WO2016142280A1

WO2016142280A1 - An emulsifiable concentrate composition comprising pethoxamid

Info

Publication number: WO2016142280A1
Application number: PCT/EP2016/054611
Authority: WO
Inventors: Anke Schuster
Original assignee: Cheminova A/S
Priority date: 2015-03-06
Filing date: 2016-03-04
Publication date: 2016-09-15

Abstract

An emulsifiable concentrate (EC) formulation comprising, in addition to any optional customary formulation diluents: a) pethoxamid; b) a compound or a mixture of compounds that is capable of forming a eutectic mixture with pethoxamid; c) one or more organic solvents; wherein compound b) is selected among compounds of the general formula (I) The compositions are of good stability during storage and usability (e diluted form) even at low temperatures.

Description

AN EMULSIFIABLE CONCENTRATE COMPOSITION COMPRISING PETHOXAMID

Introduction

The present invention relates to emulsifiable concentrates (EC) compositions comprising pethoxamid and a method for controlling unwanted plants and plant growth using such compositions.

Background

Crystallization of the active ingredient(s) is a problem sometimes encountered, when diluting concentrated compositions comprising pesticidal active compounds such as herbicides. The problem may arise prior to application, e.g. when diluting the concentrate with water in spray tanks for aqueous spray liquid application. Filters and/or nozzles in the spray equipment are more or less easily blocked as a result of the crystallizing active ingredient during application. The crystallization often increases over time meaning that application of the spray liquid must take place immediately or within a few hours after dilution of the concentrated composition. This however, is not always easily done as seen from a practical point of view. Further, some actives are also prone to crystallize out of solution, e.g. in concentrated compositions, when stored at low temperatures.

Pethoxamid, also known by its chemical name 2-chloro-N-(2-ethoxyethyl)- N-(2-methyl-l-phenylprop-l-enyl)acetamide, is a herbicidal active compound used for controlling unwanted plants and plant growth (e.g. weeds), see for example European patent application no. EP 206251-Al. Processes for its preparation is further known from Agric. Biol. Chem. 55 (11) 2737-2743 (1991), Bull. Chem. Soc. Jpn., 65, 674-678 (1992) and European patent application no. EP 774456-A1. Commercially available pethoxamid is an amorphous substance of low melting point (37-38°C) and is available as an emulsifiable concentrate (EC) - see CPC Conference - Weeds (2001), (Vol. 1), 23-28. The commercially available product is based on a water immiscible (non-polar) petroleum-derived solvent. For EC formulations water immiscible solvents capable of dissolving the active ingredient are often the preferred choice as they aid in keeping the active ingredient solubilized upon dilution in water, e.g. prior to application. However, and especially under low temperature conditions it has sometimes been observed that such compositions comprising pethoxamid gives rise to crystallization of the pethoxamid after dilution with water in e.g. spray tanks over a relatively short period of time. These crystals are of a nature that potentially may cause blocking of spraying equipment, e.g. filters and/or nozzles in the spray equipment if not removed by whatever means available, e.g. physical removal and/or re-dissolving the crystals. Active material may be lost and not readily available for its intended purpose, i.e. use in crop protection. In International patent publication no. WO 2014/139805 it is suggested to prepare cold stable EC compositions that are based on optionally alkyl substituted alkyl benzoate (e.g. n-butyl benzoate) in combination with certain C5-C19-fatty acid amides. In the same publication it is also illustrated that comparative compositions using either the alkylbenzoate or the fatty acid amide alone does not provide cold stable compositions and in particular using alkyl benzoate only also results in non- homogeneous solutions. United States patent no. US 5,977,024 discloses dimethenamid in combination with certain precipitation point lowering agents. Such agents are selected among benzoic acids comprising at least one chloro substituent in the ortho position on the benzene ring, and a methoxy or chloro substituent in the other ortho position. The positions of these substituents on the benzoic acid are said to be accountable for an interaction with dimethenamid resulting in a lower precipitating point. An example of such substituted benzoic acid is the herbicidal compound dicamba (3,6- dichloro-2-methoxybenzoic acid). There is a need to provide improved pethoxamid compositions in a form which permits the application of pethoxamid with minimal risk of equipment failure, e.g. of blocking of spray equipment, even when applied at low temperatures, including stability of the concentrate compositions when stored at prolonged periods of time and in some instances under varying temperature conditions. These requirements are met with the present invention.

Description of the invention

It has now been found that emulsifiable concentrates (EC) compositions comprising, in addition to pethoxamid and one or more organic solvents, one or more compounds capable of forming a eutectic mixture with pethoxamid, are of particular good stability during storage and usability (e.g. in diluted form) even at low temperatures e.g. around 5°C.

Accordingly, there is provided an emulsifiable concentrate (EC) composition emulsifiable concentrate (EC) formulation comprising, in addition to any optional customary formulation diluents:

a) pethoxamid;

b) a compound or a mixture of compounds that is capable of forming a eutectic mixture with pethoxamid;

c) one or more organic solvents;

wherein compound b) is selected among compounds of the general formula (I)

wherein, when Ri represents H,

then R₂ represents CI -CIO alkyl, C2-C10 alkenyl, C2-C 10 alkynyl, or aryl, said groups optionally being substituted with one or more electron withdrawing groups selected among C1-C6 alkoxy, aryl C1-C6 alkoxy, COH, aryl- or C1-C6 alkyl-sulfonyl, CN, N0₂, COOH, hydroxyl, F, CI, Br, I, and haloalkyl, or

when Ri represents CI -CIO alkyl, C2-C10 alkenyl, C2-C10 alkynyl optionally substituted by one more substituents selected from the group comprising cyano, F, CI, Br, I, hydroxy, nitro, acyl, acylamino, acyloxy, CI -CIO alkyl, C2 CIO alkenyl, C2-C10 alkynyl, aryl, CI -CIO alkoxy, CI -CIO alkylsulfonyl, methylsulfonyl, triflouromethyl, amino, aminocarbonyl, aminothiocarbonyl, amino- carbonylamino, aminothiocarbonylamino, amino carbonyloxy, amino- sulfonyl, aminosulfonyloxy, aminosulfonylamino, amidino, carboxyl, carboxyl ester, (carboxyl ester)amino, (carboxyl ester)oxy, sulfonyl, sulfonyloxy, thioacyl, thiol, thiocarbonyl, CI -CIO alkylthio, heteroaryl, and C3-C7 cycloalkyl,

then R₂ represents a CI -CIO alkyl, C2-C10 alkenyl, C2-C10 alkynyl, or aryl, said groups being substituted with one or more electron withdrawing groups selected among C1-C6 alkoxy, aryl Cl- C6 alkoxy, COH, aryl- or CI -CIO alkyl-sulfonyl, CN, N0₂, COOH, hydroxyl, F, CI, Br, I, and haloalkyl.

The compositions may optionally comprise adjuvants and/or customary formulation auxiliaries, i.e. an emulsifiable concentrate (EC) formulation comprising:

a) pethoxamid;

b) a compound or a mixture of compounds that is capable of forming a eutectic mixture with pethoxamid thereof, wherein the component b) is selected among compounds of the general formula (I);

c) one or more organic solvents; a) optionally one or more adjuvants;

b) optionally one or more customary formulation auxiliaries.

A compound of the formula (I), i.e. component b), that is capable of forming a eutectic mixture with pethoxamid is a compound that, when intermixed with pethoxamid, is capable of forming a eutectic mixture having a minimum melting point (eutectic point) that is lower than the melting point of both the pethoxamid and the component b). It is preferred that the component b) is one that has a melting point that is above normal ambient temperature, i.e. is a solid at ambient temperature. As used herein, a "eutectic mixture" is a mixture of two or more materials having the lowest melting point that is obtainable by varying the proportions of the materials. However, liquid compounds (i.e. liquid at ambient temperature) may also be useful, and may even serve the purpose as solvent (i.e. as component c) in total or in part as a component in a solvent mixture. In such case the component b) and c) may be considered as one. In a preferred embodiment, the component b) is selected among solids, i.e. solids at ambient temperature (around 20-25°C), and more preferably selected as to have a melting point above that of pethoxamid, e.g. a melting point equal to or above 37°C and more preferably equal to or above 50°C and even more preferably equal to or above 60°C.

The term "electron-withdrawing group" (EWG) is recognized in the art and denotes the tendency of a substituent to attract valence electrons from neighboring atoms, i.e., the substituent is electronegative with respect to neighboring atoms. Thus for the purpose herein the term relates primarily to the Inductive effect of a substituent. For example, the inductive effect of a F atom or a CF₃ group is that they withdraw electron density. A C¾ group fragment, just like all other alkyl groups, is a fragment which donate electron density inductively, because electronegativity of H and C atoms is the lowest. The inventors have realised, as an example, that compounds of formula (I) wherein Ri represents groups different from H and R₂ represent aryls, such as phenyl, not comprising any electron withdrawing groups, the properties to form euthetic mixtures are inferior. Thus, compounds like alkyl esters of 3- methylbenzoic acid are no part of the scope of the present invention.

Examples of electron withdrawing groups comprise alkoxy (e.g. CI -CIO alkoxy such as methoxy or ethoxy), arylalkoxy (e.g aryl-Cl-CIO alkoxy, such as phenylmethoxy), COH, aryl- or alkyl- sulfonyl (e.g. phenylsulfonyl or Cl-ClO-alkylsulfonyl), CN, N0₂, COOH, hydroxyl, optionally substituted phenyl e.g. phenyl comprising one or more hydroxyl groups (e.g. mono or di- hydroxy substituted phenyl), halogens (e.g. F, CI, Br or I), haloalkyl (e.g. Cl- CIO haloalkyl such as CF₃, CHF₂, CH₂F or CC1₃). Preferred are halogen, OH, COOH, or phenyl substituted with one or more hydroxyl groups (e.g. 4-hydroxyphenyl or 2,4-dihydroxy phenyl).

Where applicable and if not stated otherwise, preferred alkyl, alkenyl, or alkynyl chains are straight, branched or cyclic, and preferably comprise 1-10 carbon atoms, more preferably 1-6 carbon atoms and most preferably 1-3 carbon atoms. This is applicable to other alkyl comprising groups as well, e.g. alkoxy groups (alkyl-O-). In the above the term "comprising one or more" is, when read in its proper chemical context, to be understood as meaning substituted with, i.e. when referring to alkyl or phenyl comprising one or more groups this means an alkyl group or phenyl group substituted with one or more substituents well known within the field of organic chemistry. Accordingly, the term "comprising one or more electron withdrawing groups" is to be understood as not excluding the presence of other substituents as long as one or more electron withdrawing substituents are present among all those substituents present on the alkyl or phenyl backbone. An example of such other substituent that may be present on a phenyl backbone are alkyl substituents, e.g. straight, branched or cyclic alkyl groups such as an alkyl substituent comprising 1 to 10 carbon atoms (CI -CIO). Thus, the phenyl substituent '2-hydroxy-3-methylphenyl' is an example of a phenyl substituent 'comprising one or more electron withdrawing groups' (OH), while also comprising a different group (methyl). Accordingly, the group '2-hydroxy-3- methylphenyl' is part of the scope of the present invention. In a prefered aspect of the invention the term is to be understood as meaning 1 to 3 substituents.

