DE1542706C - Fungicidal agent. Arun; California Research Corp., San Francisco, Calif. (V.St.A.) - Google Patents

Description

The invention relates to fungicidal agents containing N- (Tetrahalogenäthyithio) -carbomonocyclo-l ^ -dicarboximides as an active ingredient, which is characterized by having the general formula

N - S - CX, - CHX ₇

(D

in which X is chlorine or bromine and R is a mononuclear carbocyclic ring with 6 core carbon atoms means.

In the not previously published German patent specification 1 203 788 is a process for the preparation of haloalkyl and haloalkenylsulfenyldicarboximides described for which fungicidal efficacy has been demonstrated. The invention Compared to these compounds, with which they are not identical, active ingredients represent an inventive factor Selection.

Parasite-killing, containing the NSCClt group Compounds are also known from German patents 887 506 and 921 290 and in the Commercially available. These compounds have a relatively strong parasite-killing activity. Attempts to improve the action of these compounds have so far been unsuccessful. One of the preferred compounds containing the group indicated above is N- (trichloromethylthio) -cisl-4-cyclohexene-1,2-dicarboximide the structural formula

HC
HC

CH-Cx

CH- C ' N-SCCl.,

LH ₂

Its homologues show a significantly lower biological effectiveness. Replacing a chlorine atom of the perchloromethyl radical by an alkyl group, e.g. B. a methyl group, one obtains one Compound with very little fungicidal activity. Will be an alkylene group between the sulfur atom and the trichloromethyl radical introduced, compounds with greatly reduced fungicidal properties are also obtained Effectiveness. The replacement of the methyl radical bound to the sulfur atom by a larger one The alkyl radical always leads to a reduction, if not to a complete loss of the fungicidal effect. Biological investigations of the homologous compounds obtained in this way showed that the compound given above with its structural formula, also called N- (trichloromethylthio) -tetrahydrophthalimide which is by far the most effective fungicidal agent.

It has now been found that in the mononuclear carbocyclic N-alkylthio-1,2-dicarboximides mentioned by exchanging the group - NSCQi for an N (Tetrahalogenäthylthio) group of the general formula

- N - S - CX ₂ - CHX ₂

55

in which X is a chlorine or bromine atom, the fungicidal effect of the dicarboximide is significantly increased.

The pesticides according to the invention preferably contain N- (Tetrahalogenäthylthio) -carbomonocyclo-1,2-dicarboximide of the general formula (1), in which the mononuclear carbocyclic 1,2-dicarboximide radical is a phthalimide or Is tetrahydrophthalimide residue.

The N - (Tetrahalogenäthylthio) -carbomonocyclo-1,2-dicarboximide are made by reacting an alkali salt of 6 carbon atoms in the nucleus mononuclear carbocyclic 1,2-dicarboximide with a 1,1,2,2 - tetrahaloethylsulfenyl halide,

z. B. 1,1,2,2-Tetrachloräthylsulfenylchlorid available. The imide can be in a suitable inert medium, e.g. B. in an aromatic solvent, such as benzene or toluene, in an alcohol such as methanol or ethanol, or in water. When using an aromatic solvent, the imide is preferably used in the form of its own Alkali salt. If, on the other hand, water or alcohol is used as the inert medium, this is the case Alkali salt preferably in situ. For this purpose, a sufficient amount is added to the reaction mixture Amount of the alkali metal cation of the salt to be formed, if an alcohol is used in the form of the corresponding alkali alcoholate, when using water in the form of an alkali hydroxide. While the addition of the sulfenyl halide, optionally together with a suitable inert solvent, like petroleum ether or a hexane mixture, the solution or suspension of the imide alkali salt vigorously stirred. After a sufficient reaction time has elapsed, the reaction product is through Filtering or distilling off the solvent isolated. The N- (tetrahalogenethylthio) -1,2-dicarboximide obtained is optionally made from a suitable solvent, e.g. B. methanol or a Hexane mixture, recrystallized.

You can also initially produce an N- (Halogenäthylthio) -dicarboximide in which the dem Sulfur atom adjacent carbon atom is not halogenated. This is then at an elevated temperature in the presence of a suitable catalyst, e.g. B. sulfuric acid or chlorosulfonic acid, in the desired N- (1,1,2,2-tetrahaloethylthio) -1,2-dicarboximld convicted. '

For the production of the active ingredients used as fungicides according to the invention, in the context of the invention does not seek protection.

In the following Table I are some of the fungicidal N- (Tetrahalogenäthylthio) -carbomonocyclo -1,2-dicarboximide listed according to formula (1).

