphatic alkylolamines.

(In the formula, n and n' are numbers from 4 to 10, and Y is a hydrogen atom or COOH.) Conventionally, well-known polycarboxylic acids generally have short molecular chains, or have α , ω
Many of them were thought to be derivatives of direct dicarboxylic acids based on a structure in which carboxyl groups were bonded to both carbon atoms.

The tetra or pentacarboxylic acid represented by the above general formula (II) has a carboxyl group at one end of its molecular chain, that is, the α-position carbon, the other end is an alkyl group, and the other carboxyl group is located at the middle carbon of the molecular chain. It is a polycarboxylic acid bonded to.

Therefore, it is a unique polycarboxylic acid that is considered to be a derivative of a normal linear basic acid. These polycarboxylic acids can be produced by using a fatty acid derivative having a cyclohexene ring as a raw material and treating it with various known oxidation methods.

The amines used in the salts of the present invention consist of aliphatic alkylamines and aliphatic alkanolamines. The former is represented by the general formula NR3, where R is hydrogen or a linear or branched alkyl group having 1 to 18 carbon atoms and 0 to 2 hydrogen atoms. The latter is represented by the general formula NR'3, where R' is hydrogen,
In the alkylol group and the alkyl group, the number of carbon atoms is 1 to 12, and the number of carbon atoms is 1 to 1. Examples of the alkylamine include N-methylamine, N-oleylamine, N-dodecylamine, N-isooctadecylamine, N,N-dihexylamine, N-
-methyldecylamine, N,N,N-trihexylamine, and the like. As alkanolamines, N-monoethanolamine, triethanolamine, N,N-
Includes diisopropylethanolamine, decanolamine, etc.

The bactericidal agent of the present invention can be applied to various uses by preparing a salt of a tetra or pentacarboxylic acid represented by the general formula (I), for example, in an aqueous solution, and usually at a concentration of 0.
．． 0005 to 2.0% by weight, preferably 0.01 to 1.0% by weight.
It is used as a 0% by weight aqueous solution.

In the present invention, 1 of Z in the compound of general formula (I)
or more are amines. The greater the number of carbon atoms and fewer hydroxyl groups in Z, the greater the number of alkyl groups and the greater the number of carbon atoms, the more oil-soluble the compound becomes. The more free carboxyl groups there are, the lower the pH of the aqueous solution. Therefore, the pH of the compound itself can be adjusted depending on the purpose.

Next, the present invention will be explained in more detail based on Examples and Reference Examples.

Note that some of the amine salts of tetra- or pentacarboxylic acids used in the examples were synthesized from amines and tetra- or pentacarboxylic acids obtained from saturated sodium salts prepared according to Reference Examples 1 to 3 below (Reference Example 4). ), but
Others are stoichiometrically mixed with 5 to 20% ethanol solutions of the same acid and the corresponding amine (special grade reagent or rectified product), either as is (1) or at a temperature sufficiently higher than the vapor pressure of the amine, depending on the case. After ethanol was distilled off under vapor pressure (vacuum degree and temperature adjustment) (2), an aqueous solution with a predetermined concentration was used for measurement. (1) is the case when the sample is diluted with water to a fairly low concentration and no effect of ethanol appears, and (2) is the opposite case. In addition, it was confirmed for representative examples that the results obtained by these methods and the results obtained using the synthetic product were in agreement.

In addition, the raw materials used in the reference examples are fatty acid derivatives having a cyclohexene ring with the structures of the following general formulas A and B, where n, n', R, R', etc. show.

The bactericidal activity test method is as explained below.

