Formulation component
10206388 · 2019-02-19
Assignee
Inventors
- Gordon Alastair Bell (Bracknell, GB)
- Julia Lynne Ramsay (Bracknell, GB)
- Raul Minguez Molina (Bracknell, ES)
- David Stock (Bracknell, GB)
- Gary Charles Walter (Bracknell, GB)
Cpc classification
A01N25/00
HUMAN NECESSITIES
A01N43/90
HUMAN NECESSITIES
A01N2300/00
HUMAN NECESSITIES
A01N2300/00
HUMAN NECESSITIES
A01N37/10
HUMAN NECESSITIES
A01N47/36
HUMAN NECESSITIES
A01N37/10
HUMAN NECESSITIES
A01N43/90
HUMAN NECESSITIES
International classification
A01N25/00
HUMAN NECESSITIES
A01N43/90
HUMAN NECESSITIES
A01N37/10
HUMAN NECESSITIES
Abstract
This invention relates to the use of aromatic esters as adjuvants in compositions, particularly for agrochemical use, as well to compositions comprising such an aromatic ester, in combination with at least one agrochemical and at least one surfactant. The invention further extends to methods of making and using such compositions. In particular the present invention relates to such compositions when formulated as, or comprised by, an emulsion concentrate (EC), an emulsion in water (EW), a suspension of particles in water (SC), a microcapsule formulation (CS), a suspension of particles with an emulsion (SE), a dispersion concentrate (DC) or an oil suspension (OD).
Claims
1. An agrochemical formulation concentrate composition suitable for further dilution wherein the composition is an emulsion concentrate (EC), a suspension of particles in water (SC), a dispersion concentrate (DC), a suspension of particles in an emulsion (SE), or a suspension of particles in oil (OD) comprising: i. an agrochemical active ingredient selected from a herbicide, a molluscicide, a fungicide, a plant growth regulator, and a safener, or a combination thereof; ii. a surfactant; iii. an adjuvant, wherein the adjuvant is an aromatic ester of formula (I) ##STR00010## wherein n is an integer selected from 0 to 20 inclusive, each A is independently C.sub.1-10alkanediyl, m is an integer selected from 1, 2 or 3; wherein when m is 1, R.sup.2 is selected from the group consisting of C.sub.7-C.sub.20alkyl, C.sub.7-C.sub.20 alkenyl, C.sub.7-C.sub.20 alkyldienyl and C.sub.7-C.sub.20 alkyltrienyl; and when m is 2 or 3, R.sup.2 is selected from the group consisting of C.sub.1-C.sub.20 alkyl, C.sub.4-C.sub.22 alkenyl, C.sub.4-C.sub.22 alkyldienyl and C.sub.6-C.sub.22 alkyltrienyl; and each m group is independently attached to any carbon atom within R.sup.2, and each A and n is independently as defined above provided that the compound of formula (I) is not dipropylene glycol dibenzoate; and iv. a solvent.
2. The agrochemical formulation concentrate composition according to claim 1, wherein n is 1.
3. The agrochemical formulation concentrate composition according to claim 1, wherein each A is independently ethanediyl, propanediyl, butanediyl or butanediyl.
4. The agrochemical formulation concentrate composition according to claim 1, wherein each A is independently each A is independently 1,2-ethanediyl, 1,2-propanediyl, 1,2-butanediyl or 1,4-butanediyl.
5. The agrochemical formulation concentrate composition according to claim 1, wherein n is 0.
6. The agrochemical formulation concentrate composition according to claim 1, wherein m is 1.
7. The agrochemical formulation concentrate composition according to claim 6, wherein R.sup.2 is C.sub.8-C.sub.18 alkyl.
8. The agrochemical formulation concentrate composition according to claim 7, wherein R.sup.2 is 2-ethylhexyl, C.sub.12 alkyl, C.sub.13 alkyl, C.sub.14 alkyl, C.sub.15 alkyl, C.sub.16 alkyl, C.sub.17 alkyl, oleyl or isooctadecyl.
9. The agrochemical formulation concentrate composition according to claim 1, wherein m is 2.
10. The agrochemical formulation concentrate composition according to claim 9, wherein R.sup.2 is C.sub.7-C.sub.18 alkyl.
11. The agrochemical formulation concentrate composition according to claim 10, wherein R.sup.2 is a C.sub.8 branched-chain alkyl, and each m group is attached to a different carbon atom in R.sup.2.
12. The agrochemical formulation concentrate composition according to claim 1, wherein the compound of formula (I) is 2,2,4-trimethyl-1,3-pentanediol dibenzoate.
13. The agrochemical formulation concentrate composition according to claim 1, wherein the active ingredient is present at a concentration in the range from about 0.001% to about 90% w/w.
14. The agrochemical formulation concentrate composition according to claim 1, wherein the active ingredient is selected from the group consisting of: bicyclopyrone, mesotrione, fomesafen, tralkoxydim, napropamide, amitraz, propanil, pyrimethanil, dicloran, tecnazene, toclofos methyl, flamprop M, 2,4-D, MCPA, mecoprop, clodinafop-propargyl, cyhalofop-butyl, diclofop methyl, haloxyfop, quizalofop-P, indol-3-ylacetic acid, 1-naphthylacetic acid, isoxaben, tebutam, chlorthal dimethyl, benomyl, benfuresate, dicamba, dichlobenil, benazolin, triazoxide, fluazuron, teflubenzuron, phenmedipham, acetochlor, alachlor, metolachlor, pretilachlor, thenylchlor, alloxydim, butroxydim, clethodim, cyclodim, sethoxydim, tepraloxydim, pendimethalin, dinoterb, bifenox, oxyfluorfen, acifluorfen, fluoroglycofen-ethyl, bromoxynil, ioxynil, imazamethabenz-methyl, imazapyr, imazaquin, imazethapyr, imazapic, imazamox, flumioxazin, flumiclorac-pentyl, picloram, amodosulfuron, chlorsulfuron, nicosulfuron, rimsulfuron, triasulfuron, triallate, pebulate, prosulfocarb, molinate, atrazine, simazine, cyanazine, ametryn, prometryn, terbuthylazine, terbutryn, sulcotrione, isoproturon, linuron, fenuron, chlorotoluron, metoxuron, isopyrazam, mandipropamid, azoxystrobin, trifloxystrobin, kresoxim methyl, famoxadone, metominostrobin and picoxystrobin, cyprodanil, carbendazim, thiabendazole, dimethomorph, vinclozolin, iprodione, dithiocarbamate, imazalil, prochloraz, fluquinconazole, epoxiconazole, flutriafol, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, hexaconazole, paclobutrazole, propiconazole, tebuconazole, triadimefon, trtiticonazole, fenpropimorph, tridemorph, fenpropidin, mancozeb, metiram, chlorothalonil, thiram, ziram, captafol, captan, folpet, fluazinam, flutolanil, carboxin, metalaxyl, bupirimate, ethirimol, dimoxystrobin, fluoxastrobin, orysastrobin, metominostrobin, and prothioconazole.
15. The agrochemical formulation concentrate composition according to claim 1, comprising at least one additional component selected from the group consisting of agrochemicals, adjuvants, surfactants, and emulsifiers.
16. The agrochemical formulation concentrate according to claim 1 diluted or dispersed in water suitable for application in agriculture.
17. A method of controlling a pest, comprising applying a composition as defined in claim 1 to said pest or a locus of said pest.
18. A method of making an agrochemical a formulation concentrate composition suitable for further dilution wherein the composition is an emulsion concentrate (EC), a suspension of particles in water (SC), a dispersion concentrate (DC), a suspension of particles in an emulsion (SE), or a suspension of particles in oil (OD), the method comprising combining: i. an agrochemical active ingredient selected from a herbicide, a molluscicide, a fungicide, a plant growth regulator, and a safener, or a combination thereof; ii. a surfactant; and iii. an aromatic ester of formula (I) as defined in claim 1.
19. The method according to claim 18, wherein the agrochemical composition is as defined in claim 13.
20. The agrochemical formulation concentrate composition according to claim 1, wherein the aromatic ester of formula (I) comprises from 10% w/w to about 40% w/w of the total agrochemical formulation concentrate composition.
21. The method of claim 18, wherein the aromatic ester is present from 10% w/w to about 40% w/w of the total agrochemical formulation concentrate composition.
Description
EXAMPLES
Example 1 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Isopyrazam
(1) The efficacy of the following benzoic acid esters Finsolv TN (C.sub.12-C.sub.15 alkyl benzoate), Benzoflex 181 (2-ethylhexylbenzoate), methyl benzoate, and butyl benzoate, as adjuvants in compositions comprising isopyrazam was tested and compared to the standard formulations (both EC and SC) of the fungicide, which lack this type of adjuvant.
(2) Wheat plants were inoculated with the fungus Septoria tritici. Four days after inoculation the plants were sprayed with a diluted emulsion concentrate or suspension concentrate formulation of the fungicide isopyrazam at rates of 3, 10, 30 and 100 mg of the fungicide per liter of spray solution, using a laboratory track sprayer which delivered the spray at a rate of 200 liters per hectare. Spray tests were also carried out with diluted suspension concentrate additionally comprising each of the benzoate adjuvants described above. These adjuvants were added to the spray solution at a rate of 0.2% w/w, based on the quantity of spray liquor. The leaves of the plants were assessed visually 14 days after the spray application and the damage was expressed as the percentage of the leaf area infected. Each spray test was replicated three times across the four application rates and the modelled means of these results are shown in Table 2 below.
(3) As can be seen from Table 2 the inclusion of a benzoate as an adjuvant for isopyrazam resulted in a significant reduction in the percentage of infection by S. tritici in comparison to that achieved by the standard isopyrazam SC. Furthermore, the C.sub.12-C.sub.15 benzoate (Finsolv TN) gave superior results in comparison to those achieved by inclusion of the short chain benzoates (methyl and butyl benzoate). As well as increasing the efficacy of the standard suspension concentrate formulation (Standard SC) of isopyrazam, inclusion of the benzoate adjuvants Benzoflex 181 (2-ethylhexyl benzoate) and Finsolv TN(C.sub.12-C.sub.15 benzoate) also resulted in isopyrazam compositions that were better at controlling S. tritici than the standard isopyrazam emulsion concentrate formulation (Standard EC).
(4) TABLE-US-00002 TABLE 2 Mean % infection of wheat plants with S. tritici treated with isopyrazam in the presence and absence of benzoic acid ester adjuvants. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean % infection Standard Isopyrazam SC 49.4 A Standard Isopyrazam EC 22.9 B Standard Isopyrazam SC plus Methyl benzoate 22.1 B Standard Isopyrazam SC plus Butyl benzoate 18.1 BC Standard Isopyrazam SC plus Benzoflex 181 11.4 CD Standard Isopyrazam SC plus Finsolv TN 5.0 D
Example 2 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Epoxyconazole
(5) The efficacy of the following benzoic acid esters, methyl benzoate, butyl benzoate, Finsolv TN (C.sub.12-C.sub.15 alkyl benzoate), and Benzoflex 181 (2-ethylhexylbenzoate), as adjuvants in compositions comprising epoxyconazole, was tested and compared to the standard formulation (SC) of the fungicide, which lacks this type of adjuvant.
(6) Wheat plants were inoculated with the fungus Septoria tritici. Four days after inoculation the plants were sprayed with a diluted suspension concentrate formulation of the fungicide epoxyconazole at rates of 3, 10, 30 and 100 mg of the fungicide per liter of spray solution, using a laboratory track sprayer which delivered the spray at a rate of 200 liters per hectare. Spray tests were also carried out with diluted suspension concentrate additionally comprising each of the benzoate adjuvants described above. These adjuvants were added to the spray solution at a rate of 0.2% w/w, based on the quantity of spray liquor. The leaves of the plants were assessed visually 14 days after the spray application and the damage was expressed as the percentage of the leaf area infected. Each spray test was replicated three times across the four application rates and the modelled means of these results are shown in Table 3 below.
(7) TABLE-US-00003 TABLE 3 Mean % infection of wheat plants with S. tritici treated with epoxyconazole in the presence and absence of benzoic acid ester adjuvants. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean % infection Standard epoxyconazole SC 32.3 B Standard epoxyconazole SC + methyl benzoate 18.7 C Standard epoxyconazole SC + butyl benzoate 18.7 C Standard epoxyconazole SC + Finsolv TN 10.8 CD Standard epoxyconazole SC + Benzoflex 181 7.5 D
(8) The results show that the mean percentage infection with S. tritici is reduced further when the wheat plants were treated with compositions of epoxyconazole comprising each of the benzoates, in comparison to the control (blank) and when treated with the standard SC composition of epoxyconazole. This shows that the benzoates are effective adjuvants for epoxyconazole, and in particular the longer chain alkyl benzoates are more effective than the shorter chain alkyl benzoates.
Example 3 Use of 2-ethylhexyl 4-dimethylaminobenzoate as an Adjuvant for Agrochemical Compositions Comprising Isopyrazam
(9) The efficacy of 2-ethylhexyl-4-dimethylamino benzoate as an adjuvant for isopyrazam was tested, and compared to the standard SC and EC formulations which lack this type of adjuvant.
(10) The test was conducted as described above in Example 1, and the modelled means of the results are shown below in Table 4.
(11) TABLE-US-00004 TABLE 4 Mean % infection of wheat plants with S. tritici treated with isopyrazam in the presence and absence of 2-ethylhexyl 4-dimethylaminobenzoate. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean infection % Standard isopyrazam SC 47.6 A Standard isopyrazam EC 19.2 B Standard isopyrazam SC + 2-ethylhexyl 18.2 B 4-dimethylaminobenzoate
(12) The inclusion of 2-ethylhexyl 4-dimethylaminobenzoate in compositions of isopyrazam resulted in a reduction S. tritici infection in comparison to treatment with the standard SC alone. Thus, 2-ethylhexyl 4-dimethylaminobenzoate is an effective adjuvant for isopyrazam and such compositions are similar in efficacy to the standard EC isopyrazam formulation.
Example 4 Use of 2-ethylhexyl 4-dimethylaminobenzoate as an Adjuvant for Agrochemical Compositions Comprising Epoxyconazole
(13) The efficacy of 2-ethylhexyl 4-dimethylamino benzoate as an adjuvant for epoxyconazole was tested, and compared to the standard SC formulation which lacks this type of adjuvant.
(14) The test was conducted as described above in Example 2, and the modelled means of the results are shown below in Table 5. These show that the inclusion of 2-ethylhexyl 4-dimethylaminobenzoate in compositions of epoxyconazole resulted in a reduction S. tritici infection in comparison to treatment with the standard SC alone. Thus 2-ethylhexyl-4-dimethylamino benzoate is an effective adjuvant for epoxyconazole.
(15) TABLE-US-00005 TABLE 5 Mean % infection of wheat plants with S. tritici treated with epoxyconazole in the presence and absence of 2-ethylhexyl- 4-dimethylaminobenzoate. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean infection % Standard epoxyconazole SC 31.1 B Standard epoxyconazole SC + 2-ethylhexyl 7.8 C 4-dimethylaminobenzoate
Example 5 Use of a C12-C15 alkyl Benzoate as an Adjuvant for Agrochemical Compositions Comprising Nicosulfuron
(16) The aromatic ester Finsolv TN (C.sub.12-C.sub.15 alkyl benzoate) was tested in a glasshouse against four weed species using the herbicide nicosulfuron. An agrochemical composition was prepared containing 0.2% v/v of the adjuvant in a track sprayer, and was applied at a volume of 200 liters per hectare. Nicosulfuron was applied at either 30 or 60 grams of pesticide per hectare on each of the weed species. The weed species and their growth stage at spraying were Abutilon theophrasti (ABUTH; growth stage 13), Chenopodium album (CHEAL; growth stage 14), Digitaria sanguinalis (DIGSA; growth stage 13), and Setaria viridis (SETVI; growth stage 13).
(17) Each spray test replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 7, 14 and 20 days following application. The results shown in Table 6 below are mean averages over the two rates of nicosulfuron, three replicates and the three assessment timings, and are compared to the efficacy of nicosulfuron in the absence of an adjuvant, and nicosulfuron in the presence of the commercially available tank-mix adjuvant, Atplus411F.
(18) A second experiment was conducted to assess the efficacy of Finsolv TN as an adjuvant in compositions of nicosulfuron. This was carried out as outlined above, with the following change: samples were assessed at 14 and 20 days post application.
(19) The results shown in Table 7 below are mean averages over the two rates of nicosulfuron, three replicates and the two assessment timings, and are compared to the efficacy of nicosulfuron in the absence of an adjuvant, and nicosulfuron in the presence of the commercially available tank-mix adjuvant, Atplus411F.
(20) TABLE-US-00006 TABLE 6 Mean percentage kill results for nicolsulfuron in the presence and absence of FinsolvTN and Atplus 411F. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Mean across Treatment SETVI DIGSA CHEAL ABUTH species Nicosulfuron + 50.6 A 50 A 40.0 A 26.1 AB 41.7 A FINSOLV TN Nicosulfuron + 41.8 B 43 A 43.9 A 30.0 A 39.6 A ATPLUS 411 F Nicosulfuron 33.3 C 1.1 B 26.7 B 19.4 B 20.1 B
(21) TABLE-US-00007 TABLE 7 Mean percentage kill results for nicolsulfuron in the presence and absence of FinsolvTN and Atplus 411F. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Mean across Treatment ABUTH CHEAL DIGSA SETVI species Nicosulfuron + 41.7 A 77.9 A 85.6 A 88.2 A 72.1 A FINSOLV TN Nicosulfuron + 43.8 A 75.4 A 80.2 A 80.0 B 69.8 A ATPLUS 411 F Nicosulfuron 29.2 B 25.8 B 0.0 B 61.3 C 29.1 B
(22) Both experiments show that the C.sub.12-C.sub.15 benzoate is an effective adjuvant (with comparable efficacy to the commercially available tank-mix adjuvant Atplus411F) for nicosulfuron.
Example 6 Use of a C12-C15 alkyl Benzoate as an Aduvant for Agrochemical Compositions Comprising Fomesafen
(23) The aromatic ester Finsolv TN (C.sub.12-C.sub.15 alkyl benzoate) was tested in a glasshouse against four weed species using the herbicide fomesafen. An agrochemical composition was prepared containing 0.2% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. Fomesafen was applied at either 60 or 120 grams of pesticide per hectare on each of the weed species. The weed species and their growth stage at spraying were Chenopodium album (CHEAL; growth stage 14), Abutilon theophrasti (ABUTH; growth stage 12), Setaria viridis (SETVI; growth stage 13), and Xanthium strumarium (XANST; growth stage 12).
(24) Each spray test was replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 7, 14 and 20 days following application. The results shown in Table 8 below are mean averages over the two rates of fomesafen, three replicates and the three assessment timings, and are compared to the efficacy of fomesafen in the absence of an adjuvant, and fomesafen in the presence of the commercially available adjuvant Turbocharge.
(25) TABLE-US-00008 TABLE 8 Mean percentage kill results for fomesafen in the presence and absence of FinsolvTN and Turbocharge. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Mean across Treatment ABUTH CHEAL SETVI XANST species Fomesafen + 82.9 A 75 A 22.8 A 94.1 A 68.7 A Turbocharge Fomesafen + 60.6 B 63.1 B 22.2 A 84.4 B 57.6 B FINSOLV TN Fomesafen 19.7 C 34.7 C 10.3 B 59.2 C 31.0 C
(26) A second experiment was conducted to assess the efficacy of Finsolv TN as an adjuvant in compositions of fomesafen. This was carried out as outlined above, with the following change: samples were assessed at 6, 14 and 20 days post application.
(27) The results shown in Table 9 below are mean averages over the two rates of fomesafen, three replicates, three assessment timings, and four weed species and are compared to the efficacy of fomesafen in the absence of an adjuvant, and fomesafen in the presence of the commercially available tank-mix adjuvant, Turbocharge.
(28) TABLE-US-00009 TABLE 9 Mean percentage kill results for fomesafen in the presence and absence of FinsolvTN or Turbocharge. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean across species Fomesafen + Turbocharge 73.8 A Fomesafen + FINSOLVTN 70.5 A Fomesafen 44.9 B
(29) The results show that the C.sub.12-C.sub.15 alkyl benzoate is an effective adjuvant for fomesafen.
Example 7 Use of a C12-C15 alkyl Benzoate as an Aduvant for Agrochemical Compositions Comprising Mesotrione
(30) The aromatic ester Finsolv TN (C.sub.12-C.sub.15 alkyl benzoate) was tested in a glasshouse against three weed species using the herbicide mesotrione. An agrochemical composition was prepared containing 0.2% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. Mesotrione was applied at either 60 or 120 grams of pesticide per hectare on weeds which had been grown to the 1.3 or 1.4 leaf stage. The weed species were Xanthium strumarium (XANST), Brachiaria platyphylla (BRAPL), and Digitaria sanguinalis (DIGSA). The commercially available surfactant Tetronic 1107 was used in the spray tank at a concentration of 0.036 g/l alongside the lower concentration of mesotrione and at a concentration of 0.072 g/l at the higher concentration of mesotrione.
(31) Each spray test was replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 7, 14 and 20 days following application. The results shown in Table 10 below are mean averages over the two rates of mesotrione, three replicates and the three assessment timings, and are compared to the efficacy of mesotrione in the absence of adjuvant and mesotrione in the presence of the well-known adjuvant Tween 20.
(32) TABLE-US-00010 TABLE 10 Mean percentage kill results for mesotrione in the presence and absence of Finsolv TN or Tween 20. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Mean across Adjuvant BRAPL DIGSA XANST species Mesotrione + 24.7 A 37.2 A 36.7 A 33.6 A FINSOLVTN Mesotrione + 18.3 A 35.6 A 41.7 A 31.9 A Tween 20 Mesotrione 5.3 B 20.0 B 36.7 A 19.9 B
(33) A second experiment was conducted to assess the efficacy of Finsolv TN as an adjuvant in compositions of mesotrione. This was carried out as outlined above, with the following change: samples were assessed at 6, 14 and 20 days post application.
(34) The results shown in Table 11 below are mean averages over the two rates of mesotrione, three replicates, the three assessment timings, and the three weed species, and are compared to the efficacy of mesotrione in the absence of adjuvant and mesotrione in the presence of the well-known adjuvant Tween 20.
(35) TABLE-US-00011 TABLE 11 Mean percentage kill results for mesotrione in the presence and absence of Finsolv TN or Tween 20. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean across species Mesotrione + FINSOLV TN 57.4 A Mesotrione + Tween 20 55.5 A Mesotrione 33.0 B
(36) The results of both experiments show that the C.sub.12-C.sub.15 benzoate is an effective adjuvant for mesotrione, and is as efficacious as the known adjuvant Tween20.
Example 8 Use of a C12-C15 alkyl Benzoate as an Aduvant for Agrochemical Compositions Comprising Pinoxaden
(37) The aromatic ester Finsolv TN (C.sub.12-C.sub.15 alkyl benzoate) was tested in a glasshouse against four weed species using the herbicide pinoxaden. An agrochemical composition was prepared containing 0.2% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. Pinoxaden was applied at either 7.5 or 15 grams of pesticide per hectare on each of the weed species. The commercially available surfactant Atlas G5000 was used in the spray tank at a concentration of 0.00375 g/l alongside the lower concentration of pinoxaden and at a concentration of 0.0075 g/l at the higher concentration of pinoxaden. The weed species and their growth stage at spraying were Alopecurus myosuroides (ALOMY; growth stage 13), Avena fatua (AVEFA; growth stage 12); Lolium perenne (LOLPE; growth stage 13), Setaria viridis (SETVI; growth stage 14).
(38) Each spray test was replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 7, 14 and 20 days following application. The results shown in Table 12 below are mean averages over the two rates of pinoxaden, three replicates and the three assessment timings, and are compared to the efficacy of pinoxaden in the absence of an adjuvant and pinoxaden in the presence of triethylhexyl phosphate.
(39) TABLE-US-00012 TABLE 12 Mean percentage kill results for pinoxaden in the presence and absence of FinsolvTN or Tween20. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Mean across Treatment ALOMY AVEFA LOLPE SETVI species Pinoxaden + 6.1 AB 70.1 A 53.3 A 68.2 A 49.43 A FINSOLVTN Pinoxaden + 7.8 A 66.2 A 55.3 A 71.4 A 50.17 A Triethylhexyl phosphate Pinoxaden 1.1 B 2.8 B 5.0 B 0.8 B 2.43 B
(40) A second experiment was conducted to assess the efficacy of Finsolv TN as an adjuvant for pinoxaden. This was carried out as outlined above, with the following change: samples were assessed at 14 and 20 days post application. The results shown below in Table 13 are mean averages over the two rates of pinoxaden, three replicates, the two assessment timings, and the four weed species, and are compared to the efficacy of pinoxaden in the absence of an adjuvant and pinoxaden in the presence of the common adjuvant methyl oleate.
(41) Both experiments show that the C.sub.12-C.sub.15 alky benzoate is an effective adjuvant for pinoxaden, and is at least as efficacious as compounds known to be useful as adjuvants in the agrochemical arena.
(42) TABLE-US-00013 TABLE 13 Mean percentage kill results for pinoxaden in the presence and absence of FinsolvTN or methyl oleate. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean across species Pinoxaden + FINSOLVTN 87.0 A Pinoxaden + methyl oleate 82.3 A Pinoxaden 0.5 B
Example 9 Synthesis of a C16-C17 benzoic acid ester: Benzoate 1
(43) The adjuvant mixture Benzoate 1 was synthesised by adding an oil comprising a mixture of linear long chain (16 and 17 carbons in length) alcohols to a flask and reacting this oil with benzoyl chloride. The resulting mixture was extracted after the reaction and purified. Analysis by nmr showed that the product consisted of long-chain (16 and 17 carbons in length) benzoates. This benzoic acid ester was tested as an adjuvant in Examples 10, 11, 12, and 13 described supra.
Example 10 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Nicosulfuron
(44) The aromatic esters Benzoate 1 (see Example 9), Benzoflex 354 (2,2,4-trimethyl-1,3-pentanediol dibenzoate) and Finsolv SB (stearyl benzoate) were tested in a glasshouse against four weed species using the herbicide nicosulfuron. Nicosulfuron was applied at either 30 or 60 grams of pesticide per hectare on each of the weed species. The weed species and their growth stage at spraying were Abutilon theophrasti (ABUTH; growth stage 13), Chenopodium album (CHEAL; growth stage 14), Digitaria sanguinalis (DIGSA; growth stage 13), and Setaria viridis (SETVI; growth stage 13).
(45) Each spray test replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 14 and 20 days following application. The results shown in Table 14 below are mean averages over the two rates of nicosulfuron, three replicates and the two assessment timings, and are compared to the efficacy of nicosulfuron in the absence of an adjuvant, and nicosulfuron in the presence of the commercially available tank-mix adjuvant, Atplus411F.
(46) TABLE-US-00014 TABLE 14 Mean percentage kill results for nicosulfuron in the presence and absence of Benzoate 1, FinsolvSB, Benzoflex 354 or Atplus 411F. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Mean across Treatment species SETVI ABUTH CHEAL DIGSA Nicosulfuron + 75.9 A 89.7 A 65.4 B 59.2 A 89.3 A BENZOATE 1 Nicosulfuron + 75.9 A 88.6 A 72.1 A 59.6 A 83.2 A BENZOFLEX 354 Nicosulfuron + 75.1 A 89.9 A 62.9 B 59.6 A 87.9 A FINSOLVSB Nicosulfuron + 74.3 A 89.2 A 63.8 B 60.0 A 84.3 A ATPLUS 411 F Nicosulfuron 59.6 B 81.0 B 56.7 C 44.6 B 56.3 B
(47) The results show that each of the benzoic acid ester is effective as an adjuvant for nicosulfruon.
Example 11 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Fomesafen
(48) The aromatic esters Benzoate 1 (see Example 9),), Benzoflex 354 (2,2,4-trimethyl-1,3-pentanediol dibenzoate) and Finsolv SB (stearyl benzoate) were tested in a glasshouse against four weed species using the herbicide fomesafen.
(49) An agrochemical composition was prepared containing 0.2% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. Fomesafen was applied at either 60 or 120 grams of pesticide per hectare on each of the weed species. The weed species and their growth stage at spraying were Chenopodium album (CHEAL; growth stage 14), Abutilon theophrasti (ABUTH; growth stage 12), Setaria viridis (SETVI; growth stage 13), and Xanthium strumarium (XANST; growth stage 12).
(50) Each spray test was replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 7, 14 and 20 days following application. The results shown in Table 15 below are mean averages over the two rates of fomesafen, three replicates the three assessment timings, and the four weed species, and are compared to the efficacy of fomesafen in the absence of an adjuvant, and fomesafen in the presence of the commercially available adjuvant Turbocharge.
(51) TABLE-US-00015 TABLE 15 Mean percentage kill results for fomesafen in the presence and absence of benzoate 1, benzoflex 354, FinsolvSB or Turbocharge. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean across species Fomesafen + FINSOLV SB 58.9 A Fomesafent + BENZOATE 1 58.5 A Fomesafen + Turbocharge (R) 58.5 A Fomesafe + BENZOFLEX 354 43.9 B Fomesafen 37.7 C
(52) The results demonstrate that all of the benzoic acid esters tested are effective as adjuvants for fomesafen and that isostearyl benzoate, and the C.sub.16-C.sub.17 alkyl benzoate (benzoate 1) are as effective as the commercially available agrochemical adjuvant Turbocharge.
Example 12 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Mesotrione
(53) The aromatic esters benzoate 1 (see Example 9), Benzoflex 354 (2,2,4-trimethyl-1,3-pentanediol dibenzoate) and Finsolv SB (stearyl benzoate) were tested in a glasshouse against three weed species using the herbicide mesotrione.
(54) An agrochemical composition was prepared containing 0.2% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. Mesotrione was applied at either 60 or 120 grams of pesticide per hectare on weeds which had been grown to the 1.3 or 1.4 leaf stage. The weed species were Xanthium strumarium (XANST), Brachiaria platyphylla (BRAPL), and Digitaria sanguinalis (DIGSA). The commercially available surfactant Tetronic 1107 was used in the spray tank at a concentration of 0.036 g/l alongside the lower concentration of mesotrione and at a concentration of 0.072 g/l at the higher concentration of mesotrione.
(55) Each spray test was replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 7, 14 and 20 days following application. The results shown in Table 10 below are mean averages over the two rates of mesotrione, three replicates and the three assessment timings, and are compared to the efficacy of mesotrione in the absence of adjuvant and mesotrione in the presence of the well-known adjuvant Brij96. The results shown in Table 16 below are mean averages over the two rates of mesotrione, three replicates, three assessment timings and three weed species. The results are compared to the efficacy of mesotrione in the absence of an adjuvant and mesotrione in the presence of the commercially available adjuvant Brij96.
(56) TABLE-US-00016 TABLE 16 Mean percentage kill results for mesotrione in the presence and absence of benzoate 1, Benzoflex 354, FinsolvSB (stearyl benzoate) or Brij96. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean across species Mesotrione + BENZOATE 1 45.5 A Mesotrione + FINSOLVSB 42.5 AB Mesotrione + BRIJ96 40.1 B Mesotrione + BENZOFLEX 354 36.4 B Mesotrione 18.0 C
(57) The results show that all of the benzoic acid esters are effective adjuvants for mesotrione, and that benzoate 1 and Finsolv SB (i.e. the longer chain alkyl benzoates) are particularly effective.
Example 13 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Pinoxaden
(58) The aromatic esters benzoate 1 (see Example 9), Benzoflex 354 (2,2,4-trimethyl-1,3-pentanediol dibenzoate) and Finsolv SB (stearyl benzoate) were tested in a glasshouse against four weed species using the herbicide pinoxaden.
(59) An agrochemical composition was prepared containing 0.2% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. Pinoxaden was applied at either 7.5 or 15 grams of pesticide per hectare on each of the weed species. The commercially available surfactant Atlas G5000 was used in the spray tank at a concentration of 0.00375 g/l alongside the lower concentration of pinoxaden and at a concentration of 0.0075 g/l at the higher concentration of pinoxaden. The weed species and their growth stage at spraying were Alopecurus myosuroides (ALOMY; growth stage 13), Avena fatua (AVEFA; growth stage 12); Lolium perenne (LOLPE; growth stage 13), Setaria viridis (SETVI; growth stage 14).
(60) Each spray test was replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 7, 14 and 20 days following application. The results shown in Table 17 below are mean averages over the two rates of pinoxaden, three replicates and the three assessment timings, and are compared to the efficacy of pinoxaden in the absence of an adjuvant and pinoxaden in the presence of Brij96.
(61) The results show that each of the benzoic acid esters tested is an effective adjuvant for pinoxaden, and that benzoate 1 and Finsolv SB (i.e. the longer chain alkyl benzoates) are particularly effective.
(62) TABLE-US-00017 TABLE 17 Mean percentage kill results for pinoxaden in the presence and absence of benzoate 1, Benzoflex 354, FinsolvSB (stearyl benzoate) or Brij96. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05).. Treatment Mean across species Pinoxaden + BENZOATE 1 57.7 A Pinoxaden + FINSOLV SB 54.3 A Pinoxaden + BRIJ96 49.7 A Pinoxaden + BENZOFLEX 354 36.4 B Pinoxaden 1.8 C
Example 14 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Pinoxaden
(63) The aromatic esters Finsolv SB (stearyl benzoate), Finsolv TN and the aromatic ester ethoxylate Dermol 25-3B were tested in a glasshouse against four weed species using the herbicide pinoxaden.
(64) An agrochemical composition was prepared containing 0.2% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. The adjuvant oils were emulsified using a small amount of the surfactant Pluronic PE 10500, which was present in the composition at a concentration of 0.02% v/v. Pinoxaden was applied at either 7.5 or 15 grams of pesticide per hectare on each of the weed species. The commercially available surfactant Atlas G5000 was used in the spray tank at a concentration of 0.00375 g/l alongside the lower concentration of pinoxaden and at a concentration of 0.0075 g/l at the higher concentration of pinoxaden. The weed species and their growth stage at spraying were Alopecurus myosuroides (ALOMY; growth stage 13), Avena fatua (AVEFA; growth stage 12); Lolium perenne (LOLPE; growth stage 13), Setaria viridis (SETVI; growth stage 13-14).
(65) Each spray test was replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 14 and 21 days following application. The results shown in Table 18 below are mean averages over the two rates of pinoxaden, three replicates and the two assessment timings, and are compared to the efficacy of pinoxaden in the absence of an adjuvant and pinoxaden in the presence of tris 2ethylhexylphosphate (TEHP).
(66) The results show that each of the benzoic acid esters tested is an effective adjuvant for pinoxaden, and that Dermot 25-3B was particularly effective.
(67) TABLE-US-00018 TABLE 18 Mean percentage kill results for pinoxaden in the presence and absence of FinsolvSB, FinsolvTN and the aromatic ester ethoxylate Dermol 25-3B or Atplus 411F. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05).. Treatment Mean across species Pinoxaden + Dermol 25-3B 77.7A Pinoxaden + TEHP 75.7A Pinoxaden + Finsolv SB 74.4A Pinoxaden + Finsolv TN 72.4A Pinoxaden 2.6B
Example 15 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Nicosulfuron
(68) The aromatic esters Finsolv SB (stearyl benzoate), Finsolv TN and the aromatic ester ethoxylate Dermol 25-3B were tested in a glasshouse against four weed species using the herbicide nicosulfuron.
(69) An agrochemical composition was prepared containing 0.2% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. The adjuvant oils were emulsified using a small amount of the surfactant Pluronic PE 10500, which was present in the composition at a concentration of 0.02% v/v. Nicosulfuron was applied at either 30 or 60 grams of pesticide per hectare on each of the weed species. The weed species and their growth stage at spraying were Abutilon theophrasti (ABUTH; growth stage 13), Chenopodium album (CHEAL; growth stage 14-15), Digitaria sanguinalis (DIGSA; growth stage 14), and Setaria viridis (SETVI; growth stage 13-14).
(70) Each spray test replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 14 and 21 days following application. The results shown in Table 19 below are mean averages over the two rates of nicosulfuron, three replicates and the two assessment timings, and are compared to the efficacy of nicosulfuron in the absence of an adjuvant, and nicosulfuron in the presence of the commercially available tank-mix adjuvant, Atplus411F.
(71) TABLE-US-00019 TABLE 19 Mean percentage kill results for nicosulfuron in the presence and absence of FinsolvSB (stearyl benzoate), FinsolvTN and the aromatic ester ethoxylate Dermol 25-3B. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean across species Nicosulfuron + Dermol 25-3B 67.5A Nicosulfuron + FinsolvSB 66.6A Nicosulfuron + FINSOLVTN 66A Nicosulfuron + ATPLUS 411 F 60.9A Nicosulfuron 29.8B
(72) The results show that each of the benzoic acid ester is effective as an adjuvant for nicosulfruon.
Example 16 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Fomesafen
(73) The aromatic esters Finsolv SB (stearyl benzoate), Finsolv TN and the aromatic ester ethoxylate Dermol 25-3B were tested in a glasshouse against four weed species using the herbicide fomesafen.
(74) An agrochemical composition was prepared containing 0.2% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. The adjuvant oils were emulsified using a small amount of the surfactant Pluronic PE 10500, which was present in the composition at a concentration of 0.02% v/v. Fomesafen was applied at either 60 or 120 grams of pesticide per hectare on each of the weed species. The weed species and their growth stage at spraying were Polygonum convolvulus (POLCO; growth stage 13-14), Brachiaria plantaginea (BRAL; growth stage 13-14), Digitaria sanguinalis (DIGSA; growth stage 14), and Commelina benghalensis (COMBE; growth stage 13-14).
(75) Each spray test was replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 14 and 21 days following application. The results shown in Table 20 below are mean averages over the two rates of fomesafen, three replicates the two assessment timings, and the four weed species, and are compared to the efficacy of fomesafen in the absence of an adjuvant, and fomesafen in the presence of the commercially available adjuvant Turbocharge.
(76) TABLE-US-00020 TABLE 20 Mean percentage kill results for fomesafen in the presence and absence of FinsolvSB (stearyl benzoate), FinsolvTN and the aromatic ester ethoxylate Dermol 25-3B or Turbocharge. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean across species Fomesafen + Dermol 25-3B 61.7A Fomesafen + Turbocharge 60.7AB Fomesafen + Finsolv SB 55.8B Fomesafe + Finsolv TN 45.4C Fomesafen 24.3D
(77) The results demonstrate that all of the benzoic acid esters tested are effective as adjuvants for fomesafen and that Finsolv SB and Dermol 25-3B are as effective as the commercially available agrochemical adjuvant Turbocharge.
Example 17 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Mesotrione
(78) The aromatic esters Finsolv SB (stearyl benzoate), Finsolv TN and the aromatic ester ethoxylate Dermol 25-3B were tested in a glasshouse against three weed species using the herbicide mesotrione.
(79) An agrochemical composition was prepared containing 0.2% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. The adjuvant oils were emulsified using a small amount of the surfactant Pluronic PE 10500, which was present in the composition at a concentration of 0.02% v/v. Mesotrione was applied at either 60 or 120 grams of pesticide per hectare on weeds which had been grown to the 1.3 or 1.4 leaf stage. The weed species were Xanthium strumarium (XANST), Brachiaria platyphylla (BRAPL), and Digitaria sanguinalis (DIGSA). The commercially available surfactant Tetronic 1107 was used in the spray tank at a concentration of 0.036 g/l alongside the lower concentration of mesotrione and at a concentration of 0.072 g/l at the higher concentration of mesotrione.
(80) Each spray test was replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 14 and 21 days following application. The results shown in Table 10 below are mean averages over the two rates of mesotrione, three replicates and the two assessment timings, and are compared to the efficacy of mesotrione in the absence of adjuvant and mesotrione in the presence of the well-known adjuvant Tween20. The results shown in Table 16 below are mean averages over the two rates of mesotrione, three replicates, three assessment timings and three weed species. The results are compared to the efficacy of mesotrione in the absence of an adjuvant and mesotrione in the presence of the commercially available adjuvant Tween20.
(81) TABLE-US-00021 TABLE 21 Mean percentage kill results for mesotrione in the presence and absence of FinsolvSB (stearyl benzoate), FinsolvTN and the aromatic ester ethoxylate Dermol25-3B or Tween20. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean across species Mesotrione + Tween 20 43.4A Mesotrione + Dermol25-3B 42A Mesotrione + FINSOLVSB 38.3A Mesotrione + FINSOLVTN 32.7B Mesotrione 19.9C
(82) The results show that all of the benzoic acid esters are effective adjuvants for mesotrione, and that Dermol25-3B and Finsolv SB (i.e. the longer chain alkyl benzoates) are particularly effective.
Example 18 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Pinoxaden
(83) The aromatic esters Finsolv TN and the aromatic ester ethoxylate Dermol 25-3B were tested in a glasshouse against four weed species using the herbicide pinoxaden. An agrochemical composition was prepared containing either 0.2, 0.1, 0.05 or 0.025% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. The adjuvant tris(2-ethylhexyl) phosphate was applied at 0.5% v/v. An agrochemical composition was prepared containing 0.2% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. Pinoxaden was applied at either 7.5 or 15 grams of pesticide per hectare on each of the weed species. The commercially available surfactant Atlas G5000 was used in the spray tank at a concentration of 0.00375 g/l alongside the lower concentration of pinoxaden and at a concentration of 0.0075 g/l at the higher concentration of pinoxaden.
(84) The weed species and their growth stage at spraying were Alopecurus myosuroides (ALOMY; growth stage 21), Avena fatua (AVEFA; growth stage 12); Lolium perenne (LOLPE; growth stage 13), Setaria viridis (SETVI; growth stage 12).
(85) Each spray test was replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 14 and 21 days following application. The results shown in Table 22 below are mean averages over the two rates of pinoxaden, three replicates and the two assessment timings, and are compared to the efficacy of pinoxaden in the absence of an adjuvant and pinoxaden in the presence of tris(2-ethylhexyl) phosphate.
(86) The results show that each of the benzoic acid esters tested is an effective adjuvant for pinoxaden, and that Dermol 25-3B was particularly effective.
(87) TABLE-US-00022 TABLE 22 Mean percentage kill results for pinoxaden in the presence and absence of FinsolvTN and the aromatic ester ethoxylate Dermol 25-3B or Atplus 411F. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05).. Adjuvant rate Mean across Treatment % v/v species Pinoxaden + FINSOLVTN 0.1 87A Pinoxaden + Dermol 25-3B 0.1 86.5A Pinoxaden + Dermol 25-3B 0.2 86.3A Pinoxaden + ATPLUS 411 F 0.5 86.1AB Pinoxaden + FINSOLVTN 0.2 86AB Pinoxaden + Dermol 25-3B 0.05 81.6AB Pinoxaden + FINSOLVTN 0.05 79.1BC Pinoxaden + Dermol 25-3B 0.025 72.9CD Pinoxaden + FINSOLVTN 0.025 69.2D Pinoxaden 3.6E
Example 19 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Nicosulfuron
(88) The aromatic ester Finsolv TN and the aromatic ester ethoxylate Dermol 25-3B were tested in a glasshouse against four weed species using the herbicide nicosulfuron. An agrochemical composition was prepared containing either 0.2, 0.1, 0.05 or 0.025% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. The commercial adjuvant Atplus411F was applied at 0.5% v/v. Nicosulfuron was applied at either 30 or 60 grams of pesticide per hectare on each of the weed species. The weed species and their growth stage at spraying were Abutilon theophrasti (ABUTH; growth stage 11-12), Chenopodium album (CHEAL; growth stage 13-15), Digitaria sanguinalis (DIGSA; growth stage 13-21), and Setaria viridis (SETVI; growth stage 13).
(89) Each spray test replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 14 and 21 days following application. The results shown in Table 23 below are mean averages over the two rates of nicosulfuron, three replicates and the two assessment timings, and are compared to the efficacy of nicosulfuron in the absence of an adjuvant, and nicosulfuron in the presence of the commercially available tank-mix adjuvant, Atplus411F.
(90) TABLE-US-00023 TABLE 23 Mean percentage kill results for nicosulfuron in the presence and absence of FinsolvTN and the aromatic ester ethoxylate Dermol25-3B. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Adjuvant rate Mean across Treatment % v/v species Nicosulfuron + Dermol 25-3B 0.1 64.4A Nicosulfuron + Dermol 25-3B 0.2 65A Nicosulfuron + ATPLUS 411 F 0.5 63.1A Nicosulfuron + FINSOLVTN 0.2 62.8A Nicosulfuron + FINSOLVTN 0.1 60.5AB Nicosulfuron + Dermol 25-3B 0.05 59.4AB Nicosulfuron + FINSOLVTN 0.05 55.6BC Nicosulfuron + FINSOLVTN 0.025 54.8BC Nicosulfuron + Dermol 25-3B 0.025 50.7C Nicosulfuron 40.1
(91) The results show that each of the benzoic acid esters was as effective as the commercial adjuvant Atplus411F but at very reduced rates of adjuvant for nicosulfruon.
Example 20 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Fomesafen
(92) The aromatic esters Finsolv TN and the aromatic ester ethoxylate Dermol 25-3B were tested in a glasshouse against four weed species using the herbicide fomesafen.
(93) An agrochemical composition was prepared containing either 0.2, 0.1, 0.05 or 0.025% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. The commercial adjuvant Turbocharge was applied at 0.5% v/v. An agrochemical composition was prepared containing 0.2% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. Fomesafen was applied at either 60 or 120 grams of pesticide per hectare on each of the weed species. The weed species and their growth stage at spraying were Polygonum convolvulus (POLCO; growth stage 13-14), Brachiaria plantaginea (BRAL; growth stage 12-13), Digitaria sanguinalis (DIGSA; growth stage 13), and Commelina benghalensis (COMBE; growth stage 12).
(94) Each spray test was replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 14 and 21 days following application. The results shown in Table 24 below are mean averages over the two rates of fomesafen, three replicates the two assessment timings, and the four weed species, and are compared to the efficacy of fomesafen in the absence of an adjuvant, and fomesafen in the presence of the commercially available adjuvant Turbocharge.
(95) TABLE-US-00024 TABLE 24 Mean percentage kill results for fomesafen in the presence and absence of FinsolvTN and the aromatic ester ethoxylate Dermol 25-3B or Turbocharge. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Adjuvant rate Mean across Treatment % v/v species Fomesafen + Dermol 25-3B 0.2 39.2A Fomesafen + Dermol 25-3B 0.1 33.4AB Fomesafen + Turbocharge 0.5 33.1ABC Fomesafen + FINSOLVTN 0.2 29.9BCD Fomesafen + Dermol 25-3B 0.05 24.4CDE Fomesafen + FINSOLVTN 0.1 24.3DE Fomesafen + FINSOLVTN 0.05 22.9DE Fomesafen + Dermol 25-3B 0.025 22.6DE Fomesafen + FINSOLVTN 0.025 21.5DE Fomesafen 17.8E
(96) The results demonstrate that all of the benzoic acid esters tested are effective as adjuvants for fomesafen and that Finsolv SB and Dermol 25-3B are as effective as the commercially available agrochemical adjuvant Turbocharge but at a much lower use rate of the adjuvant.
Example 21 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Mesotrione
(97) The aromatic esters Finsolv SB (stearyl benzoate), Finsolv TN and the aromatic ester ethoxylate Dermol 25-3B were tested in a glasshouse against three weed species using the herbicide mesotrione.
(98) An agrochemical composition was prepared containing either 0.2, 0.1, 0.05 or 0.025% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. The commercial adjuvant Tween20 was applied at 0.2% v/v. Mesotrione was applied at either 60 or 120 grams of pesticide per hectare on weeds which had been grown to the 1.3 or 1.4 leaf stage. The commercially available surfactant Tetronic 1107 was used in the spray tank at a concentration of 0.036 g/l alongside the lower concentration of mesotrione and at a concentration of 0.072 g/l at the higher concentration of mesotrione. The weed species were Polygonum convolvulus (POLCO) 13, Brachiaria platyphylla (BRAPL) 12-13, Comelina berghalensis (COMBE) 12 and Digitaria sanguinalis (DIGSA) 13.
(99) Each spray test was replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 14 and 21 days following application. The results shown in Table 25 below are mean averages over the two rates of mesotrione, three replicates, four weed species and the two assessment timings. The adjuvants are compared to the efficacy of mesotrione in the absence of adjuvant and mesotrione in the presence of the well-known adjuvant Tween20.
(100) TABLE-US-00025 TABLE 25 Mean percentage kill results for mesotrione in the presence and absence of FinsolvTN and the aromatic ester ethoxylate Dermol25-3B or Tween20. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Adjuvant rate Mean across Treatment % v/v species Mesotrione + FINSOLVTN 0.2 70.1A Mesotrione + Dermol 25-3B 0.2 69.7A Mesotrione + Dermol 25-3B 0.1 69.6AB Mesotrione + Tween20 0.2 66.8AB Mesotrione + FINSOLVTN 0.1 65AB Mesotrione + Dermol 25-3B 0.05 61.5BC Mesotrione + Dermol 25-3B 0.025 56.9C Mesotrione + FINSOLVTN 0.025 55.3C Mesotrione + FINSOLVTN 0.05 55.2C Mesotrione 33.7D
(101) The results show that all of the benzoic acid esters are effective adjuvants for mesotrione, and that they are as effective as the commercial Adjuvant Tween20 at a much lower rate of adjuvant.
Example 22 Synthesis of Novel Adjuvants Benzoate 2 and Benzoate 3
(102) In this example the novel compounds oleyl-2-ethoxy-benzoate and oleyl-10-ethoxy-benzoate are synthesised. The adjuvant mixture Benzoate 2 was synthesised by adding an ethoxylated surfactant (Brij O-2) comprising a mixture of linear long chain (primarily oleyl, 18 carbons in length) alcohols to a flask and reacting this oil with benzoyl chloride. The resulting mixture was extracted after the reaction and purified. Analysis by nmr showed that the product consisted of long-chain (18 carbons in length) alcohol ethoxylates with a terminal benzoate. Similarly the surfactant Brij O-10 was reacted with benzoyl chloride to form the benzoate Benzoate 3. These benzoic acid esters were tested as adjuvants in Examples 23, 24, 25, and 26 described infra.
Example 23 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Pinoxaden
(103) The two aromatic esters prepared in example 22 tested in a glasshouse against four weed species using the herbicide pinoxaden.
(104) An agrochemical composition was prepared containing 0.2% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. Pinoxaden was applied at either 7.5 or 15 grams of pesticide per hectare on each of the weed species. The commercially available surfactant Atlas G5000 was used in the spray tank at a concentration of 0.00375 g/l alongside the lower concentration of pinoxaden and at a concentration of 0.0075 g/l at the higher concentration of pinoxaden. The weed species and their growth stage at spraying were Alopecurus myosuroides (ALOMY; growth stage 13), Avena fatua (AVEFA; growth stage 12); Lolium perenne (LOLPE; growth stage 13), Setaria viridis (SETVI; growth stage 13-14).
(105) Each spray test was replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 14 and 21 days following application. The results shown in Table 26 below are mean averages over the two rates of pinoxaden, three replicates and the two assessment timings, and are compared to the efficacy of pinoxaden in the absence of an adjuvant and pinoxaden in the presence of tris 2-ethylhexyl phosphate.
(106) The results show that each of the benzoic acid esters tested is an effective adjuvant for pinoxaden, and that Benzoate 2 was particularly effective.
(107) TABLE-US-00026 TABLE 26 Mean percentage kill results for pinoxaden in the presence and absence of Benzoate 2 and Benzoate 3 or TEHP. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05).. Treatment Mean across species Pinoxaden + TEHP 80.6A Pinoxaden + Benzoate 2 75.5A Pinoxaden + Benzoate 3 66.5B Pinoxaden 4.0C
Example 24 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Nicosulfuron
(108) The two aromatic esters prepared in example 22 tested in a glasshouse against four weed species using the herbicide nicosulfuron. Nicosulfuron was applied at either 30 or 60 grams of pesticide per hectare on each of the weed species. The weed species and their growth stage at spraying were Abutilon theophrasti (ABUTH; growth stage 13), Chenopodium album (CHEAL; growth stage 14-15), Digitaria sanguinalis (DIGSA; growth stage 14), and Setaria viridis (SETVI; growth stage 13-14).
(109) Each spray test replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 14 and 21 days following application. The results shown in Table 27 below are mean averages over the two rates of nicosulfuron, three replicates and the two assessment timings, and are compared to the efficacy of nicosulfuron in the absence of an adjuvant, and nicosulfuron in the presence of the commercially available tank-mix adjuvant, Atplus411F.
(110) TABLE-US-00027 TABLE 27 Mean percentage kill results for nicosulfuron in the presence and absence of Benzoate 2 and Benzoate 3. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean across species Nicosulfuron + Atplus 411F 69.2A Pinoxaden + Benzoate 2 65.6AB Pinoxaden + Benzoate 3 61.2B Pinoxaden 46.6C
(111) The results show that each of the benzoic acid ester is effective as an adjuvant for nicosulfruon.
Example 25 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Fomesafen
(112) The two aromatic esters prepared in example 22 tested in a glasshouse against four weed species using the herbicide fomesafen.
(113) An agrochemical composition was prepared containing 0.2% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. Fomesafen was applied at either 60 or 120 grams of pesticide per hectare on each of the weed species. The weed species and their growth stage at spraying were Polygonum convolvulus (POLCO; growth stage 13), Brachiaria plantaginea (BRAL; growth stage 13), Digitaria sanguinalis (DIGSA; growth stage 12-13), and Commelina benghalensis (COMBE; growth stage 11-12).
(114) Each spray test was replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 14 and 21 days following application. The results shown in Table 28 below are mean averages over the two rates of fomesafen, three replicates the two assessment timings, and the four weed species, and are compared to the efficacy of fomesafen in the absence of an adjuvant, and fomesafen in the presence of the commercially available adjuvant Turbocharge.
(115) TABLE-US-00028 TABLE 28 Mean percentage kill results for fomesafen in the presence and absence of Benzoate 2 and Benzoate 3 or Turbocharge. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean across species Fomesafen + Benzoate 2 57.5A Fomesafen + Turbocharge 51.5B Fomesafen + Benzoate 3 48.9B Fomesafen 32.8C
(116) The results demonstrate that all of the benzoic acid esters tested are effective as adjuvants for fomesafen and that Finsolv SB and Dermol 25-3B are as effective as the commercially available agrochemical adjuvant Turbocharge.
Example 26 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Mesotrione
(117) The two aromatic esters prepared in example 22 tested in a glasshouse against four weed species using the herbicide mesotrione.
(118) An agrochemical composition was prepared containing 0.2% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. Mesotrione was applied at either 60 or 120 grams of pesticide per hectare on weeds which had been grown to the 1.3 or 1.4 leaf stage. The commercially available surfactant Tetronic 1107 was used in the spray tank at a concentration of 0.036 g/l alongside the lower concentration of mesotrione and at a concentration of 0.072 g/l at the higher concentration of mesotrione. The weed species were Xanthium strumarium (XANST), Brachiaria platyphylla (BRAPL), and Digitaria sanguinalis (DIGSA).
(119) Each spray test was replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 14 and 21 days following application. The results shown in Table 29 below are mean averages over the two rates of mesotrione, three replicates and the two assessment timings, and are compared to the efficacy of mesotrione in the absence of adjuvant and mesotrione in the presence of the well-known adjuvant Tween20. The results shown in Table 29 below are mean averages over the two rates of mesotrione, three replicates, three assessment timings and three weed species. The results are compared to the efficacy of mesotrione in the absence of an adjuvant and mesotrione in the presence of the commercially available adjuvant Tween20.
(120) TABLE-US-00029 TABLE 29 Mean percentage kill results for mesotrione in the presence and absence of Benzoate 2 and Benzoate 3 or Tween20. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean across species Mesotrione + Benzoate 2 61.4A Mesotrione + Tween20 60.8AB Mesotrione + Benzoate 3 55.5B Mesotrione 39.4C
(121) The results show that the two benzoic acid esters are effective adjuvants for mesotrione, and that Benzoate 2 was particularly effective.
Example 27 A Further Example of a Novel Benzoate Capped Ethoxylated Adjuvant
(122) The commercial product Arosurf 66E20 (branched C18 alcohol ethoxylate with an average of 20 moles of ethoxylate) was reacted with benzoyl chloride. The product of this reaction was purified by chromatography and shown by nmr analysis to have a terminal benzoate ester group on the ethoxylate.
Example 28 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Isopyrazam
(123) The efficacy of the benzoic acid esters Finsolv SB, and the benzoate end capped ethoxylate Dermol25-3B as adjuvants in compositions comprising isopyrazam was tested and compared to the standard formulations (both EC and SC) of the fungicide, which lack this type of adjuvant.
(124) Wheat plants were inoculated with the fungus Septoria tritici. Four days after inoculation the plants were sprayed with a diluted emulsion concentrate or suspension concentrate formulation of the fungicide isopyrazam at rates of 3, 10, 30 and 100 mg of the fungicide per liter of spray solution, using a laboratory track sprayer which delivered the spray at a rate of 200 liters per hectare. Spray tests were also carried out with diluted suspension concentrate additionally comprising each of the benzoate adjuvants described above. These adjuvants were added to the spray solution at a rate of 0.2% w/w, based on the quantity of spray liquor. The leaves of the plants were assessed visually 14 days after the spray application and the damage was expressed as the percentage of the leaf area infected. Each spray test was replicated three times across the four application rates and the modelled means of these results are shown in Table 30 below.
(125) As can be seen from Table 30 the inclusion of a benzoate as an adjuvant for isopyrazam resulted in a significant reduction in the percentage of infection by S. tritici in comparison to that achieved by the standard isopyrazam SC. As well as increasing the efficacy of the standard suspension concentrate formulation (Standard SC) of isopyrazam, inclusion of the benzoate adjuvants Finsolv SB or Dermol 25-3B also resulted in isopyrazam compositions that were as effective at controlling S. triticias the standard isopyrazam emulsion concentrate formulation (Standard EC).
(126) TABLE-US-00030 TABLE 30 Mean % infection of wheat plants with S. tritici treated with isopyrazam in the presence and absence of benzoic acid ester adjuvants. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean % infection Control (blank) 60 A Standard Isopyrazam SC 38.6 B Standard Isopyrazam SC plus Dermol 26.2 C 25-3B Standard Isopyrazam EC 25.7 C Standard Isopyrazam SC plus Finsolv SB 25.4 C
Example 29 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Epoxyconazole
(127) The efficacy of the benzoic acid ester Finsolv SB, and the benzoate end capped ethoxylate Dermol25-3B as adjuvants in compositions comprising isopyrazam was tested and as adjuvants in compositions comprising epoxyconazole, was tested and compared to the standard formulation (SC) of the fungicide, which lacks this type of adjuvant.
(128) Wheat plants were inoculated with the fungus Septoria tritici. Four days after inoculation the plants were sprayed with a diluted suspension concentrate formulation of the fungicide epoxyconazole at rates of 3, 10, 30 and 100 mg of the fungicide per liter of spray solution, using a laboratory track sprayer which delivered the spray at a rate of 200 liters per hectare. Spray tests were also carried out with diluted suspension concentrate additionally comprising each of the benzoate adjuvants described above. These adjuvants were added to the spray solution at a rate of 0.2% w/w, based on the quantity of spray liquor. The leaves of the plants were assessed visually 14 days after the spray application and the damage was expressed as the percentage of the leaf area infected. Each spray test was replicated three times across the four application rates and the modelled means of these results are shown in Table 31 below.
(129) TABLE-US-00031 TABLE 31 Mean % infection of wheat plants with S. tritici treated with epoxyconazole in the presence and absence of benzoic acid ester adjuvants. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean % infection Control (blank) 57.6 A Standard epoxyconazole SC 44.5 A Standard epoxyconazole SC + Finsolv SB 18.7 B Standard epoxyconazole SC + Dermol 25-3B 10.8 C
(130) The results show that the mean percentage infection with S. tritici is reduced further when the wheat plants were treated with compositions of epoxyconazole comprising each of the benzoates, in comparison to the control (blank) and when treated with the standard SC composition of epoxyconazole. This shows that the benzoates are effective adjuvants for epoxyconazole.
Example 30
(131) Sunspray 11N is a commercially available oil which can be used to formulate adjuvants for tank mixing with agrochemical peroducts. One of the problems with ethoxylated adjuvants is that they are often incompatible with such oils and cannot therefore be formulated with this oil. This is a limitation. An advantage of a benzoate ester end capped adjuvant is that it has excellent compatibility with oils such as Sunspray 11N. Equal portions were prepared of Sunspray 11N and either Oleyl 10 ethoxylate with a butyl end cap (Agnique OC9 FOH 10B) or oleyl 12 ethoxylate with a benzoate end cap. The Agnique FOH OC9 10B formed two distinct layers whereas the benzoate end cap formed a single layer.
(132) This demonstrates the superior miscibility of benzoate end capped adjuvants to butyl end capped adjuvants.
Example 31 Further Benzoate End Capped Ethoxylated Surfactants
(133) The following commercially available ethoxylated surfactants were reacted with benzoyl chloride to form benzoate ester end capped adjuvants. The surfactants were dissolved in dichloromethane at which point triethylamine and benzoyl chloride were successively added. The mixture was stirred for 12 hours at 20 C. After this time the solvent was removed and the residue dissolved in ethyl acetate and aqueous sodium bicarbonate. The aqueous layer was washed with ethyl acetate which was then dried over anhydrous magnesium sulphate, filtered and concentrated. The product was identified by nmr spectroscopy.
(134) TABLE-US-00032 Surfactant Formula of product Reaction yield % Brij 98V C.sub.18H.sub.35(OCH.sub.2CH.sub.2).sub.20OCOPh 99 Genapol O 120 C.sub.18H.sub.35(OCH.sub.2CH.sub.2).sub.12OCOPh 94 Brij 92V C.sub.18H.sub.35(OCH.sub.2CH.sub.2).sub.2OCOPh 100 Arosurf 66E12 C.sub.18H.sub.37(OCH.sub.2CH.sub.2).sub.12OCOPh 91 Arosurf 66E10 C.sub.18H.sub.37(OCH.sub.2CH.sub.2).sub.10OCOPh 87 Synperonic C.sub.13H.sub.27(OCH.sub.2CH.sub.2).sub.5OCOPh 72 13/5
Example 32 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Pinoxaden
(135) The aromatic compound tridecyl salicylate was tested in a glasshouse against four weed species using the herbicide pinoxaden.
(136) An agrochemical composition was prepared containing 0.2% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. Pinoxaden was applied at either 7.5 or 15 grams of pesticide per hectare on each of the weed species. The commercially available surfactant Atlas G5000 was used in the spray tank at a concentration of 0.00375 g/l alongside the lower concentration of pinoxaden and at a concentration of 0.0075 g/l at the higher concentration of pinoxaden. The weed species and their growth stage at spraying were Alopecurus myosuroides (ALOMY; growth stage 13), Avena fatua (AVEFA; growth stage 12); Lolium perenne (LOLPE; growth stage 13), Setaria viridis (SETVI; growth stage 13-14).
(137) Each spray test was replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 14 and 21 days following application. The results shown in Table 18 below are mean averages over the two rates of pinoxaden, three replicates and the two assessment timings, and are compared to the efficacy of pinoxaden in the absence of an adjuvant and pinoxaden in the presence of tris 2-ethylhexyl phosphate (TEHP).
(138) The results show that tridecyl salicylate is an effective adjuvant for pinoxaden.
(139) TABLE-US-00033 TABLE 32 Mean percentage kill results for pinoxaden in the presence and absence of tridecyl salicylate or TEHP. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05).. Treatment Mean across species Pinoxaden + TEHP 86.1A Pinoxaden + Tridecyl salicylate 85A Pinoxaden 3.6B
Example 33 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Nicosulfuron
(140) The aromatic compound tridecyl salicylate was tested in a glasshouse against four weed species using the herbicide nicosulfuron. Nicosulfuron was applied at either 30 or 60 grams of pesticide per hectare on each of the weed species. The weed species and their growth stage at spraying were Abutilon theophrasti (ABUTH; growth stage 13), Chenopodium album (CHEAL; growth stage 14-15), Digitaria sanguinalis (DIGSA; growth stage 14), and Setaria viridis (SETVI; growth stage 13-14).
(141) Each spray test replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 14 and 21 days following application. The results shown in Table 19 below are mean averages over the two rates of nicosulfuron, three replicates and the two assessment timings, and are compared to the efficacy of nicosulfuron in the absence of an adjuvant, and nicosulfuron in the presence of the commercially available tank-mix adjuvant, Atplus411F.
(142) TABLE-US-00034 TABLE 33 Mean percentage kill results for nicosulfuron in the presence and absence of tridecyl salicylate. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean across species Nicosulfuron + ATPLUS 411 F 63.1A Nicosulfuron + Tridecyl salicylate 61.5A Nicosulfuron 40.1B
(143) The results show that tridecyl salicylate is effective as an adjuvant for nicosulfruon.
Example 34 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Fomesafen
(144) The aromatic compound tridecyl salicylate was tested in a glasshouse against four weed species using the herbicide fomesafen.
(145) An agrochemical composition was prepared containing 0.2% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. Fomesafen was applied at either 60 or 120 grams of pesticide per hectare on each of the weed species. The weed species and their growth stage at spraying were Polygonum convolvulus (POLCO; growth stage 13-14), Brachiaria plantaginea (BRAL; growth stage 13-14), Digitaria sanguinalis (DIGSA; growth stage 14), and Commelina benghalensis (COMBE; growth stage 13-14).
(146) Each spray test was replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 14 and 21 days following application. The results shown in Table 34 below are mean averages over the two rates of fomesafen, three replicates the two assessment timings, and the four weed species, and are compared to the efficacy of fomesafen in the absence of an adjuvant, and fomesafen in the presence of the commercially available adjuvant Turbocharge.
(147) TABLE-US-00035 TABLE 34 Mean percentage kill results for fomesafen in the presence and absence of tridecyl salicylate or Turbocharge. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean across species Fomesafen + Turbocharge 33.0A Fomesafen + Tridecyl salicylate 28.2A Fomesafen 17.8B
(148) The results demonstrate that tridecyl salicylate is effective as adjuvants for fomesafen
Example 35 Use of Benzoic Acid Ester Adjuvants in Agrochemical Compositions Comprising Mesotrione
(149) The aromatic compound tridecyl salicylate was tested in a glasshouse against three weed species using the herbicide mesotrione.
(150) An agrochemical composition was prepared containing 0.2% v/v of the adjuvant in a track sprayer and was applied at a volume of 200 liters per hectare. Mesotrione was applied at either 60 or 120 grams of pesticide per hectare on weeds which had been grown to the 1.3 or 1.4 leaf stage. The commercially available surfactant Tetronic 1107 was used in the spray tank at a concentration of 0.036 g/l alongside the lower concentration of mesotrione and at a concentration of 0.072 g/l at the higher concentration of mesotrione. The weed species were Xanthium strumarium (XANST), Brachiaria platyphylla (BRAPL), and Digitaria sanguinalis (DIGSA).
(151) Each spray test was replicated three times. The efficacy of the herbicide was assessed visually and expressed as a percentage of the leaf area killed. Samples were assessed at time periods of 14 and 21 days following application. The results shown in Table 10 below are mean averages over the two rates of mesotrione, three replicates and the two assessment timings, and are compared to the efficacy of mesotrione in the absence of adjuvant and mesotrione in the presence of the well-known adjuvant Tween20. The results shown in Table 16 below are mean averages over the two rates of mesotrione, three replicates, three assessment timings and three weed species. The results are compared to the efficacy of mesotrione in the absence of an adjuvant and mesotrione in the presence of the commercially available adjuvant Tween20.
(152) TABLE-US-00036 TABLE 35 Mean percentage kill results for mesotrione in the presence and absence of tridecyl salicylate or Tween20. A standard Tukey HSD test was carried out to assess whether each result was statistically different from the other results and this is expressed as a letter: tests with the same letter are not statistically different (p < 0.05). Treatment Mean across species Mesotrione + Tween20 67.1A Mesotrione + Tridecyl salicylate 63.6A Mesotrione 33.8B
(153) The results show that tridecyl salicylate is an effective adjuvant for mesotrione.
Example 36 Use of Aromatic Ester Adjuvants in Agrochemical Compositions Containing Abamectin
(154) The efficacy of the benzoic acid esters Finsolv SB (isostearyl benzoate) and Finsolv TN (C.sub.12-C.sub.15 alkyl benzoate) and the aromatic ester ethoxylate Dermol25-3B (C.sub.12-C.sub.15 alkyl ethoxy (3) benzoate) as adjuvants in compositions containing abamectin was tested and compared to the efficacy of abamectin compositions which lack this type of adjuvant. The adjuvants were present at 0.1% v/v in the abamectin compositions. The surfactants polyoxyethylene sorbitan monooleate and an ethoxylated castor oil were also present in all the abamectin compositions tested.
(155) Two week old French bean (Phaseolus vulgaris) plants were infested with a mixed population of two spotted spider mite Tetranychus urticae. One day after infestation the plants were treated with the test compositions, with a track sprayer from the top with a rate of 200 liters per hectare. Plants were incubated in the greenhouse for 10 days and the evaluation was done on mortality against Larva and Adults, just on the lower side (untreated) of the leaves. Each experiment was replicated twice and the results were averaged. The mortality against Larva and Adults was then averaged.
(156) In the control experiment the beans were sprayed with water and no mortality was observed. The beans were sprayed with aromatic ester compositions without abamectin present, containing 0.1% v/v Finsolv TN, 0.1% v/v Finsolv SB or 0.1% v/v Dermol 25-3B and no mortality was observed in each case.
(157) TABLE-US-00037 TABLE 36 % Mortality of Tetranychus urticae treated with abamectin in the presence and absence of aromatic ester adjuvants. % mortality of Tetranychus urticae at different abamectin concentrations (ppm) Treatment 3 ppm 1.5 ppm 0.8 ppm 0.4 ppm 0.2 ppm 0.1 ppm 0.05 ppm 0.025 ppm 0.0125 ppm Abamectin 95 70 27 0 0 Abamectin + 100 90 60 50 47 FINSOLV TN Abamectin + 100 99 75 65 50 FINSOLV SB Abamectin + 100 99 75 60 0 Dermol 25-3B
(158) As can be seen from Table 36 the inclusion of the aromatic esters as adjuvants for abamectin provided effective control of Tetranychus urticae at much lower concentrations of abamectin than are required in the absence of adjuvant.