CA1119012A - Herbicidal compositions containing two herbicides - Google Patents

Abstract

ABSTRACT

Mixtures of (a) herbicidal compounds of formula:

Description

_ This invention relates to herbicides, and in particular to mixtures containing certain novel pyridine derivatives having herbicidal properties.
In our copending Canadian Patent Application No.
309182 we disclose inter alia herbicidal pyridine compounds of the formula (I):

Z Y

~ - O ~ OCH - R (I) wherein at least one of Y and Z represents a trifluoro-methyl radical, the other being hydrogen, fluorine, chlorine, bromine, iodine or a trifluoromethyl radical, and R is carboxyl or a salt, ester, amide or nitrile thereof.
Examples of such compounds include those in which the group Z is a CF3 radical and Y is a hydrogen atom or a chlorine atom, and R is a carboxyl radical or an ester thereof, in particular a Cl-C6 alkyl ester.
Particular examples of such compounds include those listed in Table (I) below:

TABLE I

Z Y

~ O ~ OCH - R

i:

:: :

`` ~119~)12

- 2 -COMPOUND NO Z Y R

1 CF3 H CO.OC2H5 2 CF3 H CO.OH

3 CF3 H CO.OC5H

4 CF3 Cl CO.OC3H7 CF3 Cl CO.OC2H5 CF3 H CO.OC4H9 These compounds are herbicides which are in general substantially more effective against grass species than against broad-leaved species of plant. They may be used to control unwanted grass species growing alone, or at suitable rates of application they may be used to control grass weeds growing among broad-leaved crop plants. The compounds may be either applied to the 50il before the emergence of the unwanted grass species (pre-emergence application) or to the above-ground parts of growing grass plants (post-emergence application).
In several agronomic situations the power of these herbicides to control grass weeds may not be sufficient to protect a crop. Accordingly, the invention provides a herbicidal composition comprising a herbicide of formula (I) above, in admixture with at least one other herbicide which is a benzo-2,1,3-thiadiazin-4-one-2,2-dioxide, a hormone herbicide, a 3[4-(4-halophenoxy)phenyl]-1,1-dialkyl urea, a dinitrophenol, a dinitroaniline, a phenyl-urea, a phenylcarbamoyloxyphenylcarbamate, a 2-phenylpyridazin-3-one, a uracil, a 1,3,5-triazine, a 1-alkoxy-1-alkyl-3-phenylurea, a thiolcarbamate, a l,2,4-triazine-5-one, a benzoic acid, an anilide, a dihalobenzonitrile, a halo-~D

~119~12 alkanoic acid, a diphenyl ether, N,N-dimethyl diphenyl-acetamide, ~-l-naphthyl-phthalamic acid, 3-amino-1,2,4-triazole, a l,l'-dimethyl-4,4-dipyridylium salt, a 1,1'-ethylene-2,2'-dipyridylium salt, a 1,1'-ethylene-2,2'-

5 dipyridylium salt, an organoarsenical her~icide or anamino acid herbicide, the composition containing 0.1 to 20, preferably 10 to 20, parts by weight of the herbicide of formula (I) per part of said other herbicide.

~L~1%

The other herbicide will generally be a herbicide having a complementary action For example, one preferred class is of mixtures comprising a herbicide active against broad-leaved weeds. A second preferred class is of mixtures comprising a contact herbicide Examples of complementary herbicides useful in the invention are:
A Benzo-2,1,3-thiadiazin-4-one-2,2-dioxides, e g.
those of formula:

Rl ~H~O2 where R is Cl-C~ alkyl, in particular the compound in which R10 is isopropyl, common name bentazon B Hormone herbicides, particularly phenoxyalkanoic acids and their derivatives (salts, esters, amides and t~e like) Examples of such acids are:
4-chloro-2-methylphenoxyacetic acid ~common name MCPA) 2-(2,4 dichlorophenoxy) propionic acid (com~on name dichlorprop) 2~4,5-trichlorophenoxyacetic acid (common name 2,4,5-T) 4-(4-chloro-2-methylphenoxy)butyric acid (cNmmon name MCPB) 2,4-dichlorophenoxyacetic acid (common name 2,4D) 4-(2,4-dichlorophenoxy)butyric acid (common name 2,4DB) 2-(4-chloro-2-methylphenoxy) propionic acid (common name mecoprop) C. 3-~ 4-(4-halophenoxy)phenyl ~-1,1 dialkyl ureas, in ~119OIi~

particular the compound 3- r4-(4-chlorophenoxy)-phenyl~ -l,l-dimethylurea (common name chloroxuron).
D Dinitrophenols, for example those of formula:
OH
02N~_~ Rll NO
where Rll is an alkyl group of 1 to 5 carbon atoms, and their derivatives, e.g. acetates; in particular such compounds wherein Rll is methyl (common name D~OC), tert-butyl (common name dinoterb); or wherein Rll is sec-butyl (common name dinoseb); and its ester dinoseb acetate.
E. Dinitroaniline herbicides, f~r5 example those of formula:

