CA1162071A - Synergistic combinations of phosphinothricine - Google Patents
Synergistic combinations of phosphinothricineInfo
- Publication number
- CA1162071A CA1162071A CA000372216A CA372216A CA1162071A CA 1162071 A CA1162071 A CA 1162071A CA 000372216 A CA000372216 A CA 000372216A CA 372216 A CA372216 A CA 372216A CA 1162071 A CA1162071 A CA 1162071A
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- Prior art keywords
- composition according
- formula
- component
- phosphinothricine
- inorganic
- Prior art date
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
Abstract
Abstract of the disclosure:
Herbicidal compositions containing phosphinothricine, its ester, salts or oligopeptides, in combination with inorganic or organic ammonium salts, amines and/or inorganic or organic chelating agents.
Herbicidal compositions containing phosphinothricine, its ester, salts or oligopeptides, in combination with inorganic or organic ammonium salts, amines and/or inorganic or organic chelating agents.
Description
~ ~2~7~
The recently found phosphinothricine type herbicides of the formula 3 \
P ~ CH2 - CH2 - CH - COOH
have a good contact activi~y and are well absorbed by leaves, so that they are suitable for non-selectively combating weeds of all botanic classes. They are therefore applicable against undesirable plant growth on farming grounds, industrial areas etc. ~see German Offenlegungsschrift No. 2,717,440).
Herbicides of the phosphinothricine type are effective against annual as well as perennial weeds and weed grasses. Some economically import-ant perennial weeds such as quack-grass (Agropyron repens), Bermuda grass (Cynodon dactylon), perennial cyperaceae and corresponding dicotyledonous weeds,however, are sufficiently combated only with increased herbicide amounts.
Surprisingly, it has now been found that the addition to phosphino-thricine and its derivatives of certain types of organic and inorganic compoundswhich for themselves have no herbicidal activity produces a pronounced syner-gistic effect, that lS, considerably increases the herbicidal efficiency againstannual and perennial weeds.
According to one aspect of the present invention there is provided a herbicidal composition which comprises an amount of:
~ A) a phosphinothricine derivative of the formula H C O
~:: 3 ~ 11 P - CH - CH - CH - COOH
~; / 2 2 in which R is hydrogen or ~Cl-C4)-alkyl, a salt thereof with an acid or base or a peptide thereof, in combination with;
"~
l 162~7~
B~ an inorganic or organic ammonium salt of the formula R2 _ N - R4 X II
R n in which Rl to R4, being identical or different, each are hydrogen, ~Cl-C4)-alkyl or hydroxyethyl, or two of the radicals Rl to R4 together with the nitro-gen atom form a 3- to 7-membered ring a -CH2 group of which may be replaced by 0, NH or N(Cl-C4)-alkyl; X is the anion of an inorganic or organic mono- or polybasic acid and n is 1, 2 or 3, or with the free base from which the salt of the formula II are derived, or with a precursor metabolizing under physiologi-cal conditions to a compound of the formula II; or C) an inorganic or organic chelating agent, selected from the group consisting of polybasic organic acids or their salts, and water-soluble poly-phosphates of different chain length which are used in the soap and detergent industry, wherein the weight ratio of components A to B or C is from 4 : 1 to 150, with the proviso that, if R in formula I is hydrogen, the compound B
is not a free base. Preferably, the peptide in component A is phosphinothricyl-alanyl-alanine.
According to another aspect of the present invention there is pro-vided a method for combating weeds which comprises applying to the areas infested by them the above composition in an amount of from 0.125 to 35 kg of active substance ~component A ~ component B or C) per hectare.
Phosphinothricine and its derivatives have an asymmetric carbon atom, and thus may be present in the form of racemates or optionally active enantlomers, the L-enantiomer of which is especially preferred in accordance wlth the invention.
; A) Due to their amphoteric nature, phosphinothricine and its esters are able to form salts with inorganic and organic bases and acidsj which salts 07~
may likewise be used for the compositions of the invention. When using bases, compounds are formed in which R is cation equivalent. The following cation equivalents are particularly important: Na , K , 1/2 Ca , lt2 Zn , 1/2 Mg N~ N~(CH3)4, H2N (CH3)2, H2N ~C2H5)2, NH ~C2H5)3' 3 3 3 3 7 4 9 2 3 7 )2~ H3N CH2CH20H, H2N (CH2CH20H), HN~CH CH OH) ~CH3)3N CH2CH20H, (CH3)2N HCH2CH20H, CH3N H2CH2CH20H, (CH3)2N HC12H25, and the guanidinium ion.
When using strong bases, the -COOH group is ionized, too, and diso-dium or dipotassium salts, for example, are obtained in these cases.
1~ For salt formation with acids, any inorganic and organic acids such as HCl, HBr, H2S04, H3PO4, }INO3 or CH3COOH may be used.
In accordance with the invention, oligopeptides of phosphinothricine are alternatively suitable as component A, such as phosphinothricyl-alanyl-alanine which is described in ~ -3a-1 182~71 Helv. Chim. Acta 55, 224 seq. (1972).
B) The B type compounds are preferably ammonium salts (R1 to R4 = H), but salts of organic ammonium bases with any anions (see A) may also be used. Preferred organic ammonium salts have cations such as enumerated sub A) and anions such as Cl , Br , S04 , HS04, P03 , Hpo42 , , '~2P04, CH3COO , (COO )22 , or SCN .
Compounds which metabolize in the ?lant to form ammo-nium ions are likewise useful, for example urea, aspartic or glutamic acid.
Instead of the ammonium salts II, the free bases from which they are derived, for example triethylamine or piperi-dine, may be used in combination with phosphinothricine - esters, salts or peptides.
C) Suit~ble complexing agents of type C are for example polybasic organic acids such as oxalic, succinic, tartaric, citric, nitrilotriacetic or ethylenediamine-tetra-acetic acid (EDTA~ or their salts, furthermore water-soluble polyphosphates of different chain length (metaphosphates, triphosphates) which are used in the soap and detergent industry. Such complexing agents are described for example in O.A. Neumuller: Rompps Chemielexikon, 7nd. ed. 1972, pp. 545 and 2768 seq.
The compounds of types B ànd C can be combined with the A type herbicides either individually, or several of them in any number may be employed.
The mixing ratio of the individual components in the combinations of the invention may vary within wide limits. A synergistic effect is observed at a ratio of A : B(C) between 4 : 1 and 1 : 150. For practical reasons, the mixing ratio is chosen in a range of from 2 : 1 to 1 : 50, preferably 1 : 1 to 1 : 10.
The mixtures of the invention may have the form of ready-to-use formulations, for example wettable powders or emulsifiable concentrates, which are applied in usual manner as aqueous dilutions, or as so-called tank mixtures which are prepared immediately before application by common~ dilu~
tion of the separately formulated components with water.
I lB207~
Alternatively, the herbicides and the synergists may be separately applied as spray liquors or aqueous solutions;
the sequence of the components being irrelevant.
The application concentration of the A type herbicides in the mixtures of active substances is generally from 0.10 to 5 kg/ha, that of B and C from 0.025 to 30 kg/ha; that iS3 the total amount of active substance combination is in the range of .rom about 0.125 to 35 kg/ha.
The compositions o. the invention can be employed in form of the usual formulations known to the expert skilled in the art, for example as wettable powders, dusts, granu-les, emulsifiable concentrates or sprayable solutions, and contain generally from 2 to 95 weight % of the combinations of active substances according to the invention.
Wettable powders are formulations which are uniformly dispersible ln water and which, in addition to the active compound, and a diluent or inert material, also contain wetting agents, for example, polyoxyethylated alkylphenols, alkylsulfonates or alkylphenylsulfonates, and dispersing agents, for example sodium ligninsulfonate, sodium-dinaph-thylmethane-disulfonate, or the sodium salt of oleoyl-methyl-taurir.e.
Emulsifiable concentrates are obtained by dissol~ing the active ^ompound in an organic solvent, for example, butanol, cyclohexanone, dimethylformamide, xylene or even higher-boiling aromatics, and adding an emulsifier, for example, a polyoxyethylated alklphenol.
In the case the herbicidai compositions, the concen-trations of the active compounds in the commercial formula-tions can vary. In wettable powders, the active compoundconcentration (herbicide and synergist) varies, for example, between about 1u and 95 %, the remainder consisting of one or more of the above-mentioned formulation additives. In the case of emulsifiable concentrates, the active compound concentration is about 10 to 80 %. Dust formulations usually contain 5 - 20 g of active compound, and sprayable solutions about 2 - 20 %. In the case of granules, the active compound content in part depends on whether the ,. .
1 16207~
active compound is in a liquid or solid form and what granu-- Lating auxiliaries, fillers and the like are used.
If necessary or desired the commercial concentrates may be diluted prior to application in the usual manner, for example by means of water in the case of wettable powders and emulsifiable concentrates. Dust, granules and sprayable solutions are generally ready for use without further dilu-tion with inerc materials. The amount of active ingredient necessary for obtaining th desired result depends on exter-nal conditions such as temperature, humidity and the like.
The actiYe compounds according to the invention can becombined with other herbicides, fungicides and insecticides.
The following examples illustrate the invention.
i5 E X A M P L E
Seeds of annual weeds and rhizomes of perennial noxious plants were placed in pots of plastic material filled with loamy soil, and left in a greenhouse under favorable growth conditions. After 3 weeks, the plants had formed 3 to 4 leaves, in which stage they were sprayed either with the herbicide at varying dosage, or with mixtures of herbicide and synergists; the application concentration being main-tained at a constant 12 kg/ha. For comparison, further test plants were treated with a solution of the synergist alone.
In all cases, the amount of liquid corresponded to 600 l/ha.
3 Weeks after the treatment, the degree of damage of the plants treated was evaluated in comparison with the ~ntreated control.
The results listed in Table 1 show that the synergist alone did not damage the plants, but in combination with the test herbiclde considerably increased the herbicidal effect.
In the case of Alopecurus, for example, a herbicide concen-tration of 0.~ kg/ha yielded an 80 % damage of the plants;
the same degree of damage was attained at a herbicide amount of 0.15 kg/ha only with the addition of 12 kg/ha of the synergist.
The improved effect in the perennial weeds Agropyron (quack-grass), Cyperus (nutsedge) and Cyanodon (Bermuda 6~71 grass) by addition of the synergists was also remarkable.
These are weeds of special economic importance, which are normally difficult to combat.
Table 1 (Plant damage in %) .. . . _, . . _ . . . . . . . .. .
Compound Dose AVF ALM SAL LO~S ECG AGR CYE CND
kg AS/ha Phosphino- 0.6 75 80100 95 90 32 65 55 .. . _ .. .. ... . .. .
thricme hydro- 0.15 32 3270 32 38 - - -.. . _ . . _ .. ...
chlori~e 0.08 0 0 32 0 11 - - -(A II) ammonium 12.0 0 0 0 0 O O O O
_. _ _ . .... ~
sulfate (B I) A II ~ B I 0.6 ~ 12.0 1OG g5100 100 94 85 85 90 0.15 ~ 12.0 65 8085 70 74 - -0.08 + 12.0 32 3265 65 38 - ~ ~
.
Abbreviation for Tables 1 to &:
.
AVF = Avena (wild oats) ECG = Echinochloa (barn-yard grass) ALM - Alopecurus (annual black- AGR = Agropyron (quack-grass) grass) SAL = Setaria (wild millet) CYE = Cyperus (nutsedge) LOM = Lolium (rye grass) CND = Cynodon (Bermuda grass3 POA = Poa (meadow grass) SRH = Sorghum 30 SDS = Sida DIS = Digitaria (crabgrass) AS = Active substance COA = Convolvulus (bind-weed) ABT = Abutylon CRS = Chrysanthemum ~; (yellow ox-eye) Seeds of Echinochloa crus-galli were sown in pots of plastic material filled with loamy soil and placed in a J
1 lB2071 greenhouseO After 3 weeks, in the stage of 3 to 4 leaves, the plants were sprayed with solutions containing the herbi-cide alone or in admixture with a synergist in varying do-sage; the application concentration of the synergist being 3.6 kg/ha in all cases. For comparison, a solution contain-ing the synergist alone was used. 2 Weeks after treatment the percent degree of plant damage was evaluated in compari-son with untreated controls. The results listed in Table 2 show that the synergist alone did not damage the plants, but in combination with the test herbicide considerably in-creased the herbicidal effect against Echinochloa crus-galli.
Table 2 damage of Echinochloa (effect i~ %) _ .. _ . .. _. .. _ _ ... . .. .. .. _ _ . _ . .. .. _ , Compound Dose ECG
-- -- _ _ kg a.s./ha _ . . . . . .. . . , , _ _ ammonium salt of 0.2 ~0 phosp~no~icine _ _ _ 0.1 50 ~A lIIj 0 05 40 -- ---------- 0.025 5 amm~nium nitrate _ _ . . .. . _ _ _ .. . . _ (B II) 3.6 0 ~ ITI ~ B ~I 0.2 + 3.6 9~
Q.1 1 3.6 80 0.05 ~ 3.6 ~5 0 025 + 3.6 ~0 Under the conditions described in Example 1 the plants listed in Table 3 were grown from seeds in pots of plastic material and treated in the stage of 3 to 4 leaves with 0.4, 0.2 and 0.1 kg/ha~ respectively, of phosphinothricine mono-ammonium salt (A III) and phosphinothricine (A I) alone and in combination with synergists. 3 Weeks after application the percent degree of plant damage was evaluated in compari-son with untreated controls. Table 3 shows that the syner-gists alone in the tested concentrations had no herbicidal -' ~ 16207~
effect. When 9 however, applying these substances together with A III and A I, the herbicidal effect of the latter was considerably increased in all concentrations. This unex-pected synergism allows reduction of the herbicide concen-tration to about one half.
Table 3 damage in % of untreated control . _ .. .. . . _ . .. ... .. . . .
Compound Dose AVF ALM LOM ECG AGR CMD POA
~g/ha urea (B III~ 3 . -.. . .
Na-EDTA
(C I) 3 0 0 0 0 0 0 phosphinothricLneo.445 40 63 0 0 30 (A I) 0.2 10 30 50 - - 15 A III 0.4 45 30 3594 13 10 0.2 15 5 2390 - - -0.1 10 0 1510 - - -. .... _ . .
A III ~ B III 0.4 + 3 4548 6010025 1~ -0.~ ~ 3 3040 309~
: 0.1 ~ 3 200 2545 - - -~ . . _ _ _ . . _ . _ .
: A III ~ B I 0.4 + 6 8075 80100 65 50 : 0.2 ~ 6 4565 68100 - ~ -: : 0.1 ~ 6 2Q20 3399 ~ . . _ .. _ . __ _ _ : A IIl ~ C I 0.4 ~ 3 5573 68100 35 20 . 0.2 ~ 3 4538 439g + 3 2020 2388 - - -: A I + B I 0.4 ~ 6 8375 93 65 55 45 0.2 + 6 2555 B8 - ~ 30 Under the conditions of Example 1, the plants listed in Table 4 were grown and sprayed in the 3 to 4 leaf stage either with herbicide or synergists alone or in combination with each other. 3 Weeks after the application, the damage .. ,~................................... .
62û7~
was evaluated. The results are listed in Table 4.
In admixture with phosphinothricine ammonium salt ~A III), the synergists produced a pronounced damage of the weeds even at very low herbicide doses, while alone they had no or little phytotoxic effect .
Table 4 (damage in %) Compound Dose CYE SDS ECG SRH DIS
kg AS/ha -B I 6.0 0 0 0 0 0 _. . _ _.. . . . ... . .
ammonium chloride (~ IV) 4.8 0 0 0 0 0 C I 3.0 0 0 5 0 0 , . . ..
~otassium triphosphate .~
3) 3 (C II~: 3.0 0 0 5 0 0 A III 0.4 30 0.2 10 98 25 40 70 0.1 - 70 13 8 ~5 A III + B I0.4 ~ 6 70 - 0~2 ~ 6 5~ 100 g0 ~ 99 0.1 + 6 - 97 58 48 _ 88 IV0.4 ~ 4.8 55 0.2 ~ 4.8 50 100 70 70 98 _0.1 ~ 4.8 - 98 30 35 68 A III ~ C I0.4 + 3.0 60 - - ~
0.2 i 3.0 50 100 90 83 80 0.1 ~ 3.0 - 90 68 55 ~5 .
:~: A III + C II 0.4 + 3.0 60 - - - ~-0.~ + 3.0 35 100 80 80 100 O.1 + 3.0 - 80 60 48 88 : ~ Under the conditions of Example 1 the plants listed in Table 5 were grown and sprayed in the stage of 3 to 4 leaves either with different phosphinothricine salts and ammonium sulfate, respectively, alone or in combination with each other. The ammonium sulfate dosage corresponded to 6 kg/ha, ....
0 7 i while the phosphinothricine salts were applied in varying doses. The water amount corresponded to 400 liters/ha.
Three weelcs after application the damage was evaluated. The results are listed in Table 5. They show that ammonium sulfate alone had no herbicidal efficiency; however, in combination with the alkali and alkaline earth metal salt and ammonium salt of phosphinothricine the herbicidal effi-ciency of the latter against mono- and dicotyledonous weed species was considerably increased. Without addition of ammonium sulfate two or even four times the amount of phosphinothricine derivative was necessary in order to attain the same herbicidal effect.
Table 5(damage in %) Compound Dose AGR LOM CRS COA
(kg AS/ha) _ _ ammonium sulfate 6.0 0 0 0 0 (B I) _ calcium salt of 0.8 75 75 phosphinothr-cine 0.4 43 47 (A IV) 0.2 33 30 53 0.1 37 . _ A IY + B Io.8 + 6.0 95 g2 0.4 + 6.0 87 63 0.2 + 6.0 70 43 90 0.1 + ~.0 73 monopotassium 0.8 78 47 salt of phosphi- 0.4 47 33 nothricine (A V) 0.2 28 25 60 0.1 27 A V + B I0.8 + 6.0 93 85 0.4 + 6.0 75 68 0.2 + 6.0 57 l~3 97 0.1 + 6.0 67 Table 5 (contd.) (damage in %) Compound Dose AGR LOM CRS COA
(kg AS/ha) .
dipotassium 0.8 60 57 salt of phosphi- 0.4 43 37 nothricine (A VI) 0.2 30 27 47 0.1 37 . . .
A VI + B I 0.8 + 5.0 94 83 0.4 + 6.0 75 63 0.2 + 6.0 53 4398 O.~ + 6.0 50 monosodium salt 0.8 7767 of phosphinothri- 0.4 50 43 85 cine (A VII) 0.2 33 3 43 0.1 23 A VII + B I0.8 + 6.0 91 80 .4 + 6.0 75 65100 0.2 ~ 6.0 63 43100 0.1 + 6.o ~o ammonium salt 0.8 87 68 of phosphino- 0.4 73 4398 53 :thricine (A III) 0.2 . 43 30 l~O 33 O.~ 20 27 A III + B Io.8 + 6.0 96 93 0.4 + 6.0 82 73 100 95 0.2 + 6.o 75 43 100 70 0.1 + 6.0 53 47 :
In combating perennial weeds, suppression of resprout-ing from underground plant organs (rhizomes, root-stocks) is particularly important. In a test on quack-grass ~Agropy-ron) the influence of addition of ammonium sulfate (4 kg/ha) to phosphinothricine ammonium salt on the long-time effect-., . ~ .
~ 1~20~1- 13 - OE 80/F 041 iveness of this herbicide ~as examined.
Quack-grass plants were grown under greenhouse condi-tions in buckets of plastic material filled with sandy loam, and in the 5 to 6 leaf stage were sprayed with varying doses of phosphinothricine ammonium salt (A III) alone and in com-bination with 4 kg/ha of ammonium sulfate (B I) (water corresp. to 400 l/ha). After a residence time of 4 weeks in the greenhouse the overground parts of the treated and un-treated plants were cut off and the recipients were placed for a further 7 weeks in the greenhouse. Thereaf~er, the leaves which had sprouted anew were cut off, dried at 100C, and the dry mass of the leaves was determined.
The dry leaf mass per recipient of treated test plants was compared with that of untreated controls. The results are l~stad in Table 6.
Addition of ammonium sulfate to all doses of active substance resulted in increased suppression of resprouting while ammonium sulfate alone had no effect at all. The results demonstrate that in the case of perennial plants ammonium sulfate obviously increases the systemic effect of phosphinothricine and thus prolongs the lasting effect of this herbicide.
Table 6 Resprouting of quack-grass 11 weeks after herbi-cide treatment (resprouted leaf mass of treated plants in percent relative to leaf mass of untreated controls) Product Dose leaf mass (kg AS/ha) (% control) -A III 2.0 16 1.0 48 0.5 81 _ A III I B I2.0 + 4.0 0.5 .0 ~ 4.~ 22 0.5 + 4.0 31 .
.
- '14 - HOE 80/F 041 A ~l ~ L ~ ~
According to the method of Example 1, plants were grown and sprayed in the 3 to 4 leaf stage with solutions of the compounds indicated in Tables 7 and 8. The water amount correspGnded to 400 l/ha (with synergists B V, B VI, B VII) and 200 l/ha (with B VIII).
4 Weeks after application the damage was evaluated.
As Tables 7 and 8 demonstrate, the ethanolamine salts and piperidine generally improved the herbicidal action of phosphinothricine ammonium salt. In combination with the synergists about one half of the amount of A III required when using the herbicide alone was sufficient to achieve the same degree of activity. When used alone, the synergists had no herbicidal activity.
t5 Table 7 (plant damage in ~) Compound ~ose LOM ABT IPP
(kg AS/ha) Monoethanol-ammonium acetate 1.0 0 0 O
(B V) Diethanolammo-nium acetate1.0 0 0 0 (B VI) Triethanolammo~
nium acetate1.0 0 0 0 (B VII) ~
ammonium salt 0.8 66 61 of phosphinthri- 0.4 20 86 50 cine (A IIT)0.2 3 58 25 O.t - 6 -A III + B V0.8 + 100 84 - 85 0,4 + 1.0 43 99 80 0.2 + 1.0 9 90 28 0.1 ~ 1.0 - 65 A III + B VIo.8 + 1.0 76 - 92 0.4 + 1.0 53 100 77 0.2 + 1.0 18 99 30 0.1 + 1.0 - 73 `` 11 162071 - 15 HOE 80/F_041 Table 7 (contd.) (plant damage in %) Compound Dose LOM ABT IPP
(kg AS~ha-) A III + B VIIo.8 ~ 1.0 76 - 93 0.4 + 1.0 48 98 70 0.2 + 1.0 20 70 30 0.1 + 1.0 - 60 :
Table 8 (p'ant damage in %) Compound Dose ALM LOM CRS
(kg AS/ha) Piperidine 2~0 0 0 0 (B VIII) ; ~ ammonium salt 0.8 65 55 100 ~: of phosphino- 0.4 30 40 98 : thri~ine tA III) 0.2 25 25 85 A III + B VIII0.8 ~ 1.0 70 70 100 :: ; 0.4 + 1.0 45 45 100 0.2 + 1.0 40 40 95 :
~ -
The recently found phosphinothricine type herbicides of the formula 3 \
P ~ CH2 - CH2 - CH - COOH
have a good contact activi~y and are well absorbed by leaves, so that they are suitable for non-selectively combating weeds of all botanic classes. They are therefore applicable against undesirable plant growth on farming grounds, industrial areas etc. ~see German Offenlegungsschrift No. 2,717,440).
Herbicides of the phosphinothricine type are effective against annual as well as perennial weeds and weed grasses. Some economically import-ant perennial weeds such as quack-grass (Agropyron repens), Bermuda grass (Cynodon dactylon), perennial cyperaceae and corresponding dicotyledonous weeds,however, are sufficiently combated only with increased herbicide amounts.
Surprisingly, it has now been found that the addition to phosphino-thricine and its derivatives of certain types of organic and inorganic compoundswhich for themselves have no herbicidal activity produces a pronounced syner-gistic effect, that lS, considerably increases the herbicidal efficiency againstannual and perennial weeds.
According to one aspect of the present invention there is provided a herbicidal composition which comprises an amount of:
~ A) a phosphinothricine derivative of the formula H C O
~:: 3 ~ 11 P - CH - CH - CH - COOH
~; / 2 2 in which R is hydrogen or ~Cl-C4)-alkyl, a salt thereof with an acid or base or a peptide thereof, in combination with;
"~
l 162~7~
B~ an inorganic or organic ammonium salt of the formula R2 _ N - R4 X II
R n in which Rl to R4, being identical or different, each are hydrogen, ~Cl-C4)-alkyl or hydroxyethyl, or two of the radicals Rl to R4 together with the nitro-gen atom form a 3- to 7-membered ring a -CH2 group of which may be replaced by 0, NH or N(Cl-C4)-alkyl; X is the anion of an inorganic or organic mono- or polybasic acid and n is 1, 2 or 3, or with the free base from which the salt of the formula II are derived, or with a precursor metabolizing under physiologi-cal conditions to a compound of the formula II; or C) an inorganic or organic chelating agent, selected from the group consisting of polybasic organic acids or their salts, and water-soluble poly-phosphates of different chain length which are used in the soap and detergent industry, wherein the weight ratio of components A to B or C is from 4 : 1 to 150, with the proviso that, if R in formula I is hydrogen, the compound B
is not a free base. Preferably, the peptide in component A is phosphinothricyl-alanyl-alanine.
According to another aspect of the present invention there is pro-vided a method for combating weeds which comprises applying to the areas infested by them the above composition in an amount of from 0.125 to 35 kg of active substance ~component A ~ component B or C) per hectare.
Phosphinothricine and its derivatives have an asymmetric carbon atom, and thus may be present in the form of racemates or optionally active enantlomers, the L-enantiomer of which is especially preferred in accordance wlth the invention.
; A) Due to their amphoteric nature, phosphinothricine and its esters are able to form salts with inorganic and organic bases and acidsj which salts 07~
may likewise be used for the compositions of the invention. When using bases, compounds are formed in which R is cation equivalent. The following cation equivalents are particularly important: Na , K , 1/2 Ca , lt2 Zn , 1/2 Mg N~ N~(CH3)4, H2N (CH3)2, H2N ~C2H5)2, NH ~C2H5)3' 3 3 3 3 7 4 9 2 3 7 )2~ H3N CH2CH20H, H2N (CH2CH20H), HN~CH CH OH) ~CH3)3N CH2CH20H, (CH3)2N HCH2CH20H, CH3N H2CH2CH20H, (CH3)2N HC12H25, and the guanidinium ion.
When using strong bases, the -COOH group is ionized, too, and diso-dium or dipotassium salts, for example, are obtained in these cases.
1~ For salt formation with acids, any inorganic and organic acids such as HCl, HBr, H2S04, H3PO4, }INO3 or CH3COOH may be used.
In accordance with the invention, oligopeptides of phosphinothricine are alternatively suitable as component A, such as phosphinothricyl-alanyl-alanine which is described in ~ -3a-1 182~71 Helv. Chim. Acta 55, 224 seq. (1972).
B) The B type compounds are preferably ammonium salts (R1 to R4 = H), but salts of organic ammonium bases with any anions (see A) may also be used. Preferred organic ammonium salts have cations such as enumerated sub A) and anions such as Cl , Br , S04 , HS04, P03 , Hpo42 , , '~2P04, CH3COO , (COO )22 , or SCN .
Compounds which metabolize in the ?lant to form ammo-nium ions are likewise useful, for example urea, aspartic or glutamic acid.
Instead of the ammonium salts II, the free bases from which they are derived, for example triethylamine or piperi-dine, may be used in combination with phosphinothricine - esters, salts or peptides.
C) Suit~ble complexing agents of type C are for example polybasic organic acids such as oxalic, succinic, tartaric, citric, nitrilotriacetic or ethylenediamine-tetra-acetic acid (EDTA~ or their salts, furthermore water-soluble polyphosphates of different chain length (metaphosphates, triphosphates) which are used in the soap and detergent industry. Such complexing agents are described for example in O.A. Neumuller: Rompps Chemielexikon, 7nd. ed. 1972, pp. 545 and 2768 seq.
The compounds of types B ànd C can be combined with the A type herbicides either individually, or several of them in any number may be employed.
The mixing ratio of the individual components in the combinations of the invention may vary within wide limits. A synergistic effect is observed at a ratio of A : B(C) between 4 : 1 and 1 : 150. For practical reasons, the mixing ratio is chosen in a range of from 2 : 1 to 1 : 50, preferably 1 : 1 to 1 : 10.
The mixtures of the invention may have the form of ready-to-use formulations, for example wettable powders or emulsifiable concentrates, which are applied in usual manner as aqueous dilutions, or as so-called tank mixtures which are prepared immediately before application by common~ dilu~
tion of the separately formulated components with water.
I lB207~
Alternatively, the herbicides and the synergists may be separately applied as spray liquors or aqueous solutions;
the sequence of the components being irrelevant.
The application concentration of the A type herbicides in the mixtures of active substances is generally from 0.10 to 5 kg/ha, that of B and C from 0.025 to 30 kg/ha; that iS3 the total amount of active substance combination is in the range of .rom about 0.125 to 35 kg/ha.
The compositions o. the invention can be employed in form of the usual formulations known to the expert skilled in the art, for example as wettable powders, dusts, granu-les, emulsifiable concentrates or sprayable solutions, and contain generally from 2 to 95 weight % of the combinations of active substances according to the invention.
Wettable powders are formulations which are uniformly dispersible ln water and which, in addition to the active compound, and a diluent or inert material, also contain wetting agents, for example, polyoxyethylated alkylphenols, alkylsulfonates or alkylphenylsulfonates, and dispersing agents, for example sodium ligninsulfonate, sodium-dinaph-thylmethane-disulfonate, or the sodium salt of oleoyl-methyl-taurir.e.
Emulsifiable concentrates are obtained by dissol~ing the active ^ompound in an organic solvent, for example, butanol, cyclohexanone, dimethylformamide, xylene or even higher-boiling aromatics, and adding an emulsifier, for example, a polyoxyethylated alklphenol.
In the case the herbicidai compositions, the concen-trations of the active compounds in the commercial formula-tions can vary. In wettable powders, the active compoundconcentration (herbicide and synergist) varies, for example, between about 1u and 95 %, the remainder consisting of one or more of the above-mentioned formulation additives. In the case of emulsifiable concentrates, the active compound concentration is about 10 to 80 %. Dust formulations usually contain 5 - 20 g of active compound, and sprayable solutions about 2 - 20 %. In the case of granules, the active compound content in part depends on whether the ,. .
1 16207~
active compound is in a liquid or solid form and what granu-- Lating auxiliaries, fillers and the like are used.
If necessary or desired the commercial concentrates may be diluted prior to application in the usual manner, for example by means of water in the case of wettable powders and emulsifiable concentrates. Dust, granules and sprayable solutions are generally ready for use without further dilu-tion with inerc materials. The amount of active ingredient necessary for obtaining th desired result depends on exter-nal conditions such as temperature, humidity and the like.
The actiYe compounds according to the invention can becombined with other herbicides, fungicides and insecticides.
The following examples illustrate the invention.
i5 E X A M P L E
Seeds of annual weeds and rhizomes of perennial noxious plants were placed in pots of plastic material filled with loamy soil, and left in a greenhouse under favorable growth conditions. After 3 weeks, the plants had formed 3 to 4 leaves, in which stage they were sprayed either with the herbicide at varying dosage, or with mixtures of herbicide and synergists; the application concentration being main-tained at a constant 12 kg/ha. For comparison, further test plants were treated with a solution of the synergist alone.
In all cases, the amount of liquid corresponded to 600 l/ha.
3 Weeks after the treatment, the degree of damage of the plants treated was evaluated in comparison with the ~ntreated control.
The results listed in Table 1 show that the synergist alone did not damage the plants, but in combination with the test herbiclde considerably increased the herbicidal effect.
In the case of Alopecurus, for example, a herbicide concen-tration of 0.~ kg/ha yielded an 80 % damage of the plants;
the same degree of damage was attained at a herbicide amount of 0.15 kg/ha only with the addition of 12 kg/ha of the synergist.
The improved effect in the perennial weeds Agropyron (quack-grass), Cyperus (nutsedge) and Cyanodon (Bermuda 6~71 grass) by addition of the synergists was also remarkable.
These are weeds of special economic importance, which are normally difficult to combat.
Table 1 (Plant damage in %) .. . . _, . . _ . . . . . . . .. .
Compound Dose AVF ALM SAL LO~S ECG AGR CYE CND
kg AS/ha Phosphino- 0.6 75 80100 95 90 32 65 55 .. . _ .. .. ... . .. .
thricme hydro- 0.15 32 3270 32 38 - - -.. . _ . . _ .. ...
chlori~e 0.08 0 0 32 0 11 - - -(A II) ammonium 12.0 0 0 0 0 O O O O
_. _ _ . .... ~
sulfate (B I) A II ~ B I 0.6 ~ 12.0 1OG g5100 100 94 85 85 90 0.15 ~ 12.0 65 8085 70 74 - -0.08 + 12.0 32 3265 65 38 - ~ ~
.
Abbreviation for Tables 1 to &:
.
AVF = Avena (wild oats) ECG = Echinochloa (barn-yard grass) ALM - Alopecurus (annual black- AGR = Agropyron (quack-grass) grass) SAL = Setaria (wild millet) CYE = Cyperus (nutsedge) LOM = Lolium (rye grass) CND = Cynodon (Bermuda grass3 POA = Poa (meadow grass) SRH = Sorghum 30 SDS = Sida DIS = Digitaria (crabgrass) AS = Active substance COA = Convolvulus (bind-weed) ABT = Abutylon CRS = Chrysanthemum ~; (yellow ox-eye) Seeds of Echinochloa crus-galli were sown in pots of plastic material filled with loamy soil and placed in a J
1 lB2071 greenhouseO After 3 weeks, in the stage of 3 to 4 leaves, the plants were sprayed with solutions containing the herbi-cide alone or in admixture with a synergist in varying do-sage; the application concentration of the synergist being 3.6 kg/ha in all cases. For comparison, a solution contain-ing the synergist alone was used. 2 Weeks after treatment the percent degree of plant damage was evaluated in compari-son with untreated controls. The results listed in Table 2 show that the synergist alone did not damage the plants, but in combination with the test herbicide considerably in-creased the herbicidal effect against Echinochloa crus-galli.
Table 2 damage of Echinochloa (effect i~ %) _ .. _ . .. _. .. _ _ ... . .. .. .. _ _ . _ . .. .. _ , Compound Dose ECG
-- -- _ _ kg a.s./ha _ . . . . . .. . . , , _ _ ammonium salt of 0.2 ~0 phosp~no~icine _ _ _ 0.1 50 ~A lIIj 0 05 40 -- ---------- 0.025 5 amm~nium nitrate _ _ . . .. . _ _ _ .. . . _ (B II) 3.6 0 ~ ITI ~ B ~I 0.2 + 3.6 9~
Q.1 1 3.6 80 0.05 ~ 3.6 ~5 0 025 + 3.6 ~0 Under the conditions described in Example 1 the plants listed in Table 3 were grown from seeds in pots of plastic material and treated in the stage of 3 to 4 leaves with 0.4, 0.2 and 0.1 kg/ha~ respectively, of phosphinothricine mono-ammonium salt (A III) and phosphinothricine (A I) alone and in combination with synergists. 3 Weeks after application the percent degree of plant damage was evaluated in compari-son with untreated controls. Table 3 shows that the syner-gists alone in the tested concentrations had no herbicidal -' ~ 16207~
effect. When 9 however, applying these substances together with A III and A I, the herbicidal effect of the latter was considerably increased in all concentrations. This unex-pected synergism allows reduction of the herbicide concen-tration to about one half.
Table 3 damage in % of untreated control . _ .. .. . . _ . .. ... .. . . .
Compound Dose AVF ALM LOM ECG AGR CMD POA
~g/ha urea (B III~ 3 . -.. . .
Na-EDTA
(C I) 3 0 0 0 0 0 0 phosphinothricLneo.445 40 63 0 0 30 (A I) 0.2 10 30 50 - - 15 A III 0.4 45 30 3594 13 10 0.2 15 5 2390 - - -0.1 10 0 1510 - - -. .... _ . .
A III ~ B III 0.4 + 3 4548 6010025 1~ -0.~ ~ 3 3040 309~
: 0.1 ~ 3 200 2545 - - -~ . . _ _ _ . . _ . _ .
: A III ~ B I 0.4 + 6 8075 80100 65 50 : 0.2 ~ 6 4565 68100 - ~ -: : 0.1 ~ 6 2Q20 3399 ~ . . _ .. _ . __ _ _ : A IIl ~ C I 0.4 ~ 3 5573 68100 35 20 . 0.2 ~ 3 4538 439g + 3 2020 2388 - - -: A I + B I 0.4 ~ 6 8375 93 65 55 45 0.2 + 6 2555 B8 - ~ 30 Under the conditions of Example 1, the plants listed in Table 4 were grown and sprayed in the 3 to 4 leaf stage either with herbicide or synergists alone or in combination with each other. 3 Weeks after the application, the damage .. ,~................................... .
62û7~
was evaluated. The results are listed in Table 4.
In admixture with phosphinothricine ammonium salt ~A III), the synergists produced a pronounced damage of the weeds even at very low herbicide doses, while alone they had no or little phytotoxic effect .
Table 4 (damage in %) Compound Dose CYE SDS ECG SRH DIS
kg AS/ha -B I 6.0 0 0 0 0 0 _. . _ _.. . . . ... . .
ammonium chloride (~ IV) 4.8 0 0 0 0 0 C I 3.0 0 0 5 0 0 , . . ..
~otassium triphosphate .~
3) 3 (C II~: 3.0 0 0 5 0 0 A III 0.4 30 0.2 10 98 25 40 70 0.1 - 70 13 8 ~5 A III + B I0.4 ~ 6 70 - 0~2 ~ 6 5~ 100 g0 ~ 99 0.1 + 6 - 97 58 48 _ 88 IV0.4 ~ 4.8 55 0.2 ~ 4.8 50 100 70 70 98 _0.1 ~ 4.8 - 98 30 35 68 A III ~ C I0.4 + 3.0 60 - - ~
0.2 i 3.0 50 100 90 83 80 0.1 ~ 3.0 - 90 68 55 ~5 .
:~: A III + C II 0.4 + 3.0 60 - - - ~-0.~ + 3.0 35 100 80 80 100 O.1 + 3.0 - 80 60 48 88 : ~ Under the conditions of Example 1 the plants listed in Table 5 were grown and sprayed in the stage of 3 to 4 leaves either with different phosphinothricine salts and ammonium sulfate, respectively, alone or in combination with each other. The ammonium sulfate dosage corresponded to 6 kg/ha, ....
0 7 i while the phosphinothricine salts were applied in varying doses. The water amount corresponded to 400 liters/ha.
Three weelcs after application the damage was evaluated. The results are listed in Table 5. They show that ammonium sulfate alone had no herbicidal efficiency; however, in combination with the alkali and alkaline earth metal salt and ammonium salt of phosphinothricine the herbicidal effi-ciency of the latter against mono- and dicotyledonous weed species was considerably increased. Without addition of ammonium sulfate two or even four times the amount of phosphinothricine derivative was necessary in order to attain the same herbicidal effect.
Table 5(damage in %) Compound Dose AGR LOM CRS COA
(kg AS/ha) _ _ ammonium sulfate 6.0 0 0 0 0 (B I) _ calcium salt of 0.8 75 75 phosphinothr-cine 0.4 43 47 (A IV) 0.2 33 30 53 0.1 37 . _ A IY + B Io.8 + 6.0 95 g2 0.4 + 6.0 87 63 0.2 + 6.0 70 43 90 0.1 + ~.0 73 monopotassium 0.8 78 47 salt of phosphi- 0.4 47 33 nothricine (A V) 0.2 28 25 60 0.1 27 A V + B I0.8 + 6.0 93 85 0.4 + 6.0 75 68 0.2 + 6.0 57 l~3 97 0.1 + 6.0 67 Table 5 (contd.) (damage in %) Compound Dose AGR LOM CRS COA
(kg AS/ha) .
dipotassium 0.8 60 57 salt of phosphi- 0.4 43 37 nothricine (A VI) 0.2 30 27 47 0.1 37 . . .
A VI + B I 0.8 + 5.0 94 83 0.4 + 6.0 75 63 0.2 + 6.0 53 4398 O.~ + 6.0 50 monosodium salt 0.8 7767 of phosphinothri- 0.4 50 43 85 cine (A VII) 0.2 33 3 43 0.1 23 A VII + B I0.8 + 6.0 91 80 .4 + 6.0 75 65100 0.2 ~ 6.0 63 43100 0.1 + 6.o ~o ammonium salt 0.8 87 68 of phosphino- 0.4 73 4398 53 :thricine (A III) 0.2 . 43 30 l~O 33 O.~ 20 27 A III + B Io.8 + 6.0 96 93 0.4 + 6.0 82 73 100 95 0.2 + 6.o 75 43 100 70 0.1 + 6.0 53 47 :
In combating perennial weeds, suppression of resprout-ing from underground plant organs (rhizomes, root-stocks) is particularly important. In a test on quack-grass ~Agropy-ron) the influence of addition of ammonium sulfate (4 kg/ha) to phosphinothricine ammonium salt on the long-time effect-., . ~ .
~ 1~20~1- 13 - OE 80/F 041 iveness of this herbicide ~as examined.
Quack-grass plants were grown under greenhouse condi-tions in buckets of plastic material filled with sandy loam, and in the 5 to 6 leaf stage were sprayed with varying doses of phosphinothricine ammonium salt (A III) alone and in com-bination with 4 kg/ha of ammonium sulfate (B I) (water corresp. to 400 l/ha). After a residence time of 4 weeks in the greenhouse the overground parts of the treated and un-treated plants were cut off and the recipients were placed for a further 7 weeks in the greenhouse. Thereaf~er, the leaves which had sprouted anew were cut off, dried at 100C, and the dry mass of the leaves was determined.
The dry leaf mass per recipient of treated test plants was compared with that of untreated controls. The results are l~stad in Table 6.
Addition of ammonium sulfate to all doses of active substance resulted in increased suppression of resprouting while ammonium sulfate alone had no effect at all. The results demonstrate that in the case of perennial plants ammonium sulfate obviously increases the systemic effect of phosphinothricine and thus prolongs the lasting effect of this herbicide.
Table 6 Resprouting of quack-grass 11 weeks after herbi-cide treatment (resprouted leaf mass of treated plants in percent relative to leaf mass of untreated controls) Product Dose leaf mass (kg AS/ha) (% control) -A III 2.0 16 1.0 48 0.5 81 _ A III I B I2.0 + 4.0 0.5 .0 ~ 4.~ 22 0.5 + 4.0 31 .
.
- '14 - HOE 80/F 041 A ~l ~ L ~ ~
According to the method of Example 1, plants were grown and sprayed in the 3 to 4 leaf stage with solutions of the compounds indicated in Tables 7 and 8. The water amount correspGnded to 400 l/ha (with synergists B V, B VI, B VII) and 200 l/ha (with B VIII).
4 Weeks after application the damage was evaluated.
As Tables 7 and 8 demonstrate, the ethanolamine salts and piperidine generally improved the herbicidal action of phosphinothricine ammonium salt. In combination with the synergists about one half of the amount of A III required when using the herbicide alone was sufficient to achieve the same degree of activity. When used alone, the synergists had no herbicidal activity.
t5 Table 7 (plant damage in ~) Compound ~ose LOM ABT IPP
(kg AS/ha) Monoethanol-ammonium acetate 1.0 0 0 O
(B V) Diethanolammo-nium acetate1.0 0 0 0 (B VI) Triethanolammo~
nium acetate1.0 0 0 0 (B VII) ~
ammonium salt 0.8 66 61 of phosphinthri- 0.4 20 86 50 cine (A IIT)0.2 3 58 25 O.t - 6 -A III + B V0.8 + 100 84 - 85 0,4 + 1.0 43 99 80 0.2 + 1.0 9 90 28 0.1 ~ 1.0 - 65 A III + B VIo.8 + 1.0 76 - 92 0.4 + 1.0 53 100 77 0.2 + 1.0 18 99 30 0.1 + 1.0 - 73 `` 11 162071 - 15 HOE 80/F_041 Table 7 (contd.) (plant damage in %) Compound Dose LOM ABT IPP
(kg AS~ha-) A III + B VIIo.8 ~ 1.0 76 - 93 0.4 + 1.0 48 98 70 0.2 + 1.0 20 70 30 0.1 + 1.0 - 60 :
Table 8 (p'ant damage in %) Compound Dose ALM LOM CRS
(kg AS/ha) Piperidine 2~0 0 0 0 (B VIII) ; ~ ammonium salt 0.8 65 55 100 ~: of phosphino- 0.4 30 40 98 : thri~ine tA III) 0.2 25 25 85 A III + B VIII0.8 ~ 1.0 70 70 100 :: ; 0.4 + 1.0 45 45 100 0.2 + 1.0 40 40 95 :
~ -
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A herbicidal composition which comprises an amount of:
A) a phosphinothricine derivative of the formula I
in which R is hydrogen or (C1-C4)-alkyl, a salt thereof with an acid or base or a peptide thereof, in combination with;
B) an inorganic or organic ammonium salt of the formula II
in which R1 to R4, being identical or different, each are hydrogen, (C1-C4)-alkyl or hydroxyethyl, or two of the radicals R1 to R4 together with the nitro-gen atom form a 3- to 7-membered ring a -CH2 group of which may be replaced by O, NH or N(C1-C4)-alkyl; X is the anion of an inorganic or organic mono- or polybasic acid and n is 1, 2 or 3, or with the free base from which the salt of the formula II are derived, or with a precursor metabolizing under physio-logical conditions to a compound of the formula II; or C) an inorganic or organic chelating agent, selected from the group consisting of polybasic organic acids or their salts, and water-soluble poly-phosphates of different chain length which are used in the soap and detergent industry, wherein the weight ratio of components A to B or C is from 4 : 1 to 1 :150, with the proviso that, if R in formula I is hydrogen, the compound B
is not a free base.
A) a phosphinothricine derivative of the formula I
in which R is hydrogen or (C1-C4)-alkyl, a salt thereof with an acid or base or a peptide thereof, in combination with;
B) an inorganic or organic ammonium salt of the formula II
in which R1 to R4, being identical or different, each are hydrogen, (C1-C4)-alkyl or hydroxyethyl, or two of the radicals R1 to R4 together with the nitro-gen atom form a 3- to 7-membered ring a -CH2 group of which may be replaced by O, NH or N(C1-C4)-alkyl; X is the anion of an inorganic or organic mono- or polybasic acid and n is 1, 2 or 3, or with the free base from which the salt of the formula II are derived, or with a precursor metabolizing under physio-logical conditions to a compound of the formula II; or C) an inorganic or organic chelating agent, selected from the group consisting of polybasic organic acids or their salts, and water-soluble poly-phosphates of different chain length which are used in the soap and detergent industry, wherein the weight ratio of components A to B or C is from 4 : 1 to 1 :150, with the proviso that, if R in formula I is hydrogen, the compound B
is not a free base.
2. A herbicidal composition according to Claim 1, wherein component A
is present in the form of the L-enantiomer.
is present in the form of the L-enantiomer.
3. A herbicidal composition according to Claim 1, wherein ammonium sulfate is used as component B.
4. A herbicidal composition according to Claim 1, 2 or 3, wherein the peptide in component A is phosphinothricyl-alanyl-alanine.
5. A composition according to Claim 1, 2 or 3,wherein the weight ratio of components A to B or C is from 2 : 1 to 1 : 50.
6. A composition according to Claim 1, 2 or 3, wherein the weight ratio of components A to B or C is from 1 : 1 to 1 : 10.
7. A method for combating weeds which comprises applying to the areas infested by them a composition according to Claim 1, 2 or 3 in an amount of 0.125 to 35 kg of active substance (component A + component B or C) per hectare.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803008186 DE3008186A1 (en) | 1980-03-04 | 1980-03-04 | SYNERGISTIC COMBINATIONS OF PHOSPHINOTHRICIN |
| DEP3008186.8 | 1980-03-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1162071A true CA1162071A (en) | 1984-02-14 |
Family
ID=6096186
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000372216A Expired CA1162071A (en) | 1980-03-04 | 1981-03-03 | Synergistic combinations of phosphinothricine |
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| Country | Link |
|---|---|
| EP (1) | EP0036106B1 (en) |
| JP (1) | JPS56135409A (en) |
| AU (1) | AU539256B2 (en) |
| BR (1) | BR8101233A (en) |
| CA (1) | CA1162071A (en) |
| CS (1) | CS221287B2 (en) |
| DD (1) | DD156892A5 (en) |
| DE (2) | DE3008186A1 (en) |
| DK (1) | DK95981A (en) |
| ES (1) | ES499839A0 (en) |
| GR (1) | GR74156B (en) |
| HU (1) | HU186384B (en) |
| IL (1) | IL62241A0 (en) |
| MA (1) | MA19085A1 (en) |
| NZ (1) | NZ196380A (en) |
| OA (1) | OA06759A (en) |
| PH (1) | PH19742A (en) |
| PL (1) | PL229976A1 (en) |
| PT (1) | PT72607B (en) |
| ZA (1) | ZA811397B (en) |
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| JP6180936B2 (en) | 2010-11-02 | 2017-08-16 | バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＢａｙｅｒ Ｉｎｔｅｌｌｅｃｔｕａｌ Ｐｒｏｐｅｒｔｙ ＧｍｂＨ | Phenyl-substituted bicyclooctane-1,3-dione derivative |
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| EP2505061A1 (en) * | 2011-03-30 | 2012-10-03 | Rhodia Opérations | New uses of choline chloride in agrochemical formulations |
| ES2550391T3 (en) | 2011-03-01 | 2015-11-06 | Bayer Intellectual Property Gmbh | 2-Acyloxy-pyrrolin-4-ones |
| WO2016001129A1 (en) | 2014-07-01 | 2016-01-07 | Bayer Cropscience Aktiengesellschaft | Improved insecticidal compositions |
| JP2021521157A (en) | 2018-04-13 | 2021-08-26 | バイエル・クロップサイエンス・アクチェンゲゼルシャフト | Oily Suspension Concentrate |
| WO2019197619A1 (en) | 2018-04-13 | 2019-10-17 | Bayer Cropscience Aktiengesellschaft | Oil-based suspension concentrates |
| CN109369712B (en) * | 2018-12-12 | 2019-10-29 | 浙江大学 | A method of with calcium salt separating-purifying glufosinate-ammonium |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3231509A (en) * | 1964-06-11 | 1966-01-25 | Betz Laboratories | Slimicidal composition and method |
| DE2717440C2 (en) * | 1976-05-17 | 1984-04-05 | Hoechst Ag, 6230 Frankfurt | Weed control with [(3-amino-3-carboxy) propyl-1] methylphosphinic acid derivatives |
| CA1120280A (en) * | 1977-11-08 | 1982-03-23 | Makoto Konnai | Herbicidal compositions and herbicidal processes |
| JPS5484529A (en) * | 1977-12-19 | 1979-07-05 | Meiji Seika Kaisha Ltd | Production of d,l-2-amino-4-methylphosphinobutyric acid |
| US4226610A (en) * | 1978-04-15 | 1980-10-07 | Meiji Selka Kaisha, Ltd. | Herbicidal compounds, preparation thereof and herbicides containing the same |
| JPS557237A (en) * | 1978-07-03 | 1980-01-19 | Meiji Seika Kaisha Ltd | Novel phosphorus-containing compound, its preparation, herbicide, agricultural and horticultural fungicide comprising it |
-
1980
- 1980-03-04 DE DE19803008186 patent/DE3008186A1/en not_active Withdrawn
-
1981
- 1981-02-23 EP EP81101282A patent/EP0036106B1/en not_active Expired
- 1981-02-23 DE DE8181101282T patent/DE3160991D1/en not_active Expired
- 1981-02-26 ES ES499839A patent/ES499839A0/en active Granted
- 1981-02-27 DD DD81227943A patent/DD156892A5/en unknown
- 1981-02-27 MA MA19289A patent/MA19085A1/en unknown
- 1981-02-27 BR BR8101233A patent/BR8101233A/en unknown
- 1981-03-02 GR GR64267A patent/GR74156B/el unknown
- 1981-03-02 PT PT72607A patent/PT72607B/en not_active IP Right Cessation
- 1981-03-02 PH PH25291A patent/PH19742A/en unknown
- 1981-03-02 IL IL62241A patent/IL62241A0/en unknown
- 1981-03-02 NZ NZ196380A patent/NZ196380A/en unknown
- 1981-03-03 HU HU81523A patent/HU186384B/en not_active IP Right Cessation
- 1981-03-03 ZA ZA00811397A patent/ZA811397B/en unknown
- 1981-03-03 DK DK95981A patent/DK95981A/en not_active Application Discontinuation
- 1981-03-03 CA CA000372216A patent/CA1162071A/en not_active Expired
- 1981-03-03 PL PL22997681A patent/PL229976A1/xx unknown
- 1981-03-03 JP JP2947781A patent/JPS56135409A/en active Granted
- 1981-03-03 AU AU68018/81A patent/AU539256B2/en not_active Ceased
- 1981-03-04 OA OA57344A patent/OA06759A/en unknown
- 1981-03-04 CS CS811548A patent/CS221287B2/en unknown
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5491125A (en) * | 1988-03-18 | 1996-02-13 | Hoechst Aktiengesellschaft | Liquid herbicidal formulations of glufosinate |
| US8541617B2 (en) | 2006-02-21 | 2013-09-24 | Bayer Cropscience Ag | Cycloalkylphenyl substituted cyclic ketoenols |
| US8013172B2 (en) | 2006-02-21 | 2011-09-06 | Bayer Cropscience Ag | Cycloalkylphenyl substituted cyclic ketoenols |
| US8067458B2 (en) | 2006-04-22 | 2011-11-29 | Bayer Cropscience Ag | Alkoxyalkyl-substituted cyclic ketoenols |
| US8173697B2 (en) | 2006-06-02 | 2012-05-08 | Bayer Cropscience Ag | Alkoxyalkyl-substituted cyclic keto-enols |
| US8507537B2 (en) | 2006-10-25 | 2013-08-13 | Bayer Cropscience Ag | Trifluromethoxyphenyl-substituted tetramic acid derivatives pesticides and/or herbicides |
| US9000189B2 (en) | 2006-12-04 | 2015-04-07 | Bayer Cropscience Ag | Biphenyl-substituted spirocyclic ketoenols |
| US8993782B2 (en) | 2006-12-04 | 2015-03-31 | Bayer Cropscience Ag | Cis-alkoxyspirocyclic biphenyl-substituted tetramic acid derivatives |
| US8604068B2 (en) | 2007-05-25 | 2013-12-10 | Bayer Cropscience Ag | Insecticidal compositions of 2-cyanobenzene sulfonamide compounds and isomeric forms thereof having improved effect |
| US8859466B2 (en) | 2007-08-02 | 2014-10-14 | Bayer Cropscience Ag | Oxaspirocyclic spiro-substituted tetramic acid and tetronic acid derivatives |
| US8435549B2 (en) | 2007-09-25 | 2013-05-07 | Bayer Cropscience Ag | Halogen alkoxy spirocyclic tetramic and tetronic acid derivatives |
| US8367873B2 (en) | 2008-10-10 | 2013-02-05 | Bayer Cropscience Ag | Phenyl-substituted bicyclooctane-1,3-dione derivatives |
| US8846946B2 (en) | 2008-12-02 | 2014-09-30 | Bayer Cropscience Ag | Germinal alkoxy/alkylspirocyclic substituted tetramate derivatives |
| US8389443B2 (en) | 2008-12-02 | 2013-03-05 | Bayer Cropscience Ag | Geminal alkoxy/alkylspirocyclic substituted tetramate derivatives |
| US8173641B2 (en) | 2008-12-15 | 2012-05-08 | Bayer Cropscience Ag | 4-amino-1,2,3-benzoxathiazine-derivatives as pesticides |
| US8324390B2 (en) | 2008-12-18 | 2012-12-04 | Bayer Cropscience Ag | Tetrazole-substituted anthranilamides as pesticides |
| US8518985B2 (en) | 2009-03-11 | 2013-08-27 | Bayer Cropscience Ag | Haloalkylmethyleneoxyphenyl-substituted ketoenols |
| US8592610B2 (en) | 2009-05-19 | 2013-11-26 | Bayer Cropscience Ag | Spiroheterocyclic tetronic acid derivatives |
| US8318956B2 (en) | 2009-05-19 | 2012-11-27 | Bayer Cropscience Ag | Spiroheterocyclic tetronic acid derivatives |
| US9809542B2 (en) | 2010-02-10 | 2017-11-07 | Bayer Intellectual Property Gmbh | Spiroheterocyclically substituted tetramic acid derivatives |
| US8889592B2 (en) | 2010-04-20 | 2014-11-18 | Bayer Cropscience Ag | Insecticidal and/or herbicidal composition having improved activity based on spiroheterocyclically substituted tetramic acid derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| PT72607B (en) | 1982-07-13 |
| JPS56135409A (en) | 1981-10-22 |
| CS221287B2 (en) | 1983-04-29 |
| EP0036106A3 (en) | 1981-09-30 |
| DD156892A5 (en) | 1982-09-29 |
| BR8101233A (en) | 1981-09-08 |
| DE3160991D1 (en) | 1983-11-03 |
| PH19742A (en) | 1986-06-23 |
| DE3008186A1 (en) | 1981-10-15 |
| ES8201001A1 (en) | 1981-12-16 |
| DK95981A (en) | 1981-09-05 |
| ES499839A0 (en) | 1981-12-16 |
| AU539256B2 (en) | 1984-09-20 |
| NZ196380A (en) | 1983-05-10 |
| PL229976A1 (en) | 1981-10-30 |
| JPH0124125B2 (en) | 1989-05-10 |
| PT72607A (en) | 1981-04-01 |
| ZA811397B (en) | 1982-03-31 |
| EP0036106A2 (en) | 1981-09-23 |
| MA19085A1 (en) | 1981-10-01 |
| GR74156B (en) | 1984-06-06 |
| EP0036106B1 (en) | 1983-09-28 |
| AU6801881A (en) | 1981-09-10 |
| OA06759A (en) | 1982-06-30 |
| IL62241A0 (en) | 1981-05-20 |
| HU186384B (en) | 1985-07-29 |
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