GB1560416A

GB1560416A - Trifluoromethylphenyl derivatives

Info

Publication number: GB1560416A
Application number: GB3548976A
Authority: GB
Original assignee: Rohm and Haas Co
Current assignee: Rohm and Haas Co
Priority date: 1975-09-03
Filing date: 1976-08-24
Publication date: 1980-02-06
Also published as: DE2639796A1; IT1070303B

Description

(54) TRIFLUOROMETHYLPHENYL DERIVATIVES (71) We, ROHM AND HAAS COMPANY, a corporation organized under the laws of the State of Delaware, United States of America, of Independence Mall West, Philadelphia, Pennsylvania 19105, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention concerns novel trifluoromethylphenyl derivatives which show activity as herbicides, to novel herbicidal compositions which contain these derivatives, and to methods of controlling weeds with these herbicidal compositions.

Certain diphenyl ethers have been shown to be effective weed control agents.

However, the herbicidal effectiveness of a given diphenyl ether cannot be predicted from an examination of the substituent groups attached to the phenyl rings in the ether, and often quite closely related compounds will have quite different weed control abilities. Various diphenyl ethers may have overlapping or complementary areas of activity or selectivity, and can thus be useful in combination to control a variety of weeds upon application of a single composition.

Furthermore, the diphenyl ethers heretofore disclosed as herbicides are not completely effective. An ideal herbicide should give selective weed control, over the full growing season, with a single administration at low rates of application. It should be able to control all common weeds by killing them as the seed, the germinating seed, the seedling, and the growing plant. At the same time, the herbicide should not be phytotoxic to the crops to which it is applied and should decompose or otherwise be dissipated so as not to poison the soil permanently. The known diphenyl ether herbicides fall short of these ideals, and it would thus be desirable to have new herbicides which show even more selective control of undesirable plants among desirable crop plants or which complement the known diphenyl ethers in activity.

In accordance with the present invention, there is provided a new class of novel diphenyl ethers having the formula

wherein R' is hydrogen or halogen, R2 is hydrogne or halogen, R is a group of the formula

wherein R3 is hydrogen, halogen, nitro, (C1-C4)alkyl, or (C1-C4)alkoxy, R4 is a divalent (C1-C5)alkylene group, R5 is cyano or a group of the formula -COR6, wherein R6 is (C1-C6)alkoxy, hydroxy (or an agronomically-acceptable salt thereof), amino, (C1-C4)alkylamino, or di(C1-C4)alkylamino, and Z is oxygen, sulfur, sulfinyl or sulfonyl.

In a modification of the class of compounds of Formula I, R4 can also represent a divalent alkenylene group of up to 5 carbon atoms and/or R6 can also represent amino(C1-C4)alkoxy, (C1-C4)alkylamino(C1-C4)alkoxy or di (C1-C4)alkylamino(C1-C4)alkoxy.

In another modification of the class of compounds of Formula I, wherein R5 is cyano, R2 (when a substituent) can occupy any vacant position in the ring and it can also represent cyano.

In yet a third modification of the class of compounds of Formula I, wherein X in sulfur, sulfinyl or sulfonyl, one or more of the following modifications are within the scope of the invention viz: (a) R can also represent cyano, nitro, (C1-C4)alkyl or trifluoromethyl, (b) the mandatory CF3 substituent can occupy any vacant position in the ring, (c) R2 (when a substituent) can occupy any vacant position in the ring and can also represent cyanc, (d) R3 (when a substituent) can occupy any vacant position in the ring and (e) R0 can also represent (C1-C8)alkoxy, allyloxy (C1-C4)alkoxy(C1-C4)alkoxy, amino(C1-C4)alkoxy, (C1-C4)alkyl- amino(C1-C4)alkoxy or di(C1-C4)alkylamino(C1-C4)alkoxy.

The alkyl or alkylene portions of the alkyl or alkylene-containing R , R6, R7, and R8 substituents as well as the group of R4 can have either a straight- or branched-chain spatial configuration.

These novel compounds have been found to show unexpected activity as selective weed control agents and the compounds of Formula I in which Z is S, SO or SO2 and the compounds of the third modified class of compounds of Formula I defined above, have particular utility in selective weed control in comparison with the wide general class of diphenyl sulfides, sulfoxides and sulfones disclosed in West German Offenlegungsschrift 2,355,115.

In the diphenyl ethers of the invention, it is preferred (a) that, when R5 is a cyano group, R2 and R3 are hydrogen atoms and R4 is a group of the formula -CHR7-, wherein R7 is a hydrogen atom or a (C1-C4)alkyl group, preferably a methyl group, and (b) that, when R5 is a group of the formula -COR6, R4 is a group of the formula CHR7CH2(CH2)n, wherein R7 is as defined above and is preferably a methyl group, and n is 0 or 1.

When Z is other than oxygen, there may be mentioned a sub-class of compounds of the invention wherein R1 is chlorine or cyano, R2 and R3 are each hydrogen and R4 is a group of the formula -CHR7- wherein R7 is as above defined, eg the group -CH(CH3W.

Typical salts embraced by Formula I i.e. salts of those compounds in which R6 is a hydroxy group, include alkali metal salts, such as sodium and potassium salts, alkaline earth metal salts, such as calcium and barium salts, heavy metal salts, such as copper and zinc salts, amine salts, such as ammonium, ethanolammonium, diethanolammonium, triethanolammonium, triethylammonium, dimethylammonium, diisopropylammonium, t-butylammonium, t-octylammonium, and similar agronomically-acceptable salts.

Examples of compounds of the invention include: LIST A.