02N - ~ ~2 wherein R12 is hydrogen or Cl-C6 alkyl, cycloalkyl or alkenyl, optionally substituted with halogen.
R13 is Cl-C6 alkyl; R14 is hydrogen, methyl or amino;
and R15 is trifluoromethyl, Cl-C6 alkyl, methyl sulphonyl or aminosulphonyl; in particular:
N'~'-diethyl-2,6-dinitro-4-trifluoromethyl-m-phenylenediamine (common name dinitramine) 2,6-dinitro-NN-dipropyl-4-trifluoromethylaniline (common name trifluralin) 4-methylsulphonyl-2,6-dinitro-NN-dipropylaniline (c~mmon name nitralin) ,~j .

:' 1~9~

F. Phenylurea herbicides, e.g, of formula:

-P~ ~ ~HCO~ (CH3)2 where R 6 and R17 are independently hydrogen, chloro, Cl-C4 alkyl or alkoxy, or trifluoromethyl; in particular the compound in which R16 and R17 are 5 both chloro (common name diuron), the compound in which R16 is hydrogen and R17 is trifluoromethyl (common name fluometuron), G. Phenylcarbamoxyloxyphenylcarbamates, e,g, those of formula:
R18 ~ ~HCO O - Q 1 9 ~HCOOR
where R18 is hydrogen or Cl-C4 alkyl and R is Cl-C4 alkyl; in particular the compound where R 8 is m-methyl and Rl9 is methyl (common name phenmedipham), and the compound where R18 is hydrogen and ~19 is ethyl (common name desmedipham).
H. 2-phenylpyridazin-3-ones, e,g. those of for~ula:

R21 o R20 R2~ ~<

where R20 is hydrogen or trifluoromethyl, R21 is chloro, bromo or methoxy and R22 is amino (optionally .. . .

methyl substituted) or methoxy; particularly 5-amino-4-chloro-2-phenylpyridazine-3-one (common name pyrazon).

I. Uracil herbicides, for example of formula:

R2~N ~

R25 ~ \ R23 wherein R23 is C3-C5 alkyl (preferably branched) or cyclohexyl, R24 is methyl, R25 is chlorine or bromine;
or R24 and R25 together represent a C3-C4 alkylene bridge; particularly:
3-cyclohexyl-5,6-trimethylene uracil (common name lenacil~
5-bromo-3-sec-butyl-6-methyluracil (common name bromacil) 3-tert-butyl-5-chloro-6-methyluracil (common name terbacil) J. Txiazine herbicides, for example of formula:

N~N
R ~ N ~ R28 wherein R is chloro, methoxy, methylthio or ethyl-thio; R27 is (Cl-C6)- alkylamino, alkoxyalkylamino or dialkylamino; and R2 is (Cl-C6)- alkylamino, alkoxyalkylamino, cyanoalkylamino, dialkylamino or azido; particularly:
2-chloro-4-ethylamino-6- _ propylamino-l~3~5-triazine .(common name atrazine) 2-chloro-4,6-di(ethylamino)-1,3,5-triazine (common 1~ ~901 2 name simazine) 2-azido-4-isopropylamino-6-methylthio-1,3,5-`triazine (common name aziprotryne) K. l-alkoxy-l-alkyl-3-phenylurea herbicides, e.g. of formula:

~ 3 NHCO.N.CH3 whereln R29 is hydrogen or chloro and R30 is chloro, bromo or ethoxy; in particular:
3-(3,4-dichloropheny])-1-methoxy-1-methylurea (common name linuron) 3-(4-chlorophenyl)-1-methoxy-1-methylurea t` ~common name monolinuron) 3(4-bromo-4-chlorophenyl~-1-methoxy-1-methylurea (common name chlorobromuron) L. Thiolcarbamate herbicides such as S-propyl dipropyl -thiocarbamate (common name vernolate).

