GB2056438A - Herbicidal diphenyl ether compounds - Google Patents
Herbicidal diphenyl ether compounds Download PDFInfo
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- GB2056438A GB2056438A GB8018916A GB8018916A GB2056438A GB 2056438 A GB2056438 A GB 2056438A GB 8018916 A GB8018916 A GB 8018916A GB 8018916 A GB8018916 A GB 8018916A GB 2056438 A GB2056438 A GB 2056438A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
- C07D295/28—Nitrogen atoms
- C07D295/32—Nitrogen atoms acylated with carboxylic or carbonic acids, or their nitrogen or sulfur analogues
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
- A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/48—Nitro-carboxylic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
- C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
- C07C205/38—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. nitrodiphenyl ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
- C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/59—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C243/40—Hydrazines having nitrogen atoms of hydrazine groups being quaternised
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A herbicidal diphenyl ether compound of the formula <IMAGE> wherein A is hydrogen, halogen, CN, NO2, CF3, or alkyl of 1 to 4 carbon atoms; B is halogen or CF3; C is hydrogen, halogen, or CF3; D is hydrogen, halogen, or NO2; R<1>, R<2> and R<3> each represent alkyl of 1 to 4 carbon atoms optionally substituted by phenyl, or R<1> represents an optionally phenyl-substituted C1-C4 alkyl radical and R<2> and R<3> together with the adjacent nitrogen atom form a 5- or 6-membered heterocyclic ring; and X<-> is an agriculturally acceptable anion; or an imide derivative of the compound of formula (I) wherein the elements of HX have been removed from formula (I).
Description
SPECIFICATION
Herbicidal compounds
This invention relates to diphenyl ether derivatives useful as herbicides and to herbicidal compositions and processes utilising them.
According to the present invention, there are provided diphenyl ether derivatives of the formula (I):
wherein A is a hydrogen, fluorine, chlorine, bromine or iodine atom or a cyano group, a nitro group, a trifluoromethyl group or an alkyl group of 1 to 4 carbon atoms;
B is a fluorine, chlorine, bromine or iodine atom or a trifluoromethyl group;
C is a hydrogen atom, a fluorine, chlorine, bromine or iodine atom or a trifluoromethyl group;
D is a hydrogen atom or a fluorine, chlorine, bromine or iodine atom, or a nitro group;;
R', R2 and R3 each represent an alkyl radical preferably of 1 to 4 carbon atoms optionally substituted by phenyl, or R' represents an alkyl radical of 1 to 4 carbon atoms optionally substituted by phenyl and R2 and R3 together with the nitrogen atom to which they are attached form a five or six membered heterocyclic ring; and X is an agriculturally acceptable anion.
When R2 and R3 form a heterocyclic ring it may be for example a pyrrolidine, piperidine or morpholine ring.
The anion X- may be any agriculturally acceptable anion. It may be for example a halide anion, preferably a chloride or bromide, or it may be for example a phosphate, nitrate, sulphate, methylsulphate, p-toluenesulphonate or other anion.
One sub-group of compounds according to the invention comprises compounds in which R1, R2 and R3 are all methyl groups.
Particular examples of compounds according to the invention are listed in Table 1.
TABLE I
Compound I Melting No. A B C D X Point C 1 Cl Cl H NO2 i 182-183 2 NO2 CF2 H NO2 i 179-181 3 Cl CF3 H NO2 1 168 decomp 4 Cl CF3 H H 5 NO2 CF3 H H 1 123-125 6 Cl CI H Br I 7 CI CF3 H CI Further examples of compounds according to the invention are listed in Table II below.
TABLE II
Melting Compound Point No. R4 X- "C CH, -NH-NCH2CH2 PTS 64-65 CH2 -NH CH 9 N\+/c 3 PTS 74-75 ID 10 -NHCH2CH3 PTS 88-89 -NH CH3CH, CN 11 PTS 94-95 -NH /CH3 NHs, /ce3 ID 12 PTS 84-85 Ns +CH3 Co) N CH3 +1 13 NH-NCH2C6H, Br 94-95 CH3 CH2 In the above table, the symbol PTS stands for the p-toluene sulphonate anion.