Propyl 2-[4-(2-chloro-4-trifluoromethylphenoxy)phenoxy] acetate Ethyl 2-[3-(2-chloro-4-trifluoromethylphenoxy)phenoxy] propionate Methyl 2-[3-(2-chloro-4-trifluoromethylphenoxy)phenoxy] butyrate Ethyl 2- [4-(2-chloroA-trifluoromethylphenoxy)-2-meth9xyphenoxyi propionate Isopropyl 2-[4-(2-chloro-4-trifluoromethylphenoxy)-2-nttrophenoxy] butyrate Methyl 2-[4-(2-ch loro-4-trifluoromethylphenoxy)-2-ethoxyphenoxyl propionate Methyl 2-[4-(2,6-dichloro-4-trifluoromethylphenoxy)-2-ethoxyphenoxyj propionate Ethyl 2-[4-(2-chloro-6-fluoro-4-trifiuoromethylphenoxy)phenoxy] propionate Methyl 2-[4-(4-trifluoromethylphenoxy)phenoxy] crotonate 2-[4-(2-chloro-4-trifluoromethylphenoxy)-2-methoxyphenoxy] butyric acid Ethyl 2-[4-(2-chloro-4-trifluoromethylphenylthio)phenoxyl propionate Methyl 2- [4-(2-chloro-4-trifluoromethylph enoxy)-2-chlorophenoxy] propionate 2-[4-(2-chloroA4rifluornmethylphenoxy)phenoxyi propionitrile 2- [4-(2-chloro-4-triflu oromethylphenoxy)-2-methylphenoxy] acetonitrile 2-[4-(2-chloro-4-trifiuoromethylphenoxyj-2-chlorophenoxy] propionitrile 2-[4-(2-ChloroA-trifluoromethylphenoxy)-2-methoxyphenoxy] butyronitrile N,N-Dimethyl 2- [4-(2-chloro-4-trifluoromethylphenoxy)-2-methylphenoxyi butyramide N,N - Di - sec - butyl 2 - [4 - (2 - chloro - 4 - trifluoromethylphenoxy) - 2 - chloro phenoxy] acetamide N-Ethyl 2-[4-(2-chloro-4-trifluoromethylphenylsulfinyl)-phenoxy] butyramide N - Methyl 2 - [4 - (2 - chloro - 4 - trifluoromethylphenylsulfonyl) - 2 - methyl phenoxy] crotonamide LIST B.

Ethyl 2-[4-(3-trifluoromethylphenylthio)phenoxy propionate 2- [4-(3-Trifluoromethylphenylsulfinyl)phenoxy3 propionic acid Triethanolammonium 2- [4-(2-trifluoromethylphenylsulfonyl)phenoxyl propionate Ethyl 3-[4-(2-methoxy-4-trifluoromethylphenylthio)phenoxy] propionate 2- [4-(2-Nitro-4-trifluoromethylphenylsulfinyl)phenoxyl propionitrile Isobutyl 2- [4-(2-ethyl-4-trifluoromethylphenylsulfonyl)phenoxy] butyrate 2-[4-(2-Cyano-4-trifluoromethylphenoxy)phenoxy]propionic acid The novel compounds of the invention are useful both as selective preemergence and, preferably, as postemergence herbicides. Preemergence herbicides are ordinarily used to treat the soil in which the desired crop is to be planted by application either before seeding, during seeding, or as in most applications after seeding and before the crop emerges. Postemergence herbicides are those which are applied after the plants have emerged and during their growth period. The compounds of the invention are most effective against monocot weed species, and can be advantageously employed to control monocot weeds in such crops as soybeans, peanuts, cotton, wheat, barley and rice.

The novel compounds of the invention are usually used to combat weeds, i.e. kill weeds or inhibit the growth thereof, by applying one or more of the compounds (a) to the growth medium prior to the emergence from such medium or (b) to weed seedlings. The amount of active compound(s) used will, of course, be sufficient to combat the growth of the weeds. Most usually the compounds of the invention will be applied to an area yielding an agronomic crop.

The compounds of the invention can be applied in any amount which will give the required control of weeds. A preferred rate of application of the herbicides of the invention is from about 1/16 to about 8 pounds of the active compound per acre, and most preferably about 1/4 to about 2 pounds of the active compound per acre.

Under some conditions, the compounds of the invention may be advantageously incorporated into the soil or other growth medium prior to planting a crop. This preplant incorporation can be carried out by any convenient means, including by simple mixing with the soil, by applying the herbicide to the surface of the soil and then disking or dragging into the soil to the desired depth, or by employing a liquid carrier to accomplish the necessary penetration and impregnation.

The compounds of the invention can be applied to the growth medium or to plants to be treated either alone or, as is generally done, as components in herbicidal compositions or formulations which also comprise an agronomicallyacceptable carrier. By agronomically-acceptable carrier is meant any substance which can be used to dissolve, disperse, or diffuse a herbicidal compound in the composition without impairing the effectiveness of the herbicidal compound and which by itself has no detrimental effect on the soil, equipment, crops, or agronomonic environment. Mixtures of the diphenyl ethers of the invention may also'be used in any of these herbicidal formulations. The herbicidal compositions of the invention can be either solid or liquid formulations or solutions. For example, the diphenyl ethers can be formulated as wettabie powders, emulsifiable concentrates, dusts, granular formulations, aerosols, or flowable emulsion concentrates. In such formulations, the compounds are extended with a liquid or solid carrier and, when desired, suitable surfactants are incorporated.

It is usually desirable, particularly in postemergence -applications, to include adjuvants, such as wetting agents, spreading agents, dispersing agents, stickers and adhesives in accordance with agricultural practices. Examples of adjuvants which are commonly used in the art can be found m the John W. McCutcheon, Inc. publication "Detergents and Emulsifiers Annual." The compounds of this invention can be dissolved in any appropriate solvent.

Examples of solvents which are useful in the practice of this invention include alcohols, ketones, aromatic hydrocarbons, halogenated hydrocarbons, dimethylformamide, dioxane and dimethyl sulfoxide. Mixtures of these solvents can also be used. The concentration of the solution can vary from about 2% to about 98% with a preferred range being about 25% to about 75%.

For the preparation of emulsifiable concentrates, the active compound can be dissolved in organic solvents, such as benzene, toluene, xylene, methylated naphthalene, corn oil, pine oil, o-dichlorobenzene, isophorone, cyclohexanone and methyl oleate, or in mixtures of these solvents, together with an emulsifying agent which permits dispersion in water. Suitable emulsifiers include, for example, the ethylene oxide derivatives of alkylphenols or long-chain alcohols, mercaptans, carboxylic acids, and reactive amines and partially esterified polyhydric alcohols.

Solvent-soluble sulfates or sulfonates, such as the alkaline earth salts or amine salts of alkylbenzenesulfonates and the fatty alcohol sodium sulfates, having surfaceactive properties can be used as emulsifiers either alone or in conjunction with an ethylene oxide reaction product. Flowable emulsion concentrates are formulated similarly to the emulsifiable concentrates and include, in addition to the above component water and a stabilizing agent such as a water-soluble cellulose derivative or a water-soluble salt of a polyacrylic acid. The concentration of the active ingredient in emulsifiable concentrates is usually about 10% to 60% and in flowable emulsion concentrates, this can be as high as about 75%.

Wettable powders suitable for spraying, can be prepared by admixing the compound with a finely divided solid, such as clays, inorganic silicates and! carbonates, and silicas and incorporating wetting agents, sticking agents, and/or dispersing agents in such mixtures. The concentration of active ingredients in such formulations is usually in the range of about 20% to 98%, preferably about 40% to 75% by weight. A dispersing agent can constitute, about 0.5% to about 3% by weight of the composition, and a wetting agent can constitute from about 0.1% to about 5% by weight of the composition.

Dusts can be prepared by mixing the compounds of the invention with finely divided inert solids which may be organic or inorganic in nature. Materials useful for this purpose include, for example, botanical flours, silicas, silicates, carbonates and clays. One convenient method of preparing a dust is to dilute a wettable powder with a finely divided carrier. Dust concentrates containing about 20, to 80% by weight of the active ingredient are commonly made and are subsequently diluted to about 1% to 10% by weight use concentration. Granular formulations can be prepared by impregnating a solid such as granular fuller's earth, vermiculite, ground corn cobs, seed hulls, including bran or other grain-hulls, or similar material. A solution of one or more of the active compounds in a volatile organic solvent can be sprayed or mixed with the granular solid and the solvent then removed by evaporation. The granular material can have any suitable size, with a preferable size range of 16 to 60 mesh (U.S. Standard Sieve Series). The active compound will usually comprise about 2 to 15% by weight of the granular formulation.

The compounds of the invention can also be mixed with fertilizers or fertilizing materials before their application. In one type of solid fertilizing composition in which the compounds of the invention can be used, particles of a fertilizer or fertilizing ingredients, such as ammonium sulfate, ammonium nitrate, or ammonium phosphate, can be coated with one or more of the ethers. The solid compounds and solid fertilizing material can also be admixed in mixing or blending equipment, or they can be incorporated with fertilizers in granular formulations.

Any relative proportion of herbicide and fertilizer can be used which is suitable for the crops and weeds to be treated. The active compound will commonly be from about 5% to about 25% of the fertilizing composition. These compositions provide fertilizing materials which promote the rapid growth of desired plants, and at the same time control the growth of undesired plants.

The compounds of the invention can be applied as herbicidal sprays by methods commonly employed, such as convention high-gallonage hydraulic sprays, low gallonage sprays, airblast spray, aerial sprays and dusts. For low volume applications a solution of the compound is usually used. The dilution and rate of application will usually depend upon such factors as the type of equipment employed, the method of application, the area to be treated and the type and stage of development of the weeds.

For some applications, it may be desirable to add one or more other herbicides along with compounds of the invention. Examples of other herbicides which can be incorporated to provide additional advantages and effectiveness include: Carboxylic Acids and Derivatives.

2,3,6-trichlorobenzoic acid and its salts 2,3,5,6-tetrachlorobenzoic acid and its salts 2-methoxy-3,5,6-trichlorobenzoic acid and its salts 2-methoxy-3,6-dichlorobenzoic acid and its salts 2-methyl-3,6-dichlorobenzoic acid and its salts 2,3-dichloro-6-methylbenzoic acid and its salts 2,4-dichlorophenoxyacetic acid and its salts and esters 2,4,5-trichlorophenoxyacetic acid and its salts and esters 2-methyl-4-chlorophenoxyacetic acid and its salts and esters 2-(2,4,5-trichlorophenoxy)propionic acid and its salts and esters 2-(2,4-dichlorophenoxy)butyric acid and its salts and esters 4-(2-methyl-4-chlorophenoxy)butyric acid and its salts and esters 2,3,6-trichlorophenylacetic acid and its salts 3,6-endoxohexahydrophthalic acid dimethyl 2,3,5,6-tetrachloroterephthalate trichloroacetic acid and its salts 2,2-dichloropropionic acid and its salts 2,3-dichloroisobutyric acid and its salts Carbamic Acid Derivatives. ethyl N,N-di(n-propyl)thiolcarbamate propyl N,N-di(n-propyl)thiolcarbamate ethyl N-ethyl-N-(n-butyl)thiolcarbamate propyl N-ethyl-N-(n-butyl)thiolcarbamate 2-chloroallyl N,N-diethyldithiocarbamate N-methyldithiocarbamic acid salts S-ethyl hexahydro- 1 H-azepine- 1 -carbothioate S-4-chlorobenzyl N,N-diethylthiocarbamate isopropyl N-phenylcarbamate isopropyl N-(m-chlorophenyl)carbamate 4-chloro-2-butyl N-(m-chlorophenyl)carbamate methyl N-(3,4-dichlorophenyl)carbamate methyl sulfanilylcarbamate Phenols. dinitro-o-(sec-butyl)phenol and its salts pentachlorophenol and its salts Substituted Ureas.

3-(3,4-dichlorophenyl) 1,1 -dimethylurea 3-phenyl-l , l-dimethylurea 3-(3 ,4-dichlorophenyl)-3 -methoxy- 1,1 -dimethylurea 3-(4-chlorophenyl)-3-methoxy- 1,1 -dimethylurea 3-(3 ,4-dichlorophenyl)- 1 -n-butyl- 1 -methylurea 3-(3,4-dichlorophenyl)- 1 -methoxy-1 -methyl urea 3-(4-chlorophenyl)- 1 -methoxy- 1 -methylurea 3-(3,4-dichlorophenyl)-1,1,3-trimethylurea 3-(3,4-dichlorophenyl)-1,1-diethylurea 1-(2-methylcyclohexyl)-3-phenylurea 1-(5-t-butyl-1,3,4-thiadiazol-2-yl)-1,3-dimethylurea 3-(3-chloro-4-methylphenyl)- 1,1 -dimethylurea 3-(3-chloro-4-methoxyphenyl)- 1,1 -dimethylurea dichloral urea Substituted Triazines.

