IL45404A - Liquid herbicidal compositions containing a dinitroaniline and an arylurea - Google Patents

Description

Liquid harbicidel compositions conta ning a dlnitroaniline and an axylurea LILLY IE3HJS5!BIE3 LIMITED C. 4345» The present invention relates to herbicidal compositions and in particular to liquid emulsifiable concentrated compositions containing a mixture of herbicidal compounds.

In the control or elimination of weeds from areas of land in which economically valuable crops and plants are growing, it is often necessary to apply more than one herbicide in order to obtain an adequate weed-killing effect. This may be due to the variety of weeds present being such that no single herbicide gives adequate control or will only give such control at dosage rates too high to prevent possible damage to the useful crops and plants. Accordingly many combinations of herbicide have been proposed in the literature to deal with this problem, one particularly useful combination being that of a dinitroaniline herbicide with an N-aryl-N' -alkoxy urea herbicide. In reports on the utility of the latter combination, either no specific formulation details are mentioned (see for example German Offenlegurgjschrift No. 2037265 filed 28th July, 1970) or the required mixture of active ingredients is prepared merely by mixing the separate ingredients in a tank immediately prior to use or the two ingredients are applied separately (see for example the Report of the Canadian National Weed Committee (Eastern Section), November 1968 and the Report of the United States Southern Weed Conference, January 1969).

Whilst the separate application of the dinitroaniline and urea herbicides, or the application of a mixture of these ingredients prepared immediately prior to use, may be a practical proposition for research purposes, it will be clear that, if such methods were to be used in commerce, the time and labour factors involved would make the process uneconomic as well as possibly ineffective due to the inevitable inaccuracies in dosage resulting from carrying out separate applications or preparing mixtures cf the ingredients on a large scale under field conditions.

Accordingly, in order to render practicable the use of the combination of dinitroaniline and urea herbicides, it is necessary to produce a concentrated composition comprising these two active ingredient^B which is both chemically and physically stable, in which the ratios of the active ingredients are accurately controlled and which may be readily and cheaply diluted prior to use to giVe a herbicidally effective concentration of the active ingredients. Due to the physical nature of the dinitroaniline herbicides, it is desirable that such a concentrated composition should be in liquid form but it has been found that, in contrast to the dinitroanilines , the N-aryl-N 1 -alkoxy ureas contemplated for use in the present invention are not sufficiently soluble in the usual non-phytotoxic solvents used in herbicidal formulations to obtain the desired concentrations, this being especially the case at temperatures approaching 0°C. at which the compositions would frequently be stored and even on occasions used. Furthermore it has been discovered that, unless certain precautions are taken in the choice of emulsifiers to be used in the desired concentrated compositions, chemical instability of the urea herbicide results.

It is an object of the present invention therefore to provide a solvent and emulsifier system in which the dinitroaniline and urea herbicides may be dissolved at the desired concentrations. It is a further object of the invention to provide liquid concentrate compositions of dinitroaniline and urea herbicides which are physically and chemically stable under the conditions in which they will normally be transported, stored and used.

According to the present invention therefore there is provided a liquid herbicidal composition comprising a dinitroaniline herbicide and an N-aryl-N* -alkoxy urea herbicide dissolved in non-phytotoxic alicyclic ketone, the ratio of dinitroaniline to urea being in the order of 4:1 to 1:4, preferably 2:1 to 1:2. The term "non-phytotoxic" as used herein to describe the alicyclic ketone includes not only those ketones which per se do not cause damage to crops and plants but also ketones which, although having some phytotoxic potential, do not display such phytotoxicity 10 15 f'~- 20 25 present invention, the upper limit of the concentration of the active ingredients will be of the order of 607» weight/volume and, to achieve the aforesaid economies, the lower limit of concentration will not normally be below 107» weight/volume.

Since a desired feature of the present invention is to provide a liquid concentrate composition which may be diluted to the required concentration with water prior to use, the compositions of the invention desirably contain an emulsifier or mixture of emulsifiers, usually in an amount of from to 157> weight/volume. As stated above, careful choice of the type of emulsifier is necessary because it has been discovered that certain commercially available emulsifiers cause chemical degradation of the urea herbicide. It has been found that this problem is associated with the alcohol content of the emulsifier, which content may result from the method of manufacture or more commonly may be due to the solvent in which the emulsifier is supplied, and accordingly it is necessary in accordance with the present invention to use only emulsifiers which have substantially no content of free alcohols or polyalcohols. The presence or absence of free alcohol may of course be readily ascertained by analysis and accordingly no attempt is made here to give a list of suitable emulsifiers.

