Dithiazoldioxides and the use thereof as microbicides

Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...

Reexamination Certificate

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Details

C548S123000

Reexamination Certificate

active

06197799

ABSTRACT:

The invention relates to novel dithiazole dioxides, to processes for their preparation and to their use in crop protection and in the protection of materials.
Dithiazoles are already described, a biological activity has not been mentioned.
(see K. Dickoré, Lieb. Ann. Chem. 671, 135 (1964); U.S. Pat No. 3,345,374).
Surprisingly, it has now been found that the novel compounds of the general formula (I)
in which
R represents hydrogen or optionally substituted alkyl, alkenyl or alkinyl and
Ar represents optionally substituted aryl
are outstandingly suitable for protecting crops and materials.
The formula (I) provides a general definition of the compounds according to the invention. Preference is given to compounds of the formula (I) in which
R represents hydrogen, straight-chain or branched alkyl having 1 is 10 carbon atoms, straight-chain or branched alkenyl having 2 to 10 carbon atoms or straight-chain or branched alkinyl having 2 to 10 carbon atoms, which is optionally mono- to polysubstituted by identical or different substituents from the group consisting of halogen, alkoxy having 1 to 6 carbon atoms, halogenoalkoxy having 1 to 6 carbon atoms and 1 to 9 identical or different halogen atoms, alkylthio having 1 to 6 carbon atoms, halogenoalkylthio having 1 to 6 carbon atoms and 1 to 9 identical or different halogen atoms, acyl having 1 to 6 carbon atoms, acyloxy having 1 to 6 carbon atoms, (alkoxy)-carbonyl having 1 to 6 carbon atoms, amino, which is optionally substituted by identical or different substituents from the group consisting of alkyl and aryl, optionally substituted phenoxy, aryl, pyridyl or pyridyloxy, nitro or cyano, and
Ar represents aryl,
which is optionally mono- to pentasubstituted by halogen, alkyl having 1 to 10 carbon atoms, halogenoalkyl having 1 to 8 carbon atoms and 1 to 8 identical or different halogen atoms, alkoxy having 1 to 10 carbon atoms, halogenoalkoxy having 1 to 8 carbon atoms and 1 to 8 identical or different halogen atoms, alkylthio having 1 to 10 carbon atoms, halogenoalkylthio having 1 to 8 carbon atoms and 1 to 8 identical or different halogen atoms, amino, monoalkylamino having straight-chain or branched alkyl radicals having 1 to 6 carbon atoms, dialkylamino having identical or different, straight-chain or branched alkyl radicals having in each case 1 to 6 carbon atoms, cycloalkyl having 1 to 6 carbon atoms, methylenedioxy, difluoromethylenedioxy, chlorofluoromethylenedioxy, dichloromethylenedioxy, nitro or cyano.
Particular preference is given to compounds of the formula (I) in which
R represents hydrogen, straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched alkenyl having 2 to 8 carbon atoms or straight-chain or branched alkinyl having 2 to 8 carbon atoms, which is optionally mono- to tetrasubstituted by identical or different substitutents from the group consisting of fluorine, chlorine, alkoxy having 1 to 5 carbon atoms, halogenoalkoxy having 1 to 5 carbon atoms and 1 to 5 fluorine and/or chlorine atoms, alylthio having 1 to 5 carbon atoms, halogenoalkylthio having 1 to 5 carbon atoms and 1 to 5 fluorine and/or chlorine atoms, acyl having 1 to 5 carbon atoms, acyloxy having 1 to 5 carbon atoms, alkoxycarbonyl having 1 to 5 carbon atoms, amino which is optionally substituted by identical or different substituents from the group consisting of alkyl having 1 to 4 carbon atoms and phenyl, optionally substituted phenoxy, aryl, pyridyl, pyridyloxy, nitro or cyano, and
Ar represents phenyl which is optionally mono- to tetrasubstituted by fluorine, chlorine, alkyl having 1 to 8 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 6 fluorine and/or chlorine atoms, alkoxy having 1 to 8 carbon atoms, halogenoalkoxy having 1 to 6 carbon atoms and 1 to 6 fluorine and/or chlorine atoms, alkylthio having 1 to 8 carbon atoms, halogenoalkylthio having 1 to 6 carbon atoms and 1 to 6 fluorine and/or chlorine atoms, amino, monoalkylamino having alkyl radicals of 1 to 4 carbon atoms, dialkylamino having identical or different alkyl radicals having in each case 1 to 4 carbon atoms, cycloalkyl having 1 to 6 carbon atoms, methylenedioxy, difluoromethylenedioxy, chlorofluoromethylenedioxy, dichloromethylenedioxy, nitro or cyano.
Very particularly preferably, R represents hydrogen, methyl, ethyl, n- and i-propyl, n-, s-, i- and t-butyl, allyl and propargyl which are optionally substituted by fluorine and/or chlorine, methoxy or methylthio, and Ar represents phenyl which is optionally mono- to trisubstituted by fluorine, chlorine, methyl, ethyl, n- and i-propyl, n-, s-, i- and t-butyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, cyano and/or phenoxy.
Furthermore, it has been found that the compounds of the formula (I) are obtained when the salts of the general formula (II)
in which
R is as defined above and
M