Reference example 1 Raw material B (n=5, n=7, both R and R' are CH3)3.
01 g and 30 ml of glacial acetic acid were each poured into a 50 ml pear-shaped three-necked flask. The flask was equipped with a gas blowing tube, a condenser, and a stirrer. For the reaction, the flask was placed in a constant temperature bath at 10 to 14° C., and ozone-oxygen mixed gas (ozone concentration of about 3 wt %) was blown into the solution for 38 minutes while stirring the solution to effect ozonation. After ozonation, manganese acetate [Mn(CH3
0.02 g of CO2)2.4H2O] was added, the temperature was raised to 80°C while stirring, and oxygen gas (flow rate 270ml/min) was blown at 80°C for 1.5 hours to decompose and oxidize ozonide. After the reaction, the reaction solution was filtered to remove the manganese compound, the acetic acid was distilled off, the reaction product was collected with ether and washed with water, and the ether was distilled off to obtain 3.18 g of the reaction product (yield: 90.3). %) was obtained. This reaction product gave the following analytical values. That is, acid number: 244.6 (theoretical value 252.4), IR spectrum (cm-1): 25
00-2700 (carboxyl group), 1710 (carbonyl group), 1H-NMR spectrum (ppm): 0.9
(terminal methyl group), 1.2-1.3 (methylene group), 3
．． 4 (methyl ester group), 8.5-8.6 (carboxyl group), 13C-NMR spectrum (ppm): 14
．． 3 (terminal methyl group), 23.0-35.5 (methylene group), 40 (methyl ester group), 174.2-181
．． 1 (carboxyl group). From these analysis results, it was confirmed that the reaction product was tetracarboxylic acid dimethyl ester having the following structure.

Reference Example 2 10.03 g of raw material A (n=5, n'=7, both R and R' are CH3) and 80 ml of glacial acetic acid were each weighed into a 100 ml pear-shaped three-necked flask. The flask was equipped with a gas blowing tube, a condenser, and a stirrer. The reaction takes place in a flask of 10~
Place it in a high temperature tank at 13℃ and add ozone while stirring the solution.
Oxygen mixed gas (ozone concentration approximately 3.5 wt%) at a flow rate of 21
Ozonation was performed by blowing at 0 ml/min for 80 minutes. After ozonation, manganese acetate [Mn(CH3CO2)2.4H2
0.07 g of O] was added, the temperature of the reaction solution was raised to 80° C. while stirring, and oxygen gas (flow rate 210 ml/min) was blown at 80° C. for 3 hours to perform oxidative decomposition of ozonide. After the reaction, the reaction solution was filtered to remove manganese compounds, then acetic acid was distilled off, the reaction product was extracted with ether, washed with water,
10.33 g of reaction product was obtained.

Various analyzes were conducted on this reaction product and the following results were obtained.

Neutralization value: 218.8 (theoretical value 223.3), IR spectrum (cm-1): 2500-2700 (carboxyl group), 1710 (carbonyl group), 1H-NMR spectrum (ppm): 0.88 (terminal methyl group), 1.3(
methylene group), 3.65 (methyl ester group), 3.0
8 (carboxyl group), 13C-NMR spectrum (p
pm): 14.0 (terminal methyl group), 22.4-34.
1 (methylene group), 51.5-52.0 (methyl ester group), 171.8-178.4 (carbonyl group) From these analysis results, the reaction product is pentacarboxylic acid trimethyl ester with the following structure. It was confirmed.

Reference Example 3 3.67 g of pentacarboxylic acid trityl ester obtained in Reference Example 2 was dissolved in 50 ml of ethanol, 70 ml of a 2% aqueous solution of sodium hydroxide was added thereto, and 80-8
The reaction was carried out at 5°C for 2 hours. After the reaction, the reaction solution is evaporated and concentrated.
5 to 10 ml of water was added to this, the total volume was made up to about 200 ml with methanol, and the precipitated inorganic salt was filtered off. Next, about 50 ml of ether was added to the filtrate, and the precipitated soap was filtered off. The obtained soap was mixed with water/methanol/ether (1
:20:5) Reprecipitation was performed several times with a mixed solution to obtain 3.8 g of white crystals. The spectral data of this product is shown below.

IR spectrum (cm-1): 1570 (carboxylate ion) 1H-NMR spectrum (■): 1.32 (terminal methyl), 1.70 (methylene) 13C-NMR spectrum (ppm): 14.5 (terminal methyl )22.6~38.5 (methylene), 51.7 (methine), 167.7~184.7 (carbonyl) From these analysis results, the reaction products are 1,9,10,11
, 12-octadecanepentacarboxylic acid pentasodium (
IV).