The component b) is preferably selected among compounds of the formula (I), wherein:

When Ri represents H,

R₂ represents CI -C IO alkyl (that may be a straight, branched or a cyclic alkyl chain), more preferably represents C1-C6 alkyl, even more preferably C1-C3, and most preferably R₂ represents the CI or C2 group; and such alkyl group comprise one or more electron withdrawing groups which may be the same or different but with a preference for one, two or three substituents, preferably such group(s) is/are selected among the following: halogen e.g. F, CI, Br or I, with a preference for the CI substituent(s); COOH; OH; and optional substituted phenyl wherein such substituents, which may be the same or different if more than one but with a preference for one, two or three substituents, may be selected when present among straight or branched CI -CIO alkyl groups and OH, and preferably selected among straight or branched C1-C6 alkyl and OH, even more preferably selected among C1-C3 alkyl and OH and most preferably OH; or

R₂ represents phenyl or phenyl substituted with one or more substituents, which may the same or different, and if any such substituent is an electron withdrawing group, then such electron withdrawing group is selected among alkoxy, arylalkoxy, COH, aryl- or alkyl-sulfonyl, CN, N0₂, COOH, hydroxyl, haloalkyl, F, Br or I;

When Ri represents alkyl, Ri preferably is selected among CI -C IO alkyl (that may be a straight, branched or a cyclic alkyl chain), more preferably a C l- C6 alkyl group and most preferably a C1-C3 alkyl group; R₂ represents phenyl comprising one or more electron withdrawing groups that may be the same or different; or

R₂ represents CI -C IO alkyl (that may be a straight, branched or a cyclic alkyl chain), more preferably represents C1-C6 alkyl, even more preferably C1-C3, and most preferably R₂ represents the CI or C2 group; and such alkyl group comprise one or more electron withdrawing groups which may be the same or different but with a preference for one, two or three substituents, preferably such group(s) is/are selected among the following: halogen e.g. F, CI, Br or I, with a preference for the CI substituent(s); COOH; OH; and optional substituted phenyl wherein such substituents, which may be the same or different if more than one but with a preference for one, two or three substituents, may be selected when present among straight or branched CI -CIO alkyl groups and OH, and preferably selected among straight or branched C1-C6 alkyl and OH, even more preferably selected among C1-C3 alkyl and OH and most preferably OH.

In a more preferred embodiment, the component b) is selected among compounds of the general formula (I)

wherein Ri represents H or alkyl;

and when Ri represents H, then

R₂ represents alkyl substituted with one or more electron withdrawing groups, which may be the same or different if more than one but with a preference for one, two or three selected from halogen, OH, COOH and optionally substituted phenyl wherein such substituents, which may be the same or different if more than one but with a preference for one, two or three substituents, may be selected when present among straight or branched CI -CIO alkyl groups and OH, and preferably selected among straight or branched C1-C6 alkyl and OH, even more preferably selected among C1-C3 alkyl and OH and most preferably OH; or

R₂ represents phenyl optionally substituted with one or more hydroxyl groups;

and when Ri represents alkyl, then

R₂ represents phenyl substituted with one or more hydroxyl groups; or R₂ represents alkyl substituted with one or more electron withdrawing groups which may be the same or different if more than one but with a preference for one, two or three selected from halogen, OH, COOH and optionally substituted phenyl wherein such substituents, which may be the same or different if more than one but with a preference for one, two or three substituents, may be selected when present among straight or branched CI -CIO alkyl groups and OH, and preferably selected among straight or branched C1-C6 alkyl and OH, even more preferably selected among Cl- C3 alkyl and OH and most preferably OH.

In an even more preferred embodiment,

Ri represents H, and

R₂ represents CI -CIO alkyl (that may be a straight, branched or a cyclic alkyl chain), more preferably represents C1-C6 alkyl, even more preferably Cl- C3, and most preferably R₂ represents the CI or C2 group; and such alkyl group is substituted with one or more electron withdrawing groups, which may be the same or different if more than one but with a preference for one, two or three selected among the following: halogen e.g. F, CI, Br or I, with a preference for the CI substituent(s); COOH; OH; and optionally substituted phenyl wherein such substituents, which may be the same or different if more than one, but with a preference for one, two or three substituents, may be selected when present among straight or branched C1-C6 alkyl and OH, and preferably selected among C1-C3 alkyl and OH and most preferably OH.

or

R₂ represents phenyl optionally substituted with one or more hydroxyl groups, preferably phenyl or phenyl substituted with one or two hydroxyl groups.

More preferably,

Ri represents H, and

R₂ represents C1-C6 alkyl (straight or branched), preferably C1-C3 alkyl, and such alkyl group substituted with one or more electron withdrawing groups, which may be the same or different if more than one but with a preference for one, two or three, and more preferably one, selected among the following: CI, COOH, OH and a substituted phenyl carrying one or two substituents, which may be the same or different, selected among straight or branched C1-C6 alkyl and OH, even more preferably selected among C1-C3 alkyl and OH and most preferably OH; or

R₂ represents phenyl optionally substituted with one hydroxyl group, and preferably represents phenyl or 4- or 2-hydroxy phenyl.

Even more preferably,

Ri represents H, and

R₂ represents a straight or branched C1-C3 alkyl, and such alkyl group substituted with one electron withdrawing group selected among the following: CI, COOH, OH and a substituted phenyl carrying one substituent selected among straight or branched C1-C3 alkyl and OH, and most preferably OH; or

R₂ represents phenyl or 4- or 2-hydroxy phenyl.

Most preferably when Ri represents H, the component b) is selected among benzoic acid, 2-hydroxy benzoic acid (salicylic acid), 4-hydroxy benzoic acid, chloroacetic acid, 4-hydroxy phenyl acetic acid, malonic acid and lactic acid. In another even more preferred embodiment,

Ri represents alkyl, and the alkyl group is selected among CI -CIO alkyl (that may be a straight, branched or a cyclic alkyl chain), more preferably a Cl- C6 alkyl group and most preferably a C1-C3 alkyl group; and

R₂ represents phenyl substituted with one or more hydroxyl groups, preferably one or two hydroxyl groups; or

R₂ preferably represents CI -CIO alkyl (that may be straight, branched or a cyclic alkyl chain), more preferably represents C1-C6 alkyl, even more preferably C1-C3, and most preferably R₂ represents the CI or C2 group; and such alkyl group is substituted with one or more electron withdrawing groups, which may be the same or different if more than one but with a preference for one, two or three, selected among the following: halogen e.g. F, CI, Br or I, with a preference for the CI substituent(s); COOH; OH; and optionally substituted phenyl wherein such substituents, which may be the same or different if more than one, but with a preference for one, two or three substituents, may be selected when present among straight or branched C1-C6 alkyl and OH, and preferably selected among C1-C3 alkyl and OH and most preferably OH.

More preferably,

Ri represents alkyl, and the alkyl group is selected among C1-C6 alkyl (that may be straight, branched or a cyclic alkyl chain), and more preferably a straight C1-C6 alkyl chain; and

R₂ represents phenyl substituted with one hydroxyl group, and preferably represents 4- or 2-hydroxy phenyl; or

R₂ represents C1-C6 alkyl (straight or branched), preferably C1-C3 alkyl, and such alkyl group substituted with one or more electron withdrawing groups, which may be the same or different if more than one but with a preference for one, two or three, more preferably one, selected among the following: CI, COOH, OH and a substituted phenyl carrying one or two substituents, which may be the same or different, selected among straight or branched C1-C6 alkyl and OH, even more preferably selected among C1-C3 alkyl and OH and most preferably OH.

Even more preferably,

Ri represents alkyl, and the alkyl group is selected among straight C1-C6 alkyl, and more preferably straight C1-C3 alkyl; and

R₂ represents 4- or 2-hydroxy phenyl; or

R₂ represents C1-C3 alkyl, and such alkyl group substituted with one electron withdrawing group selected among the following: CI, COOH, OH and a substituted phenyl carrying one substituent selected among straight or branched C1-C3 alkyl and OH, and most preferably OH.

Even yet more preferably,

Ri is propyl; and

R₂ represents 4- or 2-hydroxy phenyl; or

R₂ represents a substituted phenyl carrying one substituent selected among straight or branched C1-C3 alkyl and OH, and most preferably OH.

Most preferably when Ri represents alkyl, the component b) is propyl 4- hydroxybenzoate (propyl paraben).

As examples of preferred embodiments, the component b) is selected compounds of the general formula (I),

wherein Ri and R₂ are selected according to the below tables

Table 2

Table 3 is the same as table 2, but Ri= CH₃CH₂ and table 4 is the same as table 2, but ¾= CH₃CH₂CH₂.

If the component b) is a mixture of two or more compounds of the formula (I), each individual compound may form a eutectic mixture with pethoxamid, but overall it is the combination of such compounds that is required to form a eutectic mixture with pethoxamid. The component b) forming a eutectic mixture with pethoxamid is preferably so selected as to result in the formation, when intermixed with pethoxamid, of a mixture having a eutectic point of the mixture that is at least about 3°C lower than the melting point of pethoxamid, more preferably at least about 4°C, 5°C, 6°C, 7°C, 8°C or at least 9°C lower, even more preferably at least about 10°C, or 1 1°C, lower, even more preferably at least about 12°C or 13°C, lower, and most preferably at least about 14°C lower than the melting point of pethoxamid. The melting point of pure pethoxamid is about 37-38°C, whereas technical material (usually 94-98% purity) has a slightly lower melting point. Thus, the above minimum values of eutectic melting point temperatures (i.e. more than 3°C lower than that of the melting point of pethoxamid) should be seen in respect of the melting point of a sample of pethoxamid of a given purity. Preferably the pethoxamid used according to the invention is of purity higher than 90%, preferably higher than 92%, more preferably higher than 94% and most preferably higher than 95%. Component b) is preferably selected as to be inert to the pethoxamid and any other ingredient present in the emulsifiable concentrate, e.g. the customary formulation diluents such as adjuvants and/or customary formulation auxiliaries, i.e. so selected as not to cause degradation or any other undesired effects on chemical or physical stability of the individual formulation components present. It may even be selected among additional pesticidal active compounds falling within the general structure of formula (I) , but is in a preferred embodiment of the present invention selected as not to poses any pesticidal effect on its own in particular not a herbicidal effect. Accordingly, the component b) is utmost preferably selected among one or more of the following: benzoic acid, 2-hydroxy benzoic acid, 4-hydroxy benzoic acid, chloroacetic acid, 4-hydroxy phenyl acetic acid and propyl 4- hydroxybenzoate.

The capability of a component b) to form a eutectic mixture when admixed with pethoxamid can be determined by simple experiments known in the art. A representative example is measuring the melting temperature, at one atmosphere, for pure pethoxamid and for pure component b) and for mixtures of e.g. 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, and 90: 10 pethoxamidxomponent b) on a weight basis. The results are then plotted (ratio vs. melting point) and the lowest melting point is identified/estimated at a given ratio (i.e. the eutectic melting point at the eutectic ratio). If no minimum lower melting temperature of the mixture in comparison to pure pethoxamid and pure component b) is seen over the entire ratio range (i.e. between 0: 1 - 1 :0), then component b) is not capable of forming a eutectic mixture with pethoxamid, i.e. in accordance with the normal perception in the art of the term of "eutectic mixture", e.g. as above defined. The addition of the component b) to emulsifiable concentrates comprising pethoxamid has been found to have an advantageous effect on the solubility of pethoxamid that is increased at a given temperature compared to compositions without the component b) present. Thus, the ability to provide high concentrated EC compositions of pethoxamid that remain stable over a broad temperature range, including storage at low temperatures, is significantly improved. Accordingly, concentrated and diluted compositions thereof, substantially free of pethoxamid crystallizing out of solution, can be prepared according to the various embodiments of the present invention. A diluted composition is an (aqueous) emulsion obtained from the emulsifiable concentrate composition.

