DE2800105A1 - USE OF DIPHENYLAETHERS AS ALGICIDES - Google Patents

Description

Use of diphenyl ethers as algicides

The present invention relates to the use of substituted diphenyl ethers for combating algae and 2 to prevent algae growth.

Hydroxydiphenyl ethers which are substituted with halogens, for example and / or whose hydrogen atom in the hydroxyl group is replaced by, for example, acyl, and their production is known. Their blending to combat microorganisms, e.g. as bactericides or fungicides, is known and described in DT-AS 1 492 346, DT-PS 526,738, DT-PS 569,726, DT-OS 2,531,386, U.S. Patents 3,629,477 and 3,506,720.

In the published Japanese patent application 46-80907, 3-alkoxy-4-nitro-diphynyl ethers are used as algicides Active ingredients described. Their effect is often too little, especially against green algae.

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TS.11.S30

It has now been found that substituted diphenyl ethers are also excellent algicidal agents when they contain an amino or hydroxyl group, or such a group that the hydroxyl group to can form, such as the acyloxy group. In the broad spectrum of activity against, different types of algae is special also highlight the effectiveness against green algae.

The present invention accordingly relates to the use of diphenyl ethers of the general formula I or the salts of the hydroxyl and acid derivatives

(D

R is optionally substituted amino or the group R ¹ O-, in which R ^{1 stands} for a hydrogen atom or the ester-bonded acid residue of an inorganic or organic oxygen acid,

2
R identical or different radicals and a hydrogen atom, a halogen atom, cyano, carboxyl, nitro, optionally substituted amino, alkoxy, cycloalkoxy, alkenyl, alkyl, cycloalkyl or acyloxy,

m integers from 1 to 5 and

η are integers from 1 to 4,

to combat algae and to prevent algae growth,

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- ßr-

1 2
The groups R and R in the diphenyl ethers of the formula I can be in any position. However, it is preferred that in each case only one of the two ortho positions in the benzene rings is substituted for the ether oxygen atom. Preferably 1 to 3, especially 1 or 2 substituents are present in one ring (m − 1 to 3, preferably 1 or 2) and 1 or 2 substituents (n = 1 or 2) in the other ring.

R is preferably the group R'O- in which R ^{1 is} preferably a hydrogen atom. When R ^{1 is} acyl, it preferably contains 1 to 18, in particular 1 to 6, carbon atoms. R ¹ is thus the residue of an organic oxygen acid, as is amidocarbonyl.

R ¹ can therefore also be amidocarbonyl, the nitrogen atom of which can be substituted by one or two hydrocarbon radicals, for example linear or branched alkyl and cycloalkyl. The amidocarbonyl preferably contains 1 to 12 carbon atoms.

Examples of these R ¹ are:

Hydrogen, formyl, acetyl, propionyl, octanoyl, octadecanoyl, Benzoyl, naphtoyl, amidocarbonyl, methylamidocarbonyl, dimethylamidocarbonyl, Ethylamidocarbonyl, dodecylamidocarbonyl.

R ¹ can also be the ester residue of a polyfunctional organic carboxylic acid, for example a 2 to 4-functional acid. Examples are: oxalic acid, malonic acid, succinic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, ortho-, iso- or terephthalic acid, naphthalenedicarboxylic acids, trimellitic acid, pyromellitic acid. In this case and also in the following cases, the acids can be partially or fully esterified with the hydroxydiphenyl ethers.

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■. T

Examples of acids in which R ^? present in its meaning as an ester residue of a mono- or polyfunctional, preferably up to 3-functional, inorganic acid are: sulfurous acid, sulfuric acid, amidosulfonic acid, nitric acid, sulfinic acids, sulfonic acids, phosphonic acids, phosphorous acid, phosphoric acid, boric acid, carbonic acid, arsenic acid, nitric acid .

1 2
R or R can be optionally substituted amino. The substituents are preferably 1 or 2 alkyl groups containing up to 12, in particular 1 to 6, carbon atoms or cyclohexyl.