The compounds of the invention may be prepared for example by the process outlined in Scheme
A.
Scheme A
In Scheme A a suitably substituted diphenyl ether (II) bearing a carboxyl group is converted to its acid chloride (III) by treatment with a chlorinating agent for example thionyl chloride, phosphorus oxychloride or phosphorus pentachloride. The reaction may be accelerated by heating. The acid chloride (III) so obtained is then treated with at least an equimolar quantity of a substituted hydrazine R1R2NNH2 in the presence of an acid acceptor and preferably in an inert solvent. Examples of acid acceptors include tertiary amines, for example triethylamine, and alkali metal carbonates, for example potassium carbonate. The hydrazide derivative (IV) so prepared is then reacted with an alkyl halide R3Hal preferably in a solvent or diluent, to give the required quaternary salt (V).The quaternisation reaction may be
accelerated by heating, for example to a temperature in the range from 50 to 1 200C. Examples of solvents include the lower alkanols, for example methanol, ethanol and propanol, and polar solvents such as dimethylformamide and nitrobenzene. The process outlined in Scheme A leads to compounds in
which the anion X is a halide. If another anion is required, the halide may be exchanged by
conventional methods, for example by passing a solution of the halide through a bed of an ion exchange
resin loaded with the appropriate anion. Compounds with an alkylsulphate orp-toluenesulphonate
anion may also be prepared by using the appropriate alkylsulphate ester or alkyl p-toluenesulphonate
ester in place of the alkyl halide R3Hal in Scheme A.
Variations in the above method of preparing the compounds of the invention will be apparent to
those skilled in the art; for example it may be possible to prepare the dimethylhydrazide (IV) by reaction
of dimethylhydrazine with an alkyl ester of the acid (II) rather than with the acid chloride (III).
The structural formula (I) given above is intended to include tautomeric forms of the structure
drawn, as well as physically distinguishable modifications of the compounds which may arise, for
example, from different ways in which the molecules are arranged in a crystal lattice or from the inability
of parts of the molecule to rotate freely in relation to other parts, or from geometrical isomerism, or from
intra-molecular or intermolecular hydrogen bonding, or otherwise.
The compounds of the invention are in general crystalline solids. When treated with alkali they may be converted into an internal zwitter-ion or imide of formula (Vl):
The imide form has biological activity similar to that of the quaternary salt (I) and forms a further part of the present invention. The imide is soluble in organic solvents.
Thus, for example, the imide corresponding to compound no. 3 of Table I may be prepared as follows.
A solution of compound no. 3 in the form of its bromide salt (0.85 g) in dichloromethane (100 ml) was shaken with excess of sodium hydroxide solution (2 molar, 100 ml). The organic phase was washed with water and then with brine, dried, and evaporated to give the imide (0.65 g), with a melting point of 1320C.
The stability of the compounds of the invention in the imide form provides a convenient method of converting one salt into another. Thus, the imide may be treated with the appropriate amount of acid to convert it back into the corresponding quaternary salt. The imide of compound 3 prepared as described above, may for example be converted into the chloride of the quaternary salt form of compound 3 by passing hydrogen chloride gas into a solution of the imide in dichloromethane.
The compounds of the invention are broad-spectrum herbicides capable of controlling the growth of a wide variety of plants. They may be applied to the soil before the emergence of'plants (pre-emergence application) or they may be applied to the above ground parts of growing plants (post-emergence application). In another aspect, therefore, the invention provides a process of inhibiting the growth of unwanted plants, by applying to the plants, or to the locus thereof, a compound of the formula (I) as hereinbefore defined.
The rate of application required to inhibit the growth of unwanted plants will depend on, for example, the particular compound of formula (I) chosen for use, and the particular species of plant it is desired to control. However, as a general guide, an amount of from 0.1 to 5.0 kilograms per hectare, and preferably 0.5 to 2 kilograms per hectare is usually suitable.
