PPO Formulations Containing Ether Sulfates

Abstract

The invention relates to a liquid herbicidal composition comprising a) protoporphyrinogen-IX oxidase inhibitors, or an agrochemically acceptable salt, stereoisomer, tautomer, or N-oxide thereof, and b) a compound of formula (I) [R-(A).sub.x-OSO.sub.3-]-M.sup.+; wherein the protoporphyrinogen-IX oxidase inhibitor is a compound of formula (II) and wherein al variables have a meaning as defined herein. The invention also relates to a method for controlling undesirable vegetation, which method comprises applying the herbicidal composition to a locus where undesirable vegetation is present or is expected to be present.

##STR00001##

Claims

1. A liquid herbicidal composition comprising a) a protoporphyrinogen-IX oxidase inhibitor, or an agrochemically acceptable salt, stereoisomer, tautomer, or N-oxide thereof; b) a compound of formula (I)
[R-(A).sub.x-OSO.sub.3.sup.−]-M.sup.+  (I); wherein R is C.sub.10-C.sub.16-alkyl, C.sub.10-C.sub.16-alkenyl, or C.sub.10-C.sub.16-alkynyl; each A is independently a group ##STR00034## wherein R.sup.A, R.sup.B, R.sup.C, and R.sup.D are independently H, CH.sub.3, or CH.sub.2CH.sub.3 with the proviso that the sum of C-atoms of R.sup.A, R.sup.B, R.sup.C, and R.sup.D is up to 2; M.sup.+ is a monovalent cation; and the index x is a number from 1 to 10; wherein the protoporphyrinogen-IX oxidase inhibitor is a compound of formula (II) ##STR00035## wherein the variables have the following meaning X is H, F, or Cl; Y is CH, or N; Z is C(═O), or N; H is a 5- to 9-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S in addition to the N-atom that connects the ring H to the remainder of formula (II), and is unsubstituted, or substituted with one or more, same or different substituents R.sup.H, and wherein said N- and S-atoms are independently oxidized, or non-oxidized; R.sup.H is C.sub.1-C.sub.4-alkyl, which is unsubstituted, or halogenated; or two geminal substituents R.sup.H form together with the atom to which they are bound a group ═O, ═S, or ═C(CH.sub.3).sub.2; R.sup.P is selected from the following groups R.sup.P31 to R.sup.P10; ##STR00036## wherein $ means the connection to the remainder of the molecule; wherein P is CH or N; and wherein W is OCH.sub.3, OCH.sub.2CH.sub.3, NHSO.sub.2CH.sub.3; G is Cl; or G and R.sup.P form together one of the following groups (II-A) or (II-B) ##STR00037## wherein & means the connection to the remainder of the molecule at the carbon atom to which the variable G is connected in formula (II), and wherein § means the connection to the remainder of the molecule at the carbon atom to which the variable R.sup.P is connected in formula (II).

2. The composition according to claim 1, wherein the index x is from 1 to 3.

3. The composition according to claim 1, wherein R.sup.A, R.sup.B, R.sup.C, and R.sup.D are H.

4. The composition of claim 4, wherein the monovalent cation M.sup.+ is Na.sup.+.

5. The composition according to claim 1, wherein M.sup.+ is selected from ammonium cations of a primary, secondary, and tertiary amines; and quaternary ammonium cations; wherein the molecular weight of the ammonium cations or of the quaternary ammonium cations is from 32 to 200 g/mol; and mixtures thereof.

6. The composition of claim 5, wherein the molecular weight of the ammonium cation c) or of the quaternary ammonium cation d) is from 55 to 180 g/mol.

7. The composition according to claim 5, wherein the primary, secondary, or tertiary amine, or the ammonium salt thereof, or the quaternary ammonium salt, contains exactly one nitrogen atom per molecule.

8. The composition according to claim 5, wherein M.sup.+ is a cation of formula (III) ##STR00038## wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are independently H, or C.sub.1-C.sub.10-alkyl, which is unsubstituted or substituted with OH, C.sub.1-C.sub.10-alkoxy, or hydroxy-C.sub.1-C.sub.10-alkoxy; or two of the substituents R.sup.1, R.sup.2, R.sup.3, and R.sup.4 form, together with the N-atom to which they are bound, a 5-, or 6-membered, saturated, partially- or fully unsaturated heterocycle containing additionally none, one or two atoms O, or S, and wherein said S-atom(s) are independently oxidized or non-oxidized.

