FORMULATION COMPONENT

Abstract

The present invention relates to agrochemical compositions comprising certain benzamide compounds and to the use of those benzamide compounds as adjuvants, especially in formulations, in particular in agrochemical formulations and in environmentally friendly formulations. The invention further extends to certain novel benzamide compounds and a process to prepare such novel compounds.

Claims

1. A method of increasing the efficacy of an herbicide when applied to unwanted plants or the locus thereof, said method comprising combining a compound of formula (I) ##STR00027## wherein, m is 1; n is an integer of 0, 1, 2, or 3; R.sup.1 is C(O)NR.sup.3R.sup.4; each is independently methyl or C.sub.6-12 alkyl; each R.sup.3 is selected from the group consisting of H, methyl, ethyl, propyl or butyl; R.sup.4 is the group -[AO].sup.XR.sup.5, -[OA].sub.xR.sup.5, or combinations thereof, wherein A is ethyl or propyl, x is an integer of 7-18; and each R.sup.5 is independently H, C.sub.1-4 alkyl, or NH.sub.2, with said herbicide, such that when said combination is applied to said unwanted plants or the locus thereof the concentration of the compound of formula (I) is in the range of 0.05% to 1% w/v or v/v of the total combination, and the efficacy of the combination in controlling unwanted plant growth is greater than that observed when the herbicide is applied in the absence of the compound of formula (I).

2. The method of claim 1, wherein at least one R.sup.2 is at the para position.

3. The method of claim 1, wherein R.sup.3 is H and R.sup.4 is the group ##STR00028## wherein b has the value of 9 and the sum of a and c is 3 or 4.

4. The method of claim 1, wherein n is 1.

5. The method of claim 1, wherein n is 0.

6. An agrochemical composition comprising (i) a compound of formula (I) ##STR00029## wherein m is 1; n is an integer of 0, 1, 2, or 3; R.sup.1 is C(O)NR.sup.3R.sup.4; each R.sup.2 is independently methyl or C.sub.6-12 alkyl; R.sup.3 is selected from the group consisting of H, methyl, ethyl, propyl or butyl, R.sup.4 is the group -[AO].sub.xR.sup.5, -[OA].sub.xR.sup.5, or combinations thereof, wherein A is ethyl or propyl, and x is an integer of 7-18; and R.sup.5 is H, C.sub.1-4 alkyl, or NH.sub.2, and (ii) an agrochemical active ingredient.

7. An agrochemical composition according to claim 6, wherein the agrochemical composition is a herbicidal composition and the agrochemical active ingredient is an herbicide.

8. An agrochemical composition according to claim 6, wherein the compound of formula (I) comprises from about 0.0005% to about 90% w/v of the total composition.

9. An agrochemical composition according to claim 6, wherein the agrochemical is selected from the group consisting of: bicyclopyrone, mesotrione, fomesafen, tralkoxydim, napropamide, 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, prothioconazole, thiamethoxam, imidacloprid, acetamiprid, clothianidin, dinotefuran, nitenpyram, fipronil, abamectin, emamectin, bendiocarb, carbaryl, fenoxycarb, isoprocarb, pirimicarb, propoxur, xylylcarb, asulam, chlorpropham, endosulfan, heptachlor, tebufenozide, bensultap, diethofencarb, pirimiphos methyl, aldicarb, methomyl, cyprmethrin, bioallethrin, deltamethrin, lambda cyhalothrin, cyhalothrin, cyfluthrin, fenvalerate, imiprothrin, permethrin, halfenprox, paclobutrazole, 1-methylcyclopropene, benoxacor, cloquintocet-mexyl, cyometrinil, dichlormid, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, mefenpyr-diethyl, MG-191, naphthalic anhydride, and oxabetrinil.

10. An agrochemical composition according to claim 6, wherein the composition is formulated as, or comprised by a microcapsule.

11. An agrochemical composition according to claim 6, wherein the composition is an emulsion concentrate (EC) or dispersion concentrate (DC).

12. An agrochemical composition according to claim 6, comprising at least one additional component selected from the group consisting of an agrochemical, an adjuvant, a surfactant, an emulsifier, and a solvent.

13. An agrochemical composition, comprising: (i) an agrochemically active adjuvant having formula (I) ##STR00030## wherein m is 1; n is an integer of 0, 1, 2, or 3; R.sup.1 is C(O)NR.sup.3R.sup.4; each R.sup.2 is independently methyl or C.sub.6-12 alkyl; R.sup.3 is selected from the group consisting of H, methyl, ethyl, propyl or butyl, and R.sup.4 is an alkoxylated chain ending with H, C.sub.1-4 alkyl, or NH.sub.2; and and (ii) an agrochemical active ingredient.

14. A method of making a benzoic acid derivative, comprising: reacting a compound of formula (II) ##STR00031## wherein R.sup.2 is C.sub.1-15 alkyl, and n is an integer of 0, 1, 2, or 3, with NR.sup.3R.sup.4, wherein R.sup.3 is selected from the group consisting of H, methyl, ethyl, propyl or butyl, and R.sup.4 is an alkoxylated chain ending with H, C.sub.1-4 alkyl, or NH.sub.2.

15. The method of claim 14, wherein the reacting comprises using SOCl.sub.2 or N,N-Dicyclohexylcarbodiimide.

Description

EXAMPLE 1

Synthesis of 4-Dodecyl-N-[2-(2-{2-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl]-benzamide (Compound No. 2)

[0066] 4-Dodecyl-N-(2-{2-[2-(2-{2-[2-(2-ethoxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-ethoxy}-ethoxy)-benzamide (Compound 2 in Table 1 above) was synthesised by reacting para-dodecylbenzoic acid with octaethylene oxide amine, using N,N-dicyclohexylcarbodiimide (DCC) as a coupling agent.

EXAMPLE 2

Use of 4-Dodecyl-N-[2-(2-{2-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl]-benzam de (Compound No. 2) as an Adjuvant in Nicosulfuron Formulations

[0067] Compound No. 2 (see Example 1 and Table 1 above) was tested in a glasshouse against four weed species in combination with 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 litres per hectare. Nicosulfuron was applied at either 30 or 60 grams of pesticide per hectare on weeds which had been grown to the 1.3 or 1.4 leaf stage. The weed species were Chenopodium album (CHEAL), Abutilon theophrasti (ABUTH), Brassica perenni (BRAPP), and Digitaria sanguinalis (DIGSA).

[0068] 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 21 days.following application. The results shown in Table 2 below are mean averages over the two rates of nicosulfuron, three replicates and the three assessment timings. The results are compared to those obtained for nicosulfuron in combination with the commercially available tank mix adjuvant Turbocharge D (Syngenta Crop Protection Canada, Inc.), and it can be seen in each case superior weed control is observed when Compound 2 is included in the formulation as an adjuvant.

TABLE-US-00002 TABLE 2 Mean percentage kill results for nicosulfuron in the presence of compound no. 2 compared to nicolsulfuron in the presence of Turbocharge D. Mean Adjuvant CHEAL ABUTH BRAPP DIGSA (g/ha) Compound No 2 80 47.1 86.4 83.1 73.9 Turbocharge 76.7 41.7 80.6 64.8 65.9

EXAMPLE 3

Use of Compound No. 2 as an Adjuvant for Fomesafen

[0069] Compound No. 2 was tested in a glasshouse against four weed species in combination with 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 litres per hectare. Fomesafen 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 Chenopodium album (CHEAL), Abutilon theophrasti (ABUTH), Setaria viridis (SETVI), and Xanthium strumarium (XANST).

[0070] Each spray test was replicated six 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 and 14 days following application. The results shown in Table 3 below are mean averages over the two rates of fomesafen, six replicates and the two assessment timings, and are compared to the efficacy of fomesafen in the absence of adjuvant.

TABLE-US-00003 TABLE 3 Mean percentage kill results for fomesafen in the presence and absence of compound 2 Mean across Adjuvant ABUTH CHEAL SETVI XANST species Compound 2 90 34.1 41.7 68.8 58.6 None 60.8 43.3 38.2 45.8 47.0

EXAMPLE 4

Use of Compound 2 as an Adjuvant for Mesotrione

[0071] Compound No. 2 was tested in a glasshouse against four weed species in combination with 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 litres 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 Amaranthus retroflexus (AMARE), Abutilon theophrasti (ABUTH), Brachiaria platyphylla (BRAPP), and Digitaria sanguinalis (DIGSA).

[0072] Each spray test was replicated six 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 6, 14 and 21 days following application. The results shown in Table 4 below are mean averages over the two rates of mesotrione, six replicates and the three assessment timings. The results are compared to those obtained for mesotrione in combination with the commercially available tank mix adjuvant Turbocharge D (Syngenta Crop Protection Canada, Inc.).

TABLE-US-00004 TABLE 4 Mean percentage kill results for nicosulfuron in the presence of compound 2 compared to nicolsulfuron in the presence of Turbocharge D. Mean across Adjuvant AMARE ABUTH BRAPP DIGSA species Compound 2 63.5 73.3 68.2 83.4 72.1 Turbocharge 67.2 73.8 58.2 79.7 69.8

EXAMPLE 5

Use of Compound 1 (N, N-Diethyl-3-Methylbenzamide) as an Adjuvant for Fomesafen

[0073] Compound 1 (N, N-diethyl-3-methylbenzamide) 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 litres 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 13/14), Abutilon theophrasti (ABUTH; growth stage 12), Setaria viridis (SETVI; growth stage 13), and Xanthium strumarium (XANST; growth stage 12).

[0074] 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 21 days following application. The results shown in Table 5 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 adjuvant.

TABLE-US-00005 TABLE 5 Mean percentage kill results for fomesafen in the presence and absence of compound 1. Mean across Adjuvant CHEAL ABUTH SETVI XANST species Compound 1 80.3 38.9 15.8 35.6 42.6 None 77.5 20 10.6 42.8 37.7

EXAMPLE 6

Use of Compound 1 as an Adjuvant for Mesotrione

[0075] Compound 1 was tested in a glasshouse against four weed species using the herbicide mesotrione. A 20% w/w stock emulsion of compound 1 was prepared additionally containing 2% w/w GohsenolGL03 and 2% w/w PluronicPE10500 as surfactants. Using this, 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 litres per hectare. Mesotrione was applied at either 45 or 90 grams of pesticide per hectare on each of the weed species. The weed species and their growth stage at spraying were Amaranthus tuberculatus (AMATE; growth stage 13/14), Brachiaria decumbens (BRADE; growth stage 13/14), Digitaria sanguinalis (DIGSA; growth stage 14), and Polygonum convolvulus (POLCO; growth stage 11/11.5).

[0076] Each 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 21 days following application. The results shown in Table 6 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 absence of adjuvant.

TABLE-US-00006 TABLE 6 Mean percentage kill results for mesotrione in the presence and absence of compound 1. Mean across Adjuvant AMATE BRADE DIGSA POLCO species Compound 1 71.7 28.9 28.6 87.2 54.1 None 65.6 26.7 23 73.3 47.1

EXAMPLE 7

Use of Compound 1 as an Adjuvant for Nicosulfuron

[0077] Compound 1 was tested in a glasshouse against four weed species using the herbicide nicosulfuron. A 20% w/w stock emulsion of compound 1 was prepared additionally containing 2%0/w/w GohsenolGL03 and 2% w/w PluronicPE10500 as surfactants. Using this, 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 litres 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).

[0078] 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 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.

TABLE-US-00007 TABLE 7 Mean percentage kill results for nicosulfuron in the presence and absence of compound 1. Mean across Adjuvant ABUTH CHEAL DIGSA SETVI species Compound 1 72.9 63.8 89.4 93.4 81.3 None 69.2 50.8 87.9 92 75

EXAMPLE 8

Use of Compound 1 as an Adjuvant for Pinoxaden

[0079] The adjuvant shown in example 1 was tested in a glasshouse against four weed species in combination with the herbicide pinoxaden. A 20% w/w stock emulsion of compound 1 was prepared additionally containing 2% w/w GohsenolGL03 and 2% w/w PluronicPE10500 as surfactants. Using this, 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 litres per hectare. Pinoxaden was applied at either 7.5 or 15 grams of pesticide per hectare on each of the weed species. 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).

[0080] 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 8 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 adjuvant.

TABLE-US-00008 TABLE 8 Mean percentage kill results for pinoxaden in the presence and absence of compound 1. Mean across Adjuvant ALOMY AVEFA LOLPE SETVI species Novel adjuvant 1 22.5 29.2 20.8 15.8 22.1 Pinoxaden 21.2 20.8 12.5 15 17.4

EXAMPLE 9

Production of Ethoxylated Aromatic Amides (Compounds 3, 4, 5, and 6)

[0081] Compounds 3, 4, 5, and 6 from table 1 above were prepared in the following manner. Four samples of monoamines of polyethylene glycol (A, B, C, & D) were purchased from St Andrews chemicals, St Andrews University, St Andrews, Scotland. These were stated as having, 5, 10, 15, and 20 ethylene oxide moieties respectively, but following nmp spectroscopic analysis were found to have the average number of ethylene oxide moieties as shown in Table 9.

TABLE-US-00009 TABLE 9 Degree of ethoxylation of polyethylene glycol monoamine samples as assessed by nmp spectroscopy. Sample Average no of EO units determined A: Monoethanolamine 4 EO 5 B: Monoethanolamine 9 EO 10.2 C: Monoethanolamine 14 EO 14.5 D: Monoethanolamine 19 EO 19.2

[0082] Each of these amines (A, B, C, and D) was used to produce an aromatic amide using the general methodology described below.

[0083] Monoethanolamine polyethylene oxide was added to a reaction flask with benzoyl chloride and the solvent tetrahydrofuran. The flask was sealed and placed in a microwave reactor. The sample was heated to 140 C. and 7 bar pressure for five minutes. Table 10 summarises reactant quantities and product yield for the individual reactions.

TABLE-US-00010 TABLE 10 Amide product (with PEG reference to monoethanolamine Benzoyl Table 1 Amide sample (g) chloride (g) THF (ml) above) yield % A (1.01) 0.687 5 Compound 3 85 B (1) 0.424 5 Compound 4 78 C (1) 0.239 5 Compound 5 93 D (0.96) 0.216 5 Compound 6 76

[0084] The resulting amide products were purified by dissolution in acetone followed by precipitation with hexane. Product structures were checked with nmr spectroscopy and confirmed as those given in Table 1 above.

EXAMPLE 10

Production of an Ethoxylated Aromatic Amide

[0085] Benzoyl chloride was reacted with the diamine of polyethylene oxide with an average of 8 EO using the methodology described in Example 8 above. This formed an aromatic amide with the structure of Compound 7 as shown in Table 1 above.

EXAMPLE 11

Production of Ethoxy/Propoxylated Aromatic Amide

[0086] Benzoyl chloride was reacted with Jeffamine ED600 (Huntsman Performance Products, Texas, USA)

[0087] The Jeffamine ED series of polyether amines are polyether diamines based on a predominantly PEG backbone. They have the following representative structure:

##STR00026##

[0088] For Jeffamine ED600 the characteristics are as follows: y9.0, (x+z)3.6, molecular weight 600.

[0089] The reaction formed a mixed benzoate amide ester of the polyethylene/polypropylene copolymer carrying a terminal amino group. The degree of ethoxylation and propoxylation is mixed, with the ester having on average 9EO moieties and on average 3.6 PO moieties.