Reference Example 4 1,9,10 obtained by hydrolyzing the pentabasic acid pentasodium salt obtained in Reference Example 3 with hydrochloric acid and partitioning with ethyl ether.
, 11,12-octadecanepentacarboxylic acid 0.30
Dissolve 0g in 6.0g of ethanol, and add 0.23% of monoethanolamine (70.5-71.5℃ to bp) to this.
When 9 g (1.2 times the theoretical amount as a saturated salt) is added and stirred, it generates heat and reacts. After stirring at about 45°C for 1 hour, 0.1 g of activated carbon was added to the slightly yellow solution, stirring for another 2 hours, suction filtration, and the filtrate was heated at about 50°C/50°C.
Drying under mmHg gave a faintly pale yellow solid. Thoroughly wash this with about 20 ml of benzene, and
Vacuum-dried under 0 mmHg to form a faintly pale yellow solid.
, 9,10,11,12-octadecanepentacarboxylic acid pentamonoethanolamine [C7C5(MEA)5] was obtained. Elemental analysis values are 50.46% carbon and 9.01% hydrogen.
, nitrogen 8.90%, (theoretical amount, C50.18%, H9.
34%, N9.14%) Next, the antibacterial activity test method used in Example 2 and below will be described.

1) In a test tube with a lid (12 x 65 mm), add 3 g of sample aqueous solution of various concentrations and agar medium (Kyoku-East standard medium; yeast extract).
Add 80mg of peptone, glucose, agar), heat and dissolve at about 80℃, cool it by tilting it, leave it outside for about 1 hour after solidifying, loosely cover it and leave it at 38℃ for 5 days to prevent airborne bacteria. The developmental status was observed.

(Note) -: No colonies occur (-): Improved, minimum inhibitory concentration ┴: Slightly occur ┼: Moderately occur ┼┼: Significantly occur ┼┼┼: Occur all over the surface 2) Add sample to arbitrary concentration After smearing and culturing the inoculating bacterial solution on a plate culture medium, the lowest concentration at which growth was inhibited was defined as the minimum inhibitory concentration. In the case of mold, potato dextrose agar medium was used as a medium and cultured at 25°C for 7 days, and for yeast, YM agar medium was used and cultured at 25°C for 2 days. This test was conducted at the request of the Japan Food Research Institute.

Example 1 Inhibitory concentrations (MICs) of monoethanolamine (MEA) salts of 1,9,10,11,12-octadecanepentacarboxylic acid (hereinafter abbreviated as pentacarboxylic acid) with different degrees of neutralization against airborne bacteria , some of them are M. flav
The results for as are shown in FIG.

Saturated salts have almost no antibacterial activity, and free acids have high concentrations of M
IC (1 and 5 days) is shown, but for unsaturated salts 1 mo
There is a maximum in l salt, which is quite strong at 200 ppm for a low toxicity substance. The same salt M. The MIC for Flavas was 400 ppm.

Example 2 The tendency of the alkyl chain length of MIC against airborne bacteria for 1- and 3-alkylamine salts of pentacarboxylic acid is shown in FIG.

As is clear from this figure, the maximum of ■ was observed near 12 carbon atoms in both cases where the number of alkyl chains was 1 and 3.

Example 3 FIG. 3 shows trends regarding the neutralization mol number of MIC against airborne bacteria for dodecylamine and cetylamine salts of pentacarboxylic acid.

As is clear from this figure, a neutralization mole number of 2 to 3 shows the strongest tendency.

Example 4 Trends regarding MEA neutralization mol number of unneutralized carboxyl for dodecylamine salt of pentacarboxylic acid were determined in the fourth example.
As shown in the figure.

As is clear from this figure, as dodecylamine increases, M
The maximum value is on the side with less EA.

Example 5 M of monoethanolamine salt, oleylamine salt and dodecylamine salt against airborne bacteria and various bacteria
The ICs are shown in Table 1.

For monoethanolamine, a lower degree of neutralization is better, and the longer the chain of substituted amine, the better;
In ol salt, M. flavas, B. The effect was extremely strong against viruses such as S.subtilis.

Claims (1)

[Claims] (1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・( I
(In the formula, n and n' are numbers from 4 to 10, X is a hydrogen atom or COOZ, Z is a hydrogen atom, an alkyl group, or a substituted ammonium ion, and at least one of Z is a substituted ammonium ion. ) A disinfectant characterized by comprising an amine salt of a tetra or pentacarboxylic acid represented by: