DE1595995A1 - Fungicidal agent - Google Patents

Description

Fungisidoo Medium

It has been found that a series of 4-cyano-iaothiazoles is very high have good fungicidal properties. The fungicidal effect was born in Teotverouohen on the famous Pilsen Vonturia inaequalio, the pathogen the Apfeiechorfn, Alternaria spec ,, the leaf · flake pathogen and on Plasmopara viticola, downy mildew the lift, according to gcwiGoen.

The subject of the invention bind fungicidal agents that have a content on one or more compounds from the * group of the isomeric 4-cyano-ioothiazoles of the formulas Ia and / or Ib have:

Ia *, Ib,

. wherein

R- alkylene with 1-4 carbon atoms _v R ₂ alkyl with 1-4 carbon atoms, phenyl or by 1-3 hydroxy or alkyl groups, oleogon atoms or. substituted by methylenedioxy

Phenyl and. R- denotes alkyl with 1-4 carbon atoms,

In addition, these fungicidal agents can be the customary carriers and / or fillers and, if appropriate, other known fungicides contain.

Inferior

909887/1656

BADORlGiNAt

The invention also relates to the use of the new Means for combating fungi, especially in agriculture and horticulture

The effect of the new compounds was determined in the Sporenkmtoet and generally Infektlonsteot. The DL ₅₀ or the DL « _{r was} determined; ho that amount of active compound (measured in mg / 100 cm **), which prevented the germination of spores in Pilsoporcn germination test and the growth of the Pilses on the sheet base in Infcktionstest 50 'BZV I / o fi 95

The new compounds were compared with the known and very effective fungicide li-trichloromethylthiotetrahydrophthalitide. In the Sporenkeinriest on Venturia are z. B. the new fungicides J-acetylthio-methylthio-S-methylthioM-cyano-iso-thiazole and S-acetylthio-methylthio-O-methylthio ^ -cyan-isothiazole two-bta three times more effective than the known comparison substance, while they had about the same effect in the spore germ test on Altornaria show., The same applies to the prevention of infection in the foliar spray test on Plasmopaiv-a viticola, where etv / a the same DLq- is achieved with N-trichloromethylthiotetrahydrophthalimido

In the new compounds of the formulas Ia and Ib, R 1 denotes methylene, ethylene and the straight-chain or branched propylene and butylene radicals. Rg lot either an alkyl radical with 1 to A C atoms, that is, ethyl, ethyl, n- or i-propyl or n-, aek, - or tert-butyl. Hg can, however, also be a pbenyl reet, which substitutes goflcbenen trap ^ For this come z, "B, o-, a-, p-hydroxyphenyl, 2,4-dihidroxyphenyl, 5 , 5-dihydroxhenyl, 2.4 _t 6 Trihydroxyphenyl, m- or p-tolyl, xyIyI or halogen-substituted phenyl residues such as 2,4-dihalophenyl, 3,5-dihalophenyl or 2, 4,6 "trihalophenyl, where the halogen atoms prevent chlorine , Bromine or iodine. R.sup.1 can also be a phenyl radical substituted by ethylenedioxy, preferably 2,3-methylenedioxyphenyl radical, all alkyl radicals R.sup.bene for hydrogen substituents.

* V-BAD ORjQlNAL

■■■ .. ■■■■. ■■■. ■ - 3 -. ■. '

1595 & 95

The new compounds can be prepared ₍ by using 4-gyan-iBothiazoles of the formula Ha and / or lib

^CM Vtt?

Ha lib

wherein

R, an alkali, ammonium or amine means an alkaline cation or equivalent and

Hr R. or R, iot,

with an α-haloalkylaoyleulfide of the formula III

^ ₁ where

R ^ and Rg have the above-mentioned Belli interpretation and.

Hal is halogen, preferably Cl or Br,

implements. If a compound of the formula Ua or Hb is used as the Auegango material, in which R ^ β is R, a treatment with an alkylating agent to introduce the sub-sequent Ry is added.

