DE2531985A1 - AGENTS WITH BACTERICIDAL, FUNGICIDAL AND ALGICIDAL EFFECT - Google Patents

Description

"Agents with" bactericidal, fungicidal and algicidal effects " Priority: July 19, 1974, Japan, No. 82 282/74

The quality of industrial raw materials is affected by bacterial and fungal attack and products severely affected. In water cycle systems Bacteria, fungi and algae cause slimy deposits that inhibit the flow of water and reduce the heat exchange performance. Algae that multiply on the floors of ships lead to a reduction in speed. All damage caused by bacteria, fungi and algae creates major problems.

There are already numerous compounds with bactericidal, fungicidal and algicidal effects known, for example organic mercury and tin compounds, substituted by halogen atoms Phenols, organic sulfur compounds, formaldehyde, cresol and quaternary ammonium salts. However, these connec-

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fertilize various disadvantages, such as high toosticity to humans and pets, they pollute the environment, they have an unpleasant odor, and they are harmful the quality of industrial raw materials and products without to satisfactorily inhibit the growth of bacteria, fungi and algae.

The object of the invention is therefore to provide agents with a bactericidal, fungicidal and aligicidal effect which do not have the disadvantages listed above. The object is achieved by the invention.

The invention thus relates to that characterized in the claims Object.

Specific examples of industrial raw materials and products with the bactericidal, fungicidal and inventive algicidal agents can be treated are organic substances, for example cellulose materials such as wood, wood products, Paper, cotton, fibers, textiles and bamboo, products based on petroleum, such as plastics, plastic products, Oils and paints, leather and pastes, inorganic materials such as metal objects, and products made from organic and inorganic Fabrics such as ships and animal stalls.

Specific examples of water cycle systems that can be used for a Treatment with the bactericidal, fungicidal according to the invention and algicidal agents are circulatory systems in cooling towers used for air conditioning, for swimming _j

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basins and cooling systems for reactors and paper mills.

According to the invention, solid and liquid carriers and diluents can be used can be used. Specific examples of solid carriers are clay, kaolin, talc, diatomaceous earth, silicon dioxide and calcium carbonate. Specific examples of liquid carriers are benzene, alcohol, acetone, xylene, methylnaphthalene, Cyclohexanone, dimethylformamide, diethyl sulfoxide, animal and vegetable oils, fatty acids and their esters as well various surfactants. Specific examples of auxiliaries which the bactericidal, fungicidal according to the invention and algicidal agents that can be added are emulsifiers, wetting agents, adhesives and surface active agents.

Industrial raw materials, industrial products and water cycle systems can in various ways with the N- (ß, ß-dichlorovinyl) salicylamide and its metal salts (hereinafter referred to as active ingredients). For example, can the materials and products listed above as well as water are treated directly with the active ingredients themselves. in the In general, however, the active ingredient is packaged and as an emulsifiable concentrate, wettable powder, dusting agent, granulate or used in the form of pellets.

The bactericidal, fungicidal and algicidal according to the invention Agents preferably consist of 2 to 70 percent by weight of the active ingredient and 98 to 50 percent by weight of one or more Carriers and / or diluents and / or auxiliaries.

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To protect the surfaces of wood, wood products, fibers, textiles, paper and leather as well as animal stalls from bacterial and fungal attack to protect, they are with the bactericidal, fungicidal and algicidal agents according to the invention with an active ingredient amount of

generally 0.1 to 10 g / m 2 sprayed, coated or in-filtered. Paints, adhesives and pastes are with the bactericidal, fungicidal and algicidal agents according to the invention, which the active ingredient in general in amounts of 0.01 to

Weight percent

0.1 / included, mixed and mixed. Ship bottom can against Infestation by bacteria, fungi and algae can be protected by adding the active ingredient to the paint. In water circulation systems 2 to 50 ppm, preferably 10 to 30 ppm, of active ingredient are generally added to the water. Best for Treatment with the bactericidal, fungicidal according to the invention and algicidal agents, organic substances are suitable.