Table I. elements Analy
theory w C ₀ )
found connection Melting point
(in C) Cl
S.
Cl
S.
N 40.4
'9.1
41.1
9.18
4.0 37.2
8.6
40.8
9.2
4.2 N- (Kl ^^ - Tetrachloräthylth jo) -cis- l-4-cyclo-
hexene-1,2-dicarboximide
N- (Kl, 2,2-tetrachloroethylthio) phthalimide 154 to 155.5
116 to 117

The fungicidal agents according to the invention have a wide field of application. You can also in Paints or other coating agents used will. In particular, they are excellent for preventing and combating a wide variety of through Fungi caused plant diseases. They are used as a spray in a liquid Applied carrier, e.g. B. as a solution in a solvent or in or on inert liquids or solids Carriers such as inert clay or xylenes. The solid carriers can be in the form of a powder, optionally together with a suitable wetting agent in order to obtain a wettable powder. The fungicidal active ingredients of the formula (1) can also be used as a mixture with one another or in conjunction with other fungicidal substances are used.

Another advantage that the fungicidal compositions according to the invention have over the known fungicides having trihalogen mercapto groups lies in their emulsifiability in aromatic and similar solvents. The N- (trichloromethylthio) -tetrahydrophthalimide and its known, Analogues containing SCCl: i groups have only such a low solubility in these solvents that that they cannot be processed into preparations for agriculture with these agents.

The fungicidal agents according to the invention can be sprayed directly onto plants or another host or otherwise applied; they can also be used on the plant seed, on the earth or another environment for the plants to be sprayed or used in a similar manner, to prevent fungal diseases or fight diseases caused by fungal infestation.

B e i s ρ i e 1 1

To prove that the N- (Tetrahalogenäthylthio) -carboinonocyclo-l ^ -dicarboximide of the general formula (1) given above are extremely effective fungicides and are far superior in this respect to other, constitutionally similar compounds, those in the table below were used II mentioned compounds were tested for their action against Monilinia fructicola. The test for fungicidal effectiveness was carried out according to the method described in the American Phytopathological Society Journal, vol. 33, pp. 627 to 632 (1943), “The Standard Spore Slide-Germination Method for Determining Fungicidal Activity”. Thereafter, the effectiveness is expressed as the percentage inhibition of the germination of fungal spores achieved by the fungicidal agents. ⁶ p

- The compounds tested were made at a dilution of 1, 0.5 and 0.25 parts per million Parts dissolved in acetone. The solutions were then pipetted into wells of microscope slides and left dry. The wells were then filled with a spore suspension of the test organism. Monilinia fructicola, filled and incubated in a humid chamber overnight. There were 100 spores on each the number of germinated and non-germinated spores examined and counted.

The results obtained are shown in Table II.

Table II ■ -

connection Parts per million 0.5 1 parts l; 0 0.25 N- (trichloromethylthio) - cis- l-4-cyclohexene 71 1,2-dicarboximide 99 4th N- (Kl, 2,2-tetrachloroethylthio) - cis- l-4-cyclohexene 100 1,2-dicarboximide 100 94 N- (1,2-dibromo-1,2-dichloro ethylthio) -cis- l-4-cyclo- 97 witch-1,2-dicarboximid .... 100 57 N- (Kl, 2,2-tetrachloroethylthio) - cis- l-1-cyclohexene 100 1,2-dicarboximide 100 6th Mixture of the isomers N- (Kl, 2,2-tetrachloroethyl thio) -cyclohexen- 100 1,2-dicarboximide 100 74 N- (1,1,2,2-tetrachloroethylthio) - 100 cyclohexane-1,2-dicarboximide 100 100

Example 2

A comparison of the effectiveness of compounds of the formula (1) with led to similar results the effectiveness of N- (TrichlormethyIthio) -cisl ^ -cyclohexen-l ^ -dicarboximide regarding other mushrooms. The compounds to be compared were found to be fungicidal after the mycelium drop test Effectiveness examined. After this test, the fungicidal effectiveness is based on the inhibition of the Mycelium growth noted.

The compounds to be investigated were in the dilutions given below in Dissolved acetone. In the middle of paper discs that you have previously mixed with an equal amount of mycelium soaked and placed on a potato dextrose agar medium was the same in each case Amount of fungicidal solutions applied. After that, the slices were put together at room temperature incubated with control discs inoculated but not treated with a fungicidal agent until the

treated control discs were filled with mycelial growth. The effectiveness of the examined Fungicide was determined by taking the radii of the mycelial growth from the edge of the fungicidal agents and untreated discs and compared them with each other. the The results obtained are shown in Table III.

Table III

connection Preliminary license 500 N-iTrichloromethylthioJ-cis- l-4-cyclo- 32 hexen-1,2-dicarboximide N- (1.1.2.2-tetrachloroethylthio) - 86 cis-l-4-cyclohexene-1,2-dicarboximide N- (i.2-dibromo-1.2-dichloroethio) - 100 cis-l-4-cyclohexene-1,2-dicarboximide

Parts per million parts

Uhizoetonia 125

66

97

100

Fusarium 501)

23
69
80

Hclminthosporium 12?

