Combating fungi with new N-sulphenylated allophanates

N-sulphenylated allophanates of the formula ##STR1## in which R.sup.1 represents a trihalogenomethyl radical, PA1 R.sup.2 represents an aliphatic, cycloaliphatic, araliphatic or aromatic radical which may in each case be optionally substituted, PA1 R.sup.3 represents an aliphatic, cycloaliphatic, araliphatic or aromatic radical which may in each case be optionally substituted and PA1 X represents oxygen or sulphur, which possess fungicidal activity.

The invention relates to certain new N-sulphenylated allophanates, to a 
process for their preparation and to their use as fungicides. 
It has already been known for a long time that N-trihalogenomethylthio 
compounds can be used as fungicides in agriculture. Thus, for example, 
N-(trichloromethylthio)-tetrahydrophthalimide and 
N,N-dimethyl-N'-phenyl-N'-fluorodichloromethylthio)-sulphamide are 
employed in practice for combating fungal diseases in fruit growing and 
viticulture (see German Pat. No. 887,506 and Angew. Chem. 76, 807 (1964)). 
However, their action in tropical crops, for example in rice, is 
inadequate. The same is true of the zinc salts of 
alkylene-bis-dithiocarbamic acids, which have also already been known for 
a long time and otherwise have worldwide importance as fungicides (see, 
for example, R. Wegler, "Chemie der Pflanzenschutz- und 
Schadlingsbekampfungsmittel" ("Chemistry of Plant Protection Agents and 
Agents for Combating Pests"), Volume 2, page 65, Springer-Verlag, 
Berlin/Heidelberg/New York (1970)). 
The present invention now provides, as new compounds, the N-sulphenylated 
allophanates of the general formula 
##STR2## 
in which 
R.sup.1 represents a trihalogenomethyl radical, 
R.sup.2 and R.sup.3, which may be identical or different, each represent an 
aliphatic, cycloaliphatic, araliphatic or aromatic radical which may in 
each case be optionally substituted and 
X represents oxygen or sulphur. 
The invention also provides a process for the preparation of a compound of 
the general formula (I), in which 
(a) an isocyanate of the general formula 
##STR3## 
in which 
R.sup.1 and R.sup.2 have the abovementioned meanings, is reacted with a 
hydroxy or mercapto compound of the general formula 
EQU H--X--R.sup.3 (III), 
in which 
R.sup.3 and X have the abovementioned meanings, if appropriate in the 
presence of a diluent and/or of a catalyst, or 
(b) a sulphenic acid amide of the general formula 
##STR4## 
in which 
R.sup.1 and R.sup.2 have the abovementioned meanings, is reacted with an 
acyl isocyanate of the general formula 
EQU OCN--CO--X--R.sup.3 (V), 
in which 
R.sup.3 and X have the abovementioned meanings, if appropriate in the 
presence of a diluent and/or of a catalyst. 
The N-sulphenylated allophanates of the formula (I) have powerful 
fungicidal properties. 
Surprisingly, the N-sulphenylated allophanates according to the invention 
exhibit a considerably more powerful fungicidal action, especially in rice 
crops, than the compounds known from the state of the art. The substances 
according to the invention thus represent an enrichment of the art. 