represents an alkali metal or alkaline earth metal ion, in particular Na
+
, K
+
are reacted with diazonium salts of the general formula (III)
Ar−N=N

A

  (III)
in which
Ar is as defined above and
A

represents the anion of a mineral acid, in aqueous/alkaline solution, if appropriate in the presence of a catalyst.
Preferably, a solution of (II) is mixed with a base and, if appropriate, with a catalyst, and then with the diazonium salt solution (III). Preferred bases are alkali metal hydroxides such as, for example, potassium hydroxide or sodium hydroxide. Suitable catalysts are all catalysts which promote the exchange of the diazonium function against sulphur-containing radicals.
Preference is given to using Cu(I) salts or copper powder. During the addition of the diazonium salt solution, the temperature may be varied within a wide range. In general, the reaction is carried out between −30° C. and +60° C., preferably between −20° C. and +40° C. The preparation of the diazonium salt solution from anilines is carried out by methods known from the literature.
The salts of the general formula (II) can also be prepared by methods known from the literature (see references on p. 1). Either salts of the formula (II) which have been isolated in solid form, or solutions prepared in situ may be used.
The active compounds according to the invention have strong microbicidal action and can be employed for controlling unwanted microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials.
In the present context, the term industrial materials refers to non-living materials which have been prepared for use in industry. Examples are industrial materials which are to be protected by the active compounds according to the invention against microbial alteration or destruction, adhesives, sizes, paper and card, textiles, leather, wood, coating compositions and plastics articles, cooling lubricants and other materials which can be infested or decomposed by microorganisms. In the context of the materials to be protected mention may also be made of parts of production plants, for example cooling water circuits, which may be adversely affected by reproduction of microorganisms. Preferred industrial materials in the context of the present invention are adhesives, sizes, papers and cards, leather, wood, coating compositions, cooling lubricants and heat transfer fluids.
Examples of microorganisms which can bring about degradation or an alteration in the industrial materials are bacteria, fungi, yeasts, algae and slime organisms. The active compounds or compositions according to the invention preferably act against bacteria, fungi, especially mould fungi, and also against slime organisms and algae.
By way of example, mention may be made of microorganisms of the following genera:
Alternaria, such as
Altemaria tenuis,
Aspergillus, such as
Aspergillus niger,
Chaetomium, such as
Chaetomium globosum,
Coniophora, such as
Coniophora puteana,
Lentinus, such as
Lentinus tigrinus,
Penicillium, such as
Penicillium glaucum,
Polyporus, such as
Polyporus versicolor,
Aureobasidium, such as
Aureobasidium pu

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