DE2014026C - N-polyhalovinyl mercaptocarboxamides - Google Patents

Description

The invention relates to N-polyhalovinyl mercaptoca rboxamide's formula

RC-NSC ₂ Cl ₁₁ H ₀ _ ",
R '

in which R is hydrogen or an alkyl radical having 1 to 3 carbon atoms and R 'is a methyl radical, or R and R' together represent a linear alkylene radical having 3 to 5 carbon atoms which is bonded to the carbonyl group and nitrogen to form a ring and α the number 2 or 3 represents.

These carboxamides have fungicidal, algicidal, nematocidal and bactericidal activity.

The carboxamides in which R and R 'are linked to form a ring can also be given by the formula

Il c

_R 2 N —SC ₂ Cl ₁₁ Z ₁₃ _ „,

in which R ^{2 is} a linear alkylene group having 3 to 5 carbon atoms and a has the meaning given above.

Typical examples of polychlorovinyl groups which can be represented by - C ₂ Cl _n H ₁₃ _ _a) are the trichlorovinyl, 1,2-dichlorovinyl and 2,2-dichlorovinyl radicals.

Typical carboxamides represented by the above formula are

N-methyl-N-trichlorovinylthioformamide,

N-methyl-N-trichlorovinylthiopropionamide,

N-trichlorovinylthiopyrrolidone,

N-trichlorovinylthiopiperidone,

N-trichlorovinylthiocaprolactam,

N ^^ - dichlorovinylthiocaprolactam.

The carboxamides of the invention can be prepared by using a sulfenyl halide a secondary carboy amide is implemented. This reaction is represented by the following reaction equation explained:

! I

RC —NHR ¹ + CIS —C ₂ Cl ₁₁ H ₁₃ _ „,

Il

> RC - N - S - C ₂ Cl ₀ H ₁₃ _ ", + HX

R '

in which R, R 'and α have the meaning given above. This reaction is expediently carried out in the presence of an inert solvent.

such as dimethyl sulfoxide, dimethylformamide, acetonitrile or dioxane. The reaction temperature is generally not critical and is usually in the range from about -20 to about 50 ° C., preferably between about 0 and 20 ^° C. Likewise, the pressure is not critical and is usually atmospheric or autogenous pressure. It is advantageous to use stoichiometric amounts of the reactants or a slight excess of sulfenyl halide.

It is also necessary to use a mild, basic halogen water acceptor in this implementation to be used. Soluble tertiary amines such as pyridine and trialkylamines, e.g. B. triethylamine or tripropylamine are preferred. It is appropriate to use an at least stoichiometric amount of Use hydrogen halide acceptor. Such acceptors, which are so strong that they can with the suI-fenylchlorid react should be avoided.

Carboxamides according to the invention can also be prepared by dehydrochlorination of corresponding N-polychloroalkylthiocarboxamides getting produced. So z. B. N- (Tetrachloräthylthio) carboxamide to N-Trichlorvinylthiocarboxamidendehydrchalogeniert will. This dehydrohalogenation is usually carried out at low temperatures, usually at about 0 to about 40 ° C, and in the presence of solvents such as benzene, toluene, ether, methylene chloride, Acetonitrile or chloroform. Usually mild dehydrochlorinating agents such as tertiary amines (trialkylamines or pyridines) or alkali metal carbonates can be used. Triethylamine is the preferred agent.

The percentages in the examples relate to weight.

example 1

7 g of N-methylformamide, 50 ml of dimethylformamide and 7 g of pyridine were placed in a vessel which was cooled in an ice bath. Fifteen grams of freshly distilled trichlorovinylsulfenyl chloride was slowly added to the mixture. After the addition was complete, the mixture was stirred at room temperature for 1 hour. Then 5CK) ml of ice water were added to the vessel. The mixture was extracted with ether and the extract was _{washed with aqueous NaHCO 3} , dried and evaporated to leave a brownish colored oil. The distillation

2,014

this oil at 75 to 80 ^c C under 0.7 mm H "yielded 8 g of N-methyl-N-trichlorovinylthioformamide. *" ~ Analysis:

Calculated
found .

S 14.51. Cl 48.02% • S 15.45. Cl 47.30%.

Example 2

IO

8.6 g of caprolactam, 6.5 g of pyridine and 100 ml of methylene chloride were placed in a vessel which was cooled in an ice bath. 15 g of trichlorovinyl sulfenyl chloride were slowly added and the mixture was _{stirred for 2} hours at ambient temperature. 100 ml of methylene chloride were then added and the contents of the vessel were washed _{successively with 100 ml of H 2} O, 100 ml of dilute HCl and 100 ml of H _{2 O.} The washed material was then dried and evaporated to an oil. This oil was chromatographed, 11 g of N-trichlorovinylthiocaprolactam being eluted with 50% ether in hexane. This oily compound showed the following S and Cl analysis:

Calculated ... S 11.64, Cl 38.70%; found .... Sl 1.68, Cl 38.65%.