The toxicity of N- (β, β-dichlorovinyl) salicylamide is very high low. The acute oral toxicity (LDj-q) of this compound is 6000 mg / kg in mice. For this reason, the bactericidal, fungicidal and algicidal agents according to the invention can be used handle safely. Specific examples of metal salts in which the metal is monovalent or divalent are sodium, Potassium, zinc, copper and manganese (II) salts, with the sodium and zinc salt are preferred.

N- (β, β-dichlorovinyl) salicylamide is prepared in that chloral is heated with salicylamide and then mixed with a mixture of zinc and acetic acid. _j

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The metal salts of N- (ß, ß-dichlorovinyl) -salicylamide are thereby prepared by reacting a metal hydroxide such as sodium hydroxide with N- (ß, ß-dichlorovinyl) salicylamide.

Example A.

Preparation of N- (β, β-dichlorovinyl) salicylamide (compound Number 1):

A mixture of 27.4 g (0.2 mol) salicylamide and 32.45 g (0.22 mol) chloral is ^{heated to 90 to 100 °} C. for 5 hours, then washed with water and dried. 56.9 g of chloralsalicylamide in the form of white crystals with a melting point of 132 to 133 ^° C. are obtained. 28.5 g (0.1 mol) of chloralsalicylamide are mixed with 150 ml of acetic acid, then 26 g (0.4 mol) of zinc powder are added ^{with stirring at a temperature of below 50 ° C. and at 70 to 80 °} C. for a further 30 minutes touched. The reaction mixture is then cooled to room temperature and filtered. The filtrate is mixed with water, and the precipitated crystals are filtered off, washed with water and dried. 15.1 g (70 % of theory ) of N- (β, β-dichlorovinyl) salicylamide are obtained in the form of white crystals with a melting point of 187 to 189 ^° C.

Example B.

Preparation of the sodium salt of N- (ß, ß-dichlorovinyl) salicylamide (compound no. 2)

43 g (1 mole) of 93 percent sodium hydroxide in 300 ml of water is dissolved, while stirring with 232 g (1 mol) of N- (β, β-dichlorovinyl) -salicylamide and another 3 hours at room-

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temperature stirred. The water is then distilled off under reduced pressure. There are 255 g of the sodium salt of N- (β, β-dichlorovinyl) salicylamide in the form of light brown crystals which decompose at 243 ° C.

The metal salts listed in Table I are prepared in the same way.

Table I.

link
No. Metal salt M.p., ⁰ ° C Appearance 3 Potassium salt 243 (decomp.) light brown
Crystals 4th Zinc salt 158-160 white crystal
le 5 Copper (II) salζ. 135 (decomp.) pale green
Crystals 6th Manganese (II) salt 191 (decomp.) yellowish gray
Crystals

The examples illustrate the invention. Unless otherwise stated, parts are by weight.

example 1

10 parts of compound no. 1, 40 parts isophorone, 31 parts Xylene, 7 parts of dimethylformamide and 12 parts of a wetting agent are mixed to form an emulsifiable concentrate and before Application Diluted 400 to 200 times with water. Wooden parts and

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Fibers are immersed in the emulsion obtained to remove bacteria and inhibit fungal growth.

In the same way, emulsifiable concentrates are made, each of which is compound No. 2, No. 3, No. 4, No. 5 and No. 6 contain.

Example 2

20 parts of compound no. 1, 40 parts of ethylene glycol monoethyl ether, 10 parts of dimethylformamide and 30 parts of xylene are mixed. Paints and cutting oils are added to the concentrate obtained, which contains compound No. 1 in an amount of 0.1 % . The growth of fungi is inhibited in the paints and cutting oils.

Example 3

55 parts of compound no. 3, 3 parts of polyethylene oxide, 5 parts of lignosulfonic acid, 20 parts of diatomaceous earth and 17 parts of clay mixed into a wettable powder that is suspended in water before use. The suspension obtained is Sprayed on the inside walls of animal stalls to prevent the growth of fungi and bacteria.