R in its meaning as optionally substituted alkoxy, cycloalkoxy, alkenyl, alkyl or cycloalkyl and Acyloxy contains preferably 1 to 18, in particular 1 to 6 C-atom. If the groups are substituted, this can be halogen, especially fluorine or chlorine, as well Act hydroxyl, carboxyl or alkoxy with preferably 1 to 6 carbon atoms.

R is particularly preferably chlorine, Bx * om, iodine, amino, nitro,

2 carboxyl and trifluoromethyl. Further examples for R are:

Methylatnino, dimethylamino, ethylamino, methylethylamino, Butylamino, hexylamino, octylamino, i-octylamino, methoxy, Ethoxy, propoxy, n-butoxy, i-butoxy, octoxy, octadecyloxy, Cyclohexyloxy, fomyloxy,, acetyloxy, propionyloxy, butanoyloxy, hexanoyloxy, octanoyloxy, methyl, ethyl, ' Propyl, 'butyl, i-butyl, t-butyl, pentyl, hexyl, octyl, Dodecyl, octadecyl, cyclopentyl, cyclohexyl, methylcyclohexyl, Vinyl, allyl, chlorocyclohexyl, carboxy! Cyclohexyl,

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28001

Methoxyethyl, ethoxyethyl, methoxypropyl, ß-hydroxyethyl, ß- or γ-hydroxypropyl, 1,2-dihydroxypropyl, chloromethyl, Dichloromethyl, fluoromethyl, trifluoromethyl, difluoromethyl, ß-chloroethyl, bromomethyl, iodomethyl, carboxy! methyl, Carboxyl methoxy, α- or β-carboxy IMthy1, hydroxyacetyloxy.

At least one of the radicals R is preferably a halogen atom j such as chlorine, bromine or iodine.

Particularly preferred compounds of the formula I are 4, 4'-dichloro-2-hydroxydiphenyl ether and 2 ', 4', 4-trichloro-2-hydroxydiphenyl ether.

If R ¹ denotes a hydrogen atom or other salt-forming groups are present in the compounds of the formula I, salts of these compounds, in particular the alkali metal salts, can also be used, which can be advantageous, for example, in the preparation of aqueous active ingredient solutions. When using the compounds of the formula I in which R ¹ denotes the ester residue of an oxygen acid, it can be assumed that the corresponding hydroxydiphenyl ether, as the actual active component, is only released by hydrolysis. Of course, the esters themselves can also contribute to the effect.

The compounds to be used according to the invention already have an outstanding effect in surprisingly low concentrations. Thus, in general, effective concentrations of 0.01 to 40, preferably 0.02 to 20 and in particular 0.03 to 10 ppm, based on the algae to be controlled, are sufficient. These concentrations are lower than they are generally required to control bacteria, for example. The compounds Si-Bd ^ LiGintaluaai ^ Dair and are suitable as

he-

algicidal active ingredients for e.g. standing and flowing water, swimming pools or cooling water systems. The connections are also resistant to pH influences and lose here not their effectiveness.

The compounds to be used according to the invention can as algicides here in pure form or in the form of concentrated or dilute solutions or emulsions be applied. Application to solid carriers is also possible. The compounds can also be in liquid Coating agents are suspended or dissolved, where appropriate to the formation of uniform dispersions Wetting agents or emulsifying agents can support the distribution of the active ingredient. According to the invention to Using compounds can also be used together with other bioeids.

A preferred area of application is the treatment of cooling water. It has been found that with other water additives like corrosion inhibitors and scale inhibitors surprisingly practically no deactivation infoige of precipitation happens. The low inhibitory concentrations are also special here Advantage. To protect against algae growth, the active ingredients can advantageously be added directly to the cooling water or the pipelines are painted on the inside into which the active ingredients are incorporated are.

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When using the compounds for water treatment Further additives can be added at the same time, e.g. corrosion inhibitors, scale inhibitors, agents for the softening of the water, masking agents such as polymer phosphites, phosphates, amides of phosphoric acid, Phosphonic acids, polymeric carboxylic acids of e.g. acrylic acid or maleic acid, their anhydrides or salts and other accessories.