M. 1,2,4-Triazine-5-one herbicides, e g. of formula:

R31 N~N

o~N ~\ R32 where R is C3-C6 alkyl or cycloalkyl, or phenyl;
and R32 is methyl or methylthio; in particular:
4-amino-4,5-dihydro-3-methyl-6-~henyl-1,2,4-triazine-5-one (common name metamitron) 4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4,-triazine-5-one (common name metribuzin).

.. , . _. ___ . , , ._ __ .. , ... , _ ~_.. ___ _, --__._ __ . . ., . .. .. _,_ . .. ~ _,.. ,.. _ __ .".. ,~_ _ . _ . _ .....
......

N, Benzoic acid herbicides, e.g. those of formula:
COOH
Cl ~ ~R33 R3 ~ Cl wherein R33 is hydrogen, chloro or methoxy and R34 is hydrogen or amino; especially 2,3,6-trichlorobenzoic acid (common name 2,3,6-TBA);
3,6-dichloro-2-methoxybenzoic acid (common name dicamba) and 3-amino-2,5-dichlorobenzoic acid (common name chloramben), O. Anilide herbicides, e,g, those of formula:

R3 ~ - CO,R

where R35 and R36 are hydrogen, chloro or methyl;
R37 and R38 are H, methyl or ethyl; R39 is hydrogen, Cl-C4 alkyl or alkynyl, optionally substituted with Cl-C4 alkoxy or ethoxycarbonyl; and R40 is Cl-C6 alkyl, cycloalkyl or alkenyl, optionally chloro-substituted: particularly ~-butoxymethyl-a-chloro-2',6'-diethylacetanilide (common name butachlor);
the corresponding ~-methoxy compound (common name alachlor); the corresponding ~-isopropyl compound (common name propachlor) and 3'4'-dichloropropion-anilide (common name propanil).

20 P. Dihalobenzonitrile herbicides: for example, 2,6-dichlorobenzonitrile (common name dichlobenil);
3,5-dibromo-4-hydroxybenzonitrile (common name bromoxynil) and 3,5-diiodo-4-hydroxybenzonitrile O~Z

(common name ioxynil).

Q. Haloalkanoic herbicides, e.g. 2,2-dichloropionic acid (common name dalapon), trichloracetic acid (common name TCA) and salts thereof.

R. Diphenylether herbicides, e.g. 4-nitrophenyl 2'-nitro-4-trifluoromethyl phenyl ether (common name fluorodifen); methyl-5-(2,4-dichlorophenoxy)-2-nitrobenzoate (common name bifenox~ 2-nitro-5-(2-chloro-4-trifluoromethylphenoxy) benzoic acid; and 2-chlorophenyl-3'-ethoxy-4'-nitro-4-trifluoromethyl phenyl ether.

S Miscellaneous herbicides including N,N-dimethyl-diphenylacetamide (common name diphenamid); N-l-naphthylphthalamic acid (common name naptalam) and 3-amino-1,2,4-triazole.

Compositions according to the invention can be used to treat a wide variety of crops. Table II below illustrates this.

~ _ . .

01~

~ a~ 0 a)s~ ~ ~ o U~~ O ~ ~ S~
u~ o m ~ ~ ~ o o -ID ~ C:l ~1 ~ ~ 0 ~1 N ~ Pq 1 Ul ) 1 S ~ IIS
.~ ~ ~ ~1 ~ ` ~ ~ ~ q-, o ~ ~,) a~ s~
,1 ~ ~I 0 ~ o ~ ~ ~ ~ ~ a) ~ ~0 ~
a) a~ s~ ~ ~ u~ ~ ~ ~ ~ ~
r-l C 5 rl O ~ ~I) ` O ~U 0 ~1 .Q X N ~ . ~; ~ ~ a) ~ ~ ~1 0 ~1 3 ~ ` O rl ~ t~
~1 ~1 ~1t) O ~:: h ~I h O ~1 0 0 ~1 td O ~4J O ~ ~ ~ ~ O ~
~ ~) ~1 S I ~ ~ aJ
U~ ~ ,C ~ 0 0 ~ S~ `
a~ o a~
` ~ ~rl O ~ ` ~ ~ rl O ~ ~) ~ ~I h rl o W ~1 ~1 ~: ` ~ >1 ~ ` 0 ~ o ~ 0 x ~ ~ ~ o ~ ~ s~ ~
N 0 ~1 0 ~:: al N p~
O t~ l O O ~ ` 0 U~
C) ~ ~ O ~ .~ ~ 0 41 .5:
~ ~1 0 o ~ a) o ~1 0 rl m ~ 'd 4~ 0 ~ N

R ~ O ~ .

_ _ _ _ .
.