Depending on the reaction conditions chosen, two icomeric compounds are formed in which the diö ν acylthio-methylthio group (R ₂ COSR ₁ *.) Is either in a 3- or 5-position and the alkyl group K * is correspondingly either in a 5- or 3-position is arranged «

As salts of the 4-cyano-iothiazoles of the formulas IXa or Hb, in particular the alkali, alkaline earth, ammonium or amine alkali can be used * 90 9887/1666

, ■ BAD ORIGINAL * 4. *

Preferred alkali salts are the sodium and potassium salts, preferred alkaline earth salts are the magnesium and calcium salts. In addition to the ammonium salt, amine salts can also be used in the reaction. Tertiary, but also secondary and primary amines are particularly suitable for this purpose ! undergoing reaction and no longer appear in the final product, tons a variety of amine salts are used in general, the substituted ammonium cations will not own more than 16 carbon atoms in each Z may be mentioned ₀ Ba following amines:.. mono-, di- and Trimethylamine, mono-, di- and triethylamine, mono-, di- and iripropylamine and their isomers with branched chains, liono-, di- and tributylamine and their isomers with branched chains, in particular IT-tert-butylamine and isobutylamine, n- or tert-octylamine, n-decylamine and isodecylamine, n-dodecylamine, tert -dodecylamine See use amines for synthesis.

For the implementation of the compounds of the formulas Ha or Hb with the a-Haloalkylacylsulfiden of the formula III and the optionally subsequent alkylation can all customarily for solvents applied to such reactions are used, e.g. water or organic solvents v / ie methanol, ethanol, propanolji-propanol, butanol, acetone, dioxane, tetrahydrofuran, Dimethylformamide and benzene or "also mixtures of these solvents.,

The formation of the two different isomers can primarily be determined by the choice of the starting material and the solvent to be influenced. This creates one of the two isomers, the ^ -acylthio-alkylthio-S-alkylthio- ^ cyano-isothiazole, when working in anhydrous solvents, which has proven to be advantageous, the reaction first of the starting material with the 2-haloalkylacyl sulfides and then the reaction with the alkylating agents. forward

• - 5 ■ -

909887/1656 BAD original

take »The isomeric S-aylthioalkyl-thio-J-alkylthio-il-cyanisothiazole is preferably obtained when starting from a compound of the formula Hb, in which R ₁ - = R, = alkyl and if this substituent R, previously by Alkylation of the underlying 4-oyan-isothiazole in the presence of water. Has been obtained. The subsequent reaction of the salt of S-alkylthio-S-mercapto- ^ cyani so thiazole (Hb), which is initially isolated in two ways, with the a-haloalkylacyl sulfides is then likewise preferably carried out in anhydrous organic solvents. Obviously, the solvent present when the alkyl group R ~ is introduced has a decisive influence on which of the isomeric compounds is formed.

The Reäktionstemperäturen for these reactions range from ¹ to 5 ° and the boiling point of the solvent used. As a rule, about 1/2 to 5 hours are required to carry out the reaction. The new compounds are isolated and worked up in a manner customary per se.

Any processes can be used for the subsequent alkylation, if appropriate are used for the alkylation of mercaptides are common. First and foremost, this is where the implementations come with alkyl sulfates, alkyl halides and aryl sulfonic acid alkyl - estern in question. Particularly good yields are achieved when using obtained from dimethyl sulfate, methyl bromide and methyl;} odide. the Reaction conditions with regard to the solvents to be used, reaction temperatures and times do not differ from the values known from the literature for such reactions.

The preparation of the salts to be used as the starting material the ^, S-Dimercapto - ^ - eyan-isothiazole takes place according to known Methods, e.g. by converting malononitrile with carbon disulfide in the presence of the corresponding salt-forming Base, preferably alcohol or acetonitrile being used as the solvent. The first thing that arises

9098877 16S6

1,1-Dieyano-2,2-dimercaptoätlien reacts with sulfur under Ring closure to the corresponding 4-cyano-isothiazolo If one as Starting material compounds of the formula Ha or Hb are used, in which Mr. = R. is, closes, then another alkylation according to usual methods.

The new isothiazoles can be used depending on the intended use. can be combined with practically all known fungicides. In particular, for example, the following are embossed:

copper-containing fungicides (for example copper oxychloride, basic copper carbonate, Bordeaux mixture, copper quinolate), sulfur-containing fungicides (for example, wettable sulfur, polysulfides, ^l Schwefelkalkbrühen), mercury-containing fungicides (for example, phenylmercury chloride, Äthylquecksilberchlorid, Äethoxyäthylquecksilberchlorid, silicate or phosphate, etc.), tin-containing fungicides (Triphenylzinhacetat) also organic fungicides, such as thiocarbamates (Na, K, Zn, Fe and Mn salts of dimethyldithio- and ethylene-bis-dithiocarbamic acids), thiurams (tetramethylthiuram disulfide, polyethylene thiuram disulfide), trachitroachlorophenol, orobenzitrobenzole (eg pentachlororophenol, orobenzitrobenzole) - and trinitrobenzene), rhodandinitrobenzene, hexachlorobenzene, ohinone derivatives (e.g. tetrachlorobenzoquinone, 2,3-dichloro-1,4-naphthoquinone, 2,3-dicarbonitrilo-1,4-dithiaanthraquinone), N-trichloromethylthiotetrahydrophthalimide, N-trichloro-tetrahydrophthalimide, N-trichloro-tetrahydrophthalimide, ^ Dinitro-e-ethylphenyl crotonate, N-dodecylguanidine acetate, 3 »5-dimethyl-1,3» 5-2H-tetrahyd rothiadiazin-2-thione, also antibiotics (tetracyclines, streptomycins) or 2,6-dichloro-3, S-dicyano- ^ phenyl-pyridine.

The new isothiazoles can be processed into all the usual forms of application for fingicidal agents. With the addition of the usual Carriers and / or fillers can be produced, for example, spray or dusting agents, also pickling agents for preservation, of seeds, all of which may optionally contain further additives such as dispersants or wetting agents. Also the processing into solutions or emulsions, which can also be sprayed as aerosols, for example, are achieved with the use of appropriate additives. All forms of application generally contain 1 to 95 # active ingredient.

- 7 -909887/1666

BAD ORlGSNAL

The new compounds are said to be used in pest control as fungicides, especially in agriculture and horticulture Find application.

Ai "Production of the active ingredients..

example 1

To 21.8 g in 300 ml of abs. Ethanol suspended 3> 5-Dlmercapto-4-cyano-isothiazol-disodium salt are added at room temperature 12.4 g Clilormethylacetylsulfid dissolved in 10 ml of ethanol was added dropwise,! Fold completion of the addition is stirred for 1-2 hours at 60 ⁰ O. 14.2 g of methyl iodide, dissolved in 20 ml of ethanol, are then added. The mixture is stirred for a further hour, cooled to 20 and then the reaction product and the precipitated inorganic salts are filtered off with suction. The residue is boiled with 150 ml of ethanol, filtered off with suction and the ethanol solution is concentrated to half. The precipitated S-acetylthio-methylthio-S-methylthio ^ -cyanisothiazole is filtered off with suction. '

Yield: 12.3 g; F. 121-123 ° C.

Similarly, the equivalent length gives chloromethylbenzoyl sulfide 3-bellzoylthio-methylthio-5-methylthio-4-cyano-isothiazole, F. 114 -

0 1

Example 2

To 21.8 g in 300 ml of abs. Ethanol suspended 3,5-dimercapto-4-cyano-isothiazole disodium salt, 12.4 g of chloromethylacetyl sulfide, dissolved in TO ml of ethanol, are added dropwise with stirring. After two-stage stirring at 60 ⁰ O, 12.6 g of dimethyl sulfate, dissolved in 20 ml of ethanol, are added dropwise. It is stirred for a further 2 hours, then cooled to 20 ° and filtered off with suction. The residue is boiled with 150 ml of ethanol and again filtered off with suction. The ethanol solution is treated with activated charcoal and concentrated. Yield 5.5 g of 3-acetylthio-methylthio-5-methylthio-4-cyano-isothiazolj F. 120 - 122 ⁰ O.

909887 / $ 56

BATH ORIGINAL

Example 3

11.3 g of 3-mercapto-5-methylthio-4-cyano-isothiazol-potassium salt are dissolved in 200 ml of ethanol and mixed with 6.2 g Ohlormethylacetylsulfid offset Subsequently, an 'hour at 60 - 70 ⁰ O heated, then Cooled 20 ° and precipitated the reaction product by carefully adding dropwise water. The S-acetylthio-methylthio ^ -methylthio ^ '- cyano-. Isothiazole is filtered off with suction and recrystallized from ethanol. Yield: 5.0 g of P. 119 - 121 ⁰ O.

Example 4

21.8 g of 3,5-dimercapto-4-cyano-isothiazol-disodium salt is dissolved in 300 ml of water and 5 - 10 ⁰ G under stirring within 10 minutes with 14.2 g of methyl} iodide was added. The _{mixture is stirred for a further 1/2} hour at 5-10 ° and then precipitated 3,5-dimethylthio-4-cyano-isothiazole, which is obtained as a by-product, is filtered off with suction. ■

The filtrate is concentrated to dryness, the residue suspended in 150 ml of ethanol and 11.2 g Ohlormethylacetylsulfid are added dropwise within 10 minutes at 60 ⁰ G. ITach completion of the addition noäh 1 hour at 60 ⁰ O is stirred. The inorganic residue is then filtered off with suction and the mother liquor is concentrated to a third of its volume. The precipitated 5-acetylthiomethylthio-5-methylthio-4-cyano-isothiazole is filtered off with suction and recrystallized from ethanol with the addition of charcoal. Yield: 5.3 g IV 70 - 71 ⁰ O.

BATH ORIGINAL

909887/1656

B: Production of the 'fungicidal agents

example 1

Wettable powder.

75 ^a / o S-acetylthio-methylthio-I-dietliylth.io- ^ cyano-isothiazole "". 15 ^ SuIfit waste liquor powder

1 fo Fa-isobutyl-napithalin-sulfonate ^s ■;

9 ■ '# white bolus

are married to each other. The powder made in this way is sprayed or sprayed in the form of a dilute aqueous suspension. . .

Example 2.
Wettable powder

70 ° / o copper oxychloride

10 $ 3-Benzoylthio * -methylthio-5-methylthio-4-cyano-isothiazole 5 $ Oleic acid-N-mei; hyltaurid
15 i * chalk. . .-

are finely ground together. The powder obtained can be mixed with water to form a suspension in the desired Concentration can be diluted. The suspension can be splashed or sprayed.

Example 3

Dust

15 io S-acetylthio-methyltMo-ij-methylthio ^ -cyan-isothiazoi 25 fo sulfur powder '15 io kaolin 42 96 pyrophyllite 3 io rosin

Example 4
Wettable powder

10 # 5-acetylthio-die feliylthio-3-äthyltliio-4-isothiazol-Oyan 40 io N-trichloromethylthiophthalimide 15 i »Sulfitablaugenpulver

2 $> Na-Isobutylnaphthalenesulfonate 33 '^ chalk

9 0 9 8 8 7/165 6 ' ⁶ AD oriqi _NAL

Claims (1)

Patent application , .- ''' 1c Fungicidal agents, characterized by a content of one or more compounds from the group of the organic 4-cyano-ioothiasBols of the formula ν R ₉ -CO-SR ₁ -S CH c. ■ Il Il τ » N IL Ia and or • I b , -S-CO-R ₂ wherein R- alkylene with 1-4 carbon atoms ». R ₂ alkyl with 1-4 carbon atoms, Phenyl or by one to three hydroxy or alkyl groups, halogen atoms or by . Methylenedioxy substituted tea Phenyl and R, alkyl with 1-4 carbon atoms means, in addition to the usual carrier and / or auxiliary substances; possibly in a mixture with other fungicides 2. Use de.3 agent according to claim 1 for combating by Fungi. New undertakings • # • 8.13622 909887/1656 ~ - 12 - 3 · Process for the preparation of τοη 4-oyan-isothlaeols of the formulas H ^{n Ia} and / odor CW wherein R ₁ alkylene old 1-4 O-Atoaen, Rg alkyl with 1 - 4 carbon atoms, phenyl odor duroh 1-3 hydroxy odor Alkyl groups, halogen atoms or eubotituierteo by methylenedoxy Phenyl and R, denotes alkyl with 1-4 C-atoms, characterized in that 4-cyano-iothlasols of the formulas ₅
JSR ₅ «ul / or. . Ha wherein R _{4 is} an alkali, ammonium or alcaline ecatlone or an equivalent an o alkaline earth metal cation and Rc -Rj or R, let, with an α-haloalkylacyle sulfide from Porael III R ₂ COSR ₁ Hal _wherein ; ■ JJ ₁ R ₁ and R ₂ dl · have the meaning given above and Hal is halogen, preferably Cl or Br, implements and, if in the Aueganger connection of? ormel Ua or Ub R ^ = R * means to introduce the subordinate a treatment with an alkylating agent attached 909887/1668 "- 15 - BATH ORIGINAL 4. Compounds of the formula Ia or Ib. ■ - ' 5ο 3-Acetylthioraetiiylthio-5-mathylthio-4-cyano-iaothiazole. 6ο 5 "acetylthlometliylthio-3-ynethylthio-4-cyano-ioothiazole 7.5 "" B3nzoylthiomethylthio-5-raothylthio-4-cyeri'-lBothiaeol. 8, 5- ^> Bsneoylthiomethylthio-3-ojethylthio-4-cyano-isothia! 5ol. 00 98 87/1 % ■ %%. : _BATH