The compounds to be used according to the invention can can also be incorporated into plastics in order to cut molded parts made from them to prevent algae growth, e.g. Plastic sheeting from which swimming pools are made or which are used to line swimming pools.

Another preferred area of application are protective paints, in particular organic-based dispersion and antifouling paints, which, in addition to the usual basic and additives 0.01 to 10, preferably 0.1 to 5 wt .-%, based on the total mixture, of a compound of formula I or mixtures thereof.

Usual base materials are the lacquer raw materials known to the person skilled in the art, such as natural ones, referred to as binders and synthetic resins, homo- and copolymeric products with the monomeric vinyl chloride, vinylidene chloride, Styrene, vinyl toluene, vinyl esters, acrylic acid and methacrylic acid and their esters, also chlorinated rubber, natural and synthetic rubber, if appropriate

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chlorinated or cyclized, also reactive resins such as epoxy resins, polyisocyanates, unsaturated polyesters, the optionally can be converted into film-forming, higher molecular weight products by adding hardeners.

The binders can be liquid or in dissolved form. In the case of dissolved binders, including thermoplastics, a protective film can also be formed by evaporation of the solvent. Solid coating agents can be applied to solid objects using conventional powder coating techniques. More usual

Basic substances are e.g. tar, modifiers, dyes, inorganic or organic pigments, hardeners and fillers.

The following examples serve to explain the invention in more detail.

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Examples 1-27

In Vitro Squirt Coagulation Test

The organizations against which the compounds are checked Vierden should be in the Erlenmeyer in nutrient medium under sterile conditions in a sledge water bath at 18 ° C Exposure (14 hours light - 10 hours dark change) bred.

Tests are carried out against 9 representative algae, namely the

4 blue-green algae

a) Trichome-forming Phortnidium faveolarum (A) living in polluted water or damp earth

b) Oscillatoria geminata that live in freshwater and seawater, thermal baths, sewage, springs, etc. and form trichomes (B)

c) Trichome-forming Nostoc spec. living in fresh water and moist soil. (C)

d) the short trichomes of the Romeria-like Anacystis nidulans found in lakes and ponds (D)

the 4 green algae

e, f) unicellular, widespread in bodies of water and in the soil Species Chlorella vulgaris (E) and Chlorella pyrenoidosa (F)

g) zoenobia occurring in the most varied of biotypes visual genus Scene.desraus spec. (G)

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- yc-

h) - which form simple threads that usually appear in fast flowing water in the colder seasons de Ulothrix subtilissima (H)

and the alga with brown chromatophores

i) common, especially in spring at low Unbranched filamentous ones that appear in bodies of water at lower temperatures or in autumn, even in mild winters Tribonema aequale (I).

The medium is composed as follows (according to Algae Broth, Difco Laboratories):.

1.0 G NaNO ₃ 0.05 G NH ₄ Cl 0.058 G CaCl ₂ 0.5 G MgSO, χ 7 H ₀ O 0.25 G K ₂ HPO ₄ 0.003 G FeCl ₃

are dissolved in 1 liter of distilled water.

To improve the growth of the various algae, earth extract can be added to the nutrient medium.

The nutrient mediura that has been given the bio-envy is combined with the respective Algae suspension inoculated so that a final dilution of 1/200 (for c, d, e, f and g) or 1/100 (for a, b, h, and i, algae divided with a stirrer) is achieved.

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Ak

After 3 weeks of incubation in the Erlenmeyer in a shaking water bath V7 is evaluated.

The effectiveness is about the minimum henim concentration (MJC in mg / 1), which indicates the algicide concentration at which the algae is still prevented from growing. The results are summarized in the table below.

