Desiccant

Novel benzohydrazide derivatives as herbicides and desiccant compositions contaning them

Desiccant Abstract
The compound of the formula 1 wherein Y, X, Z, T and Q are defined in the specification.

Desiccant Claims
What we claimed is:

4. A herbicidal composition, characterized in that it contains at least one compound according to claim 1.

5. A herbicidal composition which comprises an effctive amount of a compound or its salt of claim 1 and an agricultural adjuvant.

6. The herbicidal composition according to claim 5 wherein the compounds are formulated into a practical use form such as emulsifiable concentrate (EC), aqueous or oil based suspension concentrate (SC), wettable powder (WP), water dispersible granule (WDG) or microenscapulated (ME) form.

7. A method for controlling the growth of undesired plant species in plantation crops which comprises applying to the locus of the crop a herbicidally effective amount of a compound or its salt according to claim 1.

8. A method for controlling undesired vegetation in a crop field such as corn, peanut, cotton, wheat, sorghum, sunflower, soybean or rice by applying to the locus of the crop to be protect a herbicidally effective amount of a compound or its salt of claim 1.

9. A method for controlling weeds, which comprises applying to the locus to be protected a herbicidally effective amount of a compound or its salt of claim 1 in combination with one or more other herbicides for providing an additive or synergistic herbicidal effect.

10. A method for controlling weeds of claim 7 wherein the compound or its salt of claim 1 is applied to the soil as a pre-plant incorporated, pre-emergent or delayed pre-emergent herbicide.

11. A method for controlling weeds of claim 9 wherein the compound or its salt of claim 1 is applied to the soil as a pre-plant incorporated, pre-emergent or delayed pre-emergent herbicide.

12. A method for controlling weeds of claim 7 wherein the compound or its salt of claim 1 is applied as a post-emergent herbicide to plant foliage.

13. A method for controlling weeds of claim 9 wherein the compound or its salt of claim 1 is applied as a post-emergent herbicide to plant foliage.

14. A method for controlling weeds of claim 9 wherein the other herbicide is an acetanilide, oxyacetamide, sulfonylurea, triazine, triketone, urea, amide, glyphosate or any referenced in the text.

15. A method to defoliate potato and cotton using a compound or its salt of claim 1.

16. A process for the preparation of the compound or its salt represented by the formula (XI) in said claim 1, which comprises reacting a compound according to formula (IX) with a compound of the formula (X). 31wherein X, Y, A.sub.1, A.sub.2, T, R.sub.1, R.sub.2, R.sub.3, R.sub.8 and R.sub.9 are as previously.

17. A process for the preparation of the compound or its salt represented by the formula (XVI) in said claim 1, which comprises reacting a compound of formula (IX) with a compound of the formula (X'). 32wherein X, Y, A.sub.1, A.sub.2, T, R.sub.1, R.sub.5, R.sub.6, R.sub.8 and R.sub.9 are as previously.

18. A process for the preparation of the compound or its salt represented by the formula (XVII) in said claim 1, which comprises reacting a compound according to formula (XXII) with aldehyde or ketone. 33wherein X, Y, A, A.sub.1, A.sub.2, T, R.sub.2, R.sub.3, R.sub.8 and R.sub.9 are previously defined.

19. A process for the preparation of the compound or its salt represented by the formula (XXVII) in said claim 1, which comprises transformation of a compound according to formula (XXIV) by Lawesson's reagent and reacting it with R.sub.4-M and R.sub.7-M. 34wherein X, Y, T, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.7, R.sub.8, R.sub.10 and R.sub.13 are previously defined.

20. A process of the preparation of the compound or its salt represented by the formula (XV) in said claim 1, which comprises reacting a compound according to formula (XIV) with R.sub.7-M. 35wherein X, Y, A, A.sub.1, A.sub.2, T, R.sub.2, R.sub.3, R.sub.4, R.sub.7, R.sub.8, R.sub.9 and M are previously defined.

21. A process of the preparation of the compound or its salt represented by the formula (XIII) in said claim 1, which comprises reacting a compound according to formula (XII) with R.sub.7-M. 36wherein X, Y, A, A.sub.1, A.sub.2, T, R.sub.1, R.sub.2, R.sub.3, R.sub.7, R.sub.8 and R.sub.9 are previously defined.

22. A process of the preparation of the compound or its salt represented by the formula (XIV) and (XII) in said claim 1, which comprises reacting a compound according to formula (IV) with R.sub.4-M and R.sub.1-M respetively. 37wherein X, Y, A, A.sub.1, A.sub.2, T, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.8 and R.sub.9 are previously defined.

23. A process of the preparation of the compound or its salt represented by the formula (XVI) and (XVIII) in said claim 1, which comprises reacting a compound according to formula (XVII) with R.sub.1-M and R.sub.4-M reapectively. 38wherein X, Y, A, A.sub.1, A.sub.2, T, R.sub.1, R.sub.4, R.sub.5, R.sub.6, R.sub.8 and R.sub.9 are previously defined.

24. A process of the preparation of the intermediate represented by the formula (XXX), which comprises reducing a compound according to formula (XXIX). 39wherein X, Y, T and Z are previously defined.

25. A process for the preparation of the intermediate represented by the formula (XXIX) in said claim 24, which comprises nitrating a compound according to formula (XXVIII) 40wherein X, Y, T and Z are previously defined.

Medical Supplies Patent

Description

DETAILED DESCRIPTION OF THE INVENTION

[0074] The compounds described by the formula (I) can be prepared by the procedures as described herein. Using commercially available starting materials or those whose synthesis is known in the art, the compounds of this invention may be prepared using methods described in the following Schemes, or using modifications thereof, which are within the scope of the art.

[0075] The starting carboxylic acid represented by formula (VIII) in Scheme 1 can be prepared according to the literature procedure (WO8810254). The carboxylic acid was converted to the corresponding acid halide represented by formula (IX) by treatment with halogenation agents such as thionyl chloride or oxalyl chloride with or without solvent at a temperature between 0.degree. C. and 100.degree. C. for 0.5 to 12 hours. Examples of solvent for this reaction include halogenated alkyl solvents such as dichloromethane, chloroform, or aromatic sovents such as benzene, toluene, xylene, etc. The solvent was removed under reduced pressure, then isolated and purified. Formula (XI) can be prepared by the condensation reaction of formula (IX) with the corresponding hydrazine derivatives represented by formula (X). The reaction was carried out with or without base such as triethyl amine or 1,8-diazabicyclo[5.4.0]undec-7-- ene (DBU) at a temperature between 0.degree. C. and 100.degree. C. for 0.5 to 24 hours. The described procedure in Scheme 1 can also be applied to the synthesis of thiobenzohydrazide analogs of formula (XI). 6

[0076] The product represented by formula (XIII) in Scheme 2 can be prepared from formula (XII) by treatment with an electrophile such as dimethyl sulfide in the presence of base such as potassium carbonate in an inert solvent such as acetone or toluene. The reaction can be carried out at a temperature between 0.degree. C. and 200.degree. C. for 0.5 to 48 hours. 7

[0077] The compounds represented by the formula (XII) and (XIV) in Scheme 3 can be prepared from the corresponding compounds represented by formula (XII') by treatment with an electrophile such as methyl iodide or acetyl chloride in an inert solvent such as dioxane in the presence of base such as potassium carbonate. Formula (XII) or (XIV) can be converted to the corresponding quaternary salt derivatives represented by formula (XIII) or (XV). The reaction can be carried out according to the general procedure described in Scheme 2. 8

[0078] The compound represented in formula (XVI) in Scheme 4 can be prepared from formula (IX) by reaction with a corresponding hydrazone derivatives represented by formula (X') in an inert solvent such as tetrahydrofuran (THF) or toluene with or without base such as