DE2428334A1 - BIOCIDAL COMPOSITIONS - Google Patents

Description

Priority ; June 12, 1973, GREAT BRITAIN No. 27870/73 .23 May 1974 (Complete Specification)

The invention relates to biocidal compositions and in particular to mixtures of known biocides, which have a better effect than the individual components. -

In GB-PS 884-541 a method for protecting a aqueous medium described against infection by microorganisms, in which the aqueous medium is a 1,2-benzisothiazolin-3-one, which can be substituted in the benzene ring by chlorine or bromine, or a salt thereof is added will.

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In GB-PS ί 2.24 663 describes the preparation of certain 3-Hydroxyisothiazolen (which are tautomeric with isothiazolin-3-ones) and the biocidal use of these compounds.

It is also different from certain other 2-thionotetrahydro-1,3,5-thiadiazines known to have biocidal activity.

It has now been found that mixtures of the latter compounds with isothiazolin-3-ones in biocidal applications have a greater effectiveness than it would from the known activity of the individual components of the mixture is to be expected.

Thus, according to the invention, there are biocidal compositions proposed, which are characterized in that they contain the following in a mixture: - (A) an isothiazolin-3-one compound of the general formula

₌ ο formula

Eyj represents a hydrogen atom, a halogen atom, an Oj-C ^ - alkyl group or a cyano group; represents a C ^ -C ^ -alkylsulfinyl group, an aralkylsulfinyl ^ - group with up to 8 carbon atoms, a C / | -C ^ -alkylsulfonyl group or an aralkylsulfonyl group with up to 8 carbon atoms, when E ^ represents a cyano group;
for a hydrogen atom, a halogen atom, an aralkyl

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group with up to 8 carbon atoms or a G ^ -C ^ - haloalkyl group, if R ^ is a C /] - C ^ -A lkylgruppe or a Halogenatorn, with the proviso that R2 is an Oj-C ^ -alkyl group can, if Rz _{1 stands} for a C] -C ^ -alkyl group, and R2 ~ stands for an aralkyl group with up to 8 carbon atoms or a C ^ -C ^ - halogeno alkyl group, if R ^ stands for a hydrogen atom;

or Ryj and Rp. together for a group of the formula -CH = CH-CH = CH-, in which one or more of the hydrogen atoms can be replaced by a substituent consisting of halogen atoms, Oj-C ^ -alkyl groups, C ^ -C ^ -alkoxy groups, the nitro group and the cyano group is selected; and

(B) a 2'-thionotetrahydro-1,3,5-thiadiazine of the general formula

I * formula

wherein (1)

R ^ for a hydrogen atom, a Cj-C ^ -alkyl group or a substituted or unsubstituted aryl group;

R ^ and Kr each independently for a C ^ -C ^ - Alkyl group substituted by hydroxyl or carboxyl can be a cycloalkyl or aralkyl group, an unsubstituted one Acyl group. or an acyl group · represented by at least one of the substituents hydrogen, alkyl,

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Alkoxyl, hydroxyl, amino, substituted amino and

Carboxyl may be substituted, or in which (2)

R, represents a hydrogen atom;
R ^ for a group of the formula Ar-X-Yr-, in which Ar is an unsubstituted or substituted aromatic radical

means, stands,
X for an oxygen or sulfur atom or a sulfinyl

or sulfonyl group,
Y stands for a saturated hydrocarbon bridging group with

2 or 3 carbon atoms in the chain, and Rc- is an aliphatic hydrocarbon radical that is unsubstituted or by hydroxyl or carboxyl is substituted, stands.

In the group of compounds defined under (B (I)) above shall "as examples of groups represented by R * are called methyl and phenyl.