The test concentrations for all algae are 0.3; 1.0; 3.0; 10 and 30

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Tabel

at
game
No. Compounds of Formula I. Seaweed A. B. C. D. E. F. G H I. 1 4-bromo-2-hydroxydiphenyl
ether 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 2 4-chloro-2-hydroxydi-
phenylether 0.3 0.3 0.3 0.3 0.3 1 0.3 0.3 0.3 3 4,4'-dichloro-2-hydroxydi-
phenylether 0.3 0.3 0.3 0.3 0.3 1 0.3 0.3 0.3 4th 2 ', 4-dichloro-2-hydroxydi-
phenylether 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 5 2 ', 4', 4-trichloro-2-hydroxy-
diphenyl ether 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 6th 2,3 ', 5' -trichloro-2-hydroxy-
diphenyl cither 0.3 0.3 0.3 0.3 3 1 0.3 0.3 0.3 7th 4,4'-dichloro-5-iodo-2-
hydroxydiphenyl ether 0.3 0.3 0.3 0.3 1 3 0.3 0.3 0.3 8th 3- (trifluoromethyl) -4,4'-
dichloro-S-bromine - '^ - hydroxy-
diphenyl ether 0.3 0.3 0.3 0.3 3 1 1 1 0.3

Tabel

at
game
No. Compounds of Formula I. Seaweed A. B. C. D. E. F. G H I. 9 2 ', 3, 4', 5-tetrachloro-2-
hydroxydiphenyl ether 0.3 0.3 0.3 0.3 1 0.3 0.3 0.3 0.3 10 4'-chloro-2-hydroxydi-
phenyl ether 0.3 0.3 0.3 0.3 3 1 0.3 0.3 0.3 11 3 ¹ , 4'-dichloro-2-hydroxydi-
phenylether 0.3 0.3 0.3 0.3 3 1 0.3 0.3 0.3 12th 2'-chloro-4 '- (trifluoro-
methyl) -2-hydroxydi-
phenylether 0.3 0.3 0.3 0.3 > 3 3 1 3 0.3

Tabel

α co co

■ ν. CD -4 CD

at
game
No. Compounds of Formula I. Seaweed A. B. C. D. E. F. G H I. 13th 3 ^! , 4'-dichloro-4-hydroxy-
diphenyl ether 0.3 0.3 0.3 0.3 1 0.3 > 3 1 0.3 14th 2 ^{tons of} 4'-dichloro-4-hydroxy ~
diphenyli.it here 0.3 0.3 0.3 0.3 3 1 0.3 0.3 0.3 15th 2 ^T -chlorine-4 '- (trifluoro-
methyl) -4-hydroxy-di-
phenylether 0.3 0.3 0.3 0.3 3 1 0.3 1 0.3 16 2'-chloro-4'-nitro-4-
hydroxydiphenyl ether 0.3 0.3 0.3 0.3 3 1 0.3 1 0.3 17th 2'-nitro-4 ^T -chlor-4-
hydroxy diphenyl ether 0.3 0.3 0.3 0.3 3 1 1 1 0.3 18th 2 ^T , 4'-dichloro-4-R-diphenyl-
ether '
R = -0-CN (CH ₃ ) ₂
O 0.3 0.3 0.3 0.3 3 1 0.3 3 0.3 "19th 4-axnino-3 ', 4'-dichloro-
diphenyl ether 0.3 0.3 0.3 0.3 3 1 0.3 1 0.3 20th 2-amino-2 ', 4', 4-trichloro
diphenyl ether 0.3 0.3 0.3 0.3 3 0.3 0.3 0.3 0.3

Tabel

example
No. Compounds of Formula I. Seaweed A. B. C. D. E. 3 F. 1 G H I. 21st 4,4 ', 6-trichloro-3-hydroxy
diphenyl ether 0.3 0.3 0.3 0.3 > 3 > 3 0.3 0.3 0.3 22nd 5-bromo-3'-chloro-3-hydroxy-
diphenyl ether 0.3 0.3 0.3 0.3 3 1 0.3 3 0.3 23 3 ', 5', 5-trichloro-3-hydroxy
diphenyl ether 0.3 0.3 0.3 0.3 > 3 > 3 0.3 0.3 0.3 24 4-carboxyl-2'-chloro-4'-
nitro-3-hydroxy-diphenyl
ether 0.3 0.3 0.3 0.3 3 3 0.3 3 0.3 25th 2 ^f , 4 ', 4-trichloro-2R-di-
phenyiather, R = (HO) ₂ PO-O- 0.3 0.3 0.3 0.3 3 3 1

Examples 26-32

The investigation of the inhibitory effect against Enteromorpha, the most important green algae in seawater fouling, is carried out in sterile conditions filtered seawater, which contains an Erd-Schreiber solution. This solution is made up of a nutrient extract, phosphate and nitrate together. The incubation of Enteromorpha intestinalis takes place in the light thermostat at a temperature of 18 ° C under a 14 h light-10 h dark change instead.

