Combating fungi with N-alkyl-carbamic acid 1,1,2-trimethyl-5-substituted-indan-4-yl esters

Fungicidally active N-alkyl-carbamic acid 1,1,2-trimethyl-5-substituted-indan-4-yl esters of the formula ##STR1## in which R.sup.1 is an alkyl group, PA1 R.sup.2 is an alkyl or aralkyl group, PA1 R.sup.3 is a hydrogen atom, an alkyl group or a halogen atom, and PA1 R.sup.4 is a hydrogen atom, an alkyl group, a halogen atom, or an alkoxy or alkylmercapto group.

The present invention provides novel fungicidally active N-alkyl-carbamic 
acid 1,1,2-trimethyl-5-substituted-indan-4-yl esters of the formula 
##STR2## 
in which R.sup.1 is an alkyl group, 
R.sup.2 is an alkyl or aralkyl group, 
R.sup.3 is a hydrogen atom, an alkyl group or a halogen atom, and 
R.sup.4 is a hydrogen atom, an alkyl group, a halogen atom, or an alkoxy or 
alkylmercapto group. 
Surprisingly, the particular indan-4-yl N-alkylcarbamates of the present 
invention, which, in contrast to compounds of similar structure which are 
already known, have, as a common criterion, in each case a methyl group in 
the 1-, 1- and 2-positions on the indane ring system, exhibit a 
considerably more powerful fungicidal action than the compounds known from 
the state of the art. 
Preferred compounds of the present invention are those in which R.sup.1 
represents an alkyl group with 1 to 4 carbon atoms, R.sup.2 represents an 
alkyl group with 1 to 4 carbon atoms or a benzyl radical, R.sup.3 
represents a hydrogen or halogen atom or a methyl group and R.sup.4 
represents a hydrogen or halogen atom, an alkyl group with 1 to 4 carbon 
atoms or a methylmercapto group. 
Compounds of the present invention which are of special interest because of 
their good fungicidal activity are, in particular, those in which R.sup.1 
and R.sup.2 denote methyl groups, R.sup.3 denotes a hydrogen or chlorine 
atom and R.sup.4 denotes a hydrogen atom or a methyl group. 
N-methylcarbamic acid 1,1,2,5-tetramethyl-indan-4-yl ester may be 
mentioned as an example of such a compound of preferred interest (see 
Example 1). 
According to the present invention there is further provided a process for 
the production of a compound of the present invention characterized in 
that: 
(a) a 4-hydroxy-indane of the general formula 
##STR3## 
in which: R.sup.2, R.sup.3 and R.sup.4 have the meaning indicated above, 
is reacted with an alkyl isocyanate of the general formula 
EQU OCN--R.sup.1 (III) 
in which 
R.sup.1 has the meaning indicated above, or, 
(b) a 4-hydroxy-indane of the general formula (II) is converted into the 
corresponding chlorocarbonic acid ester with an excess of phosgene in a 
first stage, and the resulting ester is reacted in a second stage with an 
alkylamine, or 
(c) a 4-hydroxy-indane of the general formula (II) is reacted with an 
equivalent amount of phosgene to give the corresponding bis-(indanyl) 
carbonate, in a first stage, and this product is split with alkylamine in 
a second stage. 
The course of the reaction in the preparation of the compounds according to 
the invention can be illustrated by the following examples: 
If 4-hydroxy-1,1,2,5-tetramethyl-indane and methyl isocyanate are used as 
starting substances, the course of the reaction in process variant (a) is 
illustrated by the following equation: 
##STR4## 
If 4-hydroxy-1,1,2,5-tetramethyl-indane, phosgene and methylamine are used 
as starting substances, the course of the reaction in process variant (b) 
is illustrated by the following equation: 
##STR5## 
If 4-hydroxy-1,1,2,5-tetramethyl-indane, phosgene and methylamine are used 
as starting substances, the course of the reaction in process variant (c) 
is illustrated by the following equation: 
##STR6## 
Particularly preferred 4-hydroxy-indanes of formula (II) to be used as 
starting compounds for the processes of the present invention are those in 
which R.sup.2, R.sup.3 and R.sup.4 have the meanings indicated above in 
the case of preferred and particularly preferred compounds of the present 
invention. 
The preparation of the starting substances of the formula (II) is known 
(compare U.S. patent specification No. 3,057,929). It is effected, for 
example, by isomerizing the corresponding chromanes in the presence of 
Friedel-Crafts catalysts. Thus, for example, 
4-hydroxy-1,1,2,5-tetramethyl-indane is producible by treatment of 
2,2,3,8-tetramethyl-chromane with aluminum-III chloride. 
The chromanes used for the preparation of the 4-hydroxy-indanes of the 
formula (II) can be obtained by reacting phenols, such as o-cresol or 
2,4-dimethylphenol, with isoprene (compare Houben-Weyl, "Methoden der 
organischen Chemie" ("Methods of Organic Chemistry"), 4th edition, Volume 
6/1c, page 987-989 (1976)). 
Compounds of the formula (II) in which R.sup.4 represents halogen can be 
obtained by halogenating the corresponding substituted 4-hydroxy-indanes. 
Thus, for example, 7-bromo-4-hydroxy-1,1,2,5-tetramethyl-indane is 
producible by bromination of 4-hydroxy-1,1,2,5-tetramethyl-indane in 
glacial acetic acid (see Houben-Weyl, "Methoden der organischen Chemie" 
("Methods of Organic Chemistry"), 4th edition, Volume 5/4, page 260 et 
seq. (1960)). 
Compounds in which R.sup.4 represents thioalkyl can be prepared by reacting 
substituted 4-hydroxy-indanes with a free 7-position with a dialkyl 
disulphide in the presence of a sulphonic acid (see Belgian patent 
specification No. 627,306), or by thiocyanates of the 4-hydroxy-indanes 
with thiocyanogen and subsequently saponifying the product (see H. P. 
Kaufmann and Weber, Arch. Pharm. 267, 192 (1929); and Kohn, M. 58, 73, 78 
(1931)). Thus, for example, 
7-methyl-thio-4-hydroxy-1,1,2,5-tetramethyl-indane is producible from 
4-hydroxy-1,1,2,5-tetramethyl-indane and thiocyanogen. 
The starting substances also required for the preparation of the compounds 
of the formula (I) according to the invention, that is to say phosgene and 
alkyl isocyanate for process variant (a) and phosgene and alkylamine for 
process variant (b) and (c), are generally known. Those alkyl isocyanates 
and alkylamines which contain an alkyl radical with 1 to 4 carbon atoms 
are preferably used. Examples which may be mentioned here are: methyl 
isocyanate, ethyl isocyanate and butyl isocyanate, and the following 
amines: methylamine, ethylamine, isopropylamine, butylamine and 
isobutylamine. 
The compounds of the formula (I) according to the invention can be prepared 
by process variants (a), (b) and (c) indicated above. 
The reaction in process variant (a) can be carried out in inert solvents. 
Examples of suitable solvents for this are hydrocarbons, such as benzine 
and benzene, chlorinated hydrocarbons, such as chlorobenzene, and also 
ethers, such as dioxane, or mixtures of these solvents. The reaction is 
generally catalyzed by adding a tertiary amine, for example triethylamine 
or diazobicyclooctane. 
The reaction temperatures can be varied within a substantial range. 
However, the reaction is in general carried out between 0.degree. and 
150.degree. C., preferably between 20.degree. and 110.degree. C. 
If the reaction is carried out according to process variant (b), the 
4-hydroxy-indane of the formula (II) is converted, in the first stage, 
into the chlorocarbonic acid ester with an excess of phosgene, preferably 
in the presence of inert solvents, such as aromatic, optionally 
chlorinated hydrocarbons, and preferably benzene, toluene, xylene or 
chlorobenzene. The hydrochloric acid formed is bonded by dropwise addition 
of a base, preferably sodium hydroxide, and the pH value of the reaction 
solution is thus kept below 7. The reaction is in general carried out at a 
temperature between -20.degree. and +20.degree. C., preferably between 
-10.degree. and +10.degree. C. In the second stage, the chlorocarbonic 
acid ester is reacted, either after isolation or directly in the reaction 
solution obtained, with an equivalent amount of an alkylamine. This 
reaction is likewise preferably carried out in the presence of inert 
solvents, such as aromatic and aliphatic, optionally chlorinated 
hydrocarbons, such as benzene, chlorobenzene, benzine or carbon 
tetrachloride, or ethers, such as dioxane. The reaction temperatures can 
again be varied within a certain range; the reaction is in general carried 
out between -20.degree. and +20.degree. C., preferably between -10.degree. 
and +10.degree. C. 
Finally, if the reaction is carried out according to process variant (c), 
the 4-hydroxy-indane of the formula (II) is reacted, in the first stage, 
with an equivalent amount of phosgene to give the bis-(indanyl) carbonate. 
The reaction is preferably carried out in inert solvents, such as aromatic 
hydrocarbons, for example benzene and toluene, the hydrochloric acid 
formed being bonded by adding a base, preferably an alkali metal 
hydroxide. The pH value of the reaction solution should be approximately 
8. The reaction temperature can be varied within a substantial range, and 
is in general between 0.degree. and 100.degree. C., preferably between 
+20.degree. and +60.degree. C. The carbonate formed in the first stage is 
then split with an alkylamine. This reaction is preferably carried out 
without a solvent. However, it can also be carried out in solvents. The 
reaction temperatures are generally between -30.degree. and +40.degree. 
C., preferably between -10.degree. and +20.degree. C. 
The active compounds according to the invention exhibit a powerful 
microbicidal action and can be employed in practice for combating 
undesired microorganisms. 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. 
The compounds of the formula (I) according to the invention have, in 
particular, a good action against Fusicladium dendriticum, the apple scab 
causative organism. They also have an activity against Pellicularia 
sasakii in rice plants. 
The active compounds can be converted into the customary formulations, such 
as solutions, emulsions, powders, suspensions, dusting agents, foams, 
pastes, soluble powders, granules, aerosols, suspension-emulsion 
concentrates, seed-treatment powders, natural and synthetic materials 
impregnated with active compound, very fine capsules in polymeric 
substances, coating compositions for use on seed, and formulations used 
with burning equipment, such as fumigating cartridges, fumigating cans and 
fumigating coils, 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 or metal phthalocyanine dyestuffs, 
and trace nutrients, such as salts of 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 by weight. 
The active compounds according to the invention can be present in the 
formulations or in the various use forms as a mixture with other known 
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 are 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 0.001 to 50 g per 
kilogram of seed, preferably 0.01 to 10 g, are generally required. 
For the treatment of soil, active compound concentrations of 0.00001 to 
0.1% by weight, preferably 0.0001 to 0.02%, are generally required 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 of liquefied 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 combating fungi which 
comprises applying 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 is 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.

PREATIVE EXAMPLES 
EXAMPLE 1 
##STR7## 
600 g (about 3.16 moles) of 4-hydroxy-1,1,2,5-tetramethyl-indane, 10 ml of 
triethylamine and 194 g (about 3.40 moles) of methyl isocyanate were 
dissolved in 3.0 liters of ligroin at room temperature and the solution 
was then warmed to 80.degree. C. and subsequently stirred at this 
temperature for about 20 hours. On cooling, the product crystallized out 
from 55.degree. C. After filtering off and drying, the product was 
recrystallized from ligroin. 
737 g of N-methyl-carbamic acid 1,1,2,5-tetramethylindan-4-yl ester of 
melting point 109.5.degree. to 110.5.degree. C. were obtained. 
The yield was 94.5% of theory. 
EXAMPLE 2 
##STR8## 
34 g of 4-hydroxy-1,1,2,5,7-pentamethyl-indane, 14.3 g of methyl isocyanate 
and a few drops of triethylamine were dissolved in 102 ml of ligroin and 
the solution was stirred under slight reflux (about 70.degree. C.) 
overnight. After cooling to 30.degree. C., the mixture was stirred with 40 
ml of water and the colorless crystals were filtered off and dried. 
Recrystallization from ligroin and toluene gave 27.7 g of 
N-methyl-carbamic acid 1,1,2,5,7-pentamethylindan-4-yl ester of melting 
point 130.5.degree.-131.degree. C. 
The following compounds of the general formula 
##STR9## 
were obtained in a corresponding manner: 
______________________________________ 
Compound Melting point 
No. R.sup.1 R.sup.2 R.sup.3 
R.sup.4 
(.degree.C.) 
______________________________________ 
3 CH.sub.3 
CH.sub.3 Cl H 156,5-158,8 
4 C.sub.2 H.sub.5 
CH.sub.3 H H 64-65 
5 i-C.sub.3 H.sub.7 
CH.sub.3 H H 77-78 
6 CH.sub.3 
CH.sub.3 H Br 127-128 
7 CH.sub.3 
CH.sub.3 H S--CH.sub.3 
104,5-106 
8 CH.sub.5 
CH.sub.2 --C.sub.6 H.sub.5 
H Cl 125,5-126 
9 CH.sub.3 
C.sub.2 H.sub.5 
H H 93-94 
10 CH.sub.3 
CH.sub.3 H Cl 105 
11 CH.sub.3 
CH.sub.3 CH.sub.3 
H 116 
______________________________________ 
The fungicidal activity of the compounds of this invention is illustrated 
by the following example wherein the compounds according to the present 
invention are each identified by the number (given in brackets) from 
Examples 1 and 2: 
EXAMPLE 3 
Fusicladium test (apple)/protective 
Solvent: 4.7 parts by weight of acetone 
Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether 
Water: 95 parts by weight 
The amount of active compound required for the desired concentration of the 
active compound in the spray liquid was mixed with the stated amount of 
solvent, and the concentrate was diluted with the stated amount of water 
which contained the stated additions. 
Young apple seedlings in the 4 to 6 leaf stage were sprayed with the spray 
liquid until dripping wet. The plants remained in a greenhouse for 24 
hours at 20.degree. C. and at a relative atmospheric humidity of 70%. They 
were then inoculated with an aqueous conidium suspension of the apple scab 
causative organism (Fusicladium dendriticum) and incubated for 18 hours in 
a humidity chamber at 18.degree. to 20.degree. C. and at a relative 
atmospheric humidity of 100%. 
The plants then again came into a greenhouse for 14 days. 
15 days after inoculation, the infection of the seedlings was determined. 
The assessment data were converted to percent infection. 0% denoted no 
infection and 100% denoted that the plants were totally infected. 
In this test, for example, the following compounds exhibited a superior 
action compared with the prior art: compounds (4), (2), (9), (3), (6), (7) 
and (1). 
It will be understood that the specification and examples are illustrative 
but not limitative of the present invention and that other embodiments 
within the spirit and scope of the invention will suggest themselves to 
those skilled in the art.