11~9012 ~:1 o 0~ al ~ 5Q~ o~ ` -~, a O- ,~
Q ~ a) ~3 ~ 'r X~ ~0 ` Ei ~ O
~ m ~ o .4 ~ ~ s~ ~ m s~
~ >~ NO ~ ~ ~ & Q la .C h ~1 .,~ ~ la ~u ~ :~: ` Q ~
~ ~ ~ ~ ~ ra O P~ ~ ~ ~ ~ ~ O Q ~1 a~ ~ ~ ~4 :,. ~1 ` :,.
Q~ ~ rl E~ C~ X ~ ` a~ ~

O C) N .,1 ~
O ,-1 115 ~1 ~ I t~ ~ ,1 n~ ~, O ~ ~ O ~ O ~ ~ -,1 0 t) ~1 ~ ::S ` O S~
, ~ 1 ~
~0 : _ ~ X l '1:) ~X~
R ~ I ~
. ~0~
~ .
~ ~U _ 0~ ~ ~ ,1 ~ ~

~l~g~ .

~ j ~ ~ G) S~
O
'u p0~ 0 Q ~ .~ ~ ~ Q S-~ ~

U~ ~

~ ~ ~ ~ ~ O O O
ta ~
~z r ~ O
H 3 o ~ ~x~
o ~ X ~

:c ~ , I ~

~n ~ ~o ~C~ I

~190~

Examples of suitable contact herbicides are the bipyridylium herbicides i.e. those in which the active entity is the l,l'-dimethyl-4,4'-dipyridylium ion (common name paraquat) and in which the active entity is the 1,1'-ethylene-2,2'-dipyridylium ion (common name diquat). In the case of mixtures with bipyridylium herbicides, it is preferred that the group R be an ester, e.g. a butyl ester; such mixtures have higher activity.
Other suitable contact herbicides are the organoarsenical herbicides, e.g. monosodium methanearsonate (common name MSM~) and aminoacid herbicides e.g. ~-(phosphonomethyl)-glycine (common name glyphosate) and salts and esters thereof.
The preferred herbicide of formula I for use in the invention is a- ~ 4-(5-trifluoromethyl-2-pyridyloxy)-phenoxy~7propionic acid, preferably in the form of its _-propyl or _-butyl ester.
Mixtures according to the invention contain from 0.1 to 20 parts, conveniently from 0.5 to 2 parts, by weight of herbicide of formula I per part by weight of other herbicide, depending on the relative activity of the components. In a number of cases the optimum benefit from the use of the combined herbicides results when the proportion of the herbicide of formula (I) is relatively high with respect to the other herbicide (e.g. from 10 to 20 parts by weight of herbicide of formula (I) per part by weight of other herbicide). Likewise, the amount of the mixture to be applied will depend upon a number of factors, for example the particular plant species whose growth is to be inhibited, but in general an amount of from 0.1 to 5 kilograms per hectare is usually suitable.
The skilled worker in the art will readily be able to determine suitable ratios and amounts for use by means of standardised routine tests, without undue experimentation.
The mixtures of the invention are preferably applied in the form of compositions, in which the active ingred-ients are mixed with a carrier comprising a solid or ~i19~Z

liquid diluent. Preferably the composition further comprises a surface-active agent.
The solid compositions of the invention may be for example, in the form of dusting powders, or may take the form of granules. Suitable solid diluents include, for example, kaolin, bentonite, keiselguhr, dolomite, calcium carbonate, talc, powdered magnesia and Fuller's earth.
Solid compositions may also be in the form of dispersible powders or grains comprising in addition to the active ingredient, a wetting agent to facilitate the dispersion of the powder or grains in liquids. Such powders or grains may include fillers, suspending agents and the like.
Liquid compositions include aqueous solutions, dispersions and emulsions containing the active ingred-ient preferably in the presence of one or more surface-active agents. Water or organic liquids may be used to prepare solutions, dispersions, or emulsions of the active ingredient. The liquid compositions of the invention may also contain one or more corrosion inhibitors for example lauryl isoquinolinium bromide Surface-active agents may be of the cationic, anionic or non-ionic type. Suitable agents of the cationic type include for example quaternary ammonium compounds, for example cetyltrimethyl ammonium bromide.
Suitable agents of the anionic type include for exampl0 soaps, salts of aliphatic mono-esters of sulphuric acid, for example sodium lauryl sulphate; and salts of sulphon-ated aromatic compounds, for example dodecylbenzene-sulphonate, sodium, calcium and ~mmonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyl- and triiso-propyl-naphthalene-sulphonic acid. Suitable agents of the non-ionic type include, for example, the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol and cetyl alcohol, or with alkyl phenols such as octyl-phenol, nonylphenol, and octylcresol. Other non-ionic i2 agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbitol mono-laurate; the condensation products of the said partial esters with ethylene oxide and the lecithins.
The compositions which are to be used in the form of aqueous solutions, dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being diluted with water before use. These concentrates are usually required to withstand storage for prolonged periods and after such storage to be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. In general concentrates may conveniently contain from 10 to 85% and preferably from 25 to 60~ by weight of active ingredient.
Dilute preparations ready for use may contain varying amounts of the active ingredient, depending upon the purpose for which they are to be used; however, dilute preparations suitable for many uses contain between 0.01%
and 10~ and preferably between 0.1% and 1% by weight of the active ingredient.
The compounds of formula I may be prepared by the route outlined in Scheme A below~

17~.

Scheme A

3 Z ` ~ O ~ OC~3 OM
(II) (III) Z ~Y
Pyridine l l l (III) > ~N ~~O ~ OH
hydrochloride \~=~

(IV) ICH3 Base (IV) + Hal- CHR ~ (I) (V) Oi'~

In Scheme A, the symbols Z and Y have the meanings previously assigned to them, Hal stands for a halogen, preferably chlorine or bromine, and M is a cation, for example sodium.
In Scheme A, a suitably substituted halogeno-pyridine (II) is reacted with a metal salt of p-methoxy~phenol, for example the sodium salt of p-methoxyphenol. The reaction is preferably carried out in a solvent or diluent, for example methyl ethyl ketone, tetrahydrofuran; dimethyl-sulphoxide or dimethylacetamide. The p-methoxy-phenoxy compound (III) so obtained is then demethylated by a standard procedure, for example by heating with pyridine hydrochloride or with hydrogen bromide in acetic acid, to obtain the corresponding p-hydroxy compound (IV).
This in turn is reacted in the form of its metal salt (for example the sodium or potassium salt) with the appropriate halogeno-alkanoic acid derivative (V) to obtain the required compound (I). Preferably this reaction is carried out in a solvent or diluent, for example methyl ethyl ketone.
The starting materials (II) used in the process of Scheme A may be prepared by halogenation of appropriate 2-halogeno-5-or 3-methylpyridines Thus, 2-chloro-5-trifluoromethylpyridine may be obtained by chlorinating 2-bromo-5-methyl-pyridine in the presence of ultra-violet to obtain 2-chloro-5-trichloromethylpyridine The 2-chloro-5-trifluoromethylpyridine is obtainable by reacting the 2-chloro-5-trichloromethylpyridine with a fluorinating agent, for example antimony trifluoride or liquid hydrogen fluoride In an alternative process, 2-halogeno-3- or 5-trifluoromethyl pyridines may be obtained by reacting a 2-halogeno-3- or -5-carboxypyridine with sulphur tetra-fluoride in the presence of hydrogen fluoride.
The invention is illustrated by the following Examples, in which all parts are by weight and all temper-atures in degrees Centigrade unless otherwise specified.

J

~1~9QiZ

This Example illustrates the preparation of a compound of formula (I), namely, ethyl ~-4(5-trifluoro-methyl-2-pyridyloxy)phenoxypropionate (Compound No.l).
(a) Preparation of 2-chloro-5-trichloromethylpyridine 2-Bromo-5-methylpyridine (27g) in dry carbon tetrachloride (500 ml) was treated with dry hydrogen chloride to give the hydrochloride salt, The solid which separated was broken up and the mixture heated to reflux. Chlorine was passed through the boiling mixture for 8 hours with irradiation by an ultra-violet lamp, The mixture was then filtered and evaporated to a pale yellow liquid which solidified on cooling, This was identified as the required chloro compound by its nuclear magnetic resonance spectrum.
(b) Preparation of 2-chloro-5-trifluoromethylpyridine The product from (a) (18g) and antimony trifluoride (50 g) were heated together at 140-145C for 1 hour. The mixture was cooled, mixed with ice and concentrated hydrochloric acid, and extracted with ether. The extracts were washed with water, dried with magnesium sulphate, and evaporated. The products from several such prep-arations were combined and distilled at atmospheric pressure through a short column packed with Fenske rings.
The product boiling at 124-154C was collected and identified as 2-chloro-5-trifluoromethylpyridine, (c) Preparation of 2-p-methoxyphenoxy-5-trifluoromethyl-pyridine The product from (b) boiling at 124-154C (1.82 g) was added in dry dimethylsulphoxide (15 ml) to a solution of p-methoxyphenol (1.24 g) in dimethylsulphoxide (20 ml) previously reacted with sodium hydride (0.48 g of a 50:50 .
'.:' .