The test concentrations are 0.1; 0.5; 1 and 5 γ / ml. The results are given in the table below.

Tabel

example
No. Compounds of Formula I. Inhibitor Concentrations
tration
(γ / ml) 26th 4-chloro-2-hydroxydiphenyl ether 5 27 4,4'-dichloro-2-hydroxydiphenyl ether 0.5 28 2 ', 4-dichloro-2-hydroxydiphenyl ether 0.5 29 2 ¹ , 4 ', 4-trichloro-2-hydroxydiphenyl
ether 5 30th 3 ', 4'-dichloro-2-hydroxydiphenyl ether 0.5 31 3 ', 4'-dichloro-4-hydroxydiphenyl ether 0.5 32 2'4 ¹ -Dichloro-4-hydroxydiphenyl ether 0.5

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Claims (11)

280010b claims 1. Use of diphenyl ethers of the general formula I or the salts of the hydroxy and acid derivatives (D wherein
1 optionally substituted amino or the group R ¹ O, in which R 'stands for a hydrogen atom or the ester-bonded acid residue of an inorganic or organic oxygen acid, identical or different radicals and a hydrogen atom, a halogen atom, cyano, carboxyl, nitro, optionally substituted amino, alkoxy, cycloalkoxy, alkenyl, alkyl, Cycloalkyl or acyloxy, whole numbers from 1 to 5 and
η are whole numbers from 1 to 4, to combat algae and to prevent algae growth, 2. Use according to claim I ^ characterized in that 2 that m is 1 to 3, preferably 1 or 2, η 1 or 2 and R denotes identical or different radicals. 809.828 / 0796 RiQiNAL INSPECTED 3. Use according to claim 1, characterized in that 2
indicates that R, as an unsubstituted or substituted hydrocarbon radical, is cycloalkyl and in particular alkyl. 4. Use according to claim 1, characterized in that R ¹ in its meaning as Ac5'l contains 1 to 18, preferably 1 to 6 carbon atoms and in its meaning as amidocarbonyl 1 to 12, preferably 1 to 6 carbon atoms. 5. Use according to claim 1, characterized in that 2
indicates that R as optionally substituted amino is substituted by one or two alkyl groups containing 1 to 12, preferably 1 to 6, carbon atoms, or cyclohexyl. 6. Use according to claim 1, characterized 2
indicates that R in its meaning as alkoxy, cycloalkoxy _; Alkenyl, optionally substituted alkyl or cycloalkyl and acyloxy contains 1 to 18, preferably 1 to 6, carbon atoms. 7. Use according to claim 1, characterized gekenri_ 2
indicates that R in its meaning as alkyl or cycloalkyl is substituted with halogen, especially fluorine and chlorine, hydroxyl, carboxyl or alkoxy with 1 to 6 carbon atoms. 809828/0796 28001 8. Use according to claim 1, characterized in that ο
that R chlorine, B: is fluoromethyl. 2
that R is chlorine, bromine, iodine, amino, nitro, carboxyl or tri 9. Use according to claim 1, characterized in that the compound of the formula I is 4,4 ^r- dichloro-2-hydroxy-diphenyl ether or 2 ', 4', 4-trichloro-2-hydroxy-diphenyl ether. 10. Use according to claim 1, characterized in that R ^{1 is} a hydrogen atom, acyl or amidocarbonyl. 11. Use according to claim 1, characterized in that the compounds of formula I are used in effective concentrations from 0.01 to 40, preferably 0.03 to 20 and in particular 0.03 to 10 parts per million (ppm) is used.