The compounds of the invention are preferably applied in the form of a composition, in which the active ingredient is mixed with a carrier comprising a solid or liquid diluent. In another aspect, therefore, the invention provides a herbicidal composition, comprising as an active ingredient a compound of the formula (I) as hereinbefore defined, in admixture with a solid or liquid diluent. Preferably the composition also 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, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, and Fuller's earth. Solid compositions also include soluble powders and granules which may comprise a compound of the invention in admixture with a water-soluble carrier.
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 ingredient 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 example soaps, salts of aliphatic mono-esters of sulphuric acid, for example sodium lauryl sulphate; and salts of sulphonated aromatic compounds, for example dodecylbenzenesulphonate, sodium, calcium and ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyl-and triisopropylnaphthalenesulphonic 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 agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbitol monolaurate; 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.
The compositions of the invention may contain, in addition to carriers and surface-active agents, various other constituents to increase their usefulness. They may contain, for example, buffering salts to
maintain the pH of the composition within a desired range; antifreeze agents, for example urea or
propylene glycol; adjuvants, for example oils and humectants; and sequestrants, for example citric acid
and ethylenediaminetetracetic acid, which help to prevent the formation of insoluble precipitates when the compositions are diluted with hard water. Aqueous dispersions may contain anti-settling agents and
anti-caking agents. The compositions may in general contain a dye or pigment to impart a characteristic
colour. Agents for increasing viscosity may be added to reduce the formation of fine droplets during
spraying, and thereby reduce spray drift.Other additives useful for particular purposes will be known to those skilled in the formulation art.
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 invention is illustrated by the following Examples in which all parts are by weight and all
temperatures in degrees Centigrade unless otherwise stated.
EXAMPLE 1
This Example illustrates the preparation of compound no 1 of Table I.
(a) 5-(2,4-Dichlorophenoxy-2-nitrobenzoic acid (23 g) was heated under reflux in thionyl chloride
(300 ml) for 3 hours. The thionyl chloride was removed under reduced pressure to leave an oil which
crystallised on standing to give 5-(2,4-dichlorophenoxy)-2-nitrobenzoyl chloride with a melting point of 60-630C.
(b) The product from (a) (5.0 g) was dissolved in ether (1 5 ml) containing triethylamine (3.0 g) and
N,N-dimethylhydrazine (0.9 g) was added to the solution while the temperature was kept at 10-1 50C by cooling. The mixture was stirred for 3 hours at room temperature and then poured into a solution of
sodium bicarbonate. The ether layer was allowed to evaporate and the remaining solid collected and recrystallised from petroleum (b.p. 80-1 000C) to give 5-(2,4-dichlorophenoxy)-2-nitro-N
dimethylaminobenzamide (2.9 g) with a melting point of 127.5-1 29.50C.
(c) The product from (b) (1.5 g) was heated at 600C in methanol (30 ml) with methyl iodide (3 ml) for
8 hours. Methyl iodide (2 ml) was then added and the mixture heated for another 6 hours. The methanol
was then removed under reduced pressure. The solid so obtained was recrystallised from methanol to
give compound no. 1 with a melting point of 182-1 83oC.
EXAMPLE 2
This Example illustrates the preparation of compound no. 2 of Table I.
(a) Preparation of 3(2-nitro-4-trifluoromethylphenoxy) benzoic acid
3-Hydroxybenzoic acid (13.8 g) was stirred in dimethylformamide (150 ml) while anhydrous
potassium carbonate (26 g) was added. 2-Chloro-5-trifluoromethylnitrobenzene (22.5 g) was then
added and the mixture heated to 1 000C for 7 hours. The dimethylformamide was removed under
reduced pressure and the residue dissolved in warm water. The solution was acidified with dilute
hydrochloric acid. The solid which separated was collected, washed with water, and recrystallised from
a mixture of methanol and water, to give the required benzoic acid derivative (24 g) with a melting
point of 183-1 850C.
(b) The product from (a) (4.91 g) was added in portions to a mixture of concentrated sulphuric acid
(20 ml) and 1,2-dichloroethane (12.5 ml) while the mixture was stirred vigorously and cooled to OOC.
When a solution was obtained, potassium nitrate (1.5 g) was added in portions over a period of 15
minutes and the mixture stirred for a further 30 minutes at 0 C.