2-chloro-4,6-bis(ethylamino)s-triazine 2-chloro-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4,6-bis(methoxypropylamino)-s-triazine 2-methoxyA,6-bis(isopropylamino)-s-triazine 2-methylmercapto-4,6-bis(isopropylamino)-s-triazine 2-methylmercapto-4,6-bis(ethylamino)-s-triazine 2-methylmercapto-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4,6-bis(isopropylamino)-s-triazine 2-methoxy-4,6-bis(ethylamino)-s-triazine 2-methoxy-4-ethylamino-6-isopropylamino-s-triazine 2-methylmercapto-4-(2-methoxyethylamino)-6-isopropylamino-s-triazine 2-(4-chloro-6-ethylamino-s-triazine-2-yl)amino-2-methylpropionitrile 4-amino-6-t-butyl-3-methylthio-1,2,4-triazine-5(4H)-one 3-cyclohexyl-6-dimethylamino- 1 -methyl-s-triazine-2,4-( 1 H,3 H)-dione Diphenyl Ether Derivatives.

2,4-dichloro-4'-nitrodiphenyl ether 2,4,6-trichloro-4'-nitrodiphenyl ether 2,4-dichloro-6-fluoro-4'-nitrodiphenyl ether 3-methyl-4'-nitrodiphenyl ether 3,5-dimethyl-4'-nitrodiphenyl ether 2,4'-dinitro-4-trifluoromethyldiphenyl ether 2,4-dichloro-3'-methoxy-4'-nitrodiphenyl ether 2-chloro-4-trifluoromethyl-4'-nitrodiphenyl ether 2-chloro-4-trifluoromethyl-3'-ethoxy-4'-nitrodiphenyl ether 2-chloro-4-trifluoromethyl-3'-carbethoxy-4'-nitrodiphenyl ether 2-chloro-4-trifluoromethyl-3'-(1-carbethoxy)ethoxy-4'-nitrodiphenyl ether Anilides.

N-(3,4-dichlorophenyl)propionamide N-(3,4-dichlorophenyl)methacrylamide N-(3-chloro-4-methylphenyl-2-methylpentanamide N-(3,4-dichlorophenyl)trimethylacetamide N-(3,4-dichlorophenyl)-α,α-dimethylvaleramide N-isopropyl-N-phenylchloroacetamide N-n-butoxymethyl-N-(2,6-diethylphenyl)chloroacetamide N-n-methoxymethyl-N-(2,6-diethylphenyl)chloroacetamide Uracils.

5-bromo-3-s-butyl-6-methyluracil 5-bromo-3-cyclohexyl- 1 ,6-dimethyluracil 3-cyclohexyl-5,6-trimethyleneuracil 5-bromo-3-isopropyl-6-methyluracil 3-tert-butyl-5-chloro-6-methyluracil Nitriles.

2,6-dichlorobenzonitrile diphenylacetonitrile 3,5-dibromo-4-hydroxybenzonitrile 3,5-diiodo-4-hydroxybenzonitrile Other Organic Herbicides.

2-chloro-N,N-diallylacetamide N-(1,1-dimethyl-2-propnyl)-3,5-dichlorobenzamide maleic hydrazide 3-amino-I ,2,4-triazole monosodium methanearsonate disodium methanearsonate N,N-dimethyl-a,a-diphenylacetamide N,N-di(n-propyl)-2,6-dinitro-4-trifluoromethylan iline N,N-di(n-propyl)-2,6-dinitro-4-methylaniline N,N-di(n-propyl)-2,6-dinitro-4-methylsulfonylaniline O-(2,4-dichlorophenyl)-O-methyl-isopropylphosphoramidothioate 4-amino-3,5,6-trichloropicolinic acid 2,3-dichloro- 1 ,4-naphthoquinone di(methoxythiocarbonyl)disulfide 3-isopropyl-1H-2,1,3-benzothiadiazine-(4)3H-one-2,2-dioxide 6,7-dihydrodipyridol[1,2-a:2';I'-c]pyrazidinium salts 1,1 '-dimethyl-4,4'-bipyridinium salts 3,4,5,6-tetrahydro-3,5-dimethyl-2-thio-2H-1,3,5-thiadiazine 1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate N-sec-butyl-2,6-dinitro-3,4-xylidine N-sec-butyl-4-t-butyl-2,6-dinitroaniline N3,N3-diethyl-2,4-dinitro-6-trifluoromethyl- 1 ,3-phenylenediamine 1,1,1 -trifluoro(4'-phenylsulfonyl)meth anesulfono-o-toluidine 2-( 1 -naphthoxy)-N,N-diethylpropionamide 2-t-butyl-4-(2,4-dichloro-5-isopropoxyphenyl)- 1 ,3,4-oxadiazolin-5-one 4-chloro-5-methylamino-2-(α,α,α-trifluoro-m-tolyl)3(2H)-pyridazinone N-cyclopropylmethyl-α,α,α-trifluoro-2,6-dinitro-N-propyl-p-toluidine N-phosphonomethylglycine When mixtures of herbicides are employed, the relative proportions which are used will depend upon the crop to be treated and the degree of selectivity in weed control which is desired.

The compounds of the invention or their precursors can be prepared by several different reaction routes. In one typical synthetic method a halobenzene of the formula

wherein R' and R2 are as defined above and X' is a halogen atom, is reacted with a phenol (or a salt thereof) of the formula

wherein R3 is as defined above and Z1 is an oxygen atom or a sulfur atom, to form a compound of the formula

wherein R1, R2, R3, and Z1 are as defined above. The reaction with a phenol is generally carried out at a temperature of 25 to 1500C., in the presence of a base such as potassium hydroxide, sodium hydroxide, potassium carbonate or sodium carbonate, with an aprotic polar solvent, such as dimethylsulfoxide, dimethylformamide, sulfolane, hexamethylphosphoric triamide or l-methyl-2pyrrolidinone. The phenol of Formula VI (or salt thereof) is then reacted with a compound of the formula Y-R4-R5 (VII) wherein Y is a chlorine or bromine atom, and R4 and R5 are as defined above. This reaction is generally carried out at a temperature of 25 to 1400C., in the presence of a base, such as potassium hydroxide, sodium hydroxide, potassium carbonate or sodium carbonate, with an aprotic polar solvent, such as dimethylsulfoxide, dimethylformamide, dioxane, a ketone, (such as acetone or methyl ethyl ketone), acetonitrile ethylene glycol dimethyl ether or tetrahydrofuran.

The phenol of Formula VI can also be prepared by reacting a compound of Formula IV with a compound of the formula

wherein R3 is defined above and R'O is an allyl group or a benzyl group, this reaction is carried out under the same conditions as the reaction of compounds IV and V. The resultant diphenyl ether is then hydrogenated using a hydrogen or catalyst (such as palladium on charcoal or platinum oxide) in an alcohol (such as methanol or - ethanol, ethyl acetate or acetic acid) as a solvent, at ambient temperatures, or at a temperature of O to 12()0C, to yield the phenol.

Compounds of the invention in which R3 is a halogen atom, a nitro group, or a (C1C4)alkyl group can also be prepared by reacting a compound of Formula IV with a compound of the formula

to give a compound of the formula

using the same general conditions as the reaction of compounds IV and V. The desired compound can then be obtained by direct electrophilic halogenation, nitration, or alkylation of the compound of Formula X. Typical halogenations can be carried out by reaction with an excess or equimolar amount of a halogenating agent, such as chlorine, in the presence of a transition metal chloride, such as ferric chloride, as a catalyst, in an inert solvent such as chlorobenzene, ethylene dichloride, or chlorinated hydrocarbon, at a temperature of 25 to 1200C. Typical nitrations can be carried out with an excess or equimolar amount of a nitrating agent, such as nitric acid, in sulfuric acid or acetic anhydride/sulfuric acid, optionally with an appropriate inert solvent, at a temperature of 25 to 1200C.

Typical alkylations can be carried out by reaction with an excess or equimolar amount of an appropriate alkylating agent, such as lower alkyl chloride, bromide, or iodide, in the presence of a Lewis acid catalyst (such as ferric chloride, titanium chloride, aluminum. trichloride or stannic chloride), in an inert solvent (such as carbon disulfide, ethylene dichloride or perchioroethylene), at a temperature of 25 to 120"C.

The compounds of the invention in which R5 is a carboxy group can be prepared by hydrolyzing a compound in which R6 is a cyano group, a carbamoyl group or a carbalkoxy (otherwise termed alkoxycarbonyl) group. The hydrolysis can be either acid catalyzed, using sulfuric acid, anhydrous hydrochloric acid in methanol, acetic acid/boron trifluoride, or similar acid catalyst, or base catalyzed using potassium hydroxide in methanol, barium hydroxide in methanol, or similar base catalyst, optionally with an appropriate inert solvent, at a temperature of 20 to 130"C. Suitable reaction conditions for carrying out the desired hydrolysis can be varied, depending on the group to be hydrolyzed and the various substituents on the diphenyl ether or diphenyl sulfide nucleus, and such modifications will be -apparent to those skilled in the art.

The diphenyl sulfides of the invention can also be prepared by reacting a thiophenol of Formula V in which Z' is a sulfur atom with cuprous oxide to produce the cuprous salt of the thiophenol. This reaction can be carried out, for example, in refluxing ethanol. The cuprous salt is generally not isolated, but reacted directly with a halobenzene of Formula IV in which X' is a bromine atom, in a solvent (such as quinoline or dimethylformamide) in the presence of a nitrogen base (such as pyridine) at a temperature of 50 to 1000C. The resulting phenol is then further reacted as noted above to produce the desired diphenyl sulfide. Other suitable methods for preparing the diphenyl sulfides of the invention include displacement of aromatic diazonium salts with a salt, such as a sodium salt. of a thiophenol of Formula V. Diphenyl sulfides, sulfoxides, and sulfones of the invention can also be prepared by the reaction of an appropriate aromatic sulfenyl, sulfinyl, or sulfonyl halide with a substituted phenol or anisole.

The compounds of the invention in which Z is a sulfinyl group can be prepared by oxidizing the corresponding diphenyl sulfide of Formula VI or X using an oxidizing agent such as an excess or equimolar amount of sodium periodate in methanoVwater, at 0 to 600 C, or one equivalent of hydrogen peroxide in acetic acid, at I

Example 11.

Preparation of 2- [4-(44rifluoromethylphenoxy)phenoxy] propionitrile.

A solution containing 6.2 g (0.02 mole) of 2-[4-(4-trifluoromethylphenoxy)- phenoxyl propanamide and 10.0 ml of phosphorus oxychloride in 50 ml of toluene is stirred at 500 until reaction is complete, as indicated by vpc techniques. The reaction mixture is cooled and poured into crushed ice, whereupon the toluene is washed with water, dried, and concentrated in vacuo. Purification is effected by elution through a pad of silica gel (50% toluene/hexane) to afford a colourless solid, mp 5356 .

Example 12.

Preparation of Ethyl 2-[3-(2-chloro-4-trifluoromethylphenoxy)phenoxy] propionate Preparation A.

3-(2-Chloro-4-trifluoromethylphenoxy) phenol (14.4 g., 0.05 mole), dimethyl sulfoxide (100 ml.) anhydrous potassium carbonate (13.8 g., 0.10 mole, excess) and ethyl 2-bromopropionate (9.05 g., 0.05 mole) are charged to a flask equipped with a stirrer, condenser and drying tube and stirred at room temperature for five days.

The reaction mixture is then poured into water (600 ml.) and the aqueous mixture extracted with carbon tetrachloride (2 x 200 ml.) and the combined carbon tetrachloride extract are again washed with water (200 ml.), dried with anhydrous sodium sulfate, and reduced in vacuo (0.10 mm) to give the desired product (15.2 g., 78% yield). Nmr analysis confirmed only O-alkylation and gas-liquid chromatographic analysis suggests the expected amount of CF3- ring positional isomer. Anal. Calcd. forC18H16ClF3O4: C, 55.61; H, 4.14; C1, 9.11; F, 14.66. Found: C,55.27; H, 4.14; Cl, 9.40; F, 13.80.

Preparation B.

3-(2-Chloro-4-trifluoromethylphenoxy)phenol (14.4 g.,) 0.05 mole, dimethyl sulfoxide (50 ml.), anhydrous potassium carbonate (15.0 g., slight excess) and ethyl 2-chloropropionate (7 g., slight excess) are charged to a flask equipped with a stirrer, condenser, drying tube and thermometer and- the reaction mixture is warmed to 100--1050C. After 2-1/2 hours at 100--1050C, gas-liquid chromatographic analysis of an aliquot (diluted with water and extracted into carbon tetrachloride) indicate the reaction is complete (product eluting at 2450 C).

Example 13.

Preparation of Ethyl 2 - [4 - (2 - Chloro - 4 - trifluoromethylphenylthio)phenoxy] propionate.

To a stirred solution containing 12.6 g. (0.1 mole) of 4-mercaptophenol in 75 ml. of dimethylformamide is added 6.6 g. (0.1 mole) of 85% potassium hydroxide pellets in one portion at 250 The resultant mixture is heated until all of the potassium hydroxide has dissolved, whereupon it is cooled to about 80" and 21.6 g.

(0.1 mole) of 3,4-dichlorobenzotrifluoride is added over a period of 15 minutes. The addition is accompanied by an immediate precipitation of potassium chloride. The resultant slurry is heated at 1000 to effect complete reaction, at which time it is cooled to 25 , diluted to a volume of 300 ml. with a dilute hydrochloric acid solution, and extracted three times with ether. The combined organic extracts are washed with a dilute hydrochloric acid solution, water, a saturated sodium chloride solution, dried with anhydrous magnesium sulfate, and concentrated in vacuo.

Purification of the crude white solid is effected by recrystallization from hexaneether to afford 17.1 g. of 4-(2-chloro-4-trifluoromethylphenylthio)phenol, MP 118120 .

A mixture containing 6.09 g. (0.02 mole) of 4-(2-chloro-4-trifluoromethylphenylthio)phenol, 3.04 g. (0.22 mole) of potassium carbonate, 3.62 g. (0.02 mole) of ethyl 2-bromopropionate, and 100 ml. of dimethyl sulfoxide is stirred at 25 for sufficient time to affect complete reaction, as indicated by vapor-phase chromatographic techniques. Upon dilution with 500 ml. of water and 100 ml of a 3.0 molar hydrochloric acid solution the product is extracted with ether. The combined organic extracts are washed with a 5% potassium carbonate solution, water, a saturated sodium chloride solution, dried with anhydrous magnesium sulfate, and concentrated in vacuo. Removal of the last traces of solvent is accomplished by subjecting the yellow liquid to high vacuum (0.05 mm) at 700 to afford 7.95 g. of ethyl 2-[s(2-chloro-4-trifluoromethylphenylthio)phenoxy] propionate. Recrystallization from methanol affords white crystals, mp.

64.5--66.5".

Example 20.

Preparation of Ethyl 2 - [4 - (2 - nitro - 4 trifluoromethylphenylthio)phenoxy] propionate.

A mixture containing 12.6 g. (0.10 mole) of 4-mercapto phenol, 7.15 g. (0.05 mole) of copper (I) oxide, and 100 ml. of absolute ethanol is heated at reflux under an atmosphere of dry nitrogen until conversion to the copper thiophenate is complete, as indicated by discharge of the reddish color of the copper (I) oxide.

The resultant yellow mixture is cooled to 250, 27.0 g. (0.10 mole) of 4-bromo-3nitro-benzotrifluoride, 100 ml. of quinoline, and 10 ml. of pyridine are added, and the reaction vessel is equipped with a Newman still head. The reaction is now slow heated with concomitant removal of the ethanol to 900 and maintained at this temperature until the conversion is complete, as indicated by vpc techniques. The dark liquid is cooled to 70"C, cautiously poured into 500 ml of an ice cold molar hydrochloric acid solution, and filtered, whereupon the residue is extracted with several portions of ether. The combined ether extracts are washed with a 3.0 molar hydrochloric acid solution, water until neutral, a saturated sodium chloride solution, dried (magnesium sulfate), and concentrated in vacuo to afford a quantitative yield of crude product as a dark solid. Recrystallization foam etherhexane provides yellow crystals, mp 131--134" of 4-(2-nitro-4-trifluoromethylphenylthio)phenol. This phenol is then reacted with ethyl 2-bromopropionate by the procedure of Example 3 above to provide the desired ethyl 2-[4-(2-nitro-4-trifluoromethylphenylthio)phenoxy] propionate, m.p. 6364 C.

Example 47.

Preparation of Ethyl 2-[4-(2-trifluoromethylphenylsulfinyl)phenoxy]propionate.

To a stirred solution containing 7.4 g (0.020 mole) of ethyl 2-(4-(2-trifluoromethylphenylthio)phenoxy) propionate and a catalytic amount of sulfuric acid (3 drops) in 50 ml of glacial acetic acid is added a solution containing 2.23 g (0.021 mold) of 32% hydrogen peroxide in 10 ml of glacial acetic acid over a period of several minutes at 25". The resultant solution is stirred for 24 hours under ambient conditions, at which time the reaction is essentially complete. After the reaction is treated with sodium bisulfite to destroy any excess peroxide the solvent is removed in vacuo at 400 and the residue taken-up in ether. The ethereal solution is washed with a 5% potassium carbonate solution until basic, water until neutral, a saturated sodium chloride solution, dried with magnesium sulfate, and concentrated in vacuo to give 6.85 g. of material. The last traces of solvent are removed by exposure to high vacuum (0.1 mm) at 70" to afford ethyl 2-[4-(2-trifluoromethylphenylsulfinyl)phenoxy] propionate.

TABLE I Diphenyl Ethers

Ex. No. R R R4 R5 m.p. (b.p.) etc. Analysis %C %H %Cl %F %N 1 Cl Cl -CH(CH3)- -CO2C2H5 oil Calcd 51.08 3.57 16.76 13.47 Found 50.95 3.49 16.90 13.15 2 Cl OCH3 -CH(CH3)- -CO2C2H5 oil Calcd 54.49 4.33 8.46 NA Found 54.90 4.47 8.54 3 Cl NO2 -CH(CH3)- -CO2C2H5 oil Calcd 49.84 3.48 8.17 3.22 NA Found 49.77 3.97 11.21 1.99 4 Cl CH3 -CH(CH3)- -CO2C2H5 oil Calcd 56.65 4.50 8.80 NA Found 56.78 4.45 9.09 5 Cl H -CH2- -CO2C2H5 oil Calcd 54.48 3.76 9.46 15.20 Found 55.30 3.56 9.48 15.04 6 Cl H -CH(CH3)- -CN oil Calcd 56.24 3.24 10.37 16.68 Found 55.77 3.26 10.31 16.42 7 Cl H -CH2 CH=CH -CO2C2H5 oil Calcd Not analysed Found TABLE I (Continued) Ex. No. R R R4 R5 m.p. (b.p.) etc. Analysis %C %H %Cl %F %N 8 Cl H -CH(CH3) -CO2CH2CH2N(CH3)2 oil Calcd 55.63 4.90 8.21 13.20 3.24 Found 55.99 4.71 7.92 14.07 3.26 9 CN H -CH(CH3)- -CO2C2H5 oil Calcd 60.16 4.25 - 15.02 3.69 Found 50.06 4.34 - 14.73 3.92 10 Cl H -CH(CH3)CH2CH2- -CO2C2H5 oil Calcd 57.63 4.84 8.51 13.67 Found 55.49 4.15 9.17 14.66 11 H H -CH(CH3)CH2CH2 -CO2C2H5 oil Calcd 62.82 5.53 - 14.90 Found 62.26 5.64 - 13.62 12 H H -CH(CH3)- -CN 53-56 Calcd 62.54 3.93 - 18.54 4.55 Found 62.67 3.97 - 18.77 4.83 TABLE IA

Analysis Product Ex. No. R R4 R5 Identification %C %H %Cl %F 13 Cl -CH(CH3)- -CO2C2H5 Oil Calcd 55.61 4.14 9.11 14.66 Found 55.27 4.14 9.40 13.80 TABLE II Diphenyl Sulfides and Sulfoxides

Analysis Ex. No. R8 R9 R4 R5 X m.p. etc. %C %H %Cl %F %S %N 14 Cl 4-CF3 -CH(CH3) -CO2C2H5 -S- 64.5-65.5 Calcd 53.40 3.98 8.76 14.08 7.92 Found 53.05 3.98 8.95 14.46 7.95 15 Cl 4-CF3 -CH(CH3)- -CO2C2H5 -SO- - Calcd 51.37 3.83 8.42 13.54 7.62 Found 51.24 3.92 8.24 13.51 7.28 16 Cl 4-CF3 -CH(CH3)- -CO2C2H5 -SO- oil Calcd 49.49 3.69 8.12 13.05 7.34 Found 47.82 3.78 8.68 13.17 7.20 17 H 2-CF3 -CH(CH3)- -CO2C2H5 -S- oil Calcd 58.37 4.63 - 15.39 8.66 Found 58.21 4.51 - 14.79 9.04 18 H 3-CF3 -CH(CH3)- -CO2C2H5 -S- oil Calcd 8.37 4.63 - 15.39 8.66 Found 58.75 4.83 - 15.15 9.01 19 H 4-CF3 -CH(CH3)- -CO2C2H5 -S- oil Calcd 58.37 4.63 - 15.39 8.66 Found 58.31 4.70 14.92 8.92 20 CN 4-CF3 -CH(CH3)- CO2C2H5 -S- - Calcd 57.71 4.08 - 14.42 8.11 3.54 Found 57.39 3.99 - 14.50 8.48 3.52 21 NO2 4-CF3 -CH(CH3)- -CO2C2H5 -S- 63-64 Calcd 52.04 3.88 - 13.72 7.72 3.37 Found 51.83 3.86 - 13.64 7.97 3.38 TABLE II (Continued) Analysis Ex. No R8 R9 R4 R5 X m.p. %C %H %Cl %F %S %N 22 H 2-CF3 -CH(CH3)- -CO2C2H5 -SO- oil Calcd 55.95 4.44 - 14.75 8.30 Found 55.76 4.34 - 14.81 8.47 23 H 3-CF3 -CH(CH3)- CO2C2H5 -SO- oil Calcd 55.95 4.44 - 14.75 8.30 Found 56.50 4.49 - 14.51 8.35 24 H 4-CF3 -CH(CH3)- -CO2C2H5 -SO- oil Calcd 55.95 4.44 - 14.75 8.30 Found 55.80 4.25 - 14.83 9.38 25 Cl 4-CF3 -CH(CH3)- -CO2C2H5 -S- oil Calcd 54.58 4.33 8.46 13.61 7.65 Found 55.11 4.70 7.85 12.60 7.37 Example 51.

This example shows the herbicidal activity of compounds of the invention.

Using the procedure described below, compounds of the invention are evaluated for control of several of the following plant species: barnyardgrass (Echinochloa crusgalli) cocklebur (Xanthium pensylvanicum) crabgrass (Digitaria spp.) downybrome (Bromus tectorum) foxtail (Setaria spp.) marigold (Tagetes spp.) morningglory (Ipomoca spp.) yellow nutsedge (Cyperus esculentus) velvetleaf (Abutilon theophrasti) wild oats (Avena fatua) tomato (Lycopersicon esculentum) corn (Zea mays) rice (Oryza sativa) soybean (Glycine max) wheat (Triticum sativum) The following test procedure is employed. Seeds of selected crops and weeds are planted in soil in flats. For preemergence tests, the flats are treated with the test compound immediately after the planting. For postemergence tests, the seeds are allowed to germinate, and after two weeks the flats are treated with the test compound. The compound to be evaluated is dissolved in acetone, diluted with water, and sprayed over the flats using a carrier volume equivalent to 50 U.S. gallons per acre at the rate of application (pounds per acre, Ib/A.) specified in the tables. About two weeks after the application of the test compound, the state of growth of the plants is observed and the phytotoxic effect of the compound is evaluated. Tables III and IV give the average percent control achieved by test compounds in terms of the percent of the plants which are killed by the compounds.