Examples of groups represented by R ^ and R ₁ - are methyl, ethyl, isopropyl, η-butyl, 2-hydroxyethyl, 2-carboxyethyl, cyclohexyl, benzyl,., 2-phenylethyl, phenyl, 0 ( - and ß-naphthyl, p-chlorophenyl, p-tolyl, p-hydroxyphenyl, p-dimethylaminophenyl, p-acetamidophenyl, m-acetamidophenyl and p-carboxyphenyl.

The groups of compounds defined under (B (2)) above and the preparation of these compounds are described in GB-PS Ί 177 34-9.

In general, 2-thionotetrahydro- ^/ l- _i -3 _i 5-thiadiazines are prepared by reacting one mole of an N-substituted dithiocarbamic acid with 1 mole of an amine and 2 moles of an aldehyde, the substituents R ^ and R ₁ - may be the same or different, depending on whether the amine, of

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the
which VN-substituted dithiocarbamic acid is derived is the same as or different from that used in the subsequent reaction with the amine and aldehyde. It is advisable to use the N-substituted dithiocarbamic acid and the amine combined in the form of a salt.

According to a modification of the above procedure, 1 mol Carbon disulfide reacted with 2 moles of an amine and 2 moles of an aldehyde, in which case the substituents R ^ and Rr are the same. Such methods are for example in Journal for Practical Chemistry, 126, 235. (1930), in GB-PSs 554 729 "and 555 795 and in DT-ASs 1 14-5 624 and 1 14-9 014.

The preferred thionothiadiazine for use according to of the invention is 2-thiono-3,5-dimethyltetrahydro-1,3,5-thiadiazine.

The preferred isothiazolin-3-one is 1,2-benzisothiazolin-3-one. ■ '

-The isothiazolin-3-one compound and the thiadiazine component the compositions according to the invention can be in weight ratios can be mixed from 10: 1 to 1:10. In general, proportions of 1.1 to 4 parts of thiadiazine are used each part isothiazolin-3-one for most purposes as proven effective.

The compositions are useful as bactericides, fungicides and algicides, especially in aqueous media. For example, they can be used in water / oil emulsions, for the protection of paints and water-based adhesives can be used in cans as well as in cooling water systems. she are also suitable for combating slime in aqueous systems

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of paper mills.

The amounts of isothiazolin-3-one compound and 2-thionotetrahydro-1,3ί5-thiadiazine compound, which are added to an aqueous medium to prevent infection by microorganisms to be combated, eliminated or prevented such that taken together they result in a concentration of at least 10 ppm by weight in the medium. The maximum amount of the two compounds together does not normally need to exceed 1000 ppm by weight, although under exceptional conditions In some circumstances up to 10,000 ppm by weight can be used.

According to the invention, aqueous media are also proposed, which are protected against infection by microorganisms or in which such an infection is controlled or eliminated, the aqueous medium being an isothiazolin-3-one compound and a 2-thionotetrahydro-1,3,5-thiadiazine compound according to the above definition in weight ratios of 10: 1 to 1:10, where their total concentration in the aqueous medium is at least 10 ppm by weight.

According to the invention there is also a method for protecting aqueous media against infection by microorganisms or to combat or eliminate such infection in aqueous media that are already infected, proposed, which is carried out by treating the microorganisms with an isothiazolin-3-one compound and a 2-thionotetrahydro-1,3,5-thiadiazine compound according to the above definition in the weight ratios of 10: 1 to 1:10, the compounds being added to the aqueous media in such an amount that that, taken together, they give a concentration of at least 10 ppm by weight.

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The isothiazolin-3-one and the thiadiazine can be used separately can be added, or they can be mixed first and then either in solid form to the medium to be protected Form or as a solution in water or an organic or aqueous-organic solvent can be added. Organic solvents that can be used are, for example, ethylene glycol and ethylene diamine.

The invention is illustrated in more detail by the following examples, in which the parts and percentages are expressed by weight, unless otherwise indicated.

example 1

fungilid test with mycelium of Aspergillus niger

2
Sterilized nylon nets of 1 cm are inoculated on malt agar with a spore suspension of Aspergillus niger and incubated for 24 hours at 25 ° C., after which the nets are covered with mycelium, but no spore formation has yet set in.