Example 4

10 parts of compound no. 1, 40 parts of ethylene glycol monoethyl ether, 38 parts of isophorone, 10 parts of polyethylene oxide and 2 parts of an alkylbenzenesulfonic acid become water-soluble Mixed concentrate. Dilute 500 to 100 times with water.

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The concentrate is sprayed on the inside walls of animal stalls to protect them from bacterial and fungal growth.

In water circulation systems, the water is mixed with the solution

slimy debris

sets to prevent the formation of «/. The concentration of Compound No. 1 in water is 10 to 20 ppm. Pastes and binders are mixed with the solution to protect against rot, which contains 0.01 to 0.1 % of compound no.

holds. Bacteria and fungal growth as well as the formation of slimy deposits
/. is prevented over a long period of time.

Example 5

The bactericidal and fungicidal action of the active ingredients according to the invention is determined using (1) the potato dextrose agar dilution method, (2) the Waksman liquid medium dilution method and (3) the glucose broth medium dilution method were tested. The minimum inhibitory concentrations are given in Table II.

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Table II

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Aspergillus
Niger '' Minimum heat concentration ig / ml) (2) No. 2 (3) No 3 (3) No. k (3) No.5 (3) No. 6 (3) Active ingredient Penicillium
citrinum number 1 10 (1) - (1) - (1) - (D - (1) - .Test method Cladosporium
harbaruin (1) 20th 10 - 10 - 10 - 10 - 10 - mushrooms Chaetomium
globosuni 10 5 10 - 10 - 10 - 10 - 10 - j bacteria Geotrichum
candium 10 10 2.5 - 5 - 2 _; 5 - 5 - 5 - Bacillus
subtilis 10 20th - - - - - - - - - StaphylococcT-
aureus 5 5 - 5 - 5 - ² ; 5 - 5 - 5 Escherichia
coli 10 V - 5 - 10 - 5 - 5 - 5 Psoudomonas
fluorescens 2.5 80 6th 60 - 6o - ho - 60 - 60 IS
² ; 5 ko - - - _ - - - - '- - - 80 - - - - - ko

Example 6

30 g milk casein, 270 ml distilled water and 1 ml 28 percent strength aqueous ammonia solution are mixed and then 5 ml of spoiled casein solution are added. The received Casein solution is mixed with the water-soluble concentrate obtained according to Example 4 and containing compound no. 1 and incubated at a temperature of 30 ° C. On the 10th, 20th and 30th day thereafter, the casein solution is checked for putrefaction. The results are shown in Table III. _,

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Table III

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Amount of in the
Casein solution
contained ver
binding no. 1 10th day 20th day 30th day 0
(no treatment) Putrefaction and
Yellowing Putrefaction and
Yellowing Putrefaction and
Yellowing 0.05 % no rot
nis no rot
nis low
Putrefaction 0.1 % no rot
nis no rot
nis low
Putrefaction

Example 7

The emulsifiable concentrate obtained according to Example 1 and containing 10% of compound no. 1 is poured into three vessels and each is diluted 500, 1000 or 200 times with water. Textile fabric samples made of silk, cotton and polyvinyl alcohol fibers are immersed in each of the three different emulsions for 3 minutes and dried at room temperature for 24 hours. The dried samples are then cut into squares with a side length of 1 cm. The surfaces of potato dextrose agar medium plates are inoculated with test bacteria and fungi and the squares of fabric are placed on the plates. The inoculated bacteria and fungi are incubated at 28 ° C. for 4 days. Then the area surrounding the squares of fabric is measured, in which the growth of bacteria and fungi is inhibited. The results are shown in Table IV.

