Herbicidal N-2-(nitro-5-phenoxy-phenyl)-aminoalkylphosphonic acid and esters

The present invention relates to (2-nitro-5-aryloxyphenylamino)alkylphosphonic, -alkylphosphinic and -alkylphosphonous acid derivatives of the general formula I ##STR1## wherein X is halogen, CF.sub.3, NO.sub.2, CN, CONH.sub.2 or CSNH.sub.2, PA1 Y is nitrogen or --CH.dbd., PA1 R is hydrogen, C.sub.1 -C.sub.4 alkyl or aralkyl containing 1 to 4 carbon atoms in the alkyl moiety, PA1 R.sub.1 is C.sub.1 -C.sub.4 alkyl, PA1 R.sub.2 is C.sub.1 -C.sub.4 alkyl, phenyl or --PO(OR.sub.6).sub.2, PA1 R.sub.3 is hydrogen or C.sub.1 -C.sub.4 alkyl, PA1 R.sub.4 is hydrogen, C.sub.1 -C.sub.4 alkyl or a cation, PA1 R.sub.5 is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, hydroxyl or an --O-cation group, PA1 R.sub.6 is hydrogen or C.sub.1 -C.sub.4 alkyl, PA1 m is a value from 0 to 3, PA1 n is 0 or 1, PA1 p is a value from 0 to 3, and PA1 q is 0 or 1, with the proviso that R.sub.1 and R.sub.3 taken together may also be an unsubstituted or substituted C.sub.1 -C.sub.3 alkylene chain and at least one of the symbols n, p and q is a value different from 0. These compounds have useful herbicidal properties.

The present invention relates to 
(2-nitro-5-aryloxyphenylamino)alkylphosphonic, -alkylphosphinic and 
-alkylphosphonous acid derivatives, to the preparation thereof, to 
herbicidal and growth regulating compositions which contain these 
compounds, and to the use of said compounds or of compositions containing 
them for controlling undesired plant growth and for influencing plant 
growth. 
The novel compounds of this invention have the general formula I 
##STR2## 
wherein X is halogen, CF.sub.3, NO.sub.2, CN, CONH.sub.2 or CSNH.sub.2, 
Y is nitrogen or --CH.dbd., 
R is hydrogen, C.sub.1 -C.sub.4 alkyl or aralkyl containing 1 to 4 carbon 
atoms in the alkyl moiety, 
R.sub.1 is C.sub.1 -C.sub.4 alkyl, 
R.sub.2 is C.sub.1 -C.sub.4 alkyl, phenyl or --PO(OR.sub.6).sub.2, 
R.sub.3 is hydrogen or C.sub.1 -C.sub.4 alkyl, 
R.sub.4 is hydrogen, C.sub.1 -C.sub.4 alkyl or a cation, 
R.sub.5 is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, 
C.sub.1 -C.sub.4 alkoxy, hydroxyl or an --O--cation group, 
R.sub.6 is hydrogen or C.sub.1 -C.sub.4 alkyl, 
m is a value from 0 to 3, 
n is 0 or 1, 
p is a value from 0 to 3, and 
q is 0 or 1, 
with the proviso that R.sub.1 and R.sub.3 taken together may also be an 
unsubstituted or substituted C.sub.1 -C.sub.3 alkylene chain and at least 
one of the symbols n, p and q is a value different from 0. 
In the definition of the formula I, alkyl generally denotes methyl, ethyl, 
n-propyl, isopropyl, butyl and the isomers thereof. Alkyl will also be 
understood as meaning the moiety of another radical, e.g. aralkyl, 
haloalkyl or alkoxy. Halogen denotes in general fluorine, chlorine, 
bromine or iodine, and is preferably fluorine and, most preferably, 
chlorine. 
Representative examples of aralkyl radicals are phenylalkyl such as benzyl, 
2-phenylethyl, 3-phenylpropyl, 1-phenylethyl, 2-phenylpropyl, 
1-phenylpropyl, with benzyl being preferred. 
Phenyl and arylkyl radicals are unsubstituted or substituted by lower 
alkyl, halogen, cyano, nitro or lower alkoxy. Unsubstituted phenyl or 
aralkyl radicals are preferred. 
The alkylene chain formed by R.sub.1 and R.sub.3 contains 1 to 3 carbon 
atoms and is preferably further substituted by lower alkyl groups. An 
ethylene or propylene bridge is preferred, with the 
2,2-dimethyl-1,3-propylene bridge being most preferred. 
Haloalkyl is accordingly in general chloromethyl, dichloromethyl, 
trichloromethyl, 2-chloroethyl, 1,1,2,2-tetrachloroethyl, perchloroethyl, 
fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 
1,1,2,2-tetrafluoroethyl and perfluoroethyl. 
The free acid functions of the phosphinic, phosphonic and phosphonous acids 
may be in salt form, i.e. their acid protons are replaced by other 
cations. Such cations are as a rule alkali metal or alkaline earth metal 
cations; e.g. sodium, potassium, calcium or magnesium cations, or they are 
substituted ammonium cations such as the cations of dimethylamine, 
ethylamine, trimethylamine, triethylamine, dishydroxyethylamine, 
diethylamine, isopropylamine or diisopropylamine; or quaternary ammonium 
cations such as the trimethylammonium ion, tetraethylammonium ion, 
trimethylethylammonium ion, triethylmethylammonium ion or 
diethyldimethylammonium ion. 
The direct alkylene chain between the amino group and the phosphonic or 
phosphinic acid group preferably contains 1 to 3 carbon atoms and may be 
substituted by further substituents such as lower alkyl radicals, phenyl 
radicals or phosphonic acid groups or phosphonic acid ester groups. 
Preferred compounds of the formula I are those in which 
(a) m is 2, 
(b) X is trifluoromethyl or chlorine, 
(c) R is hydrogen, 
(d) the sum of n, p and q together does not exceed 3, 
(e) R.sub.4 is hydrogen or C.sub.1 -C.sub.3 alkyl and 
(f) R.sub.5 is methyl, ethyl, C.sub.1 -C.sub.3 alkoxy or hydroxyl. 
Further preferred compounds of the formula I are those in which Y is the 
--CH.dbd. group and m is 2, and both radicals X are chlorine in the 
2-position and trifluoromethyl in the 4-position, R is hydrogen, R.sub.4 
is hydrogen or C.sub.1 -C.sub.3 alkyl and R.sub.5 is hydrogen, methyl, 
ethyl, C.sub.1 -C.sub.3 alkoxy or hydroxyl, and the sum of n, p and q 
together does not exceed 3. 
Also preferred are the compounds of formula I in which Y is nitrogen, the 
pyridine ring is etherified in the 2-position, m is 1 and X is 
trifluoromethyl in the 5-position, R is hydrogen, R.sub.4 is hydrogen or 
C.sub.1 -C.sub.4 alkyl and R.sub.5 is hydrogen, methyl, ethyl, C.sub.1 
-C.sub.3 alkoxy or hydroxyl, and the sum of n, p and q together does not 
exceed 3. 
Especially preferred are the compounds of the subformulae 
##STR3## 
wherein R.sub.4 is hydrogen, methyl or ethyl and R.sub.5 is methyl or 
ethyl; 
##STR4## 
wherein R is hydrogen, methyl or benzyl, R.sub.4 is hydrogen, ethyl or 
isopropyl, R.sub.5 is hydrogen, hydroxyl, ethoxy or isopropoxy, and p is a 
value from 1 to 3; 
##STR5## 
wherein R.sub.2 is methyl, R.sub.3 is hydrogen or methyl, R.sub.4 is 
hydrogen, ethyl or isopropyl, and R.sub.5 is hydroxyl, ethoxy or 
isopropoxy; 
##STR6## 
wherein R.sub.4 is hydrogen, ethyl or isopropyl, and R.sub.5 is hydroxyl, 
ethoxy or isopropoxy; and 
##STR7## 
wherein R.sub.4 is hydrogen, ethyl or isopropyl, R.sub.5 is methyl, 
hydroxyl, ethoxy or 1-propoxy, and p is a value from 1 to 3. 
Preferred individual compounds are: 
ethyl 
N-[2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)phenyl]-P-methylaminomethy 
lphosphinate, 
diethyl 
N-[2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)phenyl]-aminomethylphospho 
nate, 
dimethyl 
N-[2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)phenyl]-aminomethylphospho 
nate, 
diethyl 
N-[2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)phenyl]-aminoethylphosphon 
ate, 
N-[2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)phenyl]-P-methylaminomethyl 
phosphinic acid, 
ethyl 
N-[2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)phenyl]-P-ethylaminomethyl 
phosphinate, 
N-[2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)phenyl]-P-ethylaminomethylp 
hosphinic acid, 
N-[2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)phenyl]-N-methylaminoethylp 
hosphonous acid, 
N-[2-nitro-5-(5-trifluoromethyl-2-pyridyloxy)phenyl]-aminopropylphosphonic 
acid, 
N-[2-nitro-5-(5-trifluoromethyl-2-pyridyloxy)phenyl]-aminoethylphosphonic 
acid, and 
diethyl 
N-[2-nitro-5-(5-trifluoromethyl-2-pyridyloxy)phenyl]aminoethylphosphonate. 