On a relative scale even ratios between component b) and pethoxamid significantly different from the eutectic ratio, e.g. lower amounts of b), have been found to be useful. As such no minimum amount of the component b) vs. the amount of pethoxamid has been established that still provide the desired effect. Even so, the ratio will depend on the choice of the component b) and accordingly the eutectic point and eutectic ratio for a given eutectic mixture between pethoxamid and the component b). From a theoretical point of view at least, the ratio between a) pethoxamid and the component b) in the EC composition should be set at the eutectic ratio or as close to as possible. Choice of organic solvent(s) and/or diluent(s) and solubility of the mixture of a) and b) in the organic solvent may however obviously also influence the final ratio of a:b for a given composition. For practical purposes however, the ratio between a) pethoxamid and component b) may be in the range between 180: 1 to 1 :2.5, preferably from 100: 1 to 1 :2, more preferably 50: 1 to 1 : 1 and most preferably 25: 1 to 1 : 1. Preferably the component(s) b) is selected as to provide a eutectic mixture with pethoxamid having a eutectic ratio within these ranges, i.e. the ratio between a) pethoxamid and component(s) b) range between 180: 1 to 1 :2.5. The component b) is generally present in the EC composition at a concentration equal to or higher than 5 g/1 and although no upper limit has been found, for practical purposes the component b) is generally present in a concentration equal to or lower than 250 g/1 (e.g. between 5-250 g/1), preferably higher or equal to 10 g/1 (e.g. between 10-250 g/1), more preferably higher or equal to 20 g/1 (e.g. between 20-250 g/1) and most preferably higher or equal to 25 g/1 (e.g. between 25-250 g/1). In a preferred embodiment the concentration of b) is between 5 and 225g/l, preferably 10 and 225 g/1, more preferably 20 and 225 g/1 and even more preferably between 25 and 225 g/1. In a more preferred embodiment the concentration of b) is between 5 and 200 g/1, preferably 10 and 200 g/1, more preferably 20 and 200 g/1 and even more preferably between 25 and 200 g/1. In an even more preferred embodiment the concentration of b) is between 5 and 175 g/1, preferably 10 and 175 g/1, more preferably 20 and 175 g/1 and even more preferably between 25 and 175 g/1. In a most preferred embodiment the concentration of b) is between 5 and 150 g/1, preferably 10 and 150 g/1, more preferably 20 and 150 g/1 and even more preferably between 25 and 150 g/1. The concentration of pethoxamid in the emulsifiable concentrate (EC) formulation is generally higher or equal to 100 g/1 and (e.g. between 100-900 g/1), preferably higher or equal to 150 g/1 (e.g. between 150-900 g/1), more preferably higher or equal to 175 g/1 (e.g. between 175-900 g/1), even more preferably higher or equal to 250 g/1 (e.g. between 250-900 g/1) and most preferably higher or equal to 300 g/1 (e.g. between 300-900 g/1). In a preferred embodiment the concentration is between 150 and 900 g/1, preferably 150 and 850 g/1, more preferably 150 and 800 g/1, even more preferably between 150 and 750 g/1 and most preferably between 150 and 700 g/1. In a more preferred embodiment the pethoxamid concentration is between 175 and 900 g/1, preferably between 175 and 850 g/1, more preferably between 175 and 800 g/1, even more preferably between 175 and 750 g/1 and most preferably between 175 and 700 g/1. In an even more preferred embodiment the pethoxamid concentration is between 200 and 900 g/1, preferably between 200 and 850 g/1, more preferably between 200 and 800 g/1, even more preferably between 200 and 750 g/1 and most preferably between 200 and 700 g/1. In an utmost preferred embodiment the pethoxamid concentration is between 225 and 700 g/1, preferably between 225 and 675 g/1, more preferably between 225 and 650 g/1, even more preferably between 225 and 625 g/1 and most preferably between 225 and 600 g/1.

In an utmost preferred embodiment the pethoxamid concentration is between 250 and 700 g/1, preferably between 250 and 675 g/1, more preferably between 250 and 650 g/1, even more preferably between 250 and 625 g/1 and most preferably between 250 and 600 g/1.

The above numbers are based on 100% pure pethoxamid, and accordingly will vary if e.g. a 96% technical pethoxamid material is used.

Accordingly, in one aspect of the invention there is provided an emulsifiable concentrate comprising:

a) 100 g/1 or more of pethoxamid;

b) 5 g/1 or more of a compound or a mixture of compounds that is

capable of forming a eutectic mixture with pethoxamid, wherein the component b) is selected among compounds of the general formula (I);

c) one or more organic solvents;

d) optionally one or more adjuvants;

e) optionally one or more customary formulation auxiliaries.

The organic solvent component c) is typically present in the emulsifiable concentrate in an amount such that a total amount of the pethoxamid, component b), the solvent component and any of the optional components, is approximately equal to 100 weight percent of the emulsifiable concentrate. In other words, the solvent component is typically present as a "balance" to the pethoxamid, component b) and any of the optional components d) and e), e.g. present in a given composition as to balance up to 1 liter. The amount of solvent(s) present in the concentrated composition should at least be in an amount adequate to dissolve the pethoxamid and component(s) b) used, and preferably all components present in the final emulsifiable concentrate (e.g. at 20°C, but preferably also lower temperatures, e.g. as low as 5°C or even lower), but the amount of solvent or solvent mixture is generally equal or higher than 50 g/1, preferably higher than 100 g/1, more preferably higher than 150 g/1, even more preferably higher than 200 g/1 and most preferably higher than 250 g/1. In a preferred embodiment the solvent is present between 50 to 800 g/1, preferably 100-700 g/1, more preferably 150-700 g/1, even more preferable between 150-650 g/1 and most preferably between 200-650 g/1. In an even more preferred embodiment the amount of solvent present is between 150 to 700 g/1, preferably 175-700 g/1, more preferably 200-650 g/1, even more preferable between 225-650 g/1 and most preferably between 250-650 g/1. Especially preferred is between 250-600 g/1.

a) 100 g/1 or more of pethoxamid;

b) 5 g/1 or more of a compound or a mixture of compounds that is

c) 50 g/1 of one or more organic solvents;

d) optionally one or more adjuvants;

e) optionally one or more customary formulation auxiliaries.

Suitable organic solvents (component c) are, for example, one or more of the following:

1) non-polar solvents such as hydrocarbons, which may be unsubstituted or substituted, for example:

la) Aromatic hydrocarbons, for example mono- or polyalkyl- substituted benzenes, such as toluene, xylenes, mesitylene, ethylbenzene, or mono- or polyalkyl- substituted naphthalenes, such as 1-methylnaphthalene, 2- methylnaphthalene or dimethylnaphthalene, or other benzene-derived aromatic hydrocarbons, such as indane or Tetralin or mixtures thereof; or lb) aliphatic hydrocarbons, for example straight-chain or branched aliphatics, for example of the formula C_nH_2n+2, such as pentane, hexane, octane, 2-methylbutane or 2,2,4-trimethylpentane; or cyclic, optionally alkyl-substituted aliphatics, such as cyclohexane or methylcyclopentane; or mixtures thereof, such as solvents of the Exxsol® D series, Isopar® series or Bayol® series, for example Bayol® 82 (ExxonMobil Chemicals), or the Isane® IP series or Hydroseal® G series

(TotalFinaElf); or lc) mixtures of aromatic and aliphatic hydrocarbons, such as solvents of the Solvesso® series, for example Solvesso® 100, Solvesso® 150 or Solvesso® 200 (ExxonMobil Chemicals); of the Solvarex®/Solvaro® series (TotalFinaElf); or the Caromax® series, for example Caromax® 28 (Petrochem Carless); or

Id) halogenated hydrocarbons, such as halogenated aromatic and aliphatic hydrocarbons, such as chlorobenzene or methylene chloride; or le) fatty acid esters, for example of natural origin, for example natural oils, such as animal oils or vegetable oils, or of synthetic origin, for example the Edenor® series, for example Edenor® MEPa or Edenor® MESU, or the Agnique® ME series or Agnique® AE series (Cognis), the Salim®

ME series (Salim), the Radia® series, for example Radia® 30167 (ICI), the Prilube® series, for example Prilube® 1530 (Petrofma), the Stepan® C series (Stepan) or the Witconol® 23 series (Witco). The fatty acid esters are preferably esters of C6-C22-, with preference to C8-C20-fatty acids. The fatty acid esters are, for example, esters of unsaturated or saturated fatty acids, in particular those having an even number of carbon atoms, for example erucic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid or linolenic acid; or f) aromatic or aliphatic esters such as methyl benzoate; or ) polar solvents, for example:

a) aprotic polar solvents, such as ethers, esters of Cl-C9-alkanoic acids which may be mono-, di- or polyfunctional, such as their mono-, di- or triesters for example with Cl-C18-alkyl alcohols; ketones (straight or cyclic) with a low tendency to tautomerize, phosphoric acid esters, lactames, lactones, amides, nitriles or sulfones; for example diisobutyl adipate, Rhodiasolv® RPDE (Rhodia), cyclohexanone, Jeffsol® PC (Huntsman), β-propio lactam, γ-butyrolactam, γ-valero lactam, dimethyl imidazolidine, N-alkyl-2-pyrrolidone, δ-valero lactam, ε-caprolactam, β- propiolactone, γ-butyrolactone, γ-valero lactone, γ-caprolactone, γ- caprylo lactone, γ-laurolactone, γ-palmito lactone, γ-stearolactone, δ- valero lactone and δ-capro lactone, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, tributylphosphatam or the Hostarex® PO series (Clariant); b) protic polar solvents such as alcohols e.g. phenyl and phenyl-alkyl alcohols and alkyl alcohols with an alkyl radical having 1 to 6 carbon atoms, for example methanol, ethanol, 1-propanol, 2-propanol, butanol, t-butanol, pentanol, hexanol, or glycols such as propylene glycol, ethylene glycol, tetraethylene glycol, triethylene glycol and trimethylene glycol; alkyl acids e.g. acetic acid, propionic acid or formic acid; esters, such as ethyl acetate, isopropyl acetate or butyl acetate.

Examples of fatty acid esters such as C8-C22-fatty acid esters are glycerol and glycol esters of fatty acids such as C8-C22-fatty acids, or transesterification products thereof, for example fatty acid alkyl esters such as C8-C22-fatty acid Cl-C20-alkyl esters, which can be obtained, for example, by transesterification of the abovementioned glycerol or glycol fatty acid esters such as C8-C22-fatty acid esters with Cl-C20-alcohols (for example methanol, ethanol, propanol or butanol).

Preferred fatty acid alkyl esters such as C8-C22-fatty acid Cl-C20-alkyl esters are methyl esters, ethyl esters, propyl esters, butyl esters, 2-ethylhexyl esters and dodecyl esters. Preferred glycol and glycerol fatty acid esters such as C8-C22-fatty acid esters are the uniform or mixed glycol esters and glycerol esters of C8-C22-fatty acids, in particular of such fatty acids having an even number of carbon atoms, for example erucic acid, lauric acid, palmitic acid and in particular C18-fatty acids such as stearic acid, oleic acid, linoleic acid or linolenic acid. Animal oils are generally known and commercially available. For the purpose of the present invention, the term "animal oils" is to be understood as meaning, for example, oils of animal origin such as whale oil, cod-liver oil, musk oil or mink oil. Vegetable oils are generally known and commercially available. For the purpose of the present invention, the term "vegetable oils" is to be understood as meaning, for example, oils of oleaginous plant species, such as soybean oil, rapeseed oil, corn oil, sunflower oil, cottonseed oil, linseed oil, coconut oil, palm oil, thistle oil, walnut oil, arachis oil, olive oil or castor oil, in particular rapeseed oil, where the vegetable oils also include their transesterification products, for example alkyl esters, such as rapeseed oil methyl ester or rapeseed oil ethyl ester. The vegetable oils are preferably esters of C8-C22-, preferably C10-C20-, fatty acids. The C10-C22-fatty acid esters are, for example, esters of unsaturated or saturated C10-C22-fatty acids having, in particular, an even number of carbon atoms, for example erucic acid, lauric acid, palmitic acid and in particular C18-fatty acids such as stearic acid, oleic acid, linoleic acid or linolenic acid.

Examples of vegetable oils are C10-C22-fatty acid esters of glycerol or glycol with C10-C22-fatty acids, or C 10-C22-fatty acid Cl-C20-alkyl esters which can be obtained, for example, by transesterification of the glycerol or glycol C10-C22-fatty acid esters mentioned above with Cl-C20-alcohols (for example methanol, ethanol, propanol or butanol). The transesterification can be carried out by known methods as described, for example, in Rompp Chemie Lexikon, 9th edition, volume 2, page 1343, Thieme Verlag Stuttgart.

The vegetable oils can be contained in the mixtures for example in the form of commercially available vegetable oils, in particular rapeseed oils, such as rapeseed oil methyl ester, for example Phytorob® B (Novance, France), Edenor® MESU and the Agnique® ME series (Cognis, Germany) the Radia® series (ICI), the Prilube® series (Petrofma), or biodiesel or in the form of commercially available plant-oil-containing formulation additives, in particular those based on rapeseed oils, such as rapeseed oil methyl esters, for example Hasten® (Victoria Chemical Company, Australia, herein below referred to as Hasten, main ingredient: rapeseed oil ethyl ester), Actirob® B (Novance, France, hereinbelow referred to as Actirob B, main ingredient: rapeseed oil methyl ester), Rako-Binol® (Bayer AG, Germany, hereinbelow referred to as Rako-Binol®, main ingredient: rapeseed oil), Renol® (Stefes, Germany, hereinbelow referred to as Renol, vegetable oil ingredient: rapeseed oil methyl ester) or stefes Mero®) (Stefes, Germany, herein below referred to as mero, main ingredient: rapeseed oil methyl ester). Examples of synthetic acid esters are, for example, those derived from fatty acids having an odd number of carbon atoms, such as CI 1-C21 -fatty acid esters. The above solvents may be present on their own or as a mixture comprising two, three or more solvents.

Preferred organic solvents are non-polar solvents, and preferably those that are totally insoluble or only sparingly soluble in water, i.e. immiscible with water. By sparingly soluble in water is meant a solubility of the solvent or solvent mixture in water of less than 10 g pr. 100 ml water (i.e. less than 10%) at 25°C, preferably less than 7% and more preferably less than 5% and even more preferably less than 1%. Among preferred non-polar solvents are hydrocarbons, in particular aromatic hydrocarbons and/or aliphatic (including hydrocarbon mixtures of aromatic and aliphatic hydrocarbons) e.g. solvents of the Solvesso® series, or the Caromax® series. Also preferred are water immiscible aromatic or aliphatic esters, such as methyl benzoate. Further examples of preferred non-polar solvents are provided under cl) mentioned below.

In one embodiment the solvent comprise one or more non-polar solvent(s) only as the organic solvent. Nonetheless, it has been found that inclusion of at least one polar solvent, even at low concentrations, may further improve low-temperature stability of the pesticidal emulsifiable concentrate composition if combined with a non-polar solvent(s). Accordingly, in an embodiment of the invention, a mixture of two or more organic solvents is used as component c) and preferably the organic solvent comprise at least two solvents cl) and c2) wherein

cl) is one or more organic solvents selected among non-polar solvents; c2) is one or more organic solvents selected among polar solvents; that is, in an embodiment of the present invention there is provided an emulsifiable concentrate comprising:

a) 100 g/1 or more of pethoxamid;

b) 5 g/1 or more of a compound or mixture of compounds that is

c) 50 g/1 or more of an organic solvent mixture comprising

cl) one or more organic solvents selected among non-polar

solvents; and

c2) one or more organic solvents selected among polar solvents; d) optionally one or more adjuvants;

e) optionally one or more customary formulation auxiliaries. The amount of either solvent(s) cl) and c2) may be equal or higher than the other, i.e. the amount of solvent cl) is equal or higher than the amount of solvent c2; or vice versa. Under some circumstances it has been observed that if the content of the polar solvent is too high when used in combination with a non-polar solvent, crystals may be separated out from an (aqueous) emulsion obtained from the emulsifiable concentrate composition. From the standpoint of the prevention of crystal separation at low temperatures, the content of the polar solvent c2) is accordingly preferably 50% by weight or less of the total amount of organic solvent present (i.e. total amount of organic solvent c = cl+c2), more preferably 40% by weight or less, even more preferably 30% or less and most preferably 25 or less. Although a minimum content of the polar solvents c2) has not been established while still providing a positive effect, for practical purposes the amount is set at 1%> by weight or more of the total amount of organic solvent present, preferably 5% or more and more preferably 10% or more. Therefore, the content of the polar solvent c2) is preferably between 1-50% by weight of the total amount of organic solvent present with the more preferred ratios accordingly set between 5-50%, 10-50%, 1-40%, 5-40%, 10-40%, 1-30%, 5-30%, 10-30%, 1-25%, 5-25 and 10-25%.

The non-polar solvent cl) used in the present invention is not specifically limited, and includes those previously mentioned, for example aromatic hydrocarbons, such as xylene, alkyl (C8 or CIO, etc.) benzene, phenylxylyl ethane and alkyl (Cl or C3, etc.)-naphthalene, aliphatic hydrocarbons, such as machine oil, normal paraffin, isoparaffin and naphthene; mixtures of aromatic hydrocarbons and aliphatic hydrocarbons, such as kerosene; fat and oil, such as soybean oil, linseed oil, rapeseed oil, coconut oil, cottonseed oil and castor oil, and the like. The non-polar solvent may be also used alone or in a combination of plural non-polar solvents, e.g. a mixture comprising two, three or more non-polar solvents. The polar solvent c2) is not specifically limited and include those previously mentioned, i.e. aprotic polar solvents, such as ethers, esters of C1-C9- alkanoic acids which may be mono-, di- or polyfunctional, such as their mono-, di- or triesters for example with Cl-C18-alkyl alcohols; ketones with a low tendency to tautomerize, phosphoric acid esters, lactames, lactones, amides, nitriles or sulfones; and protic polar solvents such as alcohols e.g. phenyl and phenyl-alkyl alcohols and alkyl alcohols with an alkyl radical having 1 to 10, preferably 1 to 6 carbon atoms; and mixtures thereof. The polar solvent is preferably selected among aprotic solvents, such as five-, six- or seven-membered lactams and lactones, and more preferably, N-alkyl pyrrolidone, dimethyl imidazolidinone and γ-butyro lactone. N-alkyl pyrrolidone includes, for example N-methyl-2-pyrrolidone, N-octyl-2- pyrrolidone and N-dodecyl-2-pyrrolidone, and particularly N-methyl-2- pyrrolidone. The lactam includes, for example β-propio lactam, γ-butyro lactam, γ-valero lactam, dimethyl imidazolidine, N-alkyl-2- pyrrolidone, δ-valerolactam and ε-caprolactam. The lactone includes, for example β-propio lactone, γ-butyro lactone, γ-valero lactone, γ-capro lactone, γ-caprylolactone, γ-lauro lactone, γ-palmito lactone, γ-stearolactone, δ-valero lactone and δ-caprolactone, with γ-butyrolactone (i.e. gamma- butyrolactone) being most preferred. Among ketone solvents, the cyclic ketones are preferred, and in particular cyclohexanone. The polar solvent may be used alone or in a combination of plural polar solvents. Although aprotic polar solvents are preferred, combinations of protic and aprotic polar solvents may also be used.

The formulation may further comprise, as component d) one or more adjuvants, e.g. surface active agents, wetters, spreading agents and dispersing agents. Wetting agents or spreading agents increases the surface area covered by a given volume of a spray mixture. The adjuvant is in the present context defined as a component capable of enhancing the herbicidal activity of the active compound(s) in the composition, and especially when applied, e.g. in diluted form, against unwanted plants and plant growth.

Adjuvants are classified by function and chemistry. Both approaches have inherent difficulties because components are often claimed to have more than one function and complex mixtures of chemicals are rarely fully chemically disclosed. Some of the terms used for adjuvants in herbicide or pesticide products are crop oil concentrate, dispersant, surfactant, thickener, vegetable oil, modified seed oil, petroleum oil, spreader and sticker.

Typical surfactants used as adjuvants come from a broad range of chemical compounds. Depending on the herbicides to be formulated, suitable surfactant compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties. Surfactants are, for example, non-aromatic-based surfactants, based for example on heterocycles, olefins, aliphatics or cycloaliphatics, examples being surface-active, mono- or poly-alkyl-substituted and subsequently derivatized, e.g. alkoxylated, sulfated, sulfonated or phosphated; pyridine, pyrimidine, triazine, pyrrole, pyrrolidine, furan, thiophene, benzoxazole, benzothiazole, and triazole compounds, and/or aromatic-based surfactants, examples being mono-, or poly-alkyl-substituted and subsequently derivatized, e.g. alkoxylated, sulfated, sulfonated or phosphated benzenes or phenols. Such surface active compounds are generally known and readily available on a commercial scale.

Examples of surfactants are listed below, wherein EO = ethylene oxide units, PO = propylene oxide units, and BO=butylene oxide units, and where the surfactants from group si -si 8 are non-aromatic based, whereas the sl9-s21 surfactants are aromatic based:

si) C10-C24 alcohols, which may be alkoxylated, with for example 1-60 alkylene oxide units, preferably 1-60 EO and/or 1-30 PO and/or 1-15 BO in any order. The terminal hydroxyl groups of these compounds may be endgroup-capped by an alkyl, cycloalkyl or acyl radical having 1-24 carbon atoms.

s2) Anionic derivatives of the products described under si), in the form of ether carboxylates, sulfonates, sulfates, and phosphates, and their inorganic (e.g. alkali metal and alkaline earth metal) and organic salts (e.g, based on amine or alkanolamine).

s3) Fatty acid alkoxylates and triglyceride alkoxylates or alkoxylated vegetable oils such as soybean oil, rapeseed oil, corn germ oil, sunflower oil, cotton seed oil, linseed oil, coconut oil, palm oil, thistle oil, walnut oil, peanut oil, olive oil or castor oil, especially rapeseed oil; salts of aliphatic, cycloaliphatic, and olefmic carboxylic acids and polycarboxylic acids.

s4) Fatty acid amide alkoxylates; alkylene oxide adducts of alkynediols; sugar derivatives such as amino sugars and amido sugars, glucitols alkylpolyglycosides or such as sorbitan esters (eg ethoxylated sorbitan esters), cyclodextrin esters or ethers.

s5) Surface-active cellulose derivatives and algin derivatives, pectin derivatives and guar derivatives; polyol-based alkylene oxide adducts. Surface-active polyglycerides and their derivatives. s6) Alkanesulfonates, paraffin sulfonates, and olefin sulfonates; sulfosuccinate-based surfactants, such as dialkylsuccinates.

s7) Alkylene oxide adducts of fatty amines, quaternary ammonium compounds having 8 to 22 carbon atoms.

s8) Surface-active zwitterionic compounds such as taurides, betaines, and sulfobetaines.

s9) Silicone-based and/or silane-based surface-active compounds.

slO) Perfluorinated or polyfluorinated surface-active compounds,

si 1) Surface-active sulfonamides such as those from Bayer.

sl2) Surface-active polyacrylic and polymethacrylic derivatives.

si 3) Surface-active polyamides such as modified gelatins or derivatized polyaspartic acid.

si 4) Polyvinyl adjuvant-type compounds such as modified polyvinylpyrrolidone (e.g. alkylpolyvinylpyrrolidone such as C4-C20 alkyl polyvinylpyrrolidone) or the derivatized polyvinyl acetates or the polyvinyl butyrates or modified polyvinyl alcohols.

si 5) Surface-active compounds based on maleic anhydride and/or reaction products of maleic anhydride, and also copolymers containing maleic anhydride and/or reaction products of maleic anhydride.

si 6) Surface-active derivatives of montan waxes, polyethylene waxes, and polypropylene waxes.

si 7) Surface-active phosphonates and phosphinates.

si 8) Polyhalogenated or perhalogenated surfactants.

si 9) Phenols, which may have been alkoxylated, examples being phenyl Cl- C4 alkyl ethers or (poly)alkoxylated phenols [i.e. phenol (poly) alkylene glycol ethers], having for example 1 to 50 alkyleneoxy units in the (poly)alkyleneoxy moiety, the alkylene moiety having preferably 1 to 4 carbon atoms in each case, preferably phenol reacted with 3 to 10 mol of alkylene oxide; (poly) alkylphenols or (poly) alkylphenol alkoxylates [i.e. polyalkylphenol (poly) alkylene glycol ethers], having for example 1 to 12 C atoms per alkyl radical and 1 to 150 alkyleneoxy units in the polyalkyleneoxy moiety, preferably triisobutylpfienol or tri-n-butylphenol reacted with 1 to 50 mol of ethylene oxide; polyarylphenols or polyarylphenol alkoxylates (i.e. polyarylphenol (poly)alkylene glycol ethers), examples being tristyrylphenol polyalkylene glycol ethers having 1 to 50 alkyleneoxy units in the polyalkyleneoxy moiety, preferably tristyrylphenol reacted with 1 to 50 mol of ethylene oxide.

s20) Compounds which, formally, constitute the reaction products of the molecules described in si 9) with sulfuric acid or phosphoric acid, and their salts neutralized with suitable bases, by way of example the acidic phosphoric ester of triply ethoxylated phenol, the acidic phosphoric ester of a nonylphenol reacted with 9 mol of ethylene oxide, and the triethanolamine- neutralized phosphoric ester of the reaction product of 20 mol of ethylene oxide and 1 mol of tristyrylphenol.

s21) Benzenesulfonates such as alkyl- or arylbenzenesulfonates, examples being (poly)alkylbenzenesulfonates and (poly)aryl-benzenesulfonates, both acidic and neutralized with suitable bases, having for example 1 to 12 carbon atoms per alkyl radical and/or having up to 3 styrene units in the polyaryl radical, preferably (linear) dodecylbenzenesulfonic acid and its oil-soluble salts such as the calcium salt or the isopropylammonium salt of dodecylbenzene-sulfonic acid.

s22) Copolymers composed of EO, PO and/or BO units such as, for example, block copolymers having a molecular weight of 400 to 10⁸.

s23) Alkylene oxide adducts of C1-C9 alcohols. The specific choice and amount of adjuvant(s) depends on the particular active ingredient(s) selected for the composition and the desired absolute and relative amounts of the individual components. Suitable amounts can be determined by routine experimentation, the test being that essentially no or only an insignificant phase separation, sedimentation or flocculation is exhibited by the composition following storage at 20-25 °C or higher, e.g. 40°C or 54°C for a period of 24 hours, or, for preferred embodiments, following a longer period of storage over a broader range of temperatures as indicated above.

The amount of adjuvant(s) is generally between 0-400 g/1, and when present, typically the total concentration of all adjuvants in the composition is 400 g/1 or less, for example 1 to 400 g/1, excluding the weight of counter ions, if present. The amount is suitably higher than 10 g/1 (e.g. between 10 - 400 g/1), preferably higher than 20 g/1 (e.g. between 20-400 g/1), more preferably between 30 to 300 g/1 and most preferably between 50 to 250 g/1. A high amount of adjuvant is however normally on the expense of having to lower the amount of active ingredient, and too much adjuvant may not necessarily provide the desired stability of the concentrate. Furthermore, if the formulation becomes too viscous then it will be difficult to handle. The compositions described herein comprising pethoxamid may also contain other formulation auxiliaries known in the art (i.e. as component e) such as protective colloids, thickeners, anti-freeze agents. UV-protectants, penetrating agents, stabilizers, sequestering agents, anti-caking agents, coloring agents, corrosion inhibitors, as well as fertilisers or other chemical agents for obtaining special effects, typically including bactericides, insecticides, fungicides, or co -herbicides. Such formulation auxiliaries are generally known within the art of formulation chemistry, and although a specific ingredient is classified as falling within one category it may well serve the purpose of any of the others. The amount of such further formulation auxiliaries is generally between 0-300 g/1 and when present between 0.001-300 g/1, more preferably between 0.001-200 g/1, and even more preferably between 0.01-150 g/1 and most preferably between 0.1-100 g/1. In a preferred embodiment the amount of further diluents is between 0.001-200 g/1, more preferably between 0.01-150 g/1, and even more preferably 0.1 - 100 g/1 and most preferably between 0.2-50 g/1. The optional formulation auxiliaries are preferably so selected as not to cause degradation or any other undesired effect on chemical or physical stability of the individual formulation components present. They are preferably individually selected as to be inert to the composition in the sense they do not cause any undesired negative effect to the overall stability of the composition, concentrated or in diluted form, or to any of the individual components present in the composition. They may however preferably, but not necessarily, be selected as to have an effect that could influence positively on the composition and its intended use e.g. improved effect of the pethoxamid, faster and easier dissolution and/or faster uptake in a crop plant or weeds.

Examples of the antifreezing agent include ethylene glycol, diethylene glycol, propylene glycol and the like.

Typical preservatives include methyl and propyl parahydroxybenzoate, 2- bromo-2-nitro-propane-l,3-diol, formaldehyde, glutaraldehyde,

O-phenylpheno 1, benzisothiazo linones, 5 -chloro-2-methyl-4-isothiazo lin-3 - one, pentachlorophenol, 2-4-dichlorobenzyl alcohol and sorbic acid and derivatives thereof.

Preferred antifoam agents are siloxan derivatives or perfluoroalkylphosphonic/perfluoroalkylphosphinc acids, in particular polydimethylsiloxanes, such as Rhodorsil 416 or Rhodosil 454 from Rhodia or mixtures comprising perfluoro-(C6-18)-alkylphosphonic acids and perfluoro-(C6-18)-alkylphosphinic acids, such as Fluowet PL80, Fluowet PP from Clariant. Also preferred are the silicone based products Silcolapse, e.g. Silcolapse 430 or Silcolapse 5020 available from Rhodia. The compositions according to the invention can be used as such but also as a mixture with known herbicides and/or with substances which improve the compatibility with cultivated plants ("safeners"), for weed control, in the form of finish formulations or tank mixes being possible. Mixtures with weed control agents which contain one or more known herbicides and a safener are therefore also possible either as part of the compositions herein described or added as separate compositions prior to application (tank mixing).

Known herbicides include, for example acetochlor, acifluorfen (sodium), aclonifen, alachlor, alloxydim (sodium), ametryne, amicarbazone, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin (ethyl), benfuresate, bensulfuron (methyl), bentazon, benzfendizone, benzobicyclon, benzofenap, benzoyl prop (ethyl), bialaphos, bicyclopyrone, bifenox, bispyribac (sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butafenacil (allyl), butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone (ethyl), chlomethoxyfen, chloramben, chloridazon, chlorimuron (ethyl), chlomitrofen, chlorsulfuron, chlortoluron, cinidon (ethyl), cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop (propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron (methyl), cloransulam (methyl), cumyluron, cyanazine, cybutryne, cycloate, cyclosulfamuron, cycloxydim, cyhalofop (butyl), 2,4-D, desmedipham, diallate, dicamba, dichlorprop (P), diclofop (methyl), diclosulam, diethatyl (ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epropodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron (methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop (P-ethyl), fenoxasulfone, fenquinotrione, fentrazamide, flamprop (isopropyl, isopropyl-L, methyl), flazasulfuron, florasulam, fluazifop (P -butyl), fluazolate, flucarbazone (sodium), flufenacet, flumetsulam, flumiclorac (pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen (ethyl), flupoxam, flupropacil, flurpyrsulfuron (methyl, sodium), flurenol, (butyl), fluridone, fluroxypyr (butoxypropyl, meptyl), flurprimidol, flurtamone, fluthiacet (methyl), fluthiamide, fomesafen, foramsulfuron, glufosinate (ammonium), glyphosate (isopropylammonium, sodium, potassium, ammonium), halosafen, haloxyfop (ethoxyethyl, P-methyl), hexazinone, imazamethabenz (methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron (methyl, sodium), ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxafiutole, isoxapyrifop, lactofen, lenacil, linuron, MCAP, mecoprop, mefenacet, mesotrione, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha) metolachlor, metosulam, metoxuron, metribuzin, metsulfuron (methyl), molinate, mono linuron, naproanilide, napropamide, neburon, nicosulfuron, norfiurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pendralin, pentoxazone, phenmedipham, picolinafen, piperophos, pretilachlor, primisulfuron (methyl), profluazol, prometryn, propachlor, propanil, propaquizafop, propisochlor, propoxycarbazone (sodium), propyzamide, prosulfocarb, prosulfuron, pyraflufen (ethyl), pyrazogyl, pyrazolate, pyrazosulfuron (ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyridatol, pyriftalid, pyriminobac (methyl), pyrithiobac (sodium), pyroxasulfone, quinchlorac, quinmerac, quinoclamine, quizalofop (P-ethyl, P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulfentrazone, sulfometuron (methyl), sulcotrione, sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thiafiuamide, thiazopyr, thidiazimin, thifensulfuron (methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron (methyl), triclopyr, tridiphane, trifiuralin, trifioxysulfuron, triflusulfuron (methyl), tritosulfuron, are suitable for the mixtures.

In particular the following combinations are preferred: pethoxamid + nicosulfuron or another ALS inhibitor herbicide such as amidosulfuron, azimsulfuron, bensulfuron-methyl, bispyribac-sodium, chlorimuron-ethyl, chlorsulfuron, cloransulam-methyl, cyclosulfamuron, diclosulam, ethametsulfuron-methyl, ethoxysulfuron, fiazasulfuron, florasulam, flucarbazone-sodium, flucetosulfuron, flumetsulam, flupyrsulfuron-methyl- sodium, foramsulfuron, halosulfuron-methyl, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, mesosulfuron, metosulam, metsulfuron-methyl, orthosulfamuron, oxasulfuron, penoxsulam, primisulfuron-methyl, propoxycarbazon-sodium, prosulfuron, pyrazosulfuron-ethyl, pyribenzoxim, pyrimisulfan, pyriftalid, pyriminobac- methyl, pyrithiobac-sodium, pyroxsulam, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thiencarbazone-methyl, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron-methyl or tritosulfuron; pethoxamid + atrazine, pethoxamid + terbuthylazine or another photosynthetic electron transport inhibitor at the photosystem II receptor site e.g. herbicides from the group of ureas, the bipyridiniums and the triazines such as ametryn, cyanazin, prometryn, and simazine; pethoxamid + glyphosate (e.g. in the form of one of its salts such as isopropyl-ammonium, ammonium or K salt); pethoxamid + acetochlor, pethoxamid + metolachlor, pethoxamid + ^-metolachlor, pethoxamid + pyroxasulfone or another herbicide causing inhibition of cell divison (inhibition of VLCFAs) such as herbicides from the group of acetamides including chloroacetamides and oxyacetamides, e.g. flufenacet, fentrazamide, alachlor, dimethenamid, propachlor and butachlor; pethoxamid + prosulfocarb or another herbicide causing inhibition of lipid synthesis (not ACCase inhibition) such as cycloate, dimepiperate, EPTC, esprocarb, molinate, orbencarb, pebulate, benthiocarb, tiocarbazil, triallate, vernolate; pethoxamid + fomesafen, pethoxamid + fluthiacet methyl, pethoxamid + carfentrazone ethyl, pethoxamid + sulfentrazone or another protoporphyrinogen-IX oxidase inhibitor such as acifluorfen-sodium, bencarbazone, benzfendizone, butafenacil, cinidon-ethyl, flufenpyr-ethyl, flumiclorac-pentyl, flumioxazin, fluorogly co fen-ethyl, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone or pyraflufen-ethyl; pethoxamid + mesotrione (including addition of triazine herbicide, e.g. atrazine or terbutylazine) or another HPPD inhibitor herbicide such as benzobicyclon, benzocenap, isoxaflutole, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione or topramezone; pethoxamid + picloram or another herbicide selected from the class of pyridinecarboxylic acid such as clopyralid, fluroxypyr, triclopyr or aminopyralid; or pethoxamid + bicyclopyrone. Especially preferred are mixtures with pethoxamid and one or more of the following herbicides: nicosulfuron, atrazine, terbuthylazine, bicyclopyrone, prosulfocarb, glyphosate, fomesafen, fluthiacet, carfentrazone, sulfentrazone, pyroxasulfone, metolachlor (and ^-metolachlor), acetochlor, picloram and mesotrione and mesotrione in combination with atrazine or terbuthylazine.

Known safeners, for example AD-67, BAS-145138, benoxacor, cloquintocet (mexyl), cyometrinil, cyprosulfamide, 2,4-D, DKA-24, dichlormid, dymron, fenclorim, fenchlorazol (ethyl), flurazole, fluxofenim, furilazole, isoxadifen (ethyl), MCPA, mecoprop (P), mefenpyr (diethyl), MG-191, oxabetrinil, PPG-1292 or R-29148, are furthermore suitable for the mixtures. If the composition comprises a safener, the weight ratio of herbicide(s) to safener is preferably 1 : 1 to 30: 1.

The abovementioned herbicides and safeners are described and characterized in "The Pesticide Manual", Twelfth Edition, 2000, Crop Protection Publications or in other customary agronomical publications.

If the herbicides have ionizable functional groups, they can also be employed in the form of their agriculturally acceptable salts. Suitable are, in general, the salts of those cations and the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the activity of the active compounds.

Preferred cations are the ions of the alkali metals, preferably of lithium, sodium and potassium, of the alkaline earth metals, preferably of calcium and magnesium, and of the transition metals, preferably of manganese, copper, zinc and iron, further ammonium and substituted ammonium in which one to four hydrogen atoms are replaced by Ci-C₄-alkyl, hydroxy-Ci-C₄-alkyl, Ci- C₄-alkoxy-Ci-C₄-alkyl, hydroxy-Ci-C₄-alkoxy-Ci-C₄-alkyl, phenyl or benzyl, preferably ammonium, methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2- hydroxyethyl-ammonium, 2-(2-hydroxyeth- 1 -oxy)eth- 1 -ylammonium, di(2- hydroxyeth-l-yl)-ammonium, benzyltrimethyl-ammonium or benzyltriethyl- ammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C₄-alkyl)sulfonium, such as trimethylsulfonium, and sulfoxonium ions, preferably tri(Ci-C₄-alkyl)sulfoxonium.

Anions of useful acid addition salts are primarily chloride, bromide, fluoride, iodide, hydrogensulfate, methylsulfate, sulfate, dihydrogenphosphate, hydrogen-phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and also the anions of Ci-C₄-alkanoic acids, preferably formate, acetate, propionate and butyrate.

In an embodiment of the present invention the compositions provided herein further comprise one or more additional herbicidal active ingredients, i.e. included as component e). The amount of such additional herbicidal active ingredient(s) depends on the activity of each individual active ingredient but is generally between 5-300 g/1, preferably 10-250 g/1, more preferably between 10-200 g/1, and even more preferably 10- 150 g/1 and most preferably between 10-100 g/1.

Any of the optional formulation auxiliaries may be added during the formulation process, after the formulation process (e.g. by the user - a farmer or custom applicator), or both. The specific choice and amount of formulation diluent(s) depends on the amount of pethoxamid and choice of any other active ingredient(s) selected for the composition and the desired absolute and relative amounts of the individual components. Suitable amounts can be determined by routine experimentation, the test being that essentially no or only an insignificant phase separation, sedimentation or flocculation is exhibited by the composition following storage at 20-25°C or higher, e.g. 40°C or 54°C for a period of 24 hours, or, for preferred embodiments, following a longer period of storage over a broader range of temperatures as indicated above, e.g. storage stability at 54°C for 2 weeks or more. In addition, the formulation diluent(s) and the amount(s) is suitable also selected as to provide concentrated compositions that in diluted form gives no or only little crystallization or sedimentation of solids and/or remain stable when stored at low temperatures, e.g. down to 5°C or even lower.

a) 100 g/1 or more of pethoxamid;

b) 5 g/1 or more of a compound or mixture of compounds that is

c) 50 g/1 or more of one or more organic solvents;

d) 0-400 g/1 of one or more adjuvants;

e) 0-300 g/1 of one or more customary formulation auxiliaries, and preferably an emulsifiable concentrate comprising

a) 100-900 g/1 of pethoxamid;

b) 5-250 g/1 of a compound or mixture of compounds that is capable of forming a eutectic mixture with pethoxamid, wherein the component b) is selected among compounds of the general formula (I); c) 50-800 g/1 of one or more organic solvents;

d) 0-400 g/1 of one or more adjuvants;

e) 0-300 g/1 of one or more customary formulation auxiliaries. The invention also relates to the preparation of the compositions of the present invention, i.e. a process for preparing an emulsifiable concentrate as herein described comprising the steps of mixing the formulation components and if appropriate with stirring and/or heating. Accordingly, the emulsifiable concentrate compositions may be prepared by admixing all of the ingredients in the organic solvent(s). The order of mixing a) pethoxamid with the component b) is not of essence, even if component b) is a mixture of two or more compounds of the general formula (I), and either a) and b) may be admixed into the organic solvent c) before the other ingredients, if present are added or both may be admixed into the solvent at the same time. If two or more organic solvents are used, they may also be added simultaneously or separately. In a preferred embodiment of this invention, the compositions are prepared by a method comprising the following steps:

I. admixing the a) pethoxamid and the component b) into the organic solvent(s) c);

II. optionally adding the adjuvants d) and/or optionally any customary formulation auxiliaries e);

III. optionally allowing cooling; and

IV. optionally filtering before packaging the emulsifiable concentrate. Agitation of the solution may be used during the mixing of the ingredients as well as heating if appropriate to ease formation of a clear solution.

The above emulsifiable concentrate is typically anhydrous, i.e., free of water. However, the emulsifiable concentrate may include less than 5, less than 2.5, less than 1, less than 0.5, or less than 0.1, parts by weight of water per 100 parts by weight of the emulsifiable concentrate. Most typically, the emulsifiable concentrate is a single oil-like, e.g. hydrophobic, phase that does not include water. If added to water or another solvent, the emulsifiable concentrate preferably forms a milky white agricultural emulsion that blooms and that has little to no phase separation, as is described in greater detail below. Trace amounts of water may be found in the formulations ingredients used, e.g. in the optional adjuvants and/or the customary formulation auxiliaries.

The emulsifiable concentrate may be added to water or another solvent to form an agricultural emulsion at point of sale and/or use. Thus, the present invention also relates to the use of an emulsifiable concentrate as herein described, optionally diluted with water, as a herbicide for the control of unwanted plants and plant growth. Accordingly, the present invention also relates to the use of an emulsifiable concentrate composition as herein described, optionally diluted with water, for controlling unwanted plants and plant growth, optionally in the presence of cultivated plants (e.g. crops), by treating the unwanted plants, plant parts, seed or the locus thereof with said composition.

The compositions of the present invention can be applied both before and after the emergence of the (unwanted) plants. It can also be incorporated into the soil prior to the sowing of useful cultivated plants (crops). Accordingly, the present invention also relates to a method of controlling unwanted plants and plant growth, optionally in the presence of cultivated plants (e.g. crops), said method comprises treating the unwanted plants, plant parts, seed or the locus thereof with a herbicidally effective amount of an optionally diluted emulsifiable concentrate as herein described.

The amount of pethoxamid used may vary within a relatively large range. A herbicidally effective amount of pethoxamid is any amount that has the ability to control unwanted plants. It depends substantially on the type of effect desired. In general, satisfactory results are obtained when the amounts applied are from 100 g to 3000 g of pethoxamid per hectare of soil area (g/ha), preferably from 200 g to 2000 g g/ha., and more preferably from 500 g to 1500 g/ha. However, higher and in particular lower doses may also provide adequate control. According to the invention, all plants and plant parts can be treated. Here, plants is understood as meaning all plants and plant populations, such as desired and unwanted wild plants or cultivated plants (including naturally occurring cultivated plants). Cultivated plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechno logical and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant varieties protectable or not protectable by plant variety protection rights. Plant parts are to be understood as meaning all above-ground and underground parts and organs of the plants, such as sprout, leaf, bloom and root, leaves, needles, stalks, stems, blooms, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes being mentioned by way of example. The plant parts also include harvest material and vegetative and generative reproductive material, for example cuttings, tubers, rhizomes, offshoots and seeds. The treatment according to the invention of the plants and plant parts is effected directly or by action on the environment, habitat or storage space thereof by the customary treatment methods, for example by immersion, spraying, evaporation, nebulizing, sprinkling or coating. The compositions of the present invention can be used, for example, in the case of the following (unwanted) plants:

Dicotyledon weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapsis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.

Dicotyledon cultures of the genera: Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia.

Monocotyledon weeds of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.

Monocotyledon cultures of the genera: Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, in particular Zea.

The use of pethoxamid composition according to the invention is, however, by no means limited to these genera but also covers other plants in the same manner.

As already mentioned above, all plants and parts thereof can be treated according to the invention. In a preferred embodiment, naturally occurring plant species or plant varieties or plant species and plant varieties obtained by conventional biological breeding methods, such as crossing and protoplast fusion, and parts thereof are treated. In a further preferred embodiment, transgenic plants and plant varieties which were obtained by genetic engineering methods if appropriate in combination with conventional methods (genetically modified organisms) and parts thereof are treated. The term "parts" or "parts of plants" or "plant parts" was explained above. Plants of the respective plant varieties which are commercially available or in use are particularly preferably treated according to the invention. Plant varieties are understood as meaning plants having certain properties ("traits") which have been acquired by conventional breeding, by mutagenesis or by recombinant DNA techniques. These may be varieties, biotypes and genotypes.

Depending on plant species or plant varieties and the location and growth conditions thereof (soils, climate, vegetation period, nutrition), synergistic effects may also occur as the result of the treatment according to the invention. Thus, for example, reduced applied amounts and/or extensions of the action spectrum and/or enhancement of the effect of the substances and agents which can be used according to the invention, also in combination with other agrochemical active substances, better plant growth of the cultivated plants, increased tolerance of the cultivated plants to high or low temperatures, increased tolerance of the cultivated plants to arid conditions or to water or soil salt content, increased blooming, easier harvesting, acceleration of ripening, higher harvest yields, higher quality and/or higher nutritional value of the harvest products, longer storability and/or better processability of the harvest products, which are over and above the effects actually to be expected, are possible.

The preferred transgenic plants or plant varieties (obtained by genetic engineering) which are to be treated according to the invention include all plants which, as a result of the modification by genetic engineering, acquired genetic material which imparts particularly advantageous valuable properties ("traits") to these plants. Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to arid conditions or to water or soil salt content, increased blooming, easier harvesting, accelerated ripening, higher harvest yields, higher quality and/or higher nutritional value of the harvest products, longer storability and/or better processability of the harvest products. Further and particularly emphasized examples of such properties are increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and an increased tolerance of the plants to certain herbicidal active substances. The important cultivated plants, such as cereals (wheat, rice), soybean, potato, cotton, rapeseed and in particular corn (maize) and fruit plants (with the fruits apples, pears, citrus fruits and grapes), are mentioned as examples of transgenic plants, very particular corn but also soybean, potato, cotton and rapeseed being especially emphasized. The increased defense of the plants against insects through toxins forming in the plants, in particular those which are produced in the plants by the genetic material from Bacillus thuringiensis (for example by the genes CrylA(a), CrylA(b), CrylA(c), CryllA, CryillA, Cryl l lB2, Cry9c, Cry2Ab, Cry3Bb and CrylF and combinations thereof) are particularly emphasized as properties ("traits") ("Bt plants" below). The increased defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins are also particularly emphasized as properties ("traits"). The increased tolerance of the plants to certain herbicidal active substances, for example imidazolinones, sulfonylureas, glyphosates or phosphinotricin (e.g. "PAT" gene), are furthermore particularly emphasized as properties ("traits"). The genes imparting in each case the desired properties ("traits") can also occur in combinations with one another in the transgenic plants. Especially corn varieties but also cotton varieties, soybean varieties and potato varieties, which are sold under the trade names YIELD GARD (e.g. corn, cotton, soybean), KnockOut (e.g. corn), StarLlnk (e.g. corn), Bollgard (cotton), Nucotn (cotton) and NewLeaf (potato) may be mentioned as examples of "Bt plants". Especially corn varieties but also cotton varieties and soybean varieties which are sold under the trade names Roundup Ready (tolerance to glyphosates, e.g. corn, cotton, soybean), Liberty Link (tolerance to phosphinotricin, e.g. rapeseed), IMI (tolerance to imidazolinones) and STS (tolerance to sulfonylureas, e.g. corn) may be mentioned as examples of herbicide-tolerant plants. The varieties (e.g. corn) sold under the name Clearfield® may also be mentioned as herbicide resistant plants (conventionally bred for herbicide tolerance). Of course, these statements also apply to plant varieties which will be developed in the future or come onto the market in the future and have these genetic properties or genetic properties which will be developed in the future ("traits").

In other embodiments, the invention includes storage and shipping systems. Typical storage and shipping systems comprise a container ranging in capacity from about 0.1 liter to about 200 liter and a compatibilized pesticidal composition as described herein located in the container. Typically the formulation will be concentrated. The container may include the standard 2.5 gallon (9.46 liter) containers widely used in the United States, which typically take the form of jugs or flasks with a replaceable screw-cap. These containers are generally designed for single use and are typically not returned to the supplier when empty, instead being disposed of by the end user in accordance with local agricultural chemical container disposal guidelines, procedures, regulations or laws. Commonly, a plurality of these small containers are packaged within a single box and a plurality of such boxes are shipped on a pallet. During shipment, the small containers (usually within boxes on pallets) can be disposed in an enclosed volume such as provided by a rail boxcar or road truck, the hold of a ship or aircraft, or a modular box container adapted for transport by road, rail and water. Larger single-use containers, ranging in capacity up to about 200 liter, for example about 50 liter to about 200 liter, are commonly in the form of drums, and can be shipped in an enclosed volume as described above, one or more per pallet or unpalleted. Formulations of the invention can also be distributed in a large refillable container sometimes known as a bulk or minibulk tank, which typically has an integral pump or connector for an external pump to permit transfer of liquid. Bulk or minibulk tanks having a capacity of about 200 to about 2000 liters or more are typically returned to the supplier when empty and are commonly shipped on a pallet.

Examples

The invention is illustrated by the following examples in which all parts and percentages are by weight unless otherwise stated. Pethoxamid used is based on approx. 96% pure material (technical grade), unless otherwise stated.

Table 1

General Formulation Procedure

Pethoxamid and optionally any solid surfactants are melted prior to use, e.g. pethoxamid melted at 50 °C. The solvent(s) is added to a suitable vessel. The surfactant(s) any additional active compounds are added to the formulation vessel while stirring. When the surfactants are completely dissolved the batch quantity of melted pethoxamid is added, and stirring is continued until a clear, homogenous phase is achieved at room temperature.

All described formulations were stable at low temperature and tested according to CIPAC MT 39.3 at 5°C.

Example 1

In order to determine whether a given compound or mixture of compounds will form a eutectic mixture with pethoxamid, several individual samples are prepared in which pethoxamid and the compound(s) are mixed in a mortar in e.g. the following proportions of 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90: 10 until homogeneous mixtures are obtained.

If the melting point of the eutectic is significantly below room temperature (20°C), the eutectic mixing ratio can already be estimated by comparing the degree of liquefaction of the samples. A mixture at the exact eutectic point will result in a clear homogeneous liquid, meaning the closer to the eutectic mixing ratio the more liquid the sample will be.

The melting points of the mixtures are determined by differential scanning calorimetry (DSC) and plotted against the mass fraction of pethoxamid in the mixture.

As an example the phase diagram of pethoxamid (melting temperature 37°C) and benzoic acid (melting temperature 121°C) is displayed in Figure 1. The melting point of the eutectic mixture is estimated at 22.4 °C at a mass fraction of benzoic acid between 17-24%.

In Figure 2, mixtures of other compounds capable of forming a eutectic mixture with pethoxamid are similarly illustrated. The eutectic points are estimated based on the visual examination of the mixtures.

Figure 3 is provided as a comparative illustration of a compound that is not capable of forming a eutectic mixture with pethoxamid. Melting points of various mixture ratios between pethoxamid and adipic acid indicate no change in melting point of pethoxamid, and a minimum melting point lower than that of pethoxamid could not be established.

Example 2

A series of compositions were prepared according to the general procedure herein provided. The compositions were prepared with or without benzoic acid, i.e. component b). At room temperature (20°C) all formulations were homogeneous liquids and free of crystals.

Example 2.5 g/L Example 2.6 g/L

Pethoxamid 540.0 Pethoxamid 540.0

Rhodacal 60/BE 20.5 Rhodacal 60/BE 20.5

Soprophor CY/8 41.0 Soprophor CY/8 41.0 γ-butyro lactone 71.7 γ-butyro lactone 71.7

Benzoic acid 51.2 Benzoic acid 102.4

Solvesso 150ND to 1L Solvesso 150ND to 1L In order to demonstrate the effect of the eutectic compound on the stability of the formulations at low temperatures, the solubility of pethoxamid was measured at 5°C and expressed as % w/w of pethoxamid dissolved in the formulation. Samples of each formulation were stored at 5°C and an excess amount of pethoxamid crystals was added into the formulation to achieve an equilibrium state. After two weeks storage the analysis was performed on the supernatant in the saturated system by gas chromatography (GC).

Without a polar solvent

Including a polar solvent

It can be seen that addition of benzoic acid increases the pethoxamid solubility and that a solvent mixture comprising a non-polar and a polar solvent further increases the solubility of the pethoxamid in the compositon. Adding an additional amount of the eutectic forming compound further improves the solubility in comparison.

Example 3

A series of compositions were prepared according to the general procedure herein provided using various compounds capable of forming a eutectic mixture with pethoxamid.

Example 2.12 g/L

Pethoxamid 540.0

Rhodacal 60/BE 20.5

Soprophor CY/8 41.0 γ-butyro lactone 71.7

4-hydroxy phenyl

51.2 acetic acid

Solvesso 150ND to 1L Example 2.14 g/L

Pethoxamid 540.0

Rhodacal 60/BE 20.5

Soprophor CY/8 41.0 γ-Butyrolactone 71.7

Salicylic acid 51.2

Solvesso 150ND to 1L

At room temperature (20°C) all compositions were homogeneous liquids and free of crystals. As in the previous example the solubility of pethoxamid was measured at 5°C and expressed as % w/w of pethoxamid dissolved in the composition.

Without a polar solvent

Including a polar solvent

As demonstrated, the inclusion of the component b) further enhances the solubility of pethoxamid in the composition. Addition of a polar solvent to the non-polar solvent further improves the cold stability of the composition in comparison. Example 4

A series of compositions were prepared according to the general procedure herein provided using various solvents and solvent mixtures.

At room temperature (20°C) all formulations were homogeneous liquids and free of crystals.

Benzoic Solubility

7% polar-solvent

acid 5°C (%)

Example 2.15 5% — 45.4

Example 2.16 5% γ-butyro lactone 51.1

Example 2.17 5% N-methyl pyrrolidone 46.8

Example 2.18 5% Cyclohexanone 49.8 Using a solvent mixture comprising both a non-polar and a polar solvent further increased the solubility of pethoxamid in the composition compared to a composition without a polar solvent.

Example 5

A series of compositions were prepared according to the general procedure herein provided using chloroacetic acid as the component b) and different amounts of pethoxamid.

At room temperature (20°C) all the following compositions homogeneous liquids and free of crystals.

Example 2.21 Example 2.22 g/L

g/L

(comparative) Pethoxamid 800.0

Pethoxamid 800.0 Rhodacal 60/BE 22.4

Rhodacal 60/BE 22.4 Soprophor CY8 44.9

Soprophor CY8 44.9 Chloroacetic acid 154.6

Solvesso 150 ND to 1L Solvesso 150 ND to 1L Pethoxamid chloroacetic acid Solubility cone. 5°C (%)

Example 2.1

— 35.2 (comparative)

540 g/L

Example 2.19 5 % 48.0

Example 2.20 14% 58.3

Example 2.21 800 g/L

— 35.4 (comparative)

Example 2.22 800 g/L 14% 68.5

As seen above, the stability at cold temperatures was improved by adding chloroacetic acid into the formulation even at high concentration of pethoxamid.

Example 6

A series of compositions were prepared according to the general procedure herein provided using methyl benzoate or cyclohexanone as solvent.

Example 2.25 g/L Example 2.26 g/L

Pethoxamid 600.0 Pethoxamid 600.0

Rhodacal 60/BE 20.9 Rhodacal 60/BE 20.0

Soprophor CY8 41.8 Soprophor CY8 41.0

Benzoic acid 104.5 γ-butyro lactone 73.15

Methyl benzoate to 1L Benzoic acid 52.25 Example 2.27 g/L Example 2.28 g/L

Pethoxamid 600.0 Pethoxamid 480.0

Rhodacal 60/BE 20.9 Rhodacal 60/BE 20.5

Soprophor CY8 41.8 Soprophor CY/8 41.0 γ-butyro lactone 73.15 Cyclohexanone 71.7

Benzoic acid 104.5 4-hydroxy benzoic acid 51.2

Methyl benzoate to 1L Solvesso 150ND to 1L

Solubility

Benzoic acid γ-butyrolactone

5°C (%)

Example 2.25 10% — 56.1

Example 2.26 5% 7% 53.8

Example 2.27 10% 7% 56.9 5% Additive 7% Solubility polar-solvent 5°C (%)

Example 2.28 4-hydroxy Cyclohexanone

benzoic acid 49.5

Example 2.29 salicylic acid Cyclohexanone 48.6

Example 7

Stability in spray solutions.

A 20% w/w dilution of the formulations in pre-cooled standard water (CIPAC water D; 342ppm) is prepared in a 250mL beaker. This 20% w/w dilution rate applies to all the following examples if not stated otherwise. The dilution is immediately prepared after the water is taken out of the refrigerator.

160g of water is poured into a beaker with a magnetic stirrer, followed by addition of 40g the formulation and finally pethoxamid seed crystals (5-10mg) are rinsed into the beaker. The beaker is covered and immediately transferred to a stirring plate in a cooling chamber (temperature set at 6°C). After 4 hours of stirring at about 300rpm (sample homogenized, but not vigorously mixed) the dilution is filtered through a 75 μιη sieve and flushed with tab water for 1-2 minutes. Thereafter, the residue on the sieve is washed to a crystallization dish, which is then dried at 70°C.

The residue is calculated as described in CIPAC method 185; wet sieve residue = (dried dish - net weight of the dish)/ formulation weight * 100. A measured residue below 10%> is preferred, more preferably below 5%>, even more preferably below 1.0% and most preferably below 0.1 % in a solution of a temperature of 6°C. The test was carried with the following results:

Without a polar solvent

Including a polar solvent

Without a polar solvent

wet sieve

5% additive

residue (%)

Example 2.1

— 24.826 (comparative)

Example 2.7 propyl paraben 2.565

Example 2.8 4-hydroxy phenyl acetic acid 3.295

Example 2.9 4-hydroxy benzoic acid 0.010

Example 2.10 salicylic acid 0.015 Including a polar solvent

Different polar solvents

7% polar wet sieve benzoic acid

solvent residue (%)

Example 2.15 5% — 0.054

Example 2.16 5% γ-butyro lactone 0.038

N-methyl

Example 2.17 5% 0.071

pyrrolidone

Example 2.18 5% Cyclohexanone 0.079

Different amounts of chloroacetic acid

pethoxamid chloroacetic wet sieve concentration acid residue (%)

Example 2.1

— 24.826 (comparative)

540 g/L

Example 2.19 5 % 3.091

Example 2.20 14% 0.349 Different amounts of chloroacetic acid

Using methyl benzoate as solvent

Using cyclohexanone as solvent

decrease the wet sieve residue. Example 8 - comparative

A series of compositions were prepared according to the general procedure herein provided using n-butyl benzoate which falls outside the scope of the present invention. The n-butyl benzoate is used with or without the presence of a fatty acid amide (N,N-dimethyldecanamide). Example 2.30 Example 2.31

g/L g/L Comparative Comparative

Pethoxamid 540.0 Pethoxamid 540.0

Rhodacal 60/BE 20.5 Rhodacal 60/BE 20.5

Soprophor CY/8 41.0 Soprophor CY/8 41.0 n-butyl benzoate 51.2 γ-butyro lactone 71.7

Solvesso 150ND to 1L n-butyl benzoate 51.2

Solvesso 150ND to 1L

Example 2.32

g/L Example 2.34

Comparative g/L

Comparative

Pethoxamid 540.0 Pethoxamid 540.0

Rhodacal 60/BE 20.5 Rhodacal 60/BE 20.5

Soprophor CY/8 41.0 Soprophor CY/8 41.0

N,N- n-butyl benzoate 93.0 dimethyldecanamide 250.5

N,N- n-butyl benzoate 51.2 dimethyldecanamide to 1L

Solvesso 150ND to 1L

Example 2.33

g/L

Comparative

Pethoxamid 540.0

Rhodacal 60/BE 20.5

Soprophor CY/8 41.0

n-butyl benzoate 140.0

N,N- dimethyldecanamide to 1L n-butyl co-solvent Solubility wet sieve benzoate 5°C (%) residue

(%)

Example 2.30

5% 40.7 11.75 (comparative)

Example 2.31

5% 7% γ-butyro lactone 49.4 15.14 (comparative)

Example 2.32 24% N,N-

5% 40.0 18.64 (comparative) dimethyldecanamide

Example 2.33 27% N,N-

14% 38.3 13.04 (comparative) dimethyldecanamide

Example 2.34 32% N,N-

9% 35.7 21.94 (comparative) dimethyldecanamide

As seen from the data above, the use of n-butyl benzoate causes an unacceptable level of the wet sieve residue, and the use n-butyl benzoate in combination with a fatty acid amide worsens this as well as negatively influencing the solubility.