The emulsifiers used in the present invention may be anionic or nonionic or preferably a mixture or blend thereof. Examples of suitable anionic emulsifiers are the alkyl and aryl sulphonates, sulphates and sulphosuccinates such as isopropylnaphthalene sulphonates, dodecyl benzene sulphonates, dioctyl esters of sulphosuccinic acids, dinonyl sulphosuccinates, lauryl polyglycol ether sulphosuccinates, lauryl sulphates and ceto-stearyl sulphates.

Examples of suitable nonionic emulsifiers are polyoxyethylene sorbitan esters of mixed fatty and resin acids such as polyoxyethylene sorbitan-monolaurates, -monopaimilates, -monostearates, -mono-oleatesj -tri-stearates and -trioleates alkyl aryl polyethoxy ethanols such as nonyl- and iso-octy1- henyl polyethoxy glyceryl dioleate and glyceryl dilaurate, and ethoxylated alkyl phenols* and cresols such as ethoxylated octyl phenol, ethoxylated nonyl phenol and ethoxylated octyl cresol.

The dinitro aniline herbicides used in the compositions of the present invention are a class of herbicides which have been known for many years. The most useful members of this class have the structural formula: 1 2 3 wherein R- represents hydrogen, C^_^ alkoxy, alkylthio or -NR R ; R 2, R3, R4 and R5 separately represent hydrogen or an aliphatic hydrocarbon radical optionally substituted by halogen, hydroxy, azido, cyano, C^_^ alkoxy, C-^ alkyl-thio, -sulphinyl or -sulphonyl, or C2_^ 2 3 4 5 acyloxy provided that at least one of R , R , R and R is not hydrogen, or 2 3 4 5 R and R or R and R together with the adjacent nitrogen represent a heterocyclic ring; and R^ represents hydrogen, C^_^ alkyl, C^_^ alkoxy, alkyl-thio, -sulphinyl or -sulphonyl, C^_^ haloalkyl, halogen, cyano, 7 8 7 8 thiocyano or -SC^NR R where R and R separately represent hydrogen, 7 8 alkyl, ^ alkenyl or ^ cycloalkyl or R and R together with the adjacent nitrogen represents a heterocyclic ring. 2 3 4 5 When R , R , R or R represent an aliphatic hydrocarbon, the latter may be alkyl, C2_& alkenyl, C2_& alkynyl, C^_g cycloalkyl, C5_g cycloalkenyl and ^ cycloalkyl-alkyl, each of which may be optionally 2 3 4 5 7 8 substituted as defined above. When groups -NR R , -NR R or -NR R represent a heterocyclic ring, the latter is a saturated ring of the structure -N' ^2 where Z is an aikylene group having from 2 to 6 carbons, one of which may be optionally replaced with an oxygen or nitrogen atom.

Examples of ^ alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, sec.butyl, Jt-butyl, amyl, isoamyl, sec. amy! t hexyl and sec.hexyl. fj^ Examples of C2_& alkenyl and C2_& alkynyl groups are ethenyl, allyl-(2-propenyl), isopropenyl, propargyl(2-propynyl), 2-butenyl, 3-butenyl, 2-methylallyl, 2-butynyl, 2-pentenyl, 4-pentenyl, 3-pentynyl, 2-methyl-2-butenyl, 2-methyl-2-pentenyl, 2-hexenyl and l-ethyl-2-propenyl.

C^_^ cycloalkyl represents cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, and examples of C^_-, cycloalkyl-alkyl include cyclopropylmethyl, cyclopropylethyl, cyclopropyl-propyl, cyclopentylmethyl, cyclobutylethyl, 2-methylcyclopropyl and 2-methylcyclohexyl- Examples of C^_g cycloalkenyl are 2-cyclopentenylf 3-cyclopentenyl, 2-cyclohexenyl and 2-cyclo-octenyl.

Examples of the aforementioned hydrocarbon radicals substituted by halogen, hydroxy, azido, cyano, ^ alkoxy, ^ alkyl-thio, -sulphinyl or -sulphonyl, or ^ acyloxy are 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, trifluoromethyl, pentafluoroethyl, 3-chloropropyl, 2-chloroallyl, 2-chloromethylallyl, 3-chloropropargyl, 2-hydroxyethyl, 2-azidoethyl, 2-cyanoethyl, 3-hydroxypropyl, 4-hydroxy-2-butenyl, 4-cyanobutyl, 2-iso-propoxypropyl, 4-azidobutyl, 2-methylthioethyl , 2-methylsulphonylethyl, 2-_t-butylthioethyl, 3-methylsulphinylpropyl, 2-acetyloxyethyl, 3-acetyloxy-propyl, 2-propionyloxyethyl and 2-butyryloxyethyl.

Examples of the aforementioned ^ alkoxy groups are methoxy, ethoxy, propoxy, isopropoxy, butoxy and _t-butoxy.

Examples of ^ alkyl-thio, -sulphinyl and -sulphonyl groups are methylthio, methylsulphinyl , methylsulphonyl, ethylthio, ethylsulphonyl, propylthio, isopropylsulphonyl , butylsulphinyl, sec.butylsulphonyl and _t-butylthio.

Examples of ^ acyloxy are acetyloxy, propionylpxy, isopropionyloxy and butyryloxy, and examples of the above-mentioned heterocyclic rings are aziridino, pyrrolidino, morpholino, piperazino, piperidino and homopi e idino- N,N-di-n-butyl-4-chloro-2, 6-dinitroaniline N-n-propyl-N-2-methylallyl-4-t^butyl-2,6-dinitroaniline N,N-di-isobutyl-4-trifluoromethyl-2,6-dinitroaniline N-ethyl-N-2-methylallyl-4-isopropyl-2,6-dinitroaniline N,N-di-sec.butyl-4-trifluoromethyl-2, 6-dinitroaniline N-allyl-N-2-methylallyl-4--t-butyl-2,6-dinitroaniline N-methyl-N-n-amyl-4-trifluoromethy1-2, 6-dinitroaniline N,N-dipropyl-4-sulphamoyl-2,6-dini:roaniline N-methyl-N-n_-buty1- 4-trifl-icromcthyl-2, 6-dinitroaniline N,N-dipropyl-4~(N-methylsulphamoyl)-2,6-dinitroaniline N-ethyl-N-n-butyl-4-trifluoromethyl-2, 6-dinitroaniline N,N-dipropyl-4-(N,N-dimethylsulphamoyl)-2,6-dinitroaniline N-ethyl-N-n-propyl-4-trifluoromethy1-2, 6-dinitroaniline N, -dipropyl-4-(N-allylsulphamoyl)-2, 6-dinitroaniline N-ethyl-N-n-propyl-2, 6-dinitroaniline N,N-dipropyl-4- (N-propy1sulphamoyl )-2,6-dinitroan line N-n-butyl-N-n-propyl-2, 6-dinitroaniline N,N-dipropy1-4-(N-ethylsulphamoyl)-2, 6-dinitroaniline N-me hyl-N-n-propyl-2 , 6-dinitroaniline NtN-diallyl-4-(N-cyclopropylsulphamoyl )-2, 6-dinitroaniline N-ethyl-N-n-butyl-2, 6-dinitro-£-toluidine N,N-dipropyl-4-(N-cyclopropyl-N-ethylsulphamoyl)-2, 6-dinitroaniline N-n-propyl-N-_t-buty1-2, 6-dinitro-£-toluidine Ν,Ν-dimethylallyl-4-sulphamoyl-2, 6-dinitroaniline N,N-dimethyl-4-trifluoromethy1-2, 6-dinitroaniline N-(2-hexyl)-4-piperidinosulphonyl-2, -dinitroan line N,N-dimethyl-4-chloro-2 ,6-dinitroaniline N-cyclopentyl-4-morpholino-3, 5-dinitrobenzenesulphonamide N,N-dimethyl-2,6-dinitro-£-toluidine>.

N-( 1-ethylpropyl)-4- ( ,Ν- methylsulphamoyl )-2, -dinitroaniline N,N-di-n-propyl-2, 6-dinitroaniline N-e hyl-N-2-meth lally1-4-trifluorometh 1-2,6-dinitroaniline N,N-di-n-propyl-4-trifluoromethy1-2, 6-dinitroaniline N-propy1-N-2-chloroethy1-4-trifluoromethyl-2, 6-dinitroaniline N,N-di-n-propyl-4-cyano-2, 6-dinitroaniline N-propyl-N-2-azidoethyl-4-chloro-2,6-dinitroaniline N,N-di-n-propyl-4-chloro-2,6-dsLnitroaniline N-propyl-N-2-cyanoethyl-4-trifluoromethyl-2, 6-dinitroaniline N,N-di-n-propyl-2,6-dinitro-£-toluidine N,N-dipropyl-4-(2-chloroethyl)-2, 6-dinitroaniline N,N-di-n-propyl-2,6-dinitro-£-anisidine N,N-dipropyl-4-methy1sulphonyl-2, 6-dinitroaniline N,N-di-n-propyl-2,6-dinitro-m-toluidine N-ethyl-N-2-methylallyl-4-methylsulphonyl-2, 6-dinitroaniline N,N-diethyl-2, 6-dinitroaniline N,N-bis(2-chloroethyl)-2,6-dinitro-£-toluidine N,N-diethyl-2,6-dinitro-4-chloroaniline N-cyclopropylmethyl-N-propyl-2,6-dinitro-£-toluidine N,N-diethyl-2,6-dinitro-£-toluidine N-(2-cyclohexenyl)-N-ethy1-4-trifluoromethy1-2, 6-dinitroaniline N,N-diethyl-2,6-dinitro-£-anisidine N-cyclopropyl-N-ethyl-4-chloro-2, 6-dinitroaniline N,N-diethyl-2, 6-dinitro-4-trifluorome hylaniline N-2-methylcyclohexy1-4-trifluoromethyl-2, 6-dinitroaniline N,N-di-n-butyl-2, 6-dinitroaniline N-(2-pentyl)-4-trifluoromethyl-2, 6-dinitroaniline N,N-di-n-but 1-2, 6-dini rc-£-toluidine N-sec.butyl-4-trifluoromethyl-2, 6-dinitroaniline N,N-di-n-butyl-4-trifluoromethyl-2, 6-dinitroaniline N-(3-hexyl)-4- trifluoromethyl-2, 6-dinitroaniline N-allyl-N-methyl-4-trifluoromethyl-2,6-dinitroaniline N-(2-chloroethyl )-N-propyL-4-sulphamoyl-2-6-dinitroaniline N-allyl-N-ethyl-4-trifluoromethyl-2,6-dinitroaniline N,N-dipropyl-4-aziridinosulphonyl-2,6-dinitroaniline N-allyl-N-ethyl-2,6-dinitro-£-toluidine N-ethyl-N-2-methylallyl-4-sulphamoyl-2,6-dinitroaniline N,N-diallyl-2,6-dinitroaniline N,N-diallyl-4-trifluoromethyl-2,6-dinitroaniline N,N-diallyl-4-methyl-2,6-dinitroaniline N-raethyl-N-3-chloroallyl-4-trifLuoromethyl-2,6-dinitroaniline N,N-dipropargyl-4-trifluoromethyl-2,6-linitroaniline N-(2,6-dinitrophenyl )pyrrolidine N-(4-trifluoromethy1-2,6-dinitrophenyl pyrrolidine N-(4-chloro-2, 6-dinitrophenyl pyrrolidine N- (4-methy1-2 , 6-dinitrophenyl )pyrrolidine N-(2, 6-dinitrophenyl)piperidine N-(4-trifluoromethyl-2, 6-dinitrophenyl )piperidine N-methyl-N-(2,2-dimethoxyethyl)-4-trifluoromethyl-2,6-dinitroaniline N-ethyl-N-(2-methoxyethyl)-4-trifluoromethyl-2,6-dinitroaniline N-n-propyl-N-(3-methoxypropyl)-4-trifluoromethyl-2, 6-dinitroaniline N-n-propyl-N-(2,2-diethoxyethyl)-4-trifluoromethyl-2,6-dinitroaniline 3 1 1 N -sec. butyl-N ,N -dimethyl-2,6-dinitro-4-trifluoromethyl-1,3- pheny1enediamine N -ethyl-N"-2-methylallyl-4-trifluoromethyl-2,6-dinitro-l,3-phenylenediamine 3 1 1 -ethyl-N ,N -diethyl-2,6-dinitro-4-trifluoromethyl-l,3-p enylenediamine 3 1 N -methyl-N - ejs.butyl-2, 6-dinitro-4-trifluoromethyl-1, 3-phenylenediamine 3 N -ethyl-N -se_c.butyl-2,6-dinitro-4-trifluoromethyl-1 ,3-phenylenediamine 3 1 1 N -methyl-N ,N -di-n-propyl-2,6-dinitro-4-trifluoromethyl-1, 3- phenylenediamine ^' ,N'-di-r-propyl-2,6-dinitro-4-trifluorcmethyl-l,3-phenylenediamine amine|A-¾. diamine e ine e N -(4-heptyl )-2,6-dinitro-4-methy1-1,3-phenylenediamine N"-(4-chloro-2-butenyl )-2,6-dinitro-4-methy1-1, 3-phenylenediamine -sec.butyl-2 , 6-dinitro-4-methyl-1 ,3-phenylenediamine In view of their excellent herbicidal activity, the dinitroanilines preferred for use in the compositions of this invention are those in which R a 4 5 haloalkenyl or ^ cycloalkyl-alkyl with at least one of R and R being 4 5 other than hydrogen, or R and R together with the adjacent nitrogen represent pyrrolidino or piperidino. .

The N-aryl-N' -alkoxy ureas used in the compositions of the present invention also constitute a well-known class of herbicides. The most useful members of the class have the structure: wherein R represents hydrogen, C^_^ alkyl, alkoxyalkyl, cycloalkyl, C^_g cycloalkenyl or C^_-? cycloalkyl-alkyl; R^ is C^_^ alkyl or C2_^ alkenyl, 11 12 R is alkyl; and R represents from one to three of the same or different groups selected from hydrogen, halogen, C^_^ alkoxy, ^ haloalkyl, haloalkoxy, C^_^ alkylthio, C^_^ haloalkylthio, alkyl, ^ alkenyl, ^ alkynyl, ^ alkenyloxy or ^ alkynyloxy.

Examples of groups covered by the terms ^ alkoxy, ^ haloalkyl, ^ alkylthio, C.^ alkyl, C2_^ alkenyl, (_2_^ alkynyl, C3_6 cycloalkyl, g cycloalkenyl and C^_-, cycloalkyl-alkyl are as given above.

Examples of haloalkyloxy and C^_^ haloalkylthio are chloromethoxy, dichloromethox , trifIiioromethoxy, difluorochlorome hoxy, pentafluoroethoxy, 2-bromethoxy, 3-chloropropoxy, 4-fluorobutoxy, chloromethylthio, trifluoromethylthio, difluorochloromethylthio, 2-chloroethylthio, 2-bromoethylthio and 4-chlorobutylthio.

Examples of ^ alkenyloxy and ^ alkynyloxy are allyloxy, isopropenyloxy, propargyloxy, 2-butenyloxy, 3-butenyloxy, 2-isobutenyloxy and 2-butynyloxy.

Examples of ^ alkoxyalkyl are methoxymethyl, ethoxymethyl, isop.:opoxymethyl, methoxyethyl, 2,2-dimethoxymethyl and ethoxyethyl.