9. The composition of claim 8, wherein the sum of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 comprises from 1 to 12 carbon atoms.

10. The composition according to claim 5, wherein M.sup.+ is a protonated amine selected from ethanolamine, diethanolamine, diglycolamine, 1-aminopropan-2-ol, 2-dimethylaminoethanol, 2-(butylamino)ethanol, 2-diethylaminoethanol, 2-(tert-butylamino)ethanol, N-(tert-butyl)diethanolamine, triethanolamine, 2-ethylaminoethanol, 2-aminoheptan, triisopropylamine, N-(2-hydroxyethyl)morpholin, N-methylmorpholine, N-butyldiethanolamin, 2-(dibutylamino)ethanol, and mixtures thereof.

11. The composition according to claim 5, wherein the ammonium cation M.sup.+ is a protonated amine selected from ethanolamine, diethanolamine, diglycolamine, 1-aminopropan-2-ol, 2-dimethylaminoethanol, triethanolamine, and mixtures thereof.

12. The composition according to claim 1, comprising a) 5 to 50 wt % of the protoporphyrinogen-IX oxidase inhibitor, or an agrochemically acceptable salt, stereoisomer, tautomer, or N-oxide thereof; b) 5 to 60 wt % of the compound of formula (I).

13. The composition according to claim 1 comprising an amine component selected from primary, secondary, tertiary amines, and ammonium salts thereof, and quaternary ammonium salts; wherein the molecular weight of the primary, secondary or tertiary amines, of the ammonium cation in the ammonium salts, or of the quaternary ammonium cation in the quaternary ammonium salts is from 32 to 200 g/mol; and wherein M.sup.+ in formula (I) is different from the cations in the ammonium salts or quaternary ammonium salts in the amine component.

14. A method for controlling undesirable vegetation, which method comprises applying the herbicidal composition as defined in claim 1 to a locus where undesirable vegetation is present or is expected to be present.

15. The composition according to claim 8 wherein at least one substituent R.sup.1, R.sup.2, R.sup.3, or R.sup.4 is not H.

Description

EXAMPLE-1: PREPARATION OF HERBICIDAL COMPOSITIONS

[0309] Six compositions A1 to A6 were prepared with the ingredients at the concentrations as provided in Table A. To prepare oil dispersions, ingredients were mixed and the resulting compositions were grinded to a mean particle size of 2 μm, upon which Adjuvant A was added and the compositions were mixed until homogenous.

TABLE-US-00001 TABLE A Ingredients of compositions A1, A2, A3, A4, A5 and A6 in [g/l]. Ingredient [wt %] A1 A2 A3 A4 A5 A6 Pesticide A 10 10 10 10 — — Pesticide B — — — — 10 10 Adjuvant A 1.0 1.0 1.0 1.0 1.0 1.0 Additive A 66.7 — — — 60.0 — Additive B — 62.6 60.4 — — 60.0 Additive C 60.4 Propylene glycol — 26.4 — — — — Dipropylene glycol 22.3 — 28.6 28.6 29.0 29.0 Apparent dynamic 602 403 465 518 543 468 viscosity [mPas]

[0310] Visual inspection of the compositions showed that compositions A1, A2, A3, A4, A5 and H6 had formed free flowing white oil dispersions.

EXAMPLE-2: BIOLOGICAL EFFICACY AND PHYTOTOXICITY

[0311] The selectivity and herbicidal activity of different liquid herbicidal compositions according to Tables D to CC combining various Pesticides and Additives were assessed by the following greenhouse experiments. The culture containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species. For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment. Depending on the species, the plants were kept at 10-25° C. or 20-35° C., respectively. The test period extended over 6-7 days. During this time, the plants were tended, and their response to the individual treatments was evaluated. Evaluation was carried out using a scale from 0 to 100. 100 means no emergence of the plants, or complete destruction of at least the aerial moieties, and 0 means no damage, or normal course of growth. The plants used in the greenhouse experiments were of the following species in Tables B and C. The results of the assessment of herbicidal damage is summarized in Tables D to CC.

TABLE-US-00002 TABLE B crops plants tested for herbicidal effect Abbreviation Scientific name ZEAMX Zea mays ORYSA Oryza sativa GLXMA Glycine max

TABLE-US-00003 TABLE C unwanted vegetation tested for herbicidal effect Abbreviation Scientific name ECHCG Echinochloa crus-galli BRADC Brachiaria decumbens SETFA Setaria faberi DIGSA Digitaria sanguinalis LOLMU Lolium multiflorum AVEFA Avena fatua LEFFI Leptochloa filiformis ERICA Erigeron canadensis KCHSC Kochia scoparia ABUTH Abutilon theophrasti AMATA Amaranthus rudis AMARE Amaranthus retroflexus IPOHE Ipomoea hederacea COMBE Commelina benghalensis AMBEL Ambrosia elatior CHEAL Chenopodium album

TABLE-US-00004 TABLE D Herbicidal effect of Pesticide A in combination with Additive D or E Pesticide + Additive g/ha ZEAMX ECHCG SORHA SETVI KCHSC AMATA IPOHE A + D 16 + 500 85 95 80 98 95 98 98 A + E 16 + 500 25 95 95 98 98 98 98

TABLE-US-00005 TABLE E Herbicidal effect of Pesticide A in combination with Additive D or F Pesticide + Additive g/ha ZEAMX BRADC ERICA KCHSC ABUTH AMARE IPOHE A + D 25 + 500 90 75 95 98 98 95 98 A + F 25 + 500 40 80 95 98 98 98 98

TABLE-US-00006 TABLE F Herbicidal effect of Pesticide A in combination with Additive D, E, F, or G Pesticide + Additive g/ha ZEAMX COMBE ABUTH A + D 2 + 1000 25 60 70 A + E.sup.  2 + 1000 20 85 75 A + F.sup.  2 + 1000 15 90 90 A + G 2 + 1000 20 95 95

TABLE-US-00007 TABLE G Herbicidal effect of Pesticide C in combination with Additive D, E, or F Pesticide + Additive g/ha ZEAMX AVEFA SETFA AMARE AMBEL IPOHE .sup. C + D 2 + 1000 70 65 25 90 95 98 C + E 2 + 1000 35 75 60 90 95 98 C + F 2 + 1000 30 75 50 90 95 98

TABLE-US-00008 TABLE H Herbicidal effect of Pesticide D in combination with Additive D or E Pesticide + Additive g/ha ORYSA LEFFI D + D 2 + 1000 30 75 D + E.sup.  2 + 1000 25 90

TABLE-US-00009 TABLE J Herbicidal effect of Pesticide D in combination with Additive D or F Pesticide + Additive g/ha ZEAMX BRADC KCHSC CHEAL AMATA AMBEL IPOHE D + D 2 + 1000 90 75 98 95 98 95 98 D + F.sup.  2 + 1000 70 85 98 95 98 95 98

TABLE-US-00010 TABLE K Herbicidal effect of Pesticide D in combination with Additive D, E, F, or G Pesticide + Additive g/ha ZEAMX ECHCG COMBE ABUTH IPOHE D + D 1 + 500 70 65 95 98 98 D + E.sup.  1 + 500 25 85 95 98 98 D + F.sup.  1 + 500 25 75 95 98 98 D + G 1 + 500 30 70 95 98 98

TABLE-US-00011 TABLE L Herbicidal effect of Pesticide E in combination with Additive D or E Pesticide + Additive g/ha ZEAMX BRADC DIGSA CHEAL ABUTH AMATA AMBEL E + D 2 + 1000 90 90 90 90 98 98 90 E + E.sup.  2 + 1000 65 90 95 98 98 98 95

TABLE-US-00012 TABLE M Herbicidal effect of Pesticide F in combination with Additive D, E, F or G Pesticide + Additive g/ha ZEAMX SETFA DIGSA ABUTH AMATA IPOHE F + D 2 + 1000 90 75 80 98 98 98 F + E.sup.  2 + 1000 60 85 80 98 98 98 F + F.sup.  2 + 1000 45 75 85 98 98 98 F + G 2 + 1000 50 85 90 98 98 98

TABLE-US-00013 TABLE N Herbicidal effect of Pesticide F in combination with Additive D, E, F or G Pesticide + Additive g/ha ZEAMX CHEAL IPOHE F + D 1 + 500 70 70 95 F + E.sup.  1 + 500 35 85 95 F + F.sup.  1 + 500 30 85 95 F + G 1 + 500 30 75 95

TABLE-US-00014 TABLE O Herbicidal effect of Pesticide F in combination with Additive D, or E Pesticide + Additive g/ha ZEAMX DIGSA AMATA F + D 1 + 1500 60 50 98 F + E.sup.  1 + 1500 35 60 98

TABLE-US-00015 TABLE P Herbicidal effect of Pesticide G in combination with Additive D, E, or F Pesticide + Additive g/ha ZEAMX LOLMU AVEFA ECHCG SETFA BRADC .sup. G + D 2 + 1000 95 65 75 95 90 65 G + E 2 + 1000 25 80 85 95 95 95 G + F 2 + 1000 25 80 85 95 90 95

TABLE-US-00016 TABLE Q Herbicidal effect of Pesticide H in combination with Additive D, or E Pesticide + Additive g/ha ZEAMX ECHCG SETFA KCHSC AMARE IPOHE H + D 1 + 500 60 75 95 90 95 98 H + E.sup.  1 + 500 25 75 95 95 95 98

TABLE-US-00017 TABLE R Herbicidal effect of Pesticide H in combination with Additive D, or F Pesticide + Additive g/ha ZEAMX AMARE IPOHE H + D 1 + 500 60 95 98 H + F.sup.  1 + 500 25 95 98

TABLE-US-00018 TABLE S Herbicidal effect of Pesticide J in combination with Additive D, E or F Pesticide + Additive g/ha ZEAMX GLXMA BRADC SETVI ABUTH AMATA AMBEL IPOHE .sup. J + D 2 + 1000 60 85 55 95 98 90 95 98 J + E 2 + 1000 50 70 65 95 98 90 95 98 J + F 2 + 1000 30 65 65 95 98 90 95 98

TABLE-US-00019 TABLE T Herbicidal effect of Pesticide K in combination with Additive D, or F Pesticide + Additive g/ha ZEAMX LOLMU SORHA CHEAL ABUTH AMBEL IPOHE K + D 16 + 1000 40 50 65 85 80 80 95 K + F.sup.  16 + 1000 25 60 85 90 95 90 98

TABLE-US-00020 TABLE U Herbicidal effect of Pesticide K in combination with Additive D, or F Pesticide + Additive g/ha ORYSA CYPIR K + D 16 + 1000 25 45 K + F.sup.  16 + 1000 20 90

TABLE-US-00021 TABLE V Herbicidal effect of Pesticide L in combination with Additive D, or E; assessment was carried out 20 days after treatment Pesticide + Additive g/ha ORYSA CYPIR L + D 16 + 1000 25 50 L + E.sup.  16 + 1000 20 95

TABLE-US-00022 TABLE W Herbicidal effect of Pesticide B in combination with Additive D, or E Pesticide + COM- Additive g/ha ZEAMX KCHSC CHEAL BE ABUTH AMATA IPOHE B + D 8 + 500 75 95 95 95 98 98 98 B + E.sup.  8 + 500 60 95 95 95 98 98 98

TABLE-US-00023 TABLE X Herbicidal effect of Pesticide B in combination with Additive D, or E Pesticide + COM- AMA- Additive g/ha GLXMA SETVI DIGSA CHEAL BE AMATA RE B + D 2 + 1000 95 55 60 80 70 95 85 B + E.sup.  2 + 1000 85 65 70 95 80 98 95

TABLE-US-00024 TABLE Y Herbicidal effect of Pesticide B in combination with Additive D, or E; assessment was carried out 20 days after treatment Pesticide + Additive g/ha ORYSA CYPIR B + D 8 + 500 75 65 B + E.sup.  8 + 500 55 95

TABLE-US-00025 TABLE Z Herbicidal effect of Pesticide B in combination with Additive D, or F Pesticide + ECHC COM- AMA- Additive g/ha ZEAMX LOLMU G DIGSA CHEAL BE RE B + D 2 + 1000 55 30 50 60 80 70 85 B + F.sup.  2 + 1000 30 60 65 70 98 75 98

TABLE-US-00026 TABLE AA Herbicidal effect of Pesticide B in combination with Additive D, or G Pesticide + COM- Additive g/ha ZEAMX SETVI CHEAL BE ABUTH AMATA AMBEL B + D 2 + 1000 55 55 80 70 90 95 85 B + G 2 + 1000 35 70 85 80 95 98 90

TABLE-US-00027 TABLE BB Herbicidal effect of Pesticide M in combination with Additive D, or E Pesticide + ECHC Additive g/ha ZEAMX G BRADC SETVI AMATA AMBEL IPOHE M + D 8 + 500 55 65 75 80 98 95 98 M + E.sup.  8 + 500 40 70 80 85 98 95 98

TABLE-US-00028 TABLE CC Herbicidal effect of Pesticide M in combination with Additive D, or F Pesticide + GLXM Additive g/ha ZEAMX A SETVI AMBEL IPOHE M + D 2 + 1000 35 80 50 75 95 M + F.sup.  2 + 1000 30 70 55 85 98

TABLE-US-00029 TABLE CC Herbicidal effect of Pesticide M in combination with Additive D, or G Pesticide + Additive g/ha ZEAMX ABUTH AMBEL M + D 2 + 1000 35 90 75 M + G 2 + 1000 30 95 90

[0312] The results show a reduced phytotoxicity of the liquid herbicidal compositions according to the invention as compared to compositions with the commercially important Additive D.

EXAMPLE-3: COMPARATIVE EXPERIMENTS ON BIOLOGICAL EFFICACY AND PHYTOTOXICITY

[0313] The selectivity and herbicidal activity of different liquid herbicidal compositions according to Table DD combining various Pesticides and Additives were assessed by greenhouse experiments as described for Example-2. Specifically, Pesticide G, falling under the definition of compounds of formula (II) in combination with Additive D or E were assessed in comparison with diphenylether Pesticides N and P. Table DD summarizes the results.

TABLE-US-00030 TABLE DD Comparison of herbicidal activity of Pesticide G vs diphenylether Pesticides N or P Pesticide + Additive g/ha ZEAMX ECHCG G + D  2 + 1000 95 95 G + E.sup.   2 + 1000 25 95 N + D 256 + 1000 65 90 N + E.sup.  256 + 1000 70 85 N + D 128 + 1000 40 80 N + E.sup.  128 + 1000 55 80 .sup. P + D 128 + 1000 70 75 P + E 128 + 1000 75 75

EXAMPLE-4: COMPARATIVE EXPERIMENTS ON BIOLOGICAL EFFICACY AND PHYTOTOXICITY

[0314] The selectivity and herbicidal activity of different liquid herbicidal compositions according to Table EE combining various Pesticides, Additives, and the ammonium salt of glufosinate (“GFA”) were assessed by greenhouse experiments as described for Example-2. Table EE summarizes the results.

[0315] Synergism can be described as an interaction where the combined effect of two or more compounds is greater than the sum of the individual effects of each of the compounds. The presence of a synergistic effect in terms of percent control, between two mixing partners (X and Y) can be calculated using the Colby equation (Colby, S. R., 1967, Calculating Synergistic and Antagonistic Responses in Herbicide Combinations, Weeds, 15, 20-22):

[00001]$E=X+Y-\frac{\mathrm{XY}}{100}$

[0316] When the observed combined control effect is greater than the expected combined control effect (E), then the combined effect is synergistic.

[0317] The following tests demonstrate the control efficacy of compounds, mixtures or compositions of this invention. The analysis of synergism or antagonism in Table EE between the mixtures or compositions was determined using Colby's equation.

TABLE-US-00031 TABLE EE combination experiments of Additives with GFA and Pesticide F expected by expected by Colby Colby (Pesticides) + (x + y − (x + y − Additive g/ha ORYSA (x*y/100)) LEFFI (x*y/100))   .sup. F + D 1 + 500 25 40 GFA + D 150 + 500  30 25 (F + GFA) + D 1 + 150 + 1000 40 48 30 55  .sup.  F + E 1 + 500 25 50 GFA + E.sup.  150 + 500  40 15 (F + GFA) + E 1 + 150 + 1000 35 55 80 58

[0318] The results showed that Additive E only conferred improved control of weeds and reduced phytotoxicity as compared to Additive D if admixed to Pesticide F or a composition containing Pesticide F.