The chemicals to be tested are prepared in the desired concentrations in a 100 ml volume of water in 250 ml conical bottles. Four mushroom-inoculated squares are transferred to the flask, which is then rotated on an orbital shaker. Two meshes are removed after 3 hours and the remaining two meshes are removed after 6 hours of incubation. Each mesh is shaken vigorously with 15 ml of sterile water before being transferred to a malt agar plate. The latter is incubated for 3 days at 25 ° 0, after which the nylon nets are then examined for the presence or absence of fungal growth.

A complete destruction of the Tilzmycels is shown in the Absence of growth on or around the nylon mesh

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on the malt agar plate. The results are as follows:

Chemical treatment " Mycelium survival after (ppm active ingredient) 3 hours 6 hours

Comparison (no biocide) +++ +++

BIT * 1000 ppm
"200 ppm
¹¹ 100 ppm

2-thiono-3,5-cLimethyl-tetra-

hydro-1,3,5-thiadiazine

(TDTTD) 1000 ppm ■ +++ + '++

BIT * (loO) + TDTTD £ 100) +++

BIT * (200) + TDTTD (200) + -.

BIT = 1 ^ -Benzisothiazolin ^ -one, added as a solution, which contains 33.1 / 3 parts of BIT, 24 parts of ethylenediamine, and 42 2/3 parts of water.

In the table:

+++ Good mushroom growth, i.e. no destruction + Slight fungal growth, i.e. partial destruction - No fungal growth, i.e. complete destruction

The above results clearly show the improved activity obtained by using a mixture of 1,2-bentisothiezolin-3-one and 2-thiono-3,5-dimethyltetrahydro-1,3,5-thiadiazine as compared to one each connection alone.

Example 2 Bactericidal test with Pseudom.onas aeruginosa

The desired test solutions were prepared in volumes of 100 ml in conical flasks, whereupon 1 ml of a suspension of a 24 hour old nutrient culture of Ps. Aeruginosa

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was added to each flask. After 24 hours of incubation at 3O ⁰ C, surviving bacteria cells were counted in each flask. The results are as follows:

Chemical treatment

BIOT (50) 200 ppm ' (200) U (50) 100 ppm (100) 11 50 ppm TDTCDD 500 ppm ti. 200 ppm BIT ⁺ + ^r . DDTTD BIT ⁺ + TDTTD

surviving bacteria

Hours of contact time (cells / ml)

3.1 χ 10 ⁵ 4.4x 10 ⁶

1.2 χ 10 ⁷ 1.6 χ 10 ⁷

<1Q '

5.3 x 10 ³

⁺ added in the form of the solution used in Example 1.

These results show that a combination of 50 ppm BIT and 200 ppm TDTTD gives an effect similar to that 200 ppm BIT alone, or gives a much better effect, than 200 ppm TDTTD alone.

Example 3 Test for antibacterial activity in an oil emulsion

The desired amounts of the test chemicals were added to volumes of 200 ml of an oil emulsion (made from an emulsifiable oil (Prosol 44, Mobil) and water in a ratio of 1:20), which was heavily contaminated with bacteria was added.

Determinations of the number of surviving bacteria were made Done 3, 6 and 8 days after adding test chemicals. the Results are as follows:

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Chemical treatment

Surviving bacteria (cells / ml) after:

3 days

6 days

8 days 6

1.91 x 10 ° 3.1 x 10- ^ 3 χ 10 1, 66 χ 10 * 1.8 χ 10 ²

3.9 χ 10 *
<10

Comparison (no biocide) BIT ⁺ 50 ppm TDTTD 50i.-ppm BIT ⁺ (25) + TDTTD (25)

- means no attempt was made. ⁺ added in the form of the solution from Example 1.