Other carboxamides according to the invention were prepared in a manner analogous to that in Examples 1 and ? described, manufactured. These carboxamides are listed in Table 1.

table

connection

N-methyl-N-trichlorovinyUhio-acetamide N-methyl-N-trichlorovinylthio-butyramide

N-trichlorovinylthio-pyrrolidone

N-trichlorovinylthio-piperidone

N-2,2-dichlorovinylthio-pyrrolidone

N-2,2-dichlorovinylthio-aprolactam

Elementaranaly.se. % Cl: calculated Cl: found F. S: calculated S: found 45.3 44.6 (Cp.) 13 62 13.28 40.5 40.5 12.18 12.38 43.1 41.9 12.96 13.10 40.7 40.9 12.18 12.29 33.50 32.70 Oily liquid 15.10 14.68 29.50 29.15 F. 91 to 102 ^D C 13.31 13.11 F. 68 to 71 ⁰ C

The inventive i. N-polychlorovinylthiocarboxamides have biological activity against a large number of organisms, in particular against fungi, algae, bacteria and worms. The nematocidal activity of the carboxamides of the invention was tested by testing typical amides of this invention using the following procedure: 0.38 ml of a 3% acetone solution of the test compound was diluted with 1 ml of acetone. The resulting solution was mixed with 20 ml of an iron-containing magnesium aluminum silicate of approximately the composition 3 MgO. (FeAl) ₂ O ₃ , 3SiO ₁ (see Hackhs, Chemical Dictionary, 3rd edition [1940], p. 894 ; Römpp. Chemie Lexikon, 5th edition [1962], Sp. 5422), that in the hands! is available under the name "Vermiculite", mixed homogeneously. The treated vermiculite was then mixed homogeneously with 750 g of soil (dry weight basis) that was heavily infected with free-living nematodes (mixed culture of Meloidogyne javanica and Meloidogyne incognita). This mixing resulted in a concentration of about 15 parts test compound per 1 million parts soil. The treated soil was stored for 4 days at 65 to 75 ° C. After that, it was divided into three equal parts, each of which was placed in a separate pot and left in it for another 3 days. A 3 week old tomato seedling (Bonny Best) was placed in each pot and incubated for 13 days under greenhouse conditions. Thereafter, the seedlings were removed and the soil was washed from the roots. The nematocidal activity of the test compound was determined by examining each plant for signs of nematode infestation (number of gall apples, wilts).

The results of this test recorded as the average of three replicates on one O-to-100 basis, where 0 = ineffective and 100 = completely effective, are shown in Table 2.

Table 2

connection Nematocide W, -
% N-methyl-N-trichlorovinylthio-
formamide
N-methyl-N-trichlorovinylthio-
acetamide
N-trichlorovinylthiopyrrolidone
N-trichlorovinylthiocaprolactam
N-methyl-N-trichlorovinyl butyramide 100
! 00
100
100
100

As can be seen from these experiments, the carboxamides according to the invention can be used for combating used by parasitic nematodes. These carboxamides are commonly found on the infected Soil applied in doses of 3.5 to 45 kg / ha. They can be in the form of liquid solutions, Be dispersions or emulsions. For their preparation, solvents such as aromatics, e.g. B. Xylene, toluene and benzenes, ketones, e.g. B. cyclohexanone, can be used. These contain liquid preparations usually a wetting agent which promotes the penetration of the carboxamide into the soil and generally increases its effectiveness. The compounds can also be in the form of solid preparations which contain carriers such as earth, sawdust, clays, etc. can be used. Following the When applied to the ground, this is watered,

so that the carboxamide is dispersed under the surface of the earth.

The carboxamides according to the invention are particularly suitable for combating microbial Organisms such as algae, bacteria, mold and aquatic weeds, industrial wastewater and cooling storms z. B. in the paper and food industry. You can also fight it such oiganisms in other waters, like lakes, Streams, canals or ponds. For this purpose, a biocidal amount is used or more of the carboxamides according to the invention are added to the environment of the organisms. The dose is usually between 0.1 and 50 ppm. In any case, the optimal dose depends on the particular one Organism and the body of water to be treated. So z. B. to combat algae the Carboxamides used in concentrations of about 0.1 to 10 ppm; this corresponds to about 0.4 to 40 kg / ha of water surface at a water depth of about 30 cm. The carboxamides can be used as dispersibles Powders or solutions in water-miscible solvents can be used.

Typical carboxamides according to the invention were tested as algicides by the following method:

An acetone solution of equal parts carboxamide and a surfactant was made prepared. This solution was mixed with a nutrient broth in such an amount that a Concentration of 2 ppm of carboxamide resulted. 150 ml plastic cups were used for repeat tests filled with this mixture. 350 to 400 mg of Euglena was added to each sample cup, and the beakers were placed in a chamber for incubation. The cups were periodically checked for algae growth examined. The algicidal effectiveness of the carboxamide was determined on the basis of a final Assessment of algae growth determined after 10 days.

The results of these tests, reported as the average of four replicates and assessed using a 0-100 scale, where 0 = ineffective and 100 = completely effective, are in Table 3 summarized.

