Cycloalkyl amino-s-triazines and their use as selective agents against weeds and noxious grasses

A herbicidal compound, and a method of use therefor, for the selective treatment of useful plant cultures, having a broad spectrum of activity against weeds and noxious grasses in pre-emergence and/or post-emergence periods having the formula: ##STR1## wherein R.sub.1 is a straight-chain or branched-chain alkyl, alkoxy, alkoxyalkyl, or alkylol radical having less than a total of 15 oxygen and carbon atoms combined, or a hydrogen atom; (R) is a lower alkyl group; A is --CH.sub.2 -- or --CH.sub.2 CH.sub.2 --; with the proviso that n is 0-6, when A is --CH.sub.2 --, and n is 3-6, when A is --CH.sub.2 CH.sub.2 --; and wherein the substituents (R) on the cycloalkyl ring are identical to or different from each other.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to certain cycloalkyl amino-s-triazines and a 
process for using these compounds as selective agents against weeds and 
noxious grasses. 
2. Description of the Prior Art 
Numerous derivatives of the 6-methylthio-s-triazines are known wherein the 
2- and 4-positions on the triazine ring are substituted by alkyl amines. 
For example, the following such derivatives are known: 
Desmetryn(2-methylamino-4-isopropyl amino), Simetryn(2,4-bis-ethylamino), 
Ametryn(2-ethyl amino-4-isopropyl amino), Prometryn(2,4-bis-isopropyl 
amino), Methoprotryn(2-isopropyl amino-4(3-methoxypropyl amino)), 
MPMT(2,4-bis-(3-methoxypropyl amino)) and, Terbutryn(2-ethyl 
amino-4-tert.butyl amino). Terbutryn is probably the best-known compound 
of this series. 
Additionally, from the 6-ethylthio derivatives, 
Dipropetryn(2,4-bis-isopropyl amino) is also known. See R. Wegler, "Chemie 
der Pflanzenschutz-und Schadlingsbekampfungsmittel" (Chemistry of Plant 
Protection and Pest Control Agents), Springer Verlag: Berlin, Heidelberg, 
New York; Vol. 2, (1970, pp. 372-374) and Vol. 5 (1977, pp. 346-50). 
Most of these compounds may be used as soil and leaf herbicides against 
mono- and dicotyledons in the pre- and/or post-emergence periods. For 
example, Terbutryn is selective in winter grains, but is not always 
sufficiently effective against noxious grasses like slender foxtail and 
corn grass. Usually, good herbicidal qualities are also found in other 
6-methylthio-1,3,5-triazines having substituents from the lower 
alkyl-substituted amine group, however, it is not always desirable to have 
the limitation of selective herbicidal action. 
JA-OS No. 47 23 436 describes the 2-cyclohexyl amino derivatives of 
6-methylthio-s-triazine, 6-propylthio-s-triazine, and 
6-butylthio-s-triazine. These substances are described as having an 
unsatisfactory degree of selectivity between useful plants and noxious 
plants. 
Therefore, a need continues to exist for herbicidal compounds which exhibit 
a broad spectrum of activity against noxious grasses and dicotyledonous 
weeds, both in pre-emergence and post-emergence application, without 
causing damage to cultivated plants. 
SUMMARY OF THE INVENTION 
Accordingly, it is an object of this invention to provide a herbicidal 
compound which exhibits a broad spectrum of activity against noxious 
grasses and dicotyledonious weeds. 
It is also an object of the present invention to provide a herbicidal 
compound with a high degree of selectivity, which exhibits a broad 
spectrum of activity against noxious grasses and dicotyledonous weeds, 
both in pre-emergence and post-emergence application, without causing 
damage to cultivated plants. 
Moreover, it is also an object of this invention to provide a herbicidal 
composition and a method for using the same in the control of noxious 
grasses and weeds. 
According to the present invention, the foregoing and other objects are 
attained by providing a herbicidal compound for the selective treatment of 
useful plant cultures with a broad spectrum of activity against noxious 
grasses and weeds before and/or after sprouting of the seed, having the 
formula: 
##STR2## 
wherein R.sub.1 is a straight-chain or branched-chain alkyl, alkoxy, 
alkoxyalkyl or alkylol radical having less than a combined total of 15 
carbon and oxygen atoms, or a hydrogen atom; (R) is a lower alkyl radical; 
A is --CH.sub.2 -- or --CH.sub.2 --CH.sub.2 --; and n is 0-6, when A is 
--CH.sub.2 --, and n is 3-6, when A is --CH.sub.2 --CH.sub.2 --, whereby 
the substituents R on the cycloalkyl ring are identical to or different 
from each other. 
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
According to the present invention, a herbicidal compound having the 
formula: 
##STR3## 
wherein R.sub.1 is a straight-chain or branched-chain alkyl, alkoxy, 
alkoxyalkyl or alkylol radical having less than a combined total of 15 
carbon and oxygen atoms, or a hydrogen atom; (R) is a lower alkyl radical; 
A is --CH.sub.2 -- or --CH.sub.2 --CH.sub.2 --; and n is 0-6 when A is 
--CH.sub.2 --, and n is 3-6 when A is --CH.sub.2 --CH.sub.2 --, whereby 
the substituents R on the cycloalkyl ring are identical to or different 
from each other, exhibits a broad spectrum of activity against noxious 
grasses and dicotyledonous weeds, both in pre-emergence and post-emergence 
application. However, the compounds of the formula I also display a wide 
range of selectivity against numerous cultivated plants, and cause no 
damage thereto when used in the presence of the cultivated plants. 
It has been surprisingly discovered that in the alkylthio-s-triazines, the 
compounds which are substituted with a lower straight-chain or lower 
branched-chain alkylamine and an unsubstituted or alkyl-substituted 
cycloaliphatic amine exhibit an action against noxious grasses which is 
superior compared to that of the previously known compounds. The compounds 
of this invention also may also be seen to be effective as selective weed 
control agents. 
The herbicidal compounds of the formula I may be used individually. 
However, the herbicidal compounds of the present invention may also be 
used in combination. For example, herbicidal compounds having different 
R.sub.1 or (R) substituents, different groups for A, or different values 
of n, or even (R) substituents being substituted, may be used in 
combination with each other. 
The herbicidal compounds of the present invention may also be mixed, 
individually or in combination, with other herbicides, fungicides or 
growth regulators, and applied to particular cultivated plants. It is also 
possible to mix the herbicidal compounds with mineral fertilizers. This is 
most easily performed with fertilizer solutions. 
Auxiliary agents such as carrier agents, diluting agents, solvents, wetting 
agents, adhesion agents and dispersing and/or emulsifying agents are 
usually added to the active substances of this invention prior to 
application. The addition of these auxiliary agents improves the spraying 
and facilitates an even distribution of the active herbicidal compounds of 
this invention. 
The herbicidal compounds of formula I exhibit a broad spectrum of activity 
against noxious grasses and dicotyledonous weeds, both in pre-emergence 
and/or post-emergence application, while also displaying a wide range of 
selectivity against numerous cultivated plants. The herbicidal compounds 
of this invention are selective in the pre-emergence application and/or 
the post-emergence application in soybeans (17), cotton (4), rice (15), 
barley (8), and wheat (22), for example. See Table 2. 
In addition, the present compounds exhibit a broad spectrum of activity 
against noxious grasses, such as slender foxtail (1), corn grass (24), 
wild oats (6), and panic grass types, Echinocloa spp., Digitaris spp., 
Setaria spp., (cf. 10). Further, the present compounds also exhibit a 
broad spectrum of activity against dicotyledonous weeds, such as chickweed 
(20), goosegrass (13), camomile (11), white goosefoot (21), field mustard 
(2), dead nettle (18), amaranth (3), corn poppy (12), redshank (5) and 
field scabious (7). 
The herbicidal compounds of this invention may be applied to plant cultures 
in an amount ranging from 0.125 to 10 kg/ha. However, these compounds are 
preferably applied in an amount ranging from 0.5 to 2.5 kg/ha. The 
present compounds have a satisfactory herbicidal activity from at least 
0.25 kg/ha, calculated for the pure active herbicidal, and may be used in 
the plant cultures listed above without damage to the cultivated plants, 
despite their broad range of activity. 
The use of the compounds of the invention is not limited to the plant 
cultures or types listed above, but may also be applied to other plants. 
Depending on their concentration, the present herbicidal compounds may 
also be used for total weed control, e.g., in industrial parks, on track 
systems or on paths with or without trees. 
Moreover, the herbicidal compounds of this invention are also suitable for 
use in weed control in permanent cultures such as, cultures of forest 
trees, decorative wood, fruit, wine, citrus fruit, nuts, bananas, coffee, 
tea, rubber, oil palms, cocoa trees, berries and hops. 
In some plant types, several of the herbicidal compounds of the present 
invention inhibit the plant height without reducing the yield. Therefore, 
they may be also be employed as growth regulators. Also, several of the 
new compounds may also be used as defoliants, dessicants, weed killers and 
germination inhibitors. 
The compounds of formula I may be produced according to known methods by 
reacting cyanuric chloride, preferably in a solvent or a solvent mixture 
such as acetone, acetone-water, dioxane, dioxane-water, tetrahydrofuran or 
dimethylformamide, with the corresponding amines at a temperature 
appropriate for each instance. The temperature is generally in the range 
of -30.degree. C. to 50.degree. C. 
Additionally, known methods may be used for selective substitution on the 
1,3,5-triazine ring. Also, the chlorine derivatives obtained, initially, 
may be reacted with sodium thiomethylate in isopropanol or other solvents 
to produce the corresponding methylthio-s-1,3,5-triazine derivative.