Phosphonomethylglycylhydroxamic acid and novel herbicidally active salts thereof

The invention relates to N-phosphonomethylglycylhydroxamic acid of the formula I ##STR1## or of the tautomeric formula Ia ##STR2## and salts thereof with strong acids, organic nitrogen bases, alkali metal or alkaline earth metal ions, as well as complex salts with aluminium or heavy metal compounds. These compounds have herbicidal and plant growth-regulating properties.

The present invention relates to N-phosphonomethylglycylhydroxamic acid and 
herbicidally active salts thereof, to the production thereof, to 
compositions containing them, and to their use as herbicides. 
The N-phosphonomethylglycylhydroxamic acid of this invention has the 
formula I 
##STR3## 
and/or the tautomeric formula Ia 
##STR4## 
The invention also comprises the salts of this compound with strong acids, 
organic nitrogen bases, alkali metal or alkaline earth metal ions, and 
complex salts with aluminium or heavy metal compounds. 
Examples of strong acids suitable for the salt formation are mineral acids 
such as hydrochloric acid, hydrobromic acid, hydriodic acid, sulfuric 
acid, nitric acid, phosphoric acid, and also organic acids such as 
sulfonic acids, halosulfonic acids or haloacetic acids. Preferred acids, 
however, are hydrochloric and hydrobromic acid. 
Examples of organic nitrogen bases suitable for the salt formation are 
primary, secondary and tertiary aliphatic and aromatic amines such as 
methylamine, ethylamine, propylamine, isopropylamine, the four isomeric 
butylamines, dodecylamine, dimethylamine, diethylamine, dipropylamine, 
diisopropylamine, di-n-butylamine, pyrrolidine, piperidine, morpholine, 
trimethylamine, triethylamine, tripropylamine, quinuclidine, pyridine, 
quinoline, isoquinoline etc., preferably ethyl-, propyl-, diethyl- or 
triethylamine, but, most preferably, isopropylamine; pyridinium cations 
such as 1-methyl-4,4'-bipyridinium cation, the 4-pyrrolidinium-pyridinium 
dication, and tetraalkylammonium cations the alkyl moieties of which, each 
independently of the other, are identical or different, straight-chain or 
branched alkyl radicals of 1 to 12 carbon atoms, preferably 
straight-chain, and are benzyl. 
Preferred salt-forming alkali metal and alkaline earth metal ions are 
lithium, sodium, potassium, magnesium or calcium, with sodium or potassium 
being most preferred. Examples of heavy metals which form complex salts 
are chromium, manganese, iron, nickel, copper, zinc, tin, mercury and 
lead. 
The preferred compound is that of the formula I or Ia as free acid, mono-, 
di- or trisodium salt, copper salt, isopropylammonium salt, 
tetrabutylammonium salt, 4-pyrrolidinium-pyridinium salt, 
1-methyl-4,4'-bipyridinium salt, dimethylbenzylammonium salt, 
dimethyldodecylammonium salt, or as hydrohalide. 
Among this group of preferred compounds, the free acid, the mono- and 
disodium salt, the copper salt, the isopropylammonium salt and the 
hydrohalides are particularly preferred. The most preferred compound is 
the free acid. 
The N-phosphonomethylglycylhydroxamic acid of the formula I and/or Ia is 
obtained by methods which are known per se. A first method of obtaining 
the compound of the formula I or Ia is in accordance with the procedure 
described in Houben-Weyl, 4th edition, Methoden der organischen Chemie 8, 
684, by reacting a N-phosphonomethylglycine compound of the formula II 
##STR5## 
wherein R is hydrogen or C.sub.1 -C.sub.4 alkyl, in the presence of a 
base, with hydroxylamine of the formula III 
EQU H--O--NH.sub.2 (III). 
The compound of the formula I or Ia can also be obtained in accordance with 
the procedure described by J. E. Franz, Adv. in Pesticide Science, Zurich 
1978, Pergamon Press, ed. H. Geissbuhler, Symp. Papers, 4th Int. Cong. 
Pest. Chem., page 139, by heating glycylhydroxamic acid of the formula IV 
EQU H--O--NH--CO--CH.sub.2 --NH.sub.2 (IV) 
in the presence of hydrochloric acid or hydrobromic acid, with formaldehyde 
and phosphorous acid. 
A further method of obtaining the compound of the formula I or Ia comprises 
reacting glycylhydroxamic acid of the formula IV, in the presence of an 
acid acceptor, with a halomethylphosphonic acid of the formula V 
##STR6## 
wherein X is chlorine or bromine, in accordance with a procedure described 
in German Auslegeschrift 2 152 826. 
Yet a further method of obtaining the compound of the formula I or Ia 
comprises reacting a halide of the formula VI 
##STR7## 
wherein X is chlorine or bromine, in the presence of an acid acceptor, 
with an aminomethylphosphonic acid of the formula VII 
##STR8## 
The compounds of the invention can also be obtained in accordance with the 
particulars of J. E. Franz, ibid., by oxidising the phosphonous acid of 
the formula VIII 
##STR9## 
with mercury(II) chloride (HgCl.sub.2) or oxygen. 
The compound of the formula I or Ia can further be obtained by heating a 
hexahydrotriazine of the formula IX 
##STR10## 
which is obtained from glycylhydroxamic acid of the formula IV and 
formaldehyde, with a dialkylphosphite of the formula X 
##STR11## 
and hydrolysing the resultant phosphonic acid ester of the formula XI 
##STR12## 
wherein R' is C.sub.1 -C.sub.4 alkyl. 
Finally, the compound of the formula I can also be obtained by heating an 
amino acid derivative of the formula XII 
EQU H--O--NH--CO--CH.sub.2 --NH--R" (XII), 
wherein R" is benzyl, benzhydryl or triphenylmethyl, in the presence of 
hydrochloric acid or hydrobromic acid, with formaldehyde and phosphorous 
acid or phosphorus trichloride which gives phosphorous acid in water, and 
when the reaction is complete, removing the group R" either with 
hydrobromic acid at elevated temperature (140.degree.-180.degree. C.) or 
with hydrogen in the presence of catalytic amounts of 5% palladium on 
carbon. 
The free acids of the formula I or Ia obtainable by the different methods 
can be converted, if desired, into their salts by methods known per se. 
It is known to use N-phosphonomethylglycine (glyphosate) and its ammonium, 
alkali metal and alkaline earth metal salts and a number of heavy metal 
salts, amides, esters and phenylhydrazides as well as N-trifluoroacetyl 
derivatives, as contact herbicides, from J. E. Franz, ibid., and from 
German Auslegeschrift 2 152 826, Japanese patent publication No. 79 036 
653, U.S. Pat. No. 4,180,394 and European patent application 7210. 
The N-phosphonomethylglycylhydroxamic acid of this invention and its salts 
are novel and have excellent herbicidal activity in pre-emergence, but 
especially in postemergence, application. 
In addition, the compound of the formula I or Ia influences plant growth in 
various ways. For example, the root growth of cereals is stimulated. 
The compound of the formula I or Ia or its salts 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, directly sprayable or dilutable solutions, 
dilute emulsions, wettable powders, soluble powders, dusts, granulates, 
and also encapsulations in e.g. polymer substances. The methods of 
application, such as spraying, atomising, dusting, scattering or pouring, 
are chosen in accordance with the intended objectives and the prevailing 
circumstances, just like the nature of the compositions. 
The formulations, i.e. the compositions or preparations containing the 
compound (active ingredient) of the formula I or Ia 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, 
surfactants. 
Suitable solvents are: aromatic hydrocarbons, preferably the fractions 
containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted 
naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, 
aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and 
glycols and their ethers and esters, such as ethanol, ethylene glycol, 
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, sepiolite 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 active ingredient 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 surfactant mixtures. 
Suitable anionic surfactants can be both water-soluble soaps and 
water-soluble synthetic surface-active compounds. 
Suitable soaps are the alkali, alkaline earth 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 methyltaurin 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, 
alkaline earth 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. 
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, ethylenediaminepolypropylene 
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 
nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, 
polypropylene/polyethylene oxide, adducts, 
tributylphenoxypolyethoxyethanol, polyethylene glycol and 
octylphenoxypolyethoxyethanol. 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 polyglycol ether or C.sub.8 
-C.sub.22 alkyl radical and, as further substituents, lower unsubstituted 
or halogenated alkyl, benzyl or lower hydroxyalkyl radicals or fatty acid. 
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., Ringwood, N.J., 1979; Sisely and 
Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co. 
Inc., New York,1964. 
When formulating the compound of the formula I or Ia or the corresponding 
salts, it is particularly advantageous to add inorganic salts, e.g. sodium 
chloride or potassium chloride. 
The pesticidal formulations usually contain 0.1 to 99%, preferably 0.1 to 
95%, of a compound of the formula I or Ia, 1 to 99.9% 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 2% 
Suspension concentrates 
active ingredients: 5 to 75%, preferably 10 to 50% 
water: 94 to 25%, preferably 90 to 30% 
surfactant: 1 to 40%, preferably 2 to 30% 
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 formulations can also contain further additives such as stabilisers, 
antifoams, viscosity regulators, binders, adhesives, as well as 
fertilisers or other active compounds, in order to attain special effects. 
Accordingly, in addition to containing the compounds of the general 
formula I or Ia or their salts, the compositions of the invention can also 
contain e.g. insecticides, fungicides, bactericides, fungistats, 
bacteriostats, nematocides or further herbicides, in order to broaden the 
activity spectrum.

The invention is further illustrated by the following Examples. 
PREATORY EXAMPLES 
Example 1: N-phosphonomethylglycylhydroxamic acid with 5 moles of NaCl 
A mixture of 10 g (0.05 mole) of ethyl N-phosphonomethylglycinate, 7 g (0.1 
mole) of hydroxylamine hydrochloride and 15 g (0.25 mole) of sodium 
methylate in 200 ml of methanol is stirred for 15 hours and then 30 ml of 
a 5 N solution of HCl in methanol are added. The precipitate is isolated 
by filtration, washed repeatedly with methanol and dried, affording 5 g of 
a colourless powder which decomposes at 60.degree.-70.degree. C. with 
foaming and has the composition of N-phosphonomethylglycylhydroxamic acid 
with 5 moles of NaCl (compound 1). 
Analysis: C.sub.3 H.sub.9 N.sub.2 O.sub.5 +5 NaCl--calculated: C 7.56, H 
1.98, N 5.88, P 6.51, Na 24.13, Cl 37.25; found: C 7.5, H 2.0, N 5.6, P 
6.3, Na 24.4, Cl 37.3. 
With iron(III) ions the compound gives the characteristic red coloration of 
hydroxamic acids. 
Example 2: Disodium salt of N-phosphonomethylglycylhydroxamic acid 
To a solution of 27.5 g (0.15 mole) of methyl N-phosphonomethylglycinate in 
700 ml of methanol is added a solution of 0.3 mole of hydroxylamine in 300 
ml of methanol, which is obtained by adding a solution of 6.9 g (0.3 
gram-atoms) of sodium in 200 ml of methanol to a suspension of 21 g (0.3 
mole) of hydroxylamine hydrochloride and filtering off the NaCl 
precipitate. To this solution is further added a solution of 6.9 g (0.3 
gram-atoms) of sodium in 250 ml of methanol until the reaction solution is 
alkaline to phenolphthalein. After a reaction time of 16 hours the 
disodium salt of N-phosphonomethylglycylhydroxyamic acid is obtained in 
95% yield in the form of a finely crystalline colourless powder which does 
not melt below 210.degree. C. (compound 2). 
Analysis: C.sub.3 H.sub.7 N.sub.2 Na.sub.2 O.sub.5 P--calculated: C 15.8, H 
3.1, N 12.3, Na 20.2, P 13.6; found: C 15.6, H 3.3, N 11.5, Na 19.5, P 
13.0, Cl 0.3. 