The compounds of formula I are prepared by reacting a dinitrophenylaryl 
ether of the formula II 
##STR8## 
wherein X, Y and m are as defined for formula I, with an 
aminoalkylphosphinic acid, aminoalkylphosphonic or aminoalkylphosphonous 
acid derivative of the formula III 
##STR9## 
wherein R, R.sub.1, R.sub.2, R.sub.3, n, p and q are as defined for 
formula I, and R.sub.4 is C.sub.1 -C.sub.4 alkyl and R.sub.5 is hydrogen, 
C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 -haloalkyl or C.sub.1 -C.sub.4 
alkoxy, and, if desired, hydrolysing the reaction product to give the free 
acid and converting the free acid into a salt by further reaction with a 
base. 
The reaction is conveniently carried out in an aprotic inert organic 
solvent in the temperature range from 50.degree. to 150.degree. C., 
preferably from 70.degree. to 120.degree. C. 
Suitable solvents are hydrocarbons such as benzene, toluene, xylene, 
cyclohexane; ethers such as ethylene glycol dimethyl ether, diethylene 
glycol dimethyl ether, tetrahydrofuran, dioxan; nitriles such as 
acetonitrile, propionitrile; and dimethyl sulfoxide. 
The starting compounds of the formulae II and III are known from European 
patent specification No. 7471 and from G. M. Kosolapoff and L. Maier, 
Organic Phosphorus Compounds, Wiley & Sons, New York, Vol. 7 (1976), or 
they may be obtained by methods corresponding to those indicated in the 
above publications. 
When applied pre- and postemergence to weeds, the compounds of formula I 
exhibit excellent herbicidal properties. The growth of cultivated plants 
is influenced only to an insignificant degree unless the compounds of 
formula I are applied at higher concentrations. The compounds of formula I 
are therefore particularly suitable for selectively controlling weeds in 
crops of useful plants such as maize, soybeans, cotton, rice, and cereals 
such as wheat, barley, rye and oats. Further, the compounds of formula I 
are particularly suitable for regulating plant growth. In particular, they 
promote the root growth of cereals and the germination of plant seeds. A 
number of the compounds of the formula I inhibit the growth of some 
dicots, e.g. cover crop leguminosae. 
Accordingly, the invention also relates to herbicidal and growth regulating 
compositions which contain a novel compound of the formula I, and to 
methods of pre- and post-emergence weed control and of growth regulation. 
The compounds of the formula I are used in unmodified form or, preferably, 
together with the adjuvants conventionally employed in the art of 
formulation, and are therefore formulated in known manner to emulsifiable 
concentrates, coatable pastes, directly sprayable or dilutable solutions, 
dilute emulsions, wettable powders, soluble powders, dusts, granulates, 
and also encapsulations in e.g. polymer substances. As with the nature of 
the compositions, the methods of application, such as spraying, atomising, 
dusting, scattering or pouring, are chosed in accordance with the intended 
objectives and the prevailing circumstances. 
The formulations, i.e. the compositions containing the compound (active 
ingredients) of the formula I and, where appropriate, a solid or liquid 
adjuvant, are prepared in known manner, e.g. by homogeneously mixing 
and/or grinding the active ingredients with extenders, e.g. solvents, 
solid carriers and, where appropriate, surface-active compounds 
(surfactants). 
Suitable solvents are: aromatic hydrocarbons, preferably the fractions 
containing 8 to 12 carbon atoms, e.g. xylene mixtures of substituted 
naphthalenes, phthalates such as dibutyl phthalates or dioctyl phthalate, 
aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and 
glycols and their ethers and esters, such as ethanol, ethylene glycol 
monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly 
polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or 
dimethyl formamide, as well as epoxidised vegetable oils such as 
epoxidised coconut oil or soybean oil; or water. 
The solid carriers used e.g. for dusts and dispersible powders, are 
normally natural mineral fillers such as calcite, talcum kaolin, 
montmorillonite or attapulgite. In order to improve the physical 
properties it is also possible to add highly dispersed silicic acid or 
highly dispersed absorbent polymers. Suitable granulated adsorptive 
carriers are porous types, for example pumice, broken brick, sepolite or 
bentonite; and suitable nonsorbent carriers are materials such as calcite 
or sand. In addition, a great number of preganulated materials of 
inorganic or organic nature can be used, e.g. especially dolomite or 
pulverised plant residues. 
Depending on the nature of the compound of the formula I to be formulated, 
suitable surface-active compounds are nonionic, cationic and/or anionic 
surfactants having good emulsifying, dispersing and wetting properties. 
The term "surfactants" will also be understood as comprising mixtures of 
surfactants. 
Suitable anionic surfactants can be both water-soluble soaps and 
water-soluble synthetic surface-active compounds. 
Suitable soaps are the alkali metal salts, alkaline earth metal salts or 
unsubstituted or substituted ammonium salts of higher fatty acids 
(C.sub.10 -C.sub.22), e.g. the sodium or potassium salts of oleic or 
stearic acid, or of natural fatty acid mixtures which can be obtained e.g. 
from coconut oil or tallow oil. Mention may also be made of fatty acid 
methyl laurin salts. 
More frequently, however, so-called synthetic surfactants are used, 
especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole 
derivatives or alkylarylsulfonates. 
The fatty sulfonates or sulfates are usually in the form of alkali metal 
salts, alkaline earth metal salts or unsubstituted or substituted ammonium 
salts and contain a C.sub.8 -C.sub.22 alkyl radical which also includes 
the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of 
lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol 
sulfates obtained from natural fatty acids. These compounds also comprise 
the salts of sulfuric acid esters and sulfonic acids of fatty 
alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives 
preferably contain 2 sulfonic acid groups and one fatty acid radical 
containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the 
sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, 
dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic 
acid/formaldehyde condensation product. Also suitable are corresponding 
phosphates, e.g. salts of the phosphoric acid ester of an adduct of 
p-nonylphenol with 4 to 14 moles of ethylene oxide, or phospholipids. 
Non-ionic surfactants are preferably polyglycol ether derivatives of 
aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty 
acids and alkylphenols, said derivatives containing 3 to 30 glycol ether 
groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 
6 to 18 carbon atoms in the alkyl moiety of the alkylphenols. 
Further suitable non-ionic surfactants are the water-soluble adducts of 
polyethylene oxide with polypropylene glycol, ethylenediamine propylene 
glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in 
the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether 
groups and 10 to 100 propylene glycol ether groups. These compounds 
usually contain 1 to 5 ethylene glycol units per propylene glycol unit. 
Representative examples of non-ionic surfactants are 
nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, 
polypropylene/polyethylene oxide adducts, 
tributylphenoxypolyethoxyethanol, polyethylene glycol and 
octylphenoxyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan 
and polyoxyethylene sorbitan trioleate are also suitable non-ionic 
surfactants. 
Cationic surfactants are preferably quaternary ammonium salts which 
contain, as N-substituent, at least one C.sub.8 -C.sub.22 -alkyl radical 
and, as further substituents, lower unsubstituted or halogenated alkyl, 
benzyl or lower hydroxyalkyl radicals. The salts are preferably in the 
form of halides, methylsulfates or ethylsulfates, e.g. 
stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium 
bromide. 
The surfactants customarily employed in the art of formulation are 
described e.g. in the following publications: "McCutcheon's Detergents and 
Emulsifiers Annual", MC Publishing Corp., Ridgewood, N.J., 1979; Sisley 
and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co. 
Inc., New York, 1964. 
The pesticidal formulations usually contain 0.1 to 99%, preferably 0.1 to 
95%, of a compound of the formula I, 1 to 99% of a solid or liquid 
adjuvant, and 0 to 25%, preferably 0.1 to 25%, of a surfactant. 
Preferred formulations are composed in particular of the following 
constituents (%=percentage by weight): 
______________________________________ 
Solutions 
active ingredient: 
5 to 95%, preferably 10 to 80% 
solvent: 95 to 5%, preferably 90 to 0% 
surfactants: 
1 to 30%, preferably 2 to 20% 
Emulsifiable concentrates 
active ingredient: 
10 to 50%, preferably 10 to 40% 
surfactant: 5 to 30%, preferably 10 to 20% 
liquid carrier: 
20 to 95%, preferably 40 to 80% 
Dusts 
active ingredient: 
0.5 to 10%, 
preferably 2 to 8% 
solid carrier: 
99.5 to 90%, 
preferably 98 to 92% 
Suspension concentrates 
active ingredient: 
5 to 75%, preferably 10 to 50% 
water: 94 to 25%, preferably 90 to 30% 
surfactant: 1 to 30%, preferably 2 to 25% 
Wettable powders 
active ingredient: 
5 to 90%, preferably 10 to 80%, and 
most preferably, 20 to 60%, 
surfactant: 0.5 to 20%, 
preferably 1 to 15% 
solid carrier: 
5 to 90%, preferably 30 to 70% 
Granulates 
active ingredient: 
0.5 to 30%, 
preferably 3 to 15% 
solid carrier: 
99.5 to 70%, 
preferably 97 to 85%. 
______________________________________ 
Whereas commercial products will be preferably formulated as concentrates, 
the end user will normally employ dilute formulations. The formulations 
can be diluted to a concentration as low as 0.001%. The rates of 
application are normally 0.1 to 10 kg a.i./ha, preferably 0.25 to 5 kg 
a.i./ha. 
The compositions may also contain further ingredients such as stabilisers, 
antifoams, viscosity regulators, binders, adhesives, as well as 
fertilisers or other active compounds, in order to attain special effects. 
The invention is illustrated in more detail by the following Examples.