Table 3

Carboxamides of this invention have also been used to control fungi such as Pythium ultimum. Rhizoctonia solani, Fusarium oxysporum f phaseoli. Helminthosporium sativum. Verticillium albo-atrum. Monilinia fructicola and Alternaria solani. as well as bacteria such as Erwinia carotovara and Pseudomonas syringae, used. For use as fungicides or bactericides, those according to the invention are used Carboxamides conditioned by conventional methods and target the fungi, bacteria or Applied hosts, in particular to those plant hosts such as plants, seeds or paper. You can combined with inert liquids and solid carriers such as powders, solutions or dispersions will.

Tests for the fungicidal effect were carried out as follows: A variant of the in "American Phytopathological Society Journal". Vol. 33 (1943), pp. 627 to 632, described »Standard Spore Slide-Germin-non Method for Determining Fungicidal Activity. It will the fungitoxic effect of the compounds to be investigated as a percentage inhibition of the Spore shoots of the fungus measured. The to test-

The compounds were dissolved in acetone in one of the concentrations (ppm) given in Table 4. These solutions were then pipetted into the cavity of appropriate microscope slides and allowed to dry. Then dL · cavities were made with a

Spore suspension of the test organism was filled, and the spores were then placed in a humid chamber incubated overnight. Each 100 spores were examined, and the number of sprouts and not sprouted spores were counted. The effect was

then recorded as percentage of sprout inhibition. The following results were obtained:

Table 4

N-methyl-N-trichlorovinyl

connection

N-methyl-N-trichlorovinylthioformamide

N-methyl-N-trichlorovinylthioacetamide

N-trichlorovinylthiopyrrolidone

N-trichlorovinylthiocaprolactam

N-methyl-N-trichlorovinylthiobutyramide

N ^ l-Dichlorovinylthiopyrrolidone ...

N ^^ - Dichtorvinylthiocaprolactam.,

Comparative substance:

N, N'-dimethyl-dipyridyl

(in trade under the name

»Diquat« available)

Algicides
effectiveness

97 (0.5)

100 (0.5) 100 (D 100 (2) 100 (2) 90 78 (2)

54 (2)

thiobutyramide

N-trichlorovinylthiopyrrolidone

N-trichlorovinylthiocaprolactam

N-trichlorovinylthiopiperidone

N-2,2-dichlorovinylthioformamide

N-2,2-dichlorovinylthiocaproiactam

Comparative substance:

Polyethylene thiuram disulfide (commercially
under the name
»Polyram« available) ..

Further comparative tests with the known fungicides N-trichloromethylthiotetrahydrophthalimide and manganese-ethylene-bis-di-diocarbamate

% Inhibition

(ppm)
Monilinia
fructicola

40 (1.6)

100 (0.25)

100 (0.25)

83 (0.25)

66 (1.6)

40 (1.6)

3 (1.6)

Alterncria solani

78 (10)

100 (Ι, ό)

100 (1.6)

91 (1.6)

51 (10)

81 (10)

28 (10)

commercially available under the name "Captan" and "Mancb") were used with the mycelium drop Tcst, which determines the fungitoxic effect in terms of the inhibition of mycelial growth, as follows carried out: The Tesl compounds were in the concentration (ppm) shown in Table 5 in Dissolved acetone. Paper disks inoculated with equal amounts of the respective fungal mycelium were opened KartolTeldextrosc-Agar-Mcdium were then placed equal amounts of the fungicide solutions are applied to the center of the discs. The so treated Disks as well as inoculated disks without fungicide treatment were kept at room temperature for so long incubated until the mycelial wax in the unbchan If the discs reached a certain distance from the disc edge, then the growth areas compared and the percentage inhibition determined.

table b llclminlhosporium sativum Khiznctonia solan % 100 (100) 98 (100) Inhibition (ppm) 100 (40) 100 (100) N-methyl-N-trichlorovinylthioacclamide l'ythuim ullimum 100 (40) 100 (40) N-methyl-N-trichlorovinylthiobutyramide 94 (16) 100 (40) 97 (40) N-trichlorovinylthiopyrrolidone 100 (16) 84 (100) N-trichlorovinylthiocaprolactam 96 (16) - N-trichlorovinylthiopiperidone 100 (40) - - N-2,2-dichlorovinylthioformamide 100 (6.4) 63 (250) 34 (125) N-l ^ -Dichlorovinylthiocaprolactam .... 100 (250) 85 (250) "Maneb" - 53 (25t ·;

Claims (2)

Patent claims:
1. N-polyhalovinyl mercapto-carboxamides the formula RC —NSC ₂ Cl ₀ H ₀ _ ",
R ' in which R is hydrogen or an alkyl radical having 1 to 3 carbon atoms and R 'is a methyl radical or R and R' together represent a linear alkylene radical having 3 to 5 carbon atoms which is bonded to the carbonyl group and nitrogen to form a ring and α die Number represents 2 or 3. 2. Use of the carboxamides according to claim 1 for combating nematodes, fungi, Aquatic weeds and bacteria.