Example 3: N-phosphonomethylglycylhydroxamic acid 
4.6 g (0.02 mole) of the disodium salt of 
N-phosphonomethylglycylhydroxaimic acid are dissolved in 40 ml of aqueous 
1 N HCl solution, whereupon N-phosphonomethylglycylhydroxamic acid 
precipitates rapidly in the form of a finely crystalline colourless powder 
which decomposes at 186.degree. C. with foaming. After washing with water 
and methanol and drying in vacuo at 60.degree. C., the product is obtained 
in 90% yield (compound 3). 
Analysis: C.sub.3 H.sub.9 N.sub.2 O.sub.5 P--calculated: C 19.58, H 4.93, N 
15.22, P 16.83; found: C 19.5, H 5.0, N 15.0, P 16.8. 
Example 4: N-phosphonomethylglycylhydroxamic acid hydrochloride 
4.6 g (0.02 mole) of the dissodium salt of 
N-phosphonomethylglycylhydroxamic acid are dissolved in 20 ml of a 5 N 
solution of HCl in methanol and the solution is stirred for 1/2 hour. 
Precipitated NaCl is then filtered off and the solution is evaporated in 
vacuo. Remaining solvent is removed in a high vacuum at 40.degree. C./0.1 
mbar, affording N-phosphonoglycylhydroxamic acid hydrochloride in a yield 
of 60% in the form of a tacky resin (compound 4). 
Example 5: Copper salt of N-phosphonomethylglycylhydroxamic acid 
Excess copper(II) acetate solution is added to an aqueous solution of 1.5 g 
of N-phosphonomethylglycylhydroxamic acid with 5 moles of NaCl. The 
bluish-green precipitate which forms at once is isolated, decocted with 
water and dried, affording 1.3 g of a green powder which does not melt in 
the temperature range up to 200.degree. C. and has the composition 
[(C.sub.3 H.sub.8 N.sub.2 O.sub.5 P).sub.2 ].sup.2- Cu.sup.2+ (compound 
5). 
Example 6: N-phosphonomethylglycylhydroxamic acid 
1.3 g of N-phosphonomethylglycylhydroxamic acid copper salt [(C.sub.3 
H.sub.8 N.sub.2 O.sub.5 P).sub.2 ].sup.2- Cu.sup.2+ are suspended in 50 ml 
of ethanol. The mixture is saturated with hydrogen sulfide and stirred for 
16 hours at 20.degree. C. The black precipitate, which consists of 
N-phosphonomethylglycylhydroxamic acid and copper sulfide, is isolated by 
filtration and dried. This precipitate is stirred in a solution of 3 g of 
isopropylamine in 20 ml of ethanol, then non-dissolved copper sulfide is 
removed by filtration and 1 g of N-phosphonomethylglycylhydroxamic acid is 
precipitated from the solution with a solution of HCl in alcohol. The 
product is a colourless powder which decomposes at 130.degree.-135.degree. 
C. (compound 3). 
After recrystallisation from water the compound is obtained in the form of 
colourless prisms which decompose at 192.degree. C. 
Example 7: Isopropylammonium salt of N-phosphonomethylglycylhydroxamic acid 
1.7 g (0.01 mole) of N-phosphonomethylglycylhydroxamic acid are dissolved 
in 10 ml of methanol by adding 1.8 g (0.03 mole) of isopropylamine. The 
solution is concentrated in vacuo and the residue solidifies to a glassy 
foam. Yield: 2.6 of the isopropylamine salt of 
N-phosphonomethylglycylhydroxamic acid in the form of a white amorphous 
powder which begins to decompose from 70.degree. C. 
The following table lists compounds of the formula I or Ia obtained in 
accordance with Examples 1 to 7, as well as corresponding salts and also 
further salts which are obtainable in analogous manner. 
__________________________________________________________________________ 
Com- (.degree.C.) Physical 
pound 
formula I or Ia data 
__________________________________________________________________________ 
1 (HO).sub.2 POCH.sub.2NHCH.sub.2CONHOH + 5 NaCl 
m.p. 60-70.degree. (decomp) 
2 [O.sub.3 PCH.sub.2NHCH.sub.2CONHOH].sup.2.crclbar. 2Na.sup..sym. 
m.p. &gt; 210.degree. 
3 (HO).sub.2 POCH.sub.2NHCH.sub.2CONHOH 
m.p. 192.degree. (decomp) 
##STR13## resin 
5 [(HO).sub.2 POCH.sub.2NHCH.sub.2CONHO].sub.2.sup..crclbar. Cu.sup.2.sy 
m. m.p. &gt; 200.degree. 
6 
##STR14## m.p. 70.degree. (decomp) 
7 
##STR15## 
8 
##STR16## 
9 
##STR17## 
10 
##STR18## 
11 [(HO)OPOCH.sub.2NHCH.sub.2CONHOH].sup..crclbar. Na.sup..sym. 
12 [O.sub.3 PCH.sub.2NHCH.sub.2CONHO].sup.3.crclbar. 3Na.sup..sym. 
13 [O.sub.3 PCH.sub.2NHCH.sub.2CONHOH].sup.2.crclbar. 2.sup..sym. 
N(C.sub.4 H.sub.9).sub.4 
__________________________________________________________________________ 
FORMULATION EXAMPLES 
Example 8 
Formulation Examples for liquid active ingredients of the formula I 
(throughout, percentages are by weight) 
______________________________________ 
(a) Emulsifiable concentrates 
(a) (b) (c) 
______________________________________ 
active ingredient 20% 40% 50% 
calcium dodecylbenzenesulfonate 
5% 8% 5.8% 
castor oil polyethylene glycol 
ether (36 moles of ethylene 
oxide) 5% -- -- 
tributylphenol polyethylene glycol 
ether (30 moles of ethylene oxide) 
-- 12% 4.2% 
cyclohexane -- 15% 20% 
xylene mixture 70% 25% 20% 
______________________________________ 
Emulsions of any required concentration can be produced from such 
concentrates by dilution with water. 
______________________________________ 
(b) Solutions (a) (b) (c) (d) 
______________________________________ 
active ingredient 80% 10% 5% 95% 
ethylene glycol monomethyl ether 
20% -- -- -- 
polyethylene glycol 400 
-- 70% -- -- 
N--methyl-2-pyrrolidone 
-- 20% -- -- 
epoxidised coconut oil 
-- -- 1% 5% 
ligroin (boiling range 160-190.degree.) 
-- -- 94% -- 
______________________________________ 
These solutions are suitable for application in the form of microdrops. 
______________________________________ 
(c) Granulates (a) (b) 
______________________________________ 
active ingredient 5% 10% 
kaolin 94% -- 
highly dispersed silicic acid 
1% -- 
attapulgite -- 90% 
______________________________________ 
The active ingredient is dissolved in methylene chloride, the solution is 
sprayed onto the carrier, and the solvent is subsequently evaporated off 
in vacuo. 
______________________________________ 
(d) Dusts (a) (b) 
______________________________________ 
active ingredient 2% 5% 
highly dispersed silicic acid 
1% 5% 
talcum 97% -- 
kaolin -- 90% 
______________________________________ 
Dusts which are ready for use are obtained by intimately mixing the 
carriers with the active ingredient. 
Example 9 
Formulation examples for solid active ingredients of the formula I 
(throughout, percentages are by weight) 
______________________________________ 
(a) Wettable powders (a) (b) 
______________________________________ 
active ingredient 20% 60% 
sodium lignosulfonate 5% 5% 
sodium laurylsulfate 3% -- 
sodium diisobutylnaphthalene- 
sulfonate -- 6% 
octylphenol polyethylene glycol 
ether (7-8 moles of ethylene oxide) 
-- 2% 
highly dispersed silicic acid 
5% 27% 
kaolin 67% -- 
______________________________________ 
The active ingredient is thoroughly mixed with the adjuvants and the 
mixture is thoroughly ground in a suitable mill, affording wettable 
powders which can be diluted with water to give suspensions of the desired 
concentration. 
______________________________________ 
(b) Emulsifiable concentrate 
______________________________________ 
active ingredient 10% 
octylphenol polyethylene glycol 
ether (4-5 moles of ethylene oxide) 
3% 
calcium dodecylbenzenesulfonate 
3% 
castor oil polyglycol ether 
(36 moles of ethylene oxide) 
4% 
cyclohexanone 30% 
xylene mixture 50%. 
______________________________________ 
Emulsions of any required concentration can be obtained from this 
concentrate by dilution with water. 
______________________________________ 
(c) Dusts (a) (b) 
______________________________________ 
active ingredient 5% 8% 
talcum 95% -- 
kaolin -- 92% 
______________________________________ 
Dusts which are ready for use are obtained by mixing the active ingredient 
with the carriers, and grinding the mixture in a suitable mill. 
______________________________________ 
(d) Extruder granulate 
______________________________________ 
active ingredient 10% 
sodium lignosulfonate 
2% 
Carboxymethylcellulose 
1% 
kaolin 87%. 
______________________________________ 
The active ingredient is mixed and ground with the adjuvants, and the 
mixture is subsequently moistened with water. The mixture is extruded and 
then dried in a stream of air. 
______________________________________ 
(e) Coated granulate 
______________________________________ 
active ingredient 3% 
polyethylene glycol 200 
3% 
kaolin 94%. 
______________________________________ 
The finely ground active ingredient is uniformly applied, in a mixer, to 
the kaolin moistened with polyethylene glycol. Non-dusty coated granulates 
are obtained in this manner. 
______________________________________ 
(f) Suspension concentrate 
______________________________________ 
active ingredient 40% 
ethylene glycol 10% 
nonylphenol polyethylene glycol ether 
(15 moles of ethylene oxide) 
6% 
sodium lignosulfonate 10% 
carboxymethylcellulose 1% 
37% aqueous formaldehyde solution 
0.2% 
silicone oil in the form of a 75% 
aqueous emulsion 0.8% 
water 32%. 
______________________________________ 
The finely ground active ingredient is intimately mixed with the adjuvants, 
giving a suspension concentrate from which suspensions of any desired 
concentration can be obtained by dilution with water. 
BIOLOGICAL EXAMPLES 
Example 10 
Preemergence herbicidal action 
In a greenhouse, immediately after sowing the test plants in seed dishes, 
the surface of the soil is treated with an aqueous dispersion of test 
compound, obtained from a 25% emulsifiable concentrate or from a 25% 
wettable powder with active ingredients which, on account of their 
insufficient solubility, cannot be processed to an emulsifiable 
concentrate. The seed dishes are kept in the greenhouse at 
22.degree.-25.degree. C. and 50-70% relative humidity, and the test is 
evaluated after 3 weeks. 
In this test the compounds of formula I exhibited a good herbicidal action 
against the monocot and dicot weeds at a rate of application of 4 kg 
a.i./ha. 
Example 11 
Postemergence herbicidal action (contact herbicide) 
A number of weeds in pots, both monococts and dicots, are sprayed 
postemergence, in the 4- to 6-leaf stage, with an aqueous active 
ingredient dispersion at a rate of application of 4 kg a.i./ha, and then 
kept at 24.degree.-26.degree. C. and 45-60% relative humidity. The test is 
evaluated at least 15 days after treatment and the results are assessed in 
accordance with the following rating: 
1=plants totally withered 
2-3=very pronounced action 
4-6=medium action 
7-8=insignificant action 
9=no action (as untreated controls) 
Postemergence action 
Rat of application: 4 kg a.i./ha 
______________________________________ 
Com- 
pound Avena Setaria Lolium 
Solanum 
Sinapis 
Stellaria 
______________________________________ 
1 1 2 2 2 2 2 
2 3 2 3 2 2 3 
3 2 1 2 2 1 2 
______________________________________ 
Example 12: Stimulation of root growth 
Seeds of the "Raineri" hard wheat variety are tested with a suspension of 
the active ingredient. The rates of application are from 4 to 1670 mg of 
active ingredient per kg of seeds. The seeds are then cultivated in 
sterilised soil for 9 days in a climatic chamber at 15.degree.-20.degree. 
C. and 75% relative humidity. The length and dry weight of the roots of 
the seedlings are then determined in comparison to untreated controls. 
In this test the compounds of the formula I or Ia and their salts increased 
both the length and weight of the roots by at least 10%.