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oil dispersion). The mixture was stirred and heated to 60 to 65 for 5 hours, poured into ice, and extracted with ether. The ether extracts gave an oil.
(d) Preparation of 2-p-hydroxyphenoxy-5-trifluoromethYl-pyridine The product from (c) (1.7 g) and excess of pyridine hydrochloride were heated together for 8 hours at 180C.
The mixture was cooled, diluted with water and 2-molar hydrochloric acid, and extracted with ether. The extracts were dried and evaporated to yield an oil identified as the required hydroxy compound.
(e) Preparation of compound no 1 The product from (d) (0.22 g), ethyl alpha-bromo-propionate (0.24 g) and potassium carbonate (0.18 g) in methyl ethyl ketone (5 ml) were stirred, and heated under reflux for 2 hours. The mixture was left to cool over-night, then filtered, and the residue washed with methyl ethyl ketone. The filtrate and washings were evaporated and the remaining oil subjected to a high vacuum to remove traces of solvent. The nuclear magnetic resonance spectrum of the oil was consistent with the structure assigned and the compound was identified as compound no 1 (f) Pre~aration of comPound no 3 The product from (e) (0.3 g) was dissolved in n-pentanol (15 ml) containing concentrated sulphuric acid (2 drops) The mixture was heated to reflux for 3 1/2 hours. The solvent was removed and the residue taken up in ether and washed with saturated sodium bicarbonate solution. The ether solution was dried and evaporated to a colourless oil which was purified by preparative scale thin layer chromatography on silica gel with an 80:20 mixture of petroleum (b.p. 60-80C) and ether as the solvent. The nuclear magnetic resonance spectrum of the product identified it as the required pentyl ester (g)l Preparation of compound no 2 The product from (e) (0 14 g) in isopropanol (2 ml) was stirred at room temperature for 1 3/4 hours with an aqueous solution of sodium hydroxide (1 6 ml of a solution containing 1 g NaOH per 100 ml water) The mixture was evaporated in a vacuum and the residue taken up in water, acidified, and extracted with ether (2 x 50 ml). The ether extracts yielded an oil identified as the required carboxylic acid This example illustrates the preparation of compound no 5 of Table I
(a) Preparation of 2-amino-3-bromo-5-methylpyridine 2-Amino 5-methylpyridine (108 g) in glacial acetic acid (300 ml) was heated to 90-100C while bromine (160 g) in acetic acid (55 ml) was slowly added with stirring.
When addition was complete, the mixture was stirred and heated for a further 30 minutes and then allowed to cool overnight The solid which separated was filtered off and mixed with ice and the mixture neutralised with concentrated ammonia, keeping the temperature at 0 to 5C. The solid was collected, washed with water, and dried to give the bromo-compound (b) Preparation of 3-bromo-2-chloro-5-methylpyridine The product from (a) (145 g) was dissolved in concentrated hydrochloric acid (750 ml) and water (450 ml) and the solution cooled to -10C Sodium nitrite (54 g) in cold water (450 ml) was added dropwise with stirring ~119012 over a period of 90 minutes while the mixture was kept at -5C. The solution was stirred for a further 2 hours, and then basified with concentrated ammonia, keeping the temperature below 20C. The solid which separated was washed with water, dried, dissolved in ether (1500 ml) and washed with cold sodium hydroxide solution (lM;
1 litre). The ether solution was washed twice with water (1 litre portions), dried, and evaporated to give the required 3-bromo-2-chloro-5-methylpyridine.
(c) Preparation of 2,3 dichloro-5-trichloromethylpYridine The product from (b) (64 g) in dry carbon tetra-chloride (650 ml) was treated with dry hydrogen chloride.
The precipitate was broken up and the suspension heated under reflux while dry chlorine was bubbled into the mixture, with illumination from an ultra-violet light source After 4 1/2 hours, the mixture was cooled, filtered, and the filtrate evaporated to give the required 2,3-dichloro-5-trichloromethylpyridine The mass spectrum was consistent with the structure assigned to this compound (d) Preparation of 2,3-dichloro-5-trifluoromethYlpyridine The product from (c) (1 0 g) and antimony trifluoride (3 0 g) were heated together at 170-180 for 30 minutes The mixture was then cooled, mixed with ice and water, and extracted with ether The ether extracts gave a brown oil containing a mixture of 2,3-dichloro-5-trifluoro-methylpyridine and 3-chloro-2-fluoro-5-trifluoromethyl-pyridine with a minor amount of 2,3-dichloro-3-chloro-difluoromethylpyridine (e) Preparation of 3-chloro-2-p-methoxyPhenoxy-5-tri-fluoromethylpyridine p-Methoxyphenol (1.5 g) was added to a suspension of sodium hydride (0 6 g 50% oil dispersion, washed with ~1~9C~2 petroleum) in dry dimethyl sulphoxide (30 ml) and the mixture stirred for 15 minutes. A solution of the com-bined products (1 5 g) from several preparations carried out as described in paragraph (d), in dimethylsulphoxide (20 ml) was added to the reaction mixture and heated to 60C for four hours A further amount of sodium hydride (0.3 g of 50% oil dispersion, washed with petroleum), and potassium carbonate (1.38 g) was added. Heating was continued for another 4 hours. The mixture was poured into ice and water, and extracted extracted with ether (400 ml). The ether extracts were washed with water, dilute sodium hydroxide, and water, dried, and evaporated to give the product.
(f) Preparation of 3-chloro-2-p-hydroxyphenoxY-5-trifluoro methylpyridine The product from (e) (2 g) was heated with pyridine hydrochloride (20 g) at 170-180C for 6 hours. The mixture was cooled, diluted with dilute hydrochloric acid, and extracted with ether. The ether extracts gave an oily solid which was purified by preparative thin layer chomatography using silica as the absorbent and 6%
ethanol-chloroform as the solvent.
(g) ~reparation of compound no 5 of Table 1 The product from (f) (0.16 g), ethyl alpha bromo-propionate (0.3 g), and potassium carbonate (0.25 g) were heated and stirred under reflux in methyl ethyl ketone (10 ml) for 2 hours. The mixture was cooled and filtered.
Evaporation of the filtrate gave an oil which was heated in a vacuum to remove traces of solvent. The oil was identified as compound no 5 by examination of its mass spectrum and its purity was confirmed by gas-liquid chromatography.
The following Examples illustrate compositions according to the invention.

:`~

This Example illustrates an aqueous solution according to the invention.
Compound no 2, as sodium salt 214 g Bentazon, sodium salt 327 g 5 Water to 1 litre The other ingredients are dissolved in the water.

This Example illustrates an aqueous fiolution according to the invention.
Compound no 2, as sodium salt 160 g MSM~
Water to 1 litre The other ingredients are dissolved in the water This Example illustrates an emulsifiable composition according to the invention.
15 Compound no 1 54 g Vernolate 400 g 'Lubrol' N 13* (emulsifier)50 g 'Arylan' CA* (emulsifier) 50 g 'Aromasol' H* (aromatic hydrocarbon solvent) to 1 litre The above ingredients are blended in a mixer.

This Example illustrates an aqueous emulsion *Denotes trademark according to the invention, Compound no 1 218 g Paraquat dichloride 138 g 'Synperonic' NPE 1800*(emulsifier) 50 g 5 'Aromasol' H* (solvent) 100 g Water to1 litre The emulsion is formed by briskly blending the ingredients, The Example illustrates a dispersible powder formulation according to the invention, 10 Compound no 7 100 g Fluometuron 400 g 'Vanisperse' CB* (dispersant) 50 g 'Aerosol' OT-B* (wetter) 20 g Spestone ` (filler) tol kg The above ingredients are ground together to produce a powdered mixture.

This Example illustrates an aqueous solution according to the invention, Compound no 2, sodium salt 212 g 2,4-DB sodium salt 109 g Water to l litre The other ingredients are dissolved in the water, This Example illustrates an emulsifiable concentrate *Denotes tradrmark 9o~z according to the invention, Compound no 5 54 g Phenmedipham 100 g 'Lubrol' N 13* (emulsifier) 50 g 'Arylan' CA* 50 g Acetophenone to1 litre The above ingredients are blended in a mixer, Below is given the constitution of the materials represented in the above Examples by Trade Marks, 10 'Lubrol' ~ 13* - nonyl phenol condensed with ethylene oxide 'Arylan' CA* - solution of calcium dodecyl benzene sulphonate in butanol 'Aromasol' H* - aromatic hydrocarbon 'Synperonic'* - nonyl phenol condensed with propylene ~PE 1800* oxide and ethylene oxide 'Vanisperse' CB* - sodium lignosulphonate 'Aerosol' OT-B* - sodium dioctylsulphosuccinate plus sodium benzoate 'Spestonel* - china clay This Example illustrates the herbicidal activity of mixtures according to the invention, Compound no 6 of Table I was mixed with various known herbicides active against broad-leaved weeds and dispersed in water to provide spray compositions, These were then sprayed on to pot plants at the 2 to 5 leaf growth stage in the greenhouse, The rates were generally lower than those which would be applied in the field, since the young greenhouse plants are generally more tender and susceptible *Denotes trademark "
:

to herbicides than plants growing out of doors. The spray volume used was equivalent to 200 litres per hectare, Compound no 6 was formulated as an emulsifiable concentrate of the following composition Constituent Amount (in grams per litre) Compound no 6 250 Arylan CA* 2.5 Geopon 365* 2,5 Aromasol H* to l litre Arylan CA* comprises calcium dodecylbenzene sulphonate, lO Ceopon 365* comprises a condensation product of castor oil with 40 molar proportions of ethylene oxide, Aromasol H* comprises a mixture of di and trimethyl benzenes, The known herbicides were used in the form of their commercially available formulations, A surface-active agent (Agral 90,* comprising a solution of a condensation product of p-nonylphenol with from 7-8 molar proportions of ethylene oxide in alcohol) was added to the spray compositions so that th~y contained 0,1% of Agral 90* in the final spray volume, The damage to the plants was assessed 20 days after treatment, on a scale of 0 to 9 where 0 is 0 to 10% damage and 9 is 90 to 100%, The results of the tests are given in Tables III and IV below, .. , . .~

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The names of the test plants were as follows:
Sb Sugar beet Rp Rape Ca Chenopodium album 5 Pi Polygonum aviculare -Av Avena fatua Bt Brom s tectorum Ag Agropyron repens Al Alopecurus myosuroides 10 Sy Soya bean Ct Cotton Xa Xanthium pensylvanium Ip Ipomoea purpurea Ec Echinochloa crus-galli 15 Dg Digitaria sanguinalis : Pn Pennisetum clandestinum Sh Sorghum halepense JED/vmc 15 Feb 79 . ~

Claims (6)

What we claim is:-

1. A herbicidal composition comprising a compound of the formula (I) (I) wherein at least one of Y and Z is trifluoromethyl, the other being hydrogen, fluorine, chlorine, bromine, iodine or trifluoromethyl and R is a carboxyl or a salt, ester, amide or nitrile thereof, in admixture with at least one other herbicide which is a benzo-2,1,3-thiadiazin-4-one-2,2-dioxide, a hormone herbicide, a 3[4-(4-halophenoxy)-phenyl]-1,1-dialkyl urea, a dinitrophenol, a dinitro-aniline, a phenyl-urea, a phenylcarbamoyloxyphenyl-carbamate, a 2-phenylpyridazin-3-one, a uracil, a 1,3,5-triazine, a 1-alkoxy-1-alkyl-3-phenylurea, a thiolcarb-amate, a 1,2,4-triazine-5-one, a benzoic acid, an anilide, a dihalobenzonitrile, a haloalkanoic acid, a diphenyl ether, N,M-dimethyl diphenylacetamide, N-1-naphthyl-phthalamic acid, 3-amino-1,2,4-triazole, a 1,1'-dimethyl-4,4-dipyridylium salt, a 1,1'-ethylene-2,2'-dipyridylium salt, a 1,1'-ethylene-2,2'-dipyridylium salt, an organo-arsenical herbicide or an amino acid herbicide, the composition containing 0.1 to 20, preferably 10 to 20, parts by weight of the herbicide of formula (I) per part of said other herbicide.

2. A composition according to claim 1 wherein the herbicide of formula (I) is the one in which Z is trifluoromethyl, Y
is hydrogen, and R is butoxycarbonyl or propoxycarbonyl.

3. A herbicidal composition according to claim 1 wherein said other herbicide is a salt of paraquat or diquat.

4. A composition according to claim 1 wherein said other herbicide is phenmedipham, metamitron, pyrazon, fluometuron, 2,4-DB or bentazon.

5. A process of inhibiting the growth of unwanted plants, characterised by applying to the plants, or the locus thereof, a composition according to any one of claims 1 to 3 in a herbicidally effective amount.

6. A process of inhibiting the growth of unwanted plants, characterised by applying to the plants, or the locus thereof, a composition according to claim 4 in a herbicidally effective amount.

RFF/bgg/D69