16

100

Pj ι hi at 50

76

100

95

Example 3

Nd.l ^ J-TetrachloräthylthioK'is- l-4-cyclohexene-1,2-dicarboximid was used in the control of celery root and tuber rot with N- (trichloromethylthio) phthalimide. the compound preferred so far for this purpose. In this study, four young, knocked-back Utah celery plants, which were planted in a standard soil mixture from the University of California and each had five petioles with a length of 10.16 to 12.7 cm, were under a pressure of 1.05 kg cm ² with an aqueous Sprayed suspension of 40 parts per million parts of the fungicidal agent to be tested. An inert wetting agent and a filler were used to produce a uniform suspension. The plants were dried at greenhouse temperatures and then inoculated by spraying with an aqueous suspension of approximately 25,000 cm ^:) spores of Septoria apii f. Graveolentus. It is this fungus that causes celery root and tuber rot. The plants were then immediately incubated in a humid room for 24 hours at a temperature of 18 to 21 C and a relative humidity of 100 "n. They were then placed for 14 days in a room at a temperature of about 22 to 27 C and the relative humidity was about 70 to 80 per cent. At the end of the incubation period, the degree of infestation was determined by counting the pustules formed on the three oldest petioles, and these counts were compared with those treated in a similar manner The results are shown in Table IV below.

Table IV

Pro / entiiulc Hekäiiipfiiiii;

N- (Trichloromethylthio) -phthalimide ..... 47

N- (1.1.2.2-Tetrachloroethylthio) -cisl-4-cyclohexene-1.2-dicarboximide '87.

The great superiority of the fungicide according to the invention can be seen from the numerical values in Table IV compared to the known substance.

Example 4

Investigations using the Spore-Slidc-Gcrmination-Tcsls described in Example 1. dos im Tests mentioned in Example 2 for determining the inhibitory effect on mycelial growth and in Example 3 explained greenhouse tests showed that the 1.1.2.2-tetrahaloethyl compounds (A) and (B) are much more effective in low concentrations than those in German Patent 1 203 788 proposed 1.2.2.2-tetrahaloethyl compounds (C) and (D). which brings not only practical, but also economic advantages. The received The results are compiled in the tables below.

Inhibition of mycelial growth (%)

concentration PWhium Hclmintho! <Porium l-'usarium Rhizoctonia Vertkiliiini Parts per million 500 69 100 86 250 100 100 62 99 26th 125 100 ■■■■ .- ■■■ 100 24 97 20th 500 51 97 51 250 100 100 28 95 26th 125 100 100 7th 57 21

Λ = N- (Ll .2.2-Tetrachloräth \ Ithio) -cis- I '-cyclohcxen-1,2-dicarboximide. B = N- (1.1.2.2-tetrachloroethylthio) '- phthalimide.

continuation

from / enlration P) lh ium rush per million 500 250 82 125 60 500 250 95 125 76

Hclminthosporium Fusarium Rhizoctonia Vcrticilium 5 77 22nd 33 0 43 15th 0 0 28 6th 16 97 20 ' 100 0 69 19th 21 0 53 13th

C = N- (1,2,2,2-tetrachloroethylthio) phthalimide.

D = N- (l ^^^ - tetrachloroethylthioj-cis-, l ^ -cyclohexene-l ^ -dicarboximide.

Greenhouse test, percentage destruction

concentration
Parts per million Uromyces bean Septoria Celery Erysiphe cucumber A. 100 97 100 95 40 89 77 ■ ■ ⁷² 16 68 77 B. 100 98 100 40 67 98 16 50 95 C. 400 . 47 ■ 100 82 89 40 83 45 16 46 · 18th D. 400 24 100 91 86 40 57 71 16 30th

Inhibitory effect on the germination of fungal spores, (%)

concentration
Parts per million Monilinia Alternaria Botyris cinera Glomcrclla Cingulata A. 1.0 100 99 100 100 0.5 100 100 100 0.25 94 100 100 B. 1.0 100 100 100 0.5 100 100 100 0.25 ' 100 100 100 C. . 1.0 100 7th 100 100 0.5 99 90 100 0.25 22nd 3 67 D. 1.0 100 0.5 46 0.25 3

Claims (1)

Claim: Fungicidal agent containing an N- (Tetrahalogenäthylthio) -carbomonocycIo-1,2-dicarboximide as an active ingredient, characterized in that the active ingredient has the formula NS-CX ₂ -CHX ₂ Il ο in which X is chlorine or bromine and R is a mononuclear carbocyclic ring with 6 core carbon atoms means.