Thus , after a 3-day incubation, a combination of 25 ppm BIT and 25 ppm TDTTD was more active than the corresponding treatments with 50 ppm BIT or 50 ppm TDTTD.

Example 4

Bactericidal test with drain water from a paper mill

The following drainage water was prepared and inoculated with a mixture of nine bacterial cultures which had been isolated from a paper mill residue water .

Gram

strength 0.3 volume 0.3 Titanium dioxide 0.2 Animal glue 0.01 Resin for wet strength 0.3 Sodium aluminate 0.2 alum up to a pH of 5 Collophonium 0.2 Peptone 10.0 Glucose 25.0 Wood pulp * " 100.0 tap water 10 1

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⁺ as a 10 # aqueous suspension of a cellulose pulp, which came from a wood pulp.

The contaminated medium is in volumes of 100 ml in Flask with a capacity of 250 ml transferred, the biocide is then added at the desired concentration and the flasks are then placed in an orbital shaker at 25 ° C incubated. At the beginning a count is made, and later samples are taken from the flasks, to determine the number of surviving bacteria after 24, 48 and 72 hours.

The results are as follows:

Treatment of surviving cells (cells / ml) after

a contact time of: 24 hours 4-8 hours 72 hours

Comparison> 3 χ 10 ⁷ > 3 χ ΊΟ ⁷ )? χ 10 ⁷

BIT, 25 ppm 6.6 χ 10 ⁵ 1, 2 χ ΊΟ ⁴ 5.4- χ 10 ⁵

BIT, 50 ppm 3.1 χ 10 ⁵ 2.2 10 ² 70

TDTTD, 25 ppm 3.2 χ 10 ⁴ . 3.2 χ 10 ⁶ 3.0 χ 10 ⁷

BIT (I2.5) + .

TDTTD (12.5) 60 <1-20

From these results it can be seen that the combination of BIT and 2-thiono-3,5-dimethyltetrahydro-1,3,5-'bJiiadiazin (TDTTD) is more effective than twice the concentration of one component alone.

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Example 5

Bactericidal test of a mixture of 1,2-BenziBothiazolin 5-one and 2-Thiono - 5-'benzyl-5-C2 ¹ -hydroxyethyl) - tetrahydro 1, 3,5-thiadiazine (TBHTI) I)) against Pseudomonas aeruginosa

The test was carried out exactly as in Example 2 above.

The results are as follows:

Treat surviving bacteria after

24 hour contact time (Cells / ml) Comparison (no biocide) 4.6 χ 10? BIT, 100 ppm <10 BIT, 50 ppm 9.8 χ 10 ⁵ TBHTDD, 500 ppm 5.4 χ 10 ^ TBHTDD, 200 ppm 1.23 x 10 ⁷ BIT (50) + .TBHTDD (200) 30th

From the above data it is evident that 200 ppm of the thiadiazines alone at a contact time of 24 hours exhibited no appreciable activity and that 50 ppm BIT bacterial growth but significantly decreased _s put the bacteria not all mortify.

The improved kill with the addition of 200 ppm thiadiazine and 50 ppm BIT showed improved effects when the two Compounds can be used in combination.

Patent claims :

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Claims (10)

PATENT CLAIMS; 1. Biocidal composition, characterized in that it contains the following in a mixture: (A) an isothiazoin-3-one compound of the general formula Formula I. R ^ for a hydrogen atom, a halogen atom, a C ^ -O ^ - Represents an alkyl group or a cyano group; I? 2 for a C 1 -C 4 alkylsulfinyl group, an aralkylsulfinyl group with 'up to 8 carbon atoms, an O / j-C ^ -alkyl- • sulfonyl group or an aralkylsulfonyl group with up to 8 carbon atoms when Rj is a cyano group stands; Rg represents a hydrogen atom, a halogen atom, an aralkyl group with up to 8 carbon atoms or a C ^ -C ^ - haloalkyl group, if Itj is a C ^ -C ₂ ^ alkyl group or a halogen atom, with the proviso that R2 is a Cj-C ^ -alkyl group when R / j is a C ^ -C ^ -alkyl group, and R ^ is an aralkyl group with up to 8 carbon atoms or a CjC ^ - haloalkyl group when R ^ is a hydrogen atom -; or R ^ j and R £ together represent a group of the formula -CH = CH-CH = CH-, in which one or more of the hydrogen atoms can be replaced by a substituent, that of halogen atoms, C / j-C ^ -alkyl groups, C ^ -C ^ -alkoxy groups, the nitro group and the cyano group is selected; 409882/1062 (B) a 2-thionotetrahydro-1,3 _t 5-thiadiazine of the general formula S = C Formula II wherein (1) R 1 represents a hydrogen atom, a C 1 -C 4 aryl group, or a substituted or unsubstituted aryl group; R ₂ ^ and Rc each independently of the other for a C ^ -C ^ - alkyl group which can be substituted by hydroxyl or carboxyl, a cycloalkyl or aralkyl group, an unsubstituted acyl group or an acyl group which is replaced by at least one of the substituents hydrogen, alkyl, Alkoxyl, hydroxyl, amino, substituted amino and carboxyl can be substituted, or where (2) R, represents a hydrogen atom; R ₁ , represents a group of the formula Ar-XY-, in which Ar is an unsubstituted or substituted aromatic radical, X stands for an oxygen or sulfur atom or a sulfinyl or sulfonyl group, Y for a saturated hydrocarbon bridging group with 409882/1062 2 or 3 carbon atoms in the chain, and Br is an aliphatic hydrocarbon radical that is unsubstituted or substituted by hydroxyl or carboxyl. 2. Composition according to claim 1, characterized in that the 2-thionotetrahydro-1,3} 5- "thiadiazine from 2-G? Hiono-3,5-dimethyltetrahydro-i, 3 * 5-ttiiadiazine consists. 3. Composition according to claim 1 or 2, characterized in that that the isothiazolin ~ 3-one "from 1,2-benzisothiezolin-3-one consists. 4. Composition according to any one of claims 1 to 3i characterized in that the isothiazolin-3-one or des 2-thionotetrahydro-1,3,5-tb.isdiazine in weight ratios from 10: 1 to 1:10 are mixed together. 5. Aqueous media against infection by microorganisms are protected or in which such an infection is combated or eliminated, characterized in that that they are an isothiazolin-3-one compound and a 2-thionotetrahydrothiadiazine compound according to claim 1 in weight ratios from 10: 1 to 1:10, wherein there is a total concentration in the aqueous medium of at least 10 ppm by weight. 6. Media according to claim 5, characterized in that the 2-thionotetr8hydro-1,3,5-thiadiazine compound from 2-thiono-3,5-dimethyltetrahydro-1,3,5-thiadiazine consists. 7. Media according to claim 5 or 6, characterized in that that the isothiazolin-3-one compound from 1,2-benzisothiazolin-3-one consists. 409882/1062 8. Process for the protection of aqueous media against Infection by microorganisms or to combat or eliminate such infection in aqueous media, which are already infected, characterized in that the microorganisms with an isothiazolin-3-onverbin ~ manure and a 2-thionotetrahydro-1,3,5-thiadiazine compound according to claim 1 in the weight ratio of 10: 1 brings together to 1:10, the compounds being added to the aqueous media in such an amount that the two compounds together give a concentration of at least 10 ppm by weight. 9. The method according to claim 8, characterized in that that as 2-thionotetr8hydro-1,3 »5-thiadiazine compound 2-Thiono-3,5-cLimethyltetrehydro-1,3,5-thiadiazine is used will. 10. The method according to claim 8 or 9 »characterized in that the isothiazolin-3-one compound is 1,2-benzisothiezolin-3-one is used. TATtNTA> W.V.-Te 409882/1062