As examples of the foregoing compounds, there may be named: N- 4-chlorophenyl )-N' -methyl-N' -methoxyurea N- 4-bromophenyl )-N' -methyl-N' -methoxyurea N- 3,4-dichlorophenyl )- 1 -methyi- 1 -methoxyurea N- 2,4,5-trichlorophenyl )- ' -methy1-N 1 -methoxyurea N- 3- trifluoromethylphenyl )-N' -methyl-N' -methoxyurea N- 2-methyl-4-chlorophenyl)-Nl -methyl-N1 -methoxyurea N- 4-chlorophenyl )-N' -ethyl-N' -methoxyurea N-pheny1- 1 -ethy1-N 1 -methoxyurea N- 3,4-dichlorophenyl )-N* -isopropyl-N' -methoxyurea N- 4-bromophenyl )-N* -n-butyl-N' -methoxyurea N- 4-methoxyphenyl )-N' -allyl-N' -methoxyurea N- 4-methylphenyl )-N ' -methyl- 1 -isopropoxyurea N- 4-isopropylphenyl)-N ' -methyl-N' -methoxyurea N- 4-methylthiophenyl )-N' -methyl-N' -methoxyurea N- 4-n-butylphenyl)-N' -methyl-N' -methoxyurea N- 4-_t-butylphenyl )-N' -methyl-N ' -methoxyurea N- 3-trifluoromethylphenyl ) -N' -methylallyl-N ' -methoxyurea N- 4- trichloromethylphenyl )-N' -methyl-N' -methoxyurea N- 3-chloro-4-ethoxyphenyl )-N' -methyl- 1 -methoxyurea N- 3- ( difluorochloromethox )phenyl j-N' -methyl-N' -methoxyurea N- 3-chloro-4~(difluorochloromethoxy )phenyl]-N 'methyl-N' -methoxyurea N-[3-chloro-4-(difluorochloromethylthio)phenyl]-N'methyl-N'methoxyurea N-(4-trifluoromethoxyphenyl )-N' -methyl-N1 -methoxyurea N-(3-chloro-4-methylthiopheny1 )-N' -methyl-N' -methoxyurea N-(4-bromomethyLthiopheny1 )-N' -methyl-N' -methoxyurea N-(3-chloro-4-isopropoxyphenyl)-N' -methyl-N' -methoxyurea N-(4-allylphenyl)-N' -methyl- '-methoxyurea N-(4-allyloxyphenyl )-N' -methyl-N' -methoxyurea N-(3-propargylphenyl)-N' -methyl-N' -methoxyurea N-(3-trifluoromethylphenyl)-N' -butyl- ' -butoxyurea N-(4-bromophenyl )-N' -methyl-N' -ethoxyurea N-(3,4-dichlorophenyl )-N' -methyl-N1 -^-butoxyurea N-( -chloropheny1 )-N,N' -dimethyl-N' -methoxyurea N-(3-trifluoromethylphenyl )-N-methoxymethyl-N' -methyl-N' -methoxyurea N-(3-difluorochloromethoxyphenyl)-N-cyclopropyl-N' -methyl-N' -methoxyurea N-(3,4-dichlorophenyl )-N-cyclopropylmethyl-N' -methyl- ' -methoxyurea N-(3, -dichlorophenyl )-N-cyclohex-l-enyl-N' -methyl- '-methoxyurea N-(3-methylthio-4-chlorophenyl)-N-ethoxymethyl-N'-allyl-N' -methoxyurea N-(3-chloro-4-methoxyphenyl)-N-n-propyl-N' -methyl-N' -methoxyurea N-(4-isopropylphenyl)-N,N' -diethyl-N' -methoxyurea N-(3-pentafluoroethoxyphenyl)-N' -methyl- '-methoxyurea N-(3-trifluoromethy1thiopheny1 )-N' -methyl-N' -methoxyurea N-(4-bromophenyl)-N-n-butyl-N' -methyl-N1 -methoxyurea N-(4->t-butylphenyl)-N-cyclopropylmethyl-N' -methyl-N' -methoxyurea N-(2-methyl-4-chloropheny1)-N-ethyl- ' -methyl-N' -methoxyurea N-(3-allyl-4-chlorophenyl)-N'-allyl-N' -methoxyurea R-(4-propargylphenyl )-N-propyl-N' -methyl-N' -methoxyurea N- (3,4-dichlorophenyl )-N' -isopropenyl-N* -methoxyurea N-(4-trifluoromethoxyphenyl )-N-methoxymethyl-N' -methyl-N' -methoxyurea N-(3-chloro-4-isopropylphenyl)-N) ' -diethyl-N' -methoxyurea N-(4-chlorophenyl )-N* -methyl-N1 -ethoxyurea N-(4-chlorophenyl )-Ν' -methyl-N * -n-propoxyurea N-(4-chlorophenyl)-N' -methyl-N1 -n-butoxyurea N- (3 , 4-dichlorophenyl )-N' -methyl- 1 -ethoxyurea N-(3, -dichlorophenyl )-N' -methyl-N' -ri-propoxyurea N-(3,4-dichlorophenyl)-N' -methylallyl-N' -methoxyurea N-(4-bromophenyl)-N' -allyl-N1 -methoxyurea N-( -bromopheny1 )-N 1 -isopropeny1-N 1 -methoxyurea N-[3-chloro-4-(difluorochloromethylthio)phenyl]-N' -allyl-N' -methoxyurea oro-^--(dif1 uorochl orome hoxy)phenyl]-N* -ally!-N* -methoxyurea In view of their spectra of herbicidal activity and their effectivene in combination with the dinitroaniline herbicides, the preferred ureas for use in the present invention have the structure: wherein R and R are as defined above and R and R separately represent hydrogen, halogen, alkyl, ^ alkoxy, halomethyl, halomethoxy or halomethylthio.

The followitig Examples are given to illustrate herbicidal compositions falling within the scope of the invention. In each case the formulation was prepared by dissolving the required quantities of the aniline and urea in the cyclic ketone and, where present, most of the aromatic solvent. The solution was then filtered and the emulsifiers, previously tested to ensure the absence of free alcohol, were stirred in. The remainder of the; aromatic solvent was added, and the solution filtered and packaged. 7» Weight/Volume EXAMPLE Dinitro Urea Anionic Nonionic Alicyclic Aromatic NO. Aniline Emulsifier Emulsifier Ketone Solvent 1 A - 40% J - 10% Y - 5% Z - 3% Q - 15% T - to 100% 2 A - 12% L - 18% Y - 6.5% - R - to 100% - 3 C - 24% K - 12% Y - 2.5% 2 - 4. 5% S - 20% U - to 100% 4 E - 25% N - 15% Y - 4% Z - 4% S - 35% V - to 100% 5 H - 36% K - 12% Y - 3% Z - 3% S - to 1007, - G I - 24% M - 1 1°7 Y - 3% Z - 4% P. - 20% X - to 100% 7 F - 24% K - 12% Y - 3% Z - 4% s - 20% X - to 100% 8 A - 24% K - 12% Y - 4% Z - 4% s - 20% u - to 100% 9 D - 18% P - 18% Y - 3% Z - 3% s -■ 257. V - to 100% 10 G - 24% K - 12% Y - 3% Z - 3% s - 20% T - to 100% 11 B - 12% J - 12% Y - 5% Z - 3% Q - 25% u - to 100% 12 E - 12% L - 18% Y - 4% . Z - 4% s - 15% u - to 100% 13 G - 6% J - 12% Y - 3% Z - 3% s - 15% •V - to 100% 14 H - 18% P - 12% Y - 6% Z - 1% Q - to 100% - 15 G - 24% N - 18% Y - 5% z - 3% s - 25% T - to 100% 16 H - 24% J - 12% Y - 4% z - Λ7. s - 20% V - to 1007» 17 C - 18% L - 18% Y - 4% z - 4% R - 25% T - to 100% 18 F - 18% J - 12% Y - 3% z - 5% Q - to 100% - 19 A - 24% L - 6% Y - 3% z - 3% s - 10% u - to 100% 20 C - 12% J - 12% Y - 4% z - 4% s - 15% V - to 100% 21 D - 24% K - 12% Y - 2.5% z - 4.5% s - 20% u - to 100% 22 D - 18% J - 6% Y - 5% z - 3% R - 20% X - to 100% 23 F - 12% L - 12% Y - 3% z - 3% s - 15% V - to 100% 24 B - 18% K - 12% Y - 4% z - 4% s - 20% T - to 100% 25 E - 36% K - 12% Y - 3% z - 5% Q - 25% X - to 100% 26 I - 24% K - 12% Y - 3% z - 3% s - 20% X - to 100% 27 G - 24% L - 12% • Y - 4% z - 3% s - 20% T - to 100% A = N,N-dipropyl-4-trifluoromethyl-2,6-dinitroaniline — B = N-ethyl-N-butyl-4-trifluoromethyl-2,6-dinitroaniline C = N1N-dipropyl-4-isopropyl-2t 6-dinitroaniline D = N,N-dipropyl-4-methylsulphonyl-2, 6-dinitroaniline E = N,N-dipropyl-4-sulphamoyl-2, 6-dinitroaniline F = N,N-diethyl-4-trifluoromethyl-l,3-phenylenediamine G = N-ethyl-N-2-methylallyl-4-trifluoromethyl-2, 6-dinitroaniline H = lI-propyl-N-2-methylallyl-4-_t-butyl-2, 6-dinitroaniline I = N,N-di(2,2-dichloroethyl)-2,6-dinitrc-£-toluidine J = N-(4-chlorophenyl)-N*-methyl-N,-methoxyurea K = N-(3,4-dichlorophenyl)-N' -methyl-N' -methoxyurea L = N-(4-brotnophenyl)-N,-methyl-N' -methoxyurea M = N-(3-trifluoromethylphenylJ-N'-methyl-N' -methoxyurea N = N- (3-chloro-4-difluorochloromethoxyphenyl )-N' -methyl-N* -methoxyurea P = N-(394-dichlorophenyl)-N,-2-methylallyl-N'-methoxyurea Q = cyclohexanone R = 3-methylcyclohexanone S = 3,5,5-trimethylcyclohex-2-en-l-one T = mixture of alkylbenzenes sold under the trade name of Solvesso U = xylene V = -chlorotoluene X = heavy aromatic naphtha Y = alkyl aryl sulphonate Z = polyoxyethylene sorbitan esters of mixed fatty and resin acids Each of the foregoing formulations is physically and chemically stable^ and is readily diluted with water prior to use. Dilution rates are usually in the order of one litre of the above emulsifiable concentrate in from 150 to 500 litres of water and the diluted solution is usually applied at a rate of from 1 to 10 litres of concentrate per hectare but rates outside that range may also be used depending on the crop to be protected, the type of ingredients being used.

The herbicidal compositions of the present invention have been found to be of particular use in soil surface pre-emergence applications (i.e. pre-emergence of the weeds but pre- or post-emergence of the crops) for cereals, peas, beans, alfalfa, clover, potatoes, tomatoes, peppers, artichokes, asparagas, carrots, parsnips and similar crops. The compositions are also useful as pre-plant soil incorporated herbicides for the above crops other than cereals and solanaceae.

Claims (10)

WHAT WE CLAIM IS

1. A method of preparing a stable liquid herbicidal composition characterised in that a dinitroaniline herbicide and a N-aryl-li-alkoxy urea herbicide are dissolved in a non-phytotoxic alicyclic ketone, the ratio of dinitroaniline to urea being from 4:1 to 1:4.

2. A method according to claim 1 wherein the concentration of active ingredients in the liquid herbicidal composition is from 10 to 607o weight/volume.

3. A method according to claim 1 or 2 in which a non-ionic or anionic emulsifier which contains substantially no free alcohol or polyalcohol is included in the mixture of herbicides and ketone.

4. A method according to any preceding claim in which the dinitroaniline herbicide has the formula wherein R is hydrogen or -Nt^; R is halogen, cyano, sulphamoyl, 4 5 C^_^ alkoxy, c^_^ haloalkyl or ^ alkylsulphonyl ; R and R separately hydrogen represent/C1_6 alkyl, C3_& alkenyl, C3_& alkynyl, haloalkyl, C2_6 alkoxyalkyl, C^_() haloalkenyl or C^_& cycloalkyl-alkyl with at 4 5 4 5 least one of R and R being other than hydrogen, or R and R together with the adjacent nitrogen represent pyrrolidino or piperidino.

5. A method according to claim 3 in which the dinitroaniline herbicide ι is N, -diprop 1-4- trifluorometh 1-2, 6-dinitroaniline; N-ethyl-N-2- methylallyl-4- trifluoromethyl-2,6-dinitroaniline or N,N-dipropyl-4- sulphsPioy1-2, 6-dinitroaniline.

6. A method according to any preceding claim wherein the Nj-aryl- -alkoxy urea has the structural formula : wherein R is ^ alkyl or ^ alkenyl and R is ^ alkyl, and 13 14 R and R separately represent hydrogen, halogen, ^ alkyl, ^ alkoxy, halomethyl, halomethoxy or halomethylthio.

7. A method according to claim 6 wherein the -aryl- ^-alkoxy urea is N-(3, -dichlorophenyl )-N 1 -methyl-N1 -methoxyurea.

8. A method according to any one of the preceding claims wherein the alicyclic ketone is a cycloalkyl or cycloalkenyl ketone.

9. A method according to claim 8 wherein the alicyclic ketone is cyclo- hexanone or 3, 5, 5-trimethylcyclohex-2-en-l-one.

10. A method of preparing a stable liquid herbicidal composition characterised in that N,N-dipropyl-4-triflaoromethyl-2,6-dinitroaniline, and N- (3,4-dichlorophenyl)-N_'-methyl-N_,-methoxyurea are dissolved in 3,5,5- trimethylcyclohex-2-en-l-one, the ratio of dinitroaniline to urea being from 4:1 to 1:4, said composition also comprising an emulsifier which is a blend or mixture of polyoxyethylene sorbitan esters of mixed fatty and resin acids and an alkyl aryl sulphate and which emulsifier A stable liquid herbicidal composition comprising a dinitroaniline herbicide and a N-aryl-_N' -alkoxy urea herbicide dissolved in a non-phytotox^i- alicyclic ketone, the ratio of dinitroaniline to urea being from 4:1 to 1:4. A stable liquid herbicidal composition as claimed in claim 12 which additionally comprises a non-ionic or anionic emulsifier. A stable liquid herbicidal composition as claimed in claim 12 or 13, wherein the dinitroaniline^ is that defined in claim 4 or 5. A stable liquid herbicidal composition as claimed in any one cf claims 12 to 14, wherein the urea herbicide is that defined in claim 6 or 7. A stable liquid herbicidal composition characterised in that it contains N,N-dipropyl-4- trifluoromethyl-2 , 6-dinitroaniline and N- (3 , 4-dichloro- phenyl)-N' -methyl-N' -methoxyurea dissolved in 3,5,5-trimethylcyclohex- 2-en-l-one, the ratio of dinitroaniline to urea being from 4:1 to 1:4 said composition also comprising an emulsifier which is a blend or mixture of polyoxyethylene sorbitan esters of mixed fatty and resin acids and an alkyl aryl sulphonate and which emulsifier is substantially free from associated alcohol or polyalcohol impurities. in that (a) a concentrated stable liquid herbicidal composition comprising a non-ionic or anionic emulsifier, a dinitroaniline herbicide and an N-aryl-N' -alkoxyurea herbicide dissolved in a non-phytotoxic alicyclic ketone, the ratio of dinitroaniline to urea being from 4:1 to 1:4, is diluted with water, (b) the aqueous diluted composition is applied to said area of land. A method according to claim 17, wherein the herbicidal composition is that claimed in any one of claims 11- 16. *