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Table IV

R Ί 1 Pt 8 5

Control
le
0 _? 005
O ₇ Ol
0.02 Width of the inhibition zone, - mm Staph
coccus
aureus mushrooms Penicil
liuin
citrenum Control
le
0.005
0 _r 01
0.02 bacteria 0
5
8th
12th Asper
gillus
Niger 0
H
6th
7th Control
le
0 _; 005
0 _; 01
0 _; 02 Bacillus
subtilis 0
5
9
13th 0
5
7th
8th 0
5 '
7th
9 .. silk 0
3
6th
10 0
H
7th
11 0
6th
8th
11 0
3
5
7th tree
wool 0
3
6th
10 0
k
6th
8th Poly
vinyl
alcohol·
fibers 0
2
5
9

Example 8

The emulsifiable concentrates obtained according to Example 1 are diluted 400 or 800 times with water to form emulsions. Square plates made of beech wood with a side length of 5 cm and a thickness of 5 mm are immersed in the emulsions for 2 minutes and dried for 2 hours at room temperature. The square plates are placed on the surfaces of agar plates. Spore suspensions of Aspergillus niger, Penicillium citrinum, Cladosporium harbarum or Chaetomium globosum are sprayed onto the agar plates and the square plates, respectively. The test mushrooms are 2 weeks at a

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relative humidity of 95 % and a temperature of 28 ⁰ C grown in the incubator. The results are shown in Table V. The growth inhibition is given in values from 3 to 1:

j5: 100 percent inhibition of the test organisms, 2: the area on which the test organisms have multiplied,

is less than a third of the test plate surface, 1: the area on which the test organisms have multiplied, is more than a third of the test plate surface.

Table V

Active ingredient / ^ 5 ^ Growth inhibition - - - 0, O ₁₂₅ , no loading
plot
0% 2
3
H
5
6th 0.025 <fo 3
3
3
3
3 cn cn cn cn cn

Example 9

The emulsifiable concentrates prepared according to Example 1 are diluted 1000-fold with water to form emulsions. Cotton ge Weave is immersed in each of the emulsions for 2 minutes, then dried at room temperature and cut into squares with cut to a side length of 1 cm. The test bacteria and

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- mushrooms are each inoculated separately on potato agar plates, and then a square of fabric is placed on each of the panels placed. The test bacteria and fungi are grown for 4 days at 28 ° C. Then the area surrounding the squares of fabric becomes measured, in which the growth of bacteria and fungi is inhibited. The results are summarized in Table VI,

Table VI

Really
material,
No. Width of the inhibition zone, mm Penicil
lium
citrinum bacteria Staph
coccus
aurous |
I. 2
k
no loading
plot mushrooms 7th
5
0 Bacillus
subtilis 7th
8th
0 Aspergillus
Niger 8th
10
0 6th
5
O

Example 10

100 parts of Waksman liquid medium are mixed with 0.02 part of active ingredient in the form of a 10 percent water-soluble concentrate obtained according to Example 4. Wood and iron parts (hereinafter referred to as slime test planks) are dipped into the Waksraan liquid medium, which is then inoculated with bacteria isolated from a water circulation system and incubated ^{at 27 to 34 ° C. with shaking.} The growth-inhibiting effect of the active ingredients used according to the invention against fungi and green algae is then examined on the Schlaim test planks.

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The results are shown in Table VII, in which the following symbols are used:

: no increase

+: the area that has increased is 1 - 25 %

++: the area that has increased is 26 - 50 %

+++: the area that has increased is 51 - 75 %

++++: the area showing the increase is 76 - 100 ° /

Table VII

Active ingredient
No. Multiplication 14th day 21st day .Bacts
rien 2
3
no loading
plot 7th day +++ +
++++
* mushrooms 2
3
no loading
plot ++ +++ ++++ Grünal
gene 2
3
no loading
plot ++ ■ +++ +
++++ ++

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Claims (2)

- 15 - 7R3 198B Claims Λ) Bactericidal, fungicidal and algicidal agents, consisting of 0.5 Ms 95 percent by weight of N- (β, β-dichlorovinyl) salicylamide and / or at least one of its metal salts and 99.5 Ms
5 percent by weight of a customary carrier and / or diluent and / or auxiliary. 2. Means according to claim 1, characterized in that the metal in the metal salt is monovalent or zv / egg-valent. 5098BB / 1O61