The formula (I) provides a general definition of the N-sulphenylated 
allophanates according to the invention. Preferably in this formula, 
R.sup.1 represents trichloromethyl or fluorodichloromethyl, 
R.sup.2 represents an optionally halogenated, saturated or unsaturated 
aliphatic radical which has up to 6 carbon atoms and can optionally be 
interrupted by one or more hetero-atoms (such as oxygen or nitrogen); a 
cycloaliphatic radical with 5 to 8 carbon atoms; an araliphatic radical 
which has 7 to 10 carbon atoms and of which the aromatic part can 
optionally carry one or more substituents selected from halogen, nitro 
groups, trifluoromethyl groups, alkyl groups and alkoxy groups with up to 
4 carbon atoms; or an aromatic radical which has 6 to 10 ring carbon atoms 
and can optionally carry one or more substituents selected from halogen, 
nitro groups, cyano groups, trifluoromethyl groups and alkyl groups, 
alkylthio groups and alkoxy groups with in each case up to 4 carbon atoms, 
and 
R.sup.3 represents an optionally halogenated, saturated or unsaturated 
aliphatic radical which has up to 8 carbon atoms and can be interrupted by 
one or more hetero-atoms (such as oxygen and/or sulphur and/or nitrogen); 
a cycloaliphatic radical which has 5 to 7 carbon atoms and is optionally 
substituted by alkyl with up to 4 carbon atoms; an araliphatic radical 
which has 7 to 10 carbon atoms and of which the aromatic part can 
optionally carry one or more substituents selected from halogen, nitro 
groups, trifluoromethyl groups and alkyl groups and alkoxy groups with in 
each case up to 4 carbon atoms; or an aromatic radical which has 6 to 10 
ring carbon atoms and can optionally carry one or more substituents 
selected from halogen, nitro groups, cyano groups, trifluoromethyl groups 
and alkyl groups, alkylthio groups and alkoxy groups with in each case up 
to 4 carbon atoms. Very particularly preferred compounds of the general 
formula (I) are those in which 
R.sup.1 represents trichloromethyl or fluorodichloromethyl, 
R.sup.2 represents an alkyl, alkenyl or halogenoalkyl group with in each 
case up to 4 carbon atoms, cyclopentyl, cyclohexyl or a benzyl or phenyl 
radical that optionally carries one or more substituents selected from 
halogen, nitro groups, methyl groups and trifluoromethyl groups, and 
R.sup.3 represents an alkyl, alkenyl or halogenoalkyl group with in each 
case up to 4 carbon atoms, cyclopentyl, cyclohexyl or a benzyl or phenyl 
radical that optionally carries one or more substituents selected from 
halogen, nitro groups, methyl groups, methoxy groups, methylthio groups, 
cyano groups and trifluoromethyl groups. 
In the preferred and particularly preferred compounds of the formula (I), 
X represents oxygen or sulphur. 
If, for the preparation of a compound of the formula (I), 
N-(fluorodichloromethylthio)-N-(methyl)-carbamoyl isocyanate and phenol 
are used as starting compounds according to process variant (a) or 
N-(fluorodichloromethylthio)-N-methylamide and phenoxycarbonyl isocyanate 
are used as starting compounds according to process variant (b), the 
course of the reaction can be represented by the following equation: 
##STR5## 
The formula (II) provides a general definition of the isocyanates to be 
used as starting substances for process variant (a). In this formula, 
R.sup.1 and R.sup.2 preferably have those meanings which have already been 
mentioned as preferred for these substituents in the description of the 
substances of the formula (I). 
The isocyanates of the formula (II) have not previously been described in 
the literature; they are, however, the subject of German Patent 
Application P.3049488.5 of 30.12.1980 [Le A 20 570]. They can be prepared 
by a process in which trihalogenomethanesulphenamides of the general 
formula 
##STR6## 
in which 
R.sup.1 and R.sup.2 have the abovementioned meanings, are reacted with 
chlorocarbonyl isocyanate of the formula 
EQU Cl--CO--NCO (VI), 
if appropriate in the presence of a diluent, in the temperature range 
between 0.degree. and 150.degree. c. (see also the preparative examples 
hereinbelow). 
Suitable isocyanates of the formula (II) are the carbonyl-isocyanates of 
N-(trichloromethylsulphenyl)-, N-fluorodichloromethylsulphenyl)- and 
N-(trifluoromethyl-sulphenyl)-methylamine, -isopropylamine, -allylamine, 
-2-methoxyethylamine, -tert.-butylamine, -cyclopentylamine, 
-cyclohexylamine, -benzylamine, -4-chlorobenzylamine, -phenethylamine, 
-aniline, -3-trifluoromethylaniline, -3,4-dichloroaniline, -3-anisidine, 
-3-toluidine, -2-aminopyridine and -2-aminofuran. 
The formula (III) provides a definition of the hydroxy or mercapto 
compounds also required for process variant (a). In this formula, X and 
R.sup.3 preferably have those meanings which have already been mentioned 
as preferred for these substituents in the description of the compounds of 
the formula (I). 
Suitable compounds of the formula (III) are methanol, ethanol and 
isopropanol, and also allyl, isobutyl, cyclohexyl, 4-methylcyclohexyl, 
benzyl, phenethyl and 4-chlorobenzyl alcohol, as well as phenol, 
4-chlorophenol, 4-cresol, hydroquinone monomethyl ether, methylmercaptan, 
butylmercaptan, thiophenol and 4-methylthiophenol. 
The compounds of the formula (III) are generally known compounds of organic 
chemistry. 
The formula (IV) provides a general definition of the sulphenic acid amides 
to be used as starting substances for process variant (b). In this 
formula, R.sup.1 and R.sup.2 preferably have those meanings which have 
already been mentioned as preferred for these substituents in the 
description of the compounds of the formula (I). The compounds can be 
obtained by reaction of the corresponding primary amines with 
trihalogenomethanesulphenic acid chloride, for example in toluene as a 
solvent, in the temperature range between +20.degree. and 30.degree. C. 
(see Chem. Abstr. 60, 5519 (1964)). 
The formula (V) provides a definition of the acyl isocyanates also required 
as starting substances for process variant (b). In this formula, X and 
R.sup.3 preferably have those meanings which have already been mentioned 
as preferred for these radicals in the description of the compounds of the 
formula (I). The acyl isocyanates of the formula (V) are known, or they 
can be prepared in a known manner from alcohols, phenols or the 
corresponding thiol compounds and chlorocarbonyl isocyanate (see Angew. 
Chem. 89, 789 (1977)). The compounds of the formula (III) listed above can 
be used as the alcohols and phenols or the corresponding thiol compounds 
in this reaction. 
Possible diluents for the reactions in process variants (a) and (b) are 
inert organic solvents. These include, as preferences, hydrocarbons, such 
as benzene or toluene, ethers, such as diethyl ether or tetrahydrofuran, 
and chlorinated hydrocarbons, such as chloroform or carbon tetrachloride. 
For the purpose of a more rapid and a complete course of the reaction, the 
reactions in process variants (a) and (b) can be carried out in the 
presence of a basic catalyst, for example an amine. Small amounts of 
triethylamine are preferably used. 
The reaction temperatures can be varied within a substantial range in 
process variants (a) and (b). In general, the reaction is carried out at 
between -10.degree. and +100.degree. C., preferably between +10.degree. 
and 50.degree. C. 
In carrying out process variants (a) and (b), 1 mol of the compound of the 
formula (III) or (V) respectively is employed per mol of the compound of 
the formula (II) or (IV), respectively. It is expedient for the 
isocyanates of the formula (II) or the acyl isocyanates of the formula (V) 
to be initially introduced and for the compounds of the formula (III) (in 
the case of process variant (a)) or of the formula (IV) (in the case of 
process variant (b)) to be added, with stirring. The end products are 
isolated in the generally customary manner; the end products are in most 
cases non-distillable oils or crystals. 
The active compounds according to the invention exhibit a powerful 
microbicidal action and can be employed in practice for combating 
undesired micro-organisms. The active compounds are suitable for use as 
plant protection agents. 
Fungicidal agents in plant protection are employed for combating 
Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, 
Ascomycetes, Basidiomycetes and Deuteromycetes. 
The good toleration, by plants, of the active compounds, at the 
concentrations required for combating plant diseases, permits treatment of 
above-ground parts of plants, of vegetative propagation stock and seeds, 
and of the soil. 
As plant protection agents, the active compounds according to the invention 
can be used with particularly good success for combating Pyricularia 
oryzae, the causative organism of Brusone disease, and Pellicularia 
sasakii, the causative organism of leaf sheath blight in rice. Good 
successes are also achieved against grey mould (Botrytis cinerea) and 
against apple scab (Venturia inaequalis). 
The active compounds can be converted into the customary formulations, such 
as solutions, emulsions, suspensions, powders, foams, pastes, granules, 
aerosols, natural and synthetic materials impregnated with active 
compound, very fine capsules in polymeric substances and in coating 
compositions for seed, and formulations used with burning equipment, such 
as fumigating cartridges, fumigating cans, fumigating coils and the like, 
as well as ULV cold mist and warm mist formulations. 
These formulations may be produced in known manner, for example by mixing 
the active compounds with extenders, that is to say liquid or liquefied 
gaseous or solid diluents or carriers, optionally with the use of 
surface-active agents, that is to say emulsifying agents and/or dispersing 
agents and/or foam-forming agents. In the case of the use of water as an 
extender, organic solvents can, for example also be used as auxiliary 
solvents. 
As liquid diluents or carriers, especially solvents, there are suitable in 
the main, aromatic hydrocarbons, such as xylene, toluene or alkyl 
naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, 
such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic 
or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example 
mineral oil fractions, alcohols, such as butanol or glycol as well as 
their ethers and esters, ketones, such as acetone, methyl ethyl ketone, 
methyl isobutyl ketone or cyclohexanone, or strongly polar solvents, such 
as dimethylformamide and dimethylsulphoxide, as well as water. 
By liquefied gaseous diluents or carriers are meant liquids which would be 
gaseous at normal temperature and under normal pressure, for example 
aerosol propellants, such as halogenated hydrocarbons as well as butane, 
propane, nitrogen and carbon dioxide. 
As solid carriers there may be used ground natural minerals, such as 
kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or 
diatomaceous earth, and ground synthetic minerals, such as 
highly-dispersed silicic acid, alumina and silicates. As solid carriers 
for granules there may be used crushed and fractionated natural rocks such 
as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic 
granules of inorganic and organic meals, and granules of organic material 
such as sawdust, coconut shells, corn cobs and tobacco stalks. 
As emulsifying and/or foam-forming agents there may be used non-ionic and 
anionic emulsifiers, such as polyoxyethylene-fatty acid esters, 
polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol 
ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as 
albumin hydrolysis products. Dispersing agents include, for example, 
lignin sulphite waste liquors and methyl-cellulose. 
Adhesives such as carboxymethylcellulose and natural and synthetic polymers 
in the form of powders, granules or latices, such as gum arabic, polyvinyl 
alcohol and polyvinyl acetate, can be used in the formulations. 
It is possible to use colorants such as inorganic pigments, for example 
iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such 
as alizarin dyestuffs, azo dyestuffs and metal-phthalocyanine dyestuffs, 
and trace nutrients such as salts or iron, manganese, boron, copper, 
cobalt, molybdenum and zinc. 
The formulations in general contain from 0.1 to 95 percent by weight of 
active compound, preferably from 0.5 to 90 percent. 
The active compounds according to the invention can be present in the 
formulations or in the various use forms as a mixture with other active 
compounds, such as fungicides, bactericides, insecticides, acaricides, 
nematicides, herbicides, bird repellents, growth factors, plant nutrients 
and agents for improving soil structure. 
The active compounds can be used as such or in the form of their 
formulations or the use forms prepared therefrom by further dilution, such 
as ready-to-use solutions, emulsions, suspensions, powders, pastes and 
granules. They may be used in the customary manner, for example by 
watering, immersion, spraying, atomizing, misting, vaporizing, injecting, 
forming a slurry, brushing on, dusting, scattering, dry dressing, moist 
dressing, wet dressing slurry dressing or encrusting. 
Especially in the treatment of parts of plants, the active compound 
concentrations in the use forms can be varied within a substantial range. 
They are, in general, between 1 and 0.0001% by weight, preferably between 
0.5 and 0.001%. 
In the treatment of seed, amounts of active compound of, in general, 0.001 
to 50 g, preferably 0.01 to 10 g, are employed per kilogram of seed. 
For the treatment of soil, active compound concentrations of, in general, 
0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are employed at the 
place of action. 
The present invention also provides a fungicidal composition containing as 
active ingredient a compound of the present invention in admixture with a 
solid or liequefied gaseous diluent or carrier or in admixture with a 
liquid diluent or carrier containing a surface-active agent. 
The present invention also provides a method of combating fungi which 
comprises apply to the fungi, or to a habitat thereof, a compound of the 
present invention alone or in the form of a composition containing as 
active ingredient a compound of the present invention in admixture with a 
diluent or carrier. 
The present invention further provides crops protected from damage by fungi 
by being grown in areas in which immediately prior to and/or during the 
time of the growing a compound of the present invention was applied alone 
or in admixture with a diluent or carrier. 
It will be seen that the usual methods of providing a harvested crop may be 
improved by the present invention.