Claims

C L A I M S

An emulsifiable concentrate (EC) formulation comprising, in addition to any optional customary formulation diluents:

a) pethoxamid;

c) one or more organic solvents;

wherein compound b) is selected among compounds of the general formula (I)

wherein,

when Ri represents H,

then R₂ represents a CI -CIO alkyl, C2-C10 alkenyl, C2-C10 alkynyl, or aryl, said groups being substituted with 1 or more electron withdrawing groups selected among C1-C6 alkoxy, aryl C1-C6 alkoxy, COH, aryl- or C1-C6 alkyl-sulfonyl, CN, N0₂, COOH, hydroxyl, F, CI, Br, I, and haloalkyl, or

when Ri represents CI -CIO alkyl, C2-C10 alkenyl, C2-C10 alkynyl optionally substituted by one or more substituents selected from the group comprising cyano, F, CI, Br, I, hydroxy, nitro, acyl, acylamino, acyloxy, CI -CIO alkyl, C2-C10 alkenyl, C2-C10 alkynyl, aryl, CI -CIO alkoxy, CI -CIO alkylsulfonyl, methylsulfonyl, triflouromethyl, amino, aminocarbonyl, aminothiocarbonyl, amino- carbonylamino, aminothiocarbonylamino, amino carbonyloxy, amino- sulfonyl, aminosulfonyloxy, aminosulfonylamino, amidino, carboxyl, carboxyl ester, (carboxyl ester)amino, (carboxyl ester)oxy, sulfonyl, sulfonyloxy, thioacyl, thiol, thiocarbonyl, CI -CIO alkylthio, heteroaryl, and C3-C7 cycloalkyl,

then R₂ represents CI -CIO alkyl, C2-C10 alkenyl, C2-C10 alkynyl, or aryl, said groups being substituted with one or more electron withdrawing groups selected among C1-C6 alkoxy, aryl, C1-C6 alkoxy, COH, aryl- or CI -CIO alkyl-sulfonyl, CN, N0₂, COOH, hydroxyl, F, CI, Br, I, and haloalkyl. 2. An emulsifiable concentrate according to claim 1, wherein the aryl group is selected among the group comprising phenyl, napthyl, anthracyl, phenantracyl, furyl, adamantyl, benzo[a]pyrenyl, tolyl, and xylyl.

3. An emulsifiable concentrate according to claim 1, wherein component b) is selected among compounds of the general formula (I) wherein

Ri represents H, and

R₂ represents CI -CIO alkyl substituted by 1-3 electron withdrawing groups selected among C1-C6 alkoxy, aryl C1-C6 alkoxy, COH, aryl- or CI -CIO alkyl-sulfonyl, CN, N0₂, COOH, hydroxyl, F, CI, Br, I, and haloalkyl, or

R₂ represents phenyl or phenyl comprising one or more electron withdrawing group selected among alkoxy, arylalkoxy, COH, aryl- or alkyl-sulfonyl, CN, N0₂, COOH, hydroxyl, haloalkyl, F, Br, CI, and I. 4. An emulsifiable concentrate according to claim 1, wherein component b) is selected among compounds of the general formula (I) wherein

Ri represents optionally substituted CI -CIO alkyl, and

R₂ represents phenyl comprising one or more electron withdrawing groups selected among C1-C6 alkoxy, aryl C1-C6 alkoxy, COH, aryl- or C 1 -C 10 alkyl-sulfonyl, CN, N0₂, COOH, hydroxyl, F, CI, Br, I, and haloalkyl; or R₂ represents CI -C IO alkyl substituted by one or more electron withdrawing groups selected among C1-C6 alkoxy, aryl C1-C6 alkoxy, COH, aryl- or CI -CIO alkyl-sulfonyl, CN, N0₂, COOH, hydroxyl, F, CI, Br, I, and haloalkyl.

5. An emulsifiable concentrate according to claim 1 , wherein component b) is selected among compounds of the general formula (I) wherein

when Ri represents H,

then R₂ represents CI -CIO alkyl substituted with 1-3 electron withdrawing groups selected from F, CI, Br, I, OH , COOH, and phenyl optionally carrying one or more hydroxyl groups; or

when Ri represents CI -CIO alkyl,

then R₂ represents phenyl comprising one to three hydroxyl groups or R₂ represents CI -CIO alkyl substituted with one to three electron withdrawing groups selected from F, CI, Br, I, OH, COOH, and phenyl optionally carrying one or more groups selected among C1-C6 alkoxy, aryl C1-C6 alkoxy, COH, aryl- or CI -CIO alkyl-sulfonyl, CN, N0₂, COOH, hydroxyl, F, CI, Br, I, or haloalkyl. 6. An emulsifiable concentrate according to claim 1 , wherein the component b) is selected among compounds of the general formula (I) wherein

Ri represents H; and

R₂ represents CI -C IO alkyl substituted with one to three electron withdrawing groups selected among F, CI, Br, I, COOH, OH, and phenyl optionally carrying 1 to 3 CI -CIO alkyl group(s) or OH; or

R₂ represents phenyl optionally comprising one to three hydroxyl groups.

7. An emulsifiable concentrate according to claim 6, wherein the component b) is selected among compounds of the general formula (I) wherein

Ri represents H; and R₂ represents C1-C6 alkyl substituted with one or more electron withdrawing groups selected among F, CI, Br, I, COOH, OH, and phenyl carrying one or more substituents selected among C1-C6 alkyl and OH; or

R₂ represents phenyl optionally comprising one or two hydroxyl group.

An emulsifiable concentrate according to claim 6 or 7, wherein the component b) is selected among compounds of the general formula (I) wherein

Ri represents H; and

R₂ represents C1-C3 alkyl substituted with one or more electron withdrawing groups selected among CI, COOH, OH, and phenyl optionally substituted with a group selected among C1-C3 alkyl and OH; or

R₂ represents phenyl or phenyl comprising one hydroxyl group in the 4 or 2 position.

An emulsifiable concentrate according to any of the claims 6 to 8, wherein component b) is selected among compounds of the general formula (I) wherein

Ri represents H; and

R₂ represents C1-C3 alkyl substituted with one electron withdrawing group selected among CI, COOH, OH, and phenyl optionally substituted with OH; or

10. An emulsifiable concentrate according to claim 6, wherein the component b) is selected among compounds of the general formula (I) wherein Ri represents CI -C IO alkyl; and

R₂ represents phenyl substituted with one to three hydroxyl groups; or R₂ represents CI -C IO alkyl substituted with one or more electron withdrawing groups selected among F, CI, Br, I,COOH, OH, and phenyl substituted with one to three groups selected among CI -CIO alkyl group and OH.

1 1. An emulsifiable concentrate according to claim 10, wherein the

component b) is selected among compounds of the general formula (I) wherein

Ri represents C1-C6 alkyl; and

R₂ represents phenyl substituted with one or two hydroxyl groups; or R₂ represents C1-C6 alkyl substituted with one to three electron withdrawing groups selected among F, CI, Br, I, COOH, OH, and phenyl substituted with one to three substituents selected among C1-C6 alkyl and OH.

12. An emulsifiable concentrate according to claims 10 or 1 1, wherein

component b) is selected among compounds of the general formula (I) wherein

Ri represents C1-C3 alkyl; and

R₂ represents phenyl substituted with one hydroxyl group in the 4 or 2 position; or

R₂ represents C1-C3 alkyl substituted with one to three electron withdrawing groups selected among CI, COOH, OH, phenyl substituted with a group selected among C1-C3 alkyl and OH.

13. An emulsifiable concentrate according to claims 10, 1 1 , or 12, wherein the component b) is selected among compounds of the general formula (I) wherein

Ri represents C1-C3 alkyl; and R₂ represents phenyl substituted with one hydroxyl group in the 4 or 2 position; or

R₂ represents C1-C3 alkyl substituted with one electron withdrawing group selected among CI, COOH, OH, and phenyl substituted with OH group.

14. An emulsifiable concentrate according to claim 1, wherein the

compound(s) b) is(are) selected among chloroacetic acid, 4-hydroxy phenyl acetic acid, benzoic acid, 2-hydroxy benzoic acid, 4-hydroxy benzoic acid and propyl 4-hydroxybenzoate.

15. An emulsifiable concentrate (EC) formulation according to any of the preceding claims, wherein the component b) is chosen among compounds that are capable of forming a eutectic mixture with pethoxamid and said mixture has a eutectic point that is at least 3°C lower than the melting point of pethoxamid.

16. An emulsifiable concentrate according to any of the preceding claims, wherein the organic solvent c) comprise at least one non-polar solvent.

17. An emulsifiable concentrate according to any of the preceding claims, wherein the organic solvent c) comprise at least one non-polar solvent selected among aromatic hydrocarbons, aliphatic hydrocarbons, mixtures of aromatic and aliphatic hydrocarbons, halogenated hydrocarbons, fatty acid esters, aromatic or aliphatic esters.

18. An emulsifiable concentrate according to any of the preceding claims, wherein the organic solvent c) comprise a mixture of at least two organic solvents.

19. An emulsifiable concentrate according to claim 18 wherein the organic solvent comprise at least two organic solvents cl) and c2) wherein cl) is one or more organic solvents selected among non-polar solvents; and

c2) is one or more organic solvents selected among polar solvents.

20. An emulsifiable concentrate according to claim 19, wherein the content of the polar solvent c2) is 50% by weight or less of the total amount of organic solvent c) present.

21. An emulsifiable concentrate according to claim 19 wherein the organic solvent c2) is selected among ethers, esters of alkanoic acids, ketones, phosphoric acid esters, lactames, lactones, amides, nitriles, sulfones or alcohols.

22. An emulsifiable concentrate (EC) formulation according to any of the preceding claims comprising:

a) pethoxamid;

b) a compound or a mixture of compounds that is capable of forming a eutectic mixture with pethoxamid, wherein the component b) is selected among compounds of the general formula (I);

c) one or more organic solvents;

d) optionally one or more adjuvants;

e) optionally one or more customary formulation auxiliaries.

23. An emulsifiable concentrate according to any of the preceding claims comprising

a) 100 g/1 or more of pethoxamid;

b) 5 g/1 or more of a compound or a mixture of compounds that is

c) one or more organic solvents;

d) optionally one or more adjuvants;

e) optionally one or more customary formulation auxiliaries.

24. An emulsifiable concentrate according to any of the preceding claims comprising

a) 100 g/1 or more of pethoxamid;

b) 5 g/1 or more of a compound or mixture of compounds that is

c) 50 g/1 or more of one or more organic solvents;

d) 0-400 g/1 of one or more adjuvants;

e) 0-300 g/1 of one or more customary formulation auxiliaries,

25. An emulsifiable concentrate according to any of the preceding claims comprising

a) 100-900 g/1 of pethoxamid;

b) 5-250 g/1 of a compound or mixture of compounds that is capable of forming a eutectic mixture with pethoxamid, wherein the component b) is selected among compounds of the general formula (I);

c) 50-800 g/1 of one or more organic solvents;

d) 0-400 g/1 of one or more adjuvants;

e) 0-300 g/1 of one or more customary formulation auxiliaries.

26. An emulsifiable concentrate according to any of the preceding claims further comprising one or more additional herbicidal active ingredients.

27. An emulsifiable concentrate according to claim 26, wherein the additional herbicidal active ingredients are selected among the following:

nicosulfuron, atrazine, terbuthylazine, bicyclopyrone, prosulfocarb, glyphosate, fomesafen, fluthiacet, carfentrazone, sulfentrazone, pyroxasulfone, metolachlor, acetochlor, picloram and mesotrione.

28. A process for preparing an emulsifiable concentrate according to any of the previous claims comprising the steps of mixing the components if appropriate with stirring and/or heating.

29. A method of controlling unwanted plants and plant growth, said method comprises treating the plants, plant parts, seed or the locus thereof with a herbicidally effective amount of an optionally diluted emulsifiable concentrate according to any of claims 1 through 27.

30. A method according to claim 29, wherein the method comprise treating the unwanted plants, plant parts, seed or the locus thereof in the presence of cultivated plants. 31. Use of an emulsifiable concentrate according to any of claim 1 through 27 optionally diluted with water as a herbicide for the control of unwanted plants and plant growth