TABLE II HERBICIDAL ACTIVITY (% control) Compound Rate Type of Morning Velvet- Barnyard- Downy (Ex. No.) (lb/A) Application Cocklebur Marigold glory Tomato leaf grass brome Foxtail Nutsedge Wild oat 1 2 Pre 0 0 0 0 0 0 0 90 0 0 2 Post 80 20 100 80 80 10 0 40 0 20 2 2 Pre 0 0 0 0 0 0 0 99 0 0 2 Post 0 0 0 0 0 0 0 0 0 0 3 2 Pre 0 0 0 0 0 0 0 0 0 0 2 Post 40 50 0 90 20 40 0 0 0 0 4 2 Pre 0 0 0 0 0 0 0 0 0 0 2 Post 40 0 80 30 40 0 0 0 0 0 5 2 Pre 0 0 0 0 0 0 0 30 0 0 2 Post 50 0 30 0 20 20 0 30 0 40 6 2 Pre 0 0 0 0 0 100 20 100 0 30 2 Post 0 0 0 0 0 99 30 99 0 90 7 2 Pre 0 0 0 0 0 60 0 60 0 0 2 Post 0 0 0 30 0 0 0 100 0 30 8 2 Pre 0 0 70 0 0 100 30 100 0 40 2 Post 60 40 80 90 80 100 100 100 0 99 9 2 Pre 0 0 40 20 20 100 95 60 0 0 2 Post 30 10 10 30 0 100 90 95 0 90 10 2 Pre 0 0 0 0 0 90 0 100 0 0 2 Post 0 0 0 0 0 100 90 100 0 99 TABLE III (Continued) HERBICIDAL ACTIVITY Compound Rate Type of Morning (% control) Velvet- Barnyard- Downy (Ex. No.) (lb/A) Application Cocklebur Marigold glory Tomato leaf grass brome Foxtail Nutsedge Wild oa 11 2 Pre 0 0 0 0 0 99 60 99 0 50 2 Post 60 0 40 20 0 100 100 100 0 100 12 2 Pre 0 0 0 0 0 99 80 100 0 70 2 Post 0 0 0 0 0 100 40 60 0 99 13 2 Pre 0 90 0 100 100 30 0 100 0 20 2 Post 90 90 100 100 100 60 40 50 0 50 14 2 Pre 0 0 0 0 0 95 40 100 0 30 2 Post 20 50 50 70 70 70 90 100 66 99 15 4 Pre 0 0 0 0 40 95 40 99 0 20 4 Post 0 0 0 0 0 0 0 0 0 0 16 4 Pre 0 50 0 0 6 0 20 0 0 0 4 Post 0 0 0 0 0 0 0 0 0 0 17 8 Pre 0 0 0 0 30 80 60 0 0 0 4 Post 0 0 0 0 20 0 0 20 0 0 18 8 Pre 0 0 0 0 0 0 0 0 0 0 4 Post 0 0 0 80 0 20 20 30 0 20 19 8 Pre 0 0 0 0 0 70 50 70 0 0 4 Post 0 0 0 80 0 50 30 30 0 20 20 2 Pre 0 0 0 0 0 100 40 95 0 100 2 Post 0 0 0 0 0 100 99 99 0 99 21 2 Pre 0 0 0 0 0 95 30 95 0 0 2 Post 0 0 0 0 0 60 0 20 0 80 TABLE III (Continued) HERBICIDAL ACTIVITY Compound Rate Type of Morning (% control) Velvet- Barnyard- Downy (Ex. No.) (lb/A) Application Cocklebur Marigold glory Tomato leaf grass brome Foxtail Nutsedge Wild oat 22 4 Pre 0 0 0 0 0 0 0 0 0 0 4 Post 0 0 0 20 20 20 0 20 0 30 23 4 Pre 0 0 0 0 0 0 0 0 0 0 4 Post 0 0 0 20 0 20 0 0 0 20 24 4 Pre 0 0 0 0 0 0 0 0 0 0 4 Post 0 0 0 0 0 20 0 0 0 20 25 4 Pre 0 0 0 0 0 40 0 70 0 0 4 Post 0 0 0 0 0 0 0 0 0 0

Claims

WHAT WE CLAIM IS:1. A compound of the formula

wherein R1 is hydrogen or halogen R2 is hydrogen or halogen, R is a group of the formula

wherein R3 is hydrogen, halogen, nitro, (C1-C4)alkyl, or (C1-C4)alkoxy, R4 is a divalent (C1-C5)alkylene group, R5 is cyano or a group of the formula -COR8, wherein R5 is (C1-C6)alkoxy, hydroxy (or an agronomically-acceptable salt thereof), amino, (C1-C4)alkylamino, or di(C1-C4)alkylamino, and Z is oxygen, sulfur, sulfinyl or sulfonyl.
2. A compound according to Claim I with at least one of the following modifications, viz. (1) R4 represents a divalent alkenylene group of up to 5 carbon atoms, (2) R6 represents amino(C1-C4)alkoxy, (C1-C4)alkylamino(C1-C4)alkoxy, or di(C1-C4)alkylamino(C1-C4)alkoxy and (3) R is cyano.
3. A compound according to Claim 1, wherein R5 is cyano, modified in that R2 (when a substituent) can occupy any vacant position in the ring and it can also represent cyano.
4. A compound according to Claim 1, wherein Z is sulfur, sulfinyl or sulfonyl, with one or more of the following modifications, viz: (a) R1 can also represent cyan, nitro, (C1-C4)alkyl, (C1-C4)alkoxy or trifluoromethyl, (b) the mandatory CF3 substituent can occupy any vacant position in the ring, (c) R2 (when a substituent) can occupy any vacant position in the ring and can also represent cyano, (d) R (when a substituent) can occupy any vacant position in the ring and (e) R6 can also represent (C1-C6)alkoxy, allyloxy, (C1-C4)alkoxy(C1-C4)alkoxy, amino(C1-C4)alkoxy, (C1-C4)alkylamino(C1-C4)alkoxy or di(C1-C4)alkyl- amino(C1-C4)alkoxy.
5. A compound according to any of Claims 1-4 wherein R is a group of Formula II.
6. A compound according to Claim 5 which is the compound of foregoing Example 2.
7. A compound according to Claim I wherein R5 is cyano, R2 and R3 are each hydrogen and R4 is a group of the formula -CHR7- in which R7 is hydrogen or (C1-C4)alkyl.
8. A compound being any of those individual compounds in foregoing List A.
9. A compound being any of those individual compounds in foregoing List B.
10. A compound according to Claim 1 or 4, wherein Z is other than oxygen and wherein R1 is chlorine or cyano, R2 and R3 are each hydrogen and R4 is a group of the formula --CHR77- wherein R7 is as defined in Claim 7.
11. The compounds of the foregoing Examples 14 to 25 inclusive.
12. A herbicidal composition containing (a), as an active ingredient, a compound according to Claim 1 and (b) an agronomically acceptable carrier for said active ingredient.
13. A compound according to any of Claims 2 to 11 when prepared by any of the general or specific methods hereinbefore described.
14. A method of combating weeds which comprises applying (a) to the growth medium prior to the emergence of the weeds therefrom or (b) to weed seedlings a compound according to Claim 1.
15. A herbicidal composition containing (a), as an active ingredient, a compound according to any of Claims 2 to 11 and (b) an agronomically acceptable carrier for said active ingredient.
16. A method according to Claim 14 modified in that there is applied a compound according to any of Claims 2 to 11.

Reference has been directed in pursuance of section 8 of the Patents Act 1949, to specification No. 1,519,334 and 1,507,159.