The mixture was allowed to warm to room temperature, and then poured on to ice and water
(200 ml). The mixture was left overnight and the solid then collected and recrystallised from a mixture
of toluene and ethyl acetate, giving 2-nitro-3(2-nitro-4-trifluoromethylphenoxy)benzoic acid (2.3 g)
with a melting point of 1 87-1 880C.
(c) The product from (b) above (5 g) was suspended in toluene and heated under reflux with thionyl
chloride (2 ml) for 3 hours. The solvent was removed under reduced pressure to give 2-nitro-3(2-nitro
4-trifluoromethylphenoxy)benzoyl chloride. This was dissolved in dry chloroform (20 ml) and added
portionwise with stirring to a solution of N,N-dimethylhydrazine (2 g) in dry methylene dichloride at a
temperature of 5--1 OOC. The mixture was stirred at 1 00C for 30 minutes and then at room
temperature for 2 hours. The solvent was removed under reduced pressure and the residue triturated
with water and extracted twice with methylene dichloride.The methylene dichloride extract was dried and evaporated to give a yellow gum (6 g) identified as the required 2-(N-dimethylaminocarbamoyl)-4- (2-nitro-4-trifluoromethylphenoxy)nitrobenzene.
(d) The product from (c) above was taken up in ethanol (50 ml). The solution was divided into two equal parts, and one part was heated under reflux with methyl iodide (2 g) for 8 hours. The solution was concentrated under reduced pressure and treated with ether. The pale yellow crystalline solid which separated was recrystallised from a mixture of methanol and water to give compound no. 2 (1.75 g) with a melting point of 179-1 81 0C.
EXAMPLE 3
This Example illustrates the preparation of compound no. 3 of Table I.
4(2-Chloro-4-trifluoromethylphenoxy)-2-chlorocarbonyinitrobenzene (5.08 g) was stirred and cooled to below 50C in solution in dry toluene while a solution of N,N-dimethylhydrazine (1.5 g) in dry toluene was slowly added. The solution was stirred for one hour and then left overnight. The solution was shaken with ether and water and the ether layer washed with water and dried. Evaporation of the solvent gave a yellow oil which crystallised on standing and was recrystallised from a mixture of ether and petroleum (b.p. 30--400C) to give 4(2-chloro-4-trifluoromethylphenoxy)-2-(N-dimethylamino- carbamoyl)nitrobenzene (2.0 g) with a melting point of 1 370C.
The product so prepared (t.5 g) was heated under reflux with methyl iodide (4 ml) in methanol (25 ml) for 6 hours. Removal of the solvent gave a solid which was recrystallised from a mixture of dichloromethane and toluene to give a compound no. 3 as a yellow solid (1.26 g) with a melting point of 1 680C (decomp). The corresponding bromide was prepared by using methyl bromide in place of methyl iodide and had a melting point of 2000C (decomp.) EXAMPLE 4
This Example illustrates the preparation of compound 12 of Table II.
N-4-Morpholino-5-(2-ch loro-4-trifl uoromethylphenoxy)-2-n itrobenza mide (1 g), prepared from 5 (2-chloro-4-trifluoromethylphenoxy)-2-nitrobenzoyl chloride and N-aminomorpholine, was fused with an excess of ethyl-p-toluenesulphonate and stirred for 2 hours at 1 650C. The mixture was then heated for a further 2 hours at 1 900 C. The mixture was then cooled and triturated with ether and then with petroleum (b.p. 30--400C) to give a beige solid. This was taken up in ethyl acetate, filtered, and the solution evaporated. The residue was identified as compound no. 12, having a melting point of 84-850C. Compounds 8, 9, 10 and 11 were similarly prepared.
EXAMPLE 5
This Example illustrates the preparation of compound no. 13 of Table II.
5-(2-chloro-4-trifluoromethylphenoxy)-N-dimethyl-amino-2-nitrobenzamide (0.5 g), prepared from 5-(2-chloro-4-trifiuoromethylphenoxy)-2-nitrobenzoyl chloride and N,N-dimethylhydrazine, was stirred in ethanol (10 ml) with benzyl bromide (1 ml) for 4 hours and then kept at room temperature for 48 hours. The solution was evaporated under reduced pressure and the yellow oil remaining was triturated with ether to give a yellow gum. This was triturated with cyclohexane to give a white solid identified as compound 13, having a melting point of 94-950C.
EXAMPLE 6
This Example illustrates the herbicidal properties of compounds of Tables I and 11. The compounds were submitted to herbicide tests as described below.
Each compound was formulated for test by mixing an appropriate amount of it with 5 ml of an emulsion prepared by diluting 160 ml of a solution containing 21.8 grams per litre of Span 80 and 78.2 grams per litre of Tween 20 in methylcyclohexanone to 500 ml with water. Span 80 is a Trade Mark for a surface-active agent comprising sorbitan monolaurate. Tween 20 is a Trade Mark for a surface-active agent comprising a condensate of 20 molar proportions of ethylene oxide with sorbitan monolaurate.
The mixture of the compound and the emulsion was then shaken with glass beads and diluted to 40 ml with water. The spray composition so prepared was sprayed on to young pot plants (post-emergence test) of the species named in Table Ill below, at a rate equivalent to 1000 litres per hectare. Damage to plants was assessed 14 days after spraying by comparison with untreated plants, on a scale of 0 to 5 where 0 is 0 to 20% damage and 5 is complete kill. In the table of results, a dash (-) means that no test was made.
A test was also carried out to detect pre-emergence herbicidal activity. Seeds of the test species were placed on the surface of fibre trays of soil and were sprayed with the compositions at the rate of 1000 litres per hectare. The seeds were then covered with further soil. Three weeks after spraying, the seedlings in the sprayed fibre trays were compared with the seedlings in unsprayed control trays, the damage being assessed on the same scale of O to 5.
The results of the tests are given in Table lil below.
TABLE III
Rate Of Pre- Or Test Plants Compound Application Post-Emergence No. kg/ha Application Sb Rp Ct Sy Mz Ww Rc Sn Ip Am Pi Ca Po Xs Ab Cv Ot/Av Dg Pu St Ec Sh Ag Cn 1 0.5 Pre 4 4 - 4 4 4 4 5 - 5 5 5 4 3 4 - 3 4 3 4 4 2 1 0 Post 5 4 3 4 2 1 - 4 4 - 4 5 - 4 5 5 0 - 1 4 3 1 0 0 1 5.0 Pre 5 5 1 4 5 5 4 5 2 5 5 5 5 4 5 - 5 5 4 5 4 4 3 0 Post 5 5 4 4 4 4 5 5 6 - 5 5 - 5 5 5 4 - 4 5 5 5 3 3 2 0.2 Pre 3 5 0 0 1 2 2 4 0 3 - 4 4 0 2 - 1 1 1 3 3 0 1 0 Post 3 4 3 2 1 1 1 4 5 5 4 4 5 4 5 5 0 1 2 4 2 3 2 0 2 5.0 Pre 4 5 3 2 4 4 4 5 3 5 5 5 5 4 5 - 4 5 4 5 5 4 4 1 Post 5 5 3 3 5 5 4 5 5 5 5 5 5 5 5 5 4 5 5 5 5 5 4 4 3 0.2 Pre 5 5 - - 4 4 4 5 0 5 5 5 - 3 5 - 4 4 4 5 4 4 1 0 Post 5 5 4 4 5 4 4 5 5 5 5 4 5 4 5 5 3 5 4 5 5 5 3 3 3 5.0 Pre 5 5 5 4 5 5 5 5 4 5 5 5 5 5 5 5 5 5 5 5 5 5 5 3 Post 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 4 4 5.0 Pre 0 4 0 0 2 0 1 5 1 2 2 4 3 2 4 - 0 3 1 3 3 2 0 1 Post 0 3 1 3 1 1 1 5 3 4 1 4 2 0 3 3 3 0 0 4 0 0 0 0 5 5.0 Pre 0 2 0 0 0 0 0 3 0 4 0 4 4 0 4 - 0 0 0 0 0 0 0 0 Post 1 2 0 1 2 0 0 3 0 2 0 4 1 0 2 0 0 3 0 2 0 1 0 0 TABLE III CONTINUED.
Rate Of Pre- Or Test Plants Compound Application Post-Emergence No. kg/ha Application Sb Rp Ct Sy Mz Ww Rc Sn Ip Am Pi Ca Po Xs Ab Cv Ot/Av Dg Pu St Ec Sh Ag Cn 6 3.0 Pre 4 4 3 3 5 4 4 5 3 4 4 5 5 3 5 - 4 4 4 5 5 3 0 0 Post 2 4 2 2 3 2 2 5 4 5 5 5 3 2 4 4 0 3 0 4 0 3 0 0 7 0.25 Pre 3 5 0 2 3 2 3 4 0 5 4 4 5 0 3 - 1 4 1 5 4 2 0 0 Post 1 2 1 1 1 0 0 5 3 5 4 3 5 2 0 4 0 4 0 1 0 0 0 0 7 2.5 Pre 5 5 3 3 5 5 5 5 3 5 5 5 5 5 5 - 5 5 5 5 5 5 4 1 Post 5 5 4 4 5 4 4 5 5 5 5 5 5 4 5 5 4 5 4 5 5 5 3 1 8 1.0 Pre 5 5 0 4 4 4 4 5 1 5 - 5 - 4 - - 5 5 - 5 5 5 0 Post 4 4 4 4 4 4 4 5 5 5 4 4 - 5 5 - 4 5 - 5 4 5 3 1 9 1.0 Pre 5 4 0 0 3 2 1 5 1 5 - 5 - 2 - - 2 1 - 4 3 3 0 Post 4 3 4 4 4 3 3 5 4 5 4 4 - 4 4 - 2 4 - 4 1 3 1 0 10 1.0 Pre 3 3 0 1 2 0 0 4 2 5 - 5 - 0 2 - 1 0 - 1 1 0 0 Post 1 4 2 4 4 2 4 5 4 5 3 3 - 4 4 - 1 3 - 3 3 4 1 0 11 1.0 Pre 5 5 1 2 4 3 3 5 3 5 - 5 - 4 - - 3 5 - 5 4 4 0 Post 4 5 4 4 3 3 2 5 4 5 4 4 - 4 4 - 3 4 - 4 3 4 2 0 12 1.0 Pre 5 4 0 1 4 2 0 5 1 5 - 5 - 1 - - 3 4 - 4 4 3 0 Post 4 2 3 4 3 3 1 5 4 4 3 4 - 4 4 - 3 4 - 3 3 3 1 0 TABLE III CONTINUED.
Rate Of Pre- Or Test Plants Compound Application Post-Emergence No. kg/ha Application Sb Rp Ct Sy Mz Ww Rc Sn Ip Am Pi Ca Po Xa Ab Cv Ot/Av Dg Pu St Ec Sh Ag Cn 13 1.0 Pre 3 2 0 0 1 0 0 4 0 5 - 5 - 1 - - 0 0 - 2 0 0 0 Post 4 3 3 3 4 3 @ 5 4 5 3 4 - 4 4 - 2 4 - 4 3 3 1 0 * 1.0 Pre 5 5 5 4 5 5 5 5 5 5 - 5 - 5 5 - - 5 5 - 5 5 5 4 Post 4 5 4 4 4 4 5 5 5 5 - 5 - 5 5 - 4 5 - 5 5 5 4 * This' compound is the imide corresponding to compound 3.
Claims (9)
1. A diphenyl ether compound of the formula (I)
wherein A is hydrogen, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, or alkyl of 1 to 4 carbon atoms;
B is fluorine, chlorine, bromine, iodine or trifluoromethyl;
C is hydrogen, fluorine, chlorine, bromine, iodine, or trifluoromethyl;
D is hydrogen, fluorine, chlorine, bromine, iodine or nitro;
R', R2, and R3 each represent an alkyl radical of 1 to 4 carbon atoms optionally substituted by phenyl, or R1 represents an alkyl of 1 to 4 carbon atoms optionally substituted by phenyl and R2 and R3 together with the nitrogen atom to which they are attached form a five or six membered heterocyclic ring;
and X- is an agriculturally acceptable anion; or an imide derivative of the compound of formula (I) in which the elements of HX have been removed from formula (I).
2. A compound as claimed in claim 1 wherein the groups R1, R2, and R3 are all methyl radicals.
3. A compound as claimed in claim 1 or claim 2 wherein A is chlorine or nitro, B is chlorine or trifluoromethyl, C is hydrogen, and D is chlorine, bromine, or nitro.
4. A compound as ciaimed in claim 1 wherein A is chlorine, B is trifluoromethyl, C is hydrogen, D is nitro, and R1, R2 and R3 are all methyl radicals.
5. A compound as claimed in any of claims 1 to 4 wherein X is chloride, bromide, phosphate, nitrate, sulphate, methylsulphate, orp-toluenesulphonate.
6. A process of inhibiting the growth of unwanted plants, which comprises applying to the plants, or to the locus thereof, a compound of the formula (I) as defined in claim 1.
7. A herbicidal composition comprising as an active ingredient at least one compound of formula (I) as defined in claim 1, in admixture with a carrier comprising a solid or liquid diluent.
8. A composition as claimed in claim 7 which further comprises a surface-active agent.
9. A process of preparing a compound of the formula (I) defined in claim 1 , which comprises reacting a 2-D-5-(2-A-4-B-6-C substituted-phenoxy) benzoyl chloride with a hydrazine R'R2N.NH2 in the presence of an acid acceptor, reacting the hydrazide derivative so obtained with a quaternising agent comprising an alkyl halide R3Hal, an alkyl sulphate (R30)2SO4, or an alkyl ptoluenesulphonate R30S02C6H4.CH3p, recovering the hydrazinium quaternary salt, and, if desired, treating the hydrazinium quaternary salt with a base and recovering the corresponding imide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8018916A GB2056438A (en) | 1979-07-18 | 1980-06-10 | Herbicidal diphenyl ether compounds |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7925034 | 1979-07-18 | ||
| GB8018916A GB2056438A (en) | 1979-07-18 | 1980-06-10 | Herbicidal diphenyl ether compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2056438A true GB2056438A (en) | 1981-03-18 |
Family
ID=26272225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8018916A Withdrawn GB2056438A (en) | 1979-07-18 | 1980-06-10 | Herbicidal diphenyl ether compounds |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2056438A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0142248A2 (en) * | 1983-10-14 | 1985-05-22 | Fbc Limited | Herbicidally active pyridinyloxy- or phenoxy-phenyl derivatives |
| GB2183231A (en) * | 1985-11-22 | 1987-06-03 | Ici Plc | Herbicidal fluoro-diphenyl ether derivatives |
-
1980
- 1980-06-10 GB GB8018916A patent/GB2056438A/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0142248A2 (en) * | 1983-10-14 | 1985-05-22 | Fbc Limited | Herbicidally active pyridinyloxy- or phenoxy-phenyl derivatives |
| EP0142248A3 (en) * | 1983-10-14 | 1986-01-02 | Fbc Limited | Herbicidally active pyridinyloxy- or phenoxy-phenyl derivatives |
| US4602944A (en) * | 1983-10-14 | 1986-07-29 | Fbc Limited | Herbicidal pyridinium compounds and compositions |
| GB2183231A (en) * | 1985-11-22 | 1987-06-03 | Ici Plc | Herbicidal fluoro-diphenyl ether derivatives |
| JPS62135452A (en) * | 1985-11-22 | 1987-06-18 | インペリアル・ケミカル・インダストリ−ズ・ピ−エルシ− | Diphenyl ether compound, manufacture and herbicidal composition |
| EP0228788A1 (en) * | 1985-11-22 | 1987-07-15 | Imperial Chemical Industries Plc | Herbicidal derivatives of substituted benzoyl-hydrazinium compounds |
| GB2183231B (en) * | 1985-11-22 | 1989-11-08 | Ici Plc | Herbicidal fluorodiphenyl ether derivatives |
| US4992089A (en) * | 1985-11-22 | 1991-02-12 | Imperial Chemical Industries Plc | Herbicidal compounds, compositions and use |
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| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |