SUBSTITUTED 4-FLUOROTHIOCARBANILIDE HERBICIDAL COMPOUNDS AND METHODS OF USE

Abstract: A compound having the structural formula R is -Cl or -CF₃; R₁ is C₁-C₄ alkyl, preferably ethyl and isopropyl and C₂-C₄ alkenyl, preferably C₃-alkenyl; and R₂ is selected from the group consisting of C₁-C₃ alkyl, preferably ethyl and C₂- C₃ alkoxyalkyl; and its use as a herbicide.

Description: SUBSTITUTED 4-FLUOROTHIOCARBANILIDE HERBICIDAL COMPOUNDS AND METHODS OF USE Background of the Invention The present invention relates to certain substituted 4-fluoro thiocarbanilide compounds which are useful as herbicides and particularly useful as pre-emergent herbicides against annual and perennial grasses and broadleaf weeds. herbicides are widely used by farmers, commercial agricultural companies, and other industries in order to increase crop yields for such staple crops as corn, soybeans, rice, and the like, and to eliminate weed growth along highways, railroad rights-of-way, and other areas. Herbs cides are effective in killing or controlling unwanted weeds which compete for soil nutrients with the crop plants, ard by reason of the fact that they kill ends, are responsible for improving the aesthetic appearance of highway and railroad rights-of-way. There are a number of different types of herbicides presently sold commercially, and these fall into to general categories. The cate- gories are pre-emergence and post-emergence herbicides. The pre-energence herbicides are normally incorporated into or applied to the soil prior to the emergence of the weed plants fran the soil, and the post-emergence herbicides are normally applied to plant surfaces after emergence of the weds or other unwanted plants from the soil. The Prior Art U.S. Patent 3,869,490 generically discloses sane of Applicant's claimed substituted thiocarbanilides but fails to disclose Applicant's specific substituted 4-fluDro thiocarbanilides. Efforts are constantly being made, however, to find canpounds which are equal to or greater in effectiveness than presently existing canpourds, or which are more economical to produce. Description of the Invention This invention relates to the production of navel substituted 4-fluors thiocarbanilide compounds ard their use as herbicides. The novel canpounds of this invention have the following structural formula EMI2.1 R is -Cl or -CF3; R1 is C1-C4 alkyl, preferably ethyl ard isopropyl and C2-C4 alkenyl, preferably C3-alkenyl; and R2 is selected fran the group consisting of C1-C3 alkyl, preferably ethyl and C2-C3 alkoxyalkyl. In the above description of the compounds of this invention, alkyl includes both staight- and branched-chain configurations; for example, methyl, ethyl, n-propyl and isopropyl. The compounds of the invention can be produced in a process in accordance with the following reaction sequence: EMI2.2 in which R, R1 and R2 are as defined above. The compounds of this invention can be prepared usirg the following method: Sodium hydride (or other strong base) is mixed with dry tetrb- hydrofuran (or other dry, non-reacting solvent) at about roan temperature and an appropriate thiocarbanilide is added to the mixture and stirred for about one hour. Then the chloroaLkyl ether i added and the mixture stirred until the reaction is complete. The product is recovered by con- ventional methods of ether nitration, water washing, drying over a desicant (sp.), filtering and stripping. Examples 1 and 2 below illustrate various methods of making the compounds of the invention using various starting materials. All intermediates and final products were identified by infrared, nuclear magnetic resonance and p:oton magnetic resonance Spectra. EXAMPLE I Nall (0.4 graTis, 0.016 mole) was added at roan temperature to 100 milliliters (ml) of tetrahydrofuran urder a dry nitrogen atmosphere. S-methyl-3-chloro-4-fluoro thiocarbanilide (4.0 g, 0.016 mole) was added and the reaction mixture was stirred for one hour. Chloramethylbutyl ether (1.7 g, 0.016 mole) was added dropwise to the stirred reaction mixture. The temperature rose to 30 C and the mixture was stirred overnight, then titrated twice with ethyl ether, water washed, dried over MgSO4, filtered and stripped to yield 4.1 g of a liquid product having an ND30 of 1.5335. The prcduct of this example will be referred to as Compound No. 2. EXAMPLE II NaH (0.3 grams, 0.013 mole) was added at roan temperature to 100 ml of tetrahydrofuran under a dry nitrogen atmosphere. S-ethyl-3-tri- fluoranethyl-4-fluoro thiolcarbanilide (3.5 g, 0.013 mole) was added and the reaction mixture was stirred for one hour. Chloromethylbutyl ether (1.2 g, 0.013 mole) was added dropwise to the stirred reaction mixture. The temperature rose to 30 C ard the mixture was stirred overnight, then titrated twice with ethyl ether, water washed, dried over MgSO4, filtered ard stripped to yield 2.9 g of a liquid product having an ND30 of 1.4835. The product of this example will be referred to as Compound No. 5. The following is a table of certain selected canpounds that are preparable accord to the procedure described herein. Canpoud nurbers are assigned to each compound and are used throughout the remainder of the application. Table I EMI4.1 Cmpd. No. R R1 R2 n@30 1 -Cl -CH3 -CH2CH3 1.5390 2 -Cl H3 -(CH2)20CH3 1.5330 3 -C1 CH2CH3 -CH2CH3 1.5310 4 -C1 -CH(CH3)2 -CH2CH3 1.5255 5 -CF3 -CH2CH3 -CH2CH3 1.4835 6 Cl -CH(CH3)CH2CH3 -CH2CH3 1.5320 7-Cl -CH2CH2CH2CH3 -CH2CH3 1.5445 8 -Cl -C(CH3)3 -CH2CH3 1.5398 9 -Cl -CH2CH=CH2 -CH2CH3 1.5610 10 -Cl -CH2CH2CH3 -CH2CH3 1.5338 11 -Cl -CH2CH(CH3)2 -CH2CH3 1.5250 Herbicidal Screening Tests As deviously mentioned, the herein described compounds produced in the above-described manner are phyototoxic compound which are useful are valuable in controlling various plant species. Selected compounds of this invention were tested as herbicides in the following manner. Pre-emergence herbicide test. On the day preceding treatment, seeds of seven different grass and broadleaf weed species are planted in loany sard soil in individual rows in 6 x 10 x 3 inch flats. The seeds used are green foxtail (ET) (Setaria viridis), watergrass (w;) (Echinochloa crusgalli), wild oat (WO) (Avena fatua), annual morningglory (AMG) (Ipomoea purpurea), velvetleaf (VL) (Abutilon theophrasti), Indian mustard (MD) (Brassica kaber), and curly dock (CD) (Rumex crispus). The flats are placed in the greenhouse, watered daily (both before and after chemical treatment) with a sprinkler and maintained at about 78 F. Chemical spray spray treatment is prepared by weighing out 333 mg of compound and dissolving in 25 ml acetone containing 1% polyoxyethylene sorbitan monolaurate emulsifier. From this stock solution 18 ml are removed ard brought up to a 40 ml volume with a 19:1 water/ acetone mixture. The carrier volune is 80 gallons/acre (748L/ha) and a 4 lbs/acre rate (4.48 kg/ha) is used. Twelve to fourteen days after treatment, the degree of injury or control is determined by comparison with untreated check plants of the same age. The injury rating from 0 to 100% is recorded for each Species as percent control with 0% representing no injury ard 100% representing complete control. The results of the tests are shown in the following Table II. TABLE II Pre-Emergence Herbicidal Activity Application Rate - 4.48 kg/ha Cmpd. AVE AVE . FT PS VL MD CD GR BL 1 100 100 100 75 50 75 100 100 75 2 15 90 90 0 0 0 0 65 0 3 100 100 100 80 100 100 100 100 95 4 100 100 100 70 60 - 90 100 73 5 100 100 95 70 60 - 100 98 77 6 100 100 90 15 0 10 100 97 31 7 100 100 80 15 75 50 100 93 60 8 90 85 65 0 0 0 90 78 23 9 100 100 95 70 100 100 100 98 93 10 100 100 85 60 95 100 90 95 86 11 100 100 50 0 0 0 15 83 4 AVE GR = The average of all grass weeds treated at the application rate. AVE BL = The average of all broadleaf weeds treated at the application rate. Post-Emergence Herbicide Test: This test is conducted in an identical manner to the testing procedure for the preenergence herbicide test, except the seeds of the seven different grass and broadleaf weed species are planted 12 days before treatment. Also, watering of the treated flats is confined to the soil surface and not to the foliage of the sprouted plants. The results of the post-emergence herbicide test are reported in Table III. TABLE III Post-Emergence Herbicidal Activity Application Rate - 4.48 kg/ha Cmpd. AVE AVE No. FT WG WO AMG VL MD CD GR BL 1 100 100 90 45 30 25 85 97 46 2 3Q 0 0 0 0 30 0 10 9 3 90 90 80 40 40 50 95 87 56 4 80 80 85 30 30 50 70 82 45 5 50 85 80 20 20 30 70 72 35 6 50 50 25 25 10 15 60 42 28 7 50 50 0 25 0 25 80 33 33 8 0 0 0 0 0 0 0 0 0 9 80 80 50 80 80 60 80 70 75 10 60 60 50 90 95 90 60 57 84 11 20 25 20 40 60 40 0 22 35 AVE GR = The average of all grass weeds treated at the application rate. AVE BL = The average of all broadleaf weeds treated at the application rate. The canpounds of the present invention are useful as herbicides, especially as pre-emergence herbicides, and can be applied in a variety of was at various concentrations. In practice, the compounds herein defined are formulated into herbicidal compositions, by mixture, in herbicidally effective amounts, with the adjuvants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the materials in a given applica- tion. Thus, these active herbicidal compounds may be formulated as gran- ules of relatively large particle size, as wettable powders, as onulsifi- able concentrates, as powdery dusts, as solutions or as any of several other known tyFes of formulations, depending upon the desired mcde of application. Preferred formulations for pre-emergence herbicidal applied tions are wettable powders, emulsifiable concentrates and granules. These formulations may contain as little as about 0.5% to as much as about 95% or more by weight of active ingredient. A herbicidally effective amount depends upon the nature of the seeds or plants to be controlled and the rate of application varies from about 0.05 to approximately 25 pounds Fer acre, preferably from about 0.1 to about 10 pounds Fer acre. Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersants. The wettable powder is ultimately applied to the soil either as a dry dust or as a dispersion in water or other liquid. Typical carriers for wettable powders include fuller's earth, kaolin clays, silicas ard other readily wet organic or inorganic diluents. Wettable powders normally are prepared to contain about 5% to about 95% of the active ingredient and usually also contain a small anount of wetting, dispersing, or emulsifying agent to facilitate wetting and dispersion. Dry flowables or water dispersible granules are agglomerated wettable powders made by either pan granulation or by fluidized bed. The dry flowable is ultimately applied to the soil as a dispersion in water or other liquid. These granules are dust-free and free flowing when dry and yet upon dilution in water, form homogeneous dispersions. Typical carriers for dry flowables include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic diluents. The dry flowables normally are prepared to contain from about 5% to about 95% of the active ingredient and usually contain a snall amount of wetting, dispersing or emulsifying agent to facilitate wettirg and dispersion. Emulsifier concentrates are homogeneous liquid compositions which are dispersible in water or other dispersant, and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aranatic naphtha, isophorone and other rcn-volatile organic solvents. For herbicidal application, these concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the area tn be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises about 0.5% to 95% of active ingredient by weight of the herbicidal composition. Granular formulations herein the toxicant is carried on relatively coarse particles, are usually applied without dilution to the area in which suppression of vegetation is desired. Typical carriers for granular formulations include sand, fuller's earth, bentonite clays, vermicu- lite, perlite and other organic or inorganic materials which absorb or which may be coated with the toxicant. Granular formulations normally are prepared to contain about 5% to about 25% of active ingredients which may include surface-active agents such as wettirg agents, dispersing agents or emulsifiers; oil such as heavy aranatic naphtas, kerosene or other petro- leun fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins. Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, for example, the alkyl ard alkylaryl sulfonates and sulfates and their sodioum salts; polyhydroxy alcoools; and other types of surface-active agents, many of which are available in com-- mercy. The surface-active agent, when used, normally comprises frcm 0.1% to 15% by weight of the herbicidal composition. Dusts, which are free-flowing admixtures of the active ingredient with finely divided solids such as talc, days, flours ard other organic and inorganic solids which act as dispersants and carriers for the taicalt, are useful formulations for soil-incorporating application. Pastes, which are homogeneous suspensions of a finely divided solid toxicant in a liquid carrier such as water or oil, are employed for specific purposes. These formulations normally contain about 5% to about 95% of active ingredient by wight, arx may also contain small amounts of a wetting, dispersing or emulsifying agent to facilitate dispersion. For application, the pastes are normally diluted am applied as a spray to the area to be affected. EXAMPLES QF TYPICAL FORMULATIONS Oil Ingredient Weight % Compound 1 1 Oil solvent-heavy aranatic naphtha 99 Total 100 Emulsifiable Concentrate Compound 2 50 Kerosene 45 Emulsifying agent (mixture of long chain ethcDcylated polyethers with long chain sulfonate) 5 Total 100 Emulsifiable Concentrate Compound 3 90 Kerosene 5 Emulsifying agent (mixture of long chain ethoxylated polyethers with long chain sulfonate) 5 Total 100 Dusts and/or Powders Ingredient Wt. % Wt. % Wt. % Ccmpound 4 0.5 50.0 90.0 Attapulgite Clay Poser 93.5 44.0 4.0 Scdiun lignin sulfonate 5.0 5.0 5.0 Sodium dioctyl sulfosuccinate 1.0 1.0 1.0 Total 100.0 100.0 100.0 Other useful fornulations for herbicidal applications include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as acetone, alkyl ated naphthalenes, xylene and other organic solvents. Pressurized sprays, typically aerosols, wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used. The phytotoxic compositions of this invention are applied to the plants in the conventional manner. Thus, the dust and liquid compositions can be applied to the plant by the use of power-dusters, boam and hand sprayers and spray dusters. The compositions can also be applied fran airplanes as a dust or a spay because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings, as a typical exanple, the dust ard liquid compositions are applied to the soil according to conventional methods and are distributed in the soil to a depth of at least 1/2 inch below the soil surface. It is not necessary that the phytotoxic compositions be admixed with the soil particles since these canpositions can also be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic composi- tions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations. The plytotoxic canpositions of this invention can also contain other additaments, for example, fertilizers ard other herbicides, pesticides and the like, used as adjuvant or in combination with any of the above-described adjuvants. Other phytotoxic compounds useful in combination with the above-described compounds include, for exanple, 2,4-di- chlorophenoxyacetic acids, 2,4,5-trichlorophenoxyacetic acid, 2-methyl-4 chlorophenoxyacetic acid and the salts, esters and anides thereof, tri- azine derivatives, such as 2,4-bis(3-methoxypropylamino)-6-methylthio-s- triazine, 2-chloro-4-ethylamino-6-isopropylamino-s-triazine, and 2 -ethyl- & ino-4- 4- isopropyl- amino-6-methyl-mercapto-s-triazine; urea derivatives, such as 3-(3,5-dichlorophenyl)-1,1-dimethylurea and 3-(p-chlorophenyl)l,l-dimethylurea; ard acetamides such as N,N-diallyl-d -chloroacetanide, and the like; benzoic acids such as 3-anino-2,5-dichloroeenzoic acid; thiocarbamates such as S-propyl N,N-dipropylthiocarbamate, S-ethyl N,N-dipropyl thiocarbamate, S-ethyl cyclohexylethylthiocarbamate, S-ethyl hexa hwral-a pine-l-carbothioate and the like; anilines such as 4-(methyl- sulfonyl)-2,6-dinitro-N,N-substituted aniline, 4-trifluoromethyl-2,6-dinitro-N,N-di-n-propyl aniline, 4-trifluoromethyl-2,6-dinitro-N-ethyl-Nbutyl aniline, 2- [4-(2 , 4-dichlorophenoxy) çhenoxy] propanoic acid, 2- [1 - (ethoxyimino) butyl] -5- [2-ethylthio) propyl ] -3-hydroxy-2-cyclohexene-1 one, (#)-butyl-2[4-[(5-trifluoromethyl)-2-pyridinyl)oxy]phenoxy]propanate, sodium 5-[2-chloro-4-(trifluoromethyl)phenoxyl]-2-nitrobenzoate, 3-isopropyl-1H-2,1,3benzothiadiazine-4(3H)-one-2,2-dioxide, and 4-amino-6-tertbutyl-3(methylthio)-as-triazin-5(4H)-one or (4-amino-6-(1,1-dimethyl ethyl )-3-(methylthio) -1,2, 4-triazin-5 (4H )-one) . Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate. other useful additaments include materials in which plant organisns take root and grow such as compost, manure, humus, sand, and the like.

Claims: WE CLAIM: I. A compound having the structural formula EMI12.1 wherein R is -Cl or R1 is selected from the group consisting of C1 < 4 alkyl and C2-C4 alkenyl; and R2 is selected fran the group consisting of C1-C3 alkyl. 2. The compound of Claim 1 wherein R is -Cl, R1 is -CH2CH3 and R2 is -CH2CH3. 3. The compound of Claim 1 wherein R is -Cl, R1 is -CH2CH2CH3 and R2 is -CH2CH3. 4. The compound of Claim 1 wherein R is -Cl, R1 is -CH2CH2CH2CH3 and R2 is -CH2CEi3. 5. The compound of Claim 1 wherein R is -Cl, R1 is -CH2CH=CH2 and R2 ?5 -CH2CH3. 6. A herbicidal composition comprising an herbicidally effective amount of a ccarrlpund having the structural formula EMI12.2 wherein R is -Cl or -CF3; R1 is selected from the group consisting of C1-C4 alkyl and C2-C4 alkenyl; and R2 is selected from the group consisting of C1-C3 alkyl; and an inert carrier. 7. The method of controlling undesirable vegetation comprising applying to the area where control is desired, an herbicidally effective amount of a compound having the formula EMI13.1 wherein R is -Cl or -CF3; R1 is selected fran the group consisting of Cl-C4 alkyl and C2-C4 alkenyl; and R2 is selected from the group consisting of C1-C3 alkyl. 8. The method of Claim 14 wherein R is -Cl, R1 is -CH2CH3 and R2 is -CH2CH3. 9. The method of Claim 14 wherein R is -Cl, R1 is -CH2CH2CH3 and R2 is -CH2CH3. 10. The method of Claim 14 wherein R is -Cl, R1 is -CH2CH2CH2CH3 and R2 is -CH2CH3.

Inventors: BAKER, DON ROBERT
Applicants: STAUFFER CHEMICAL COMPANY
Application year: 1985
Main classification: C07C155
IPC codes: C07C333, A01N57, C07C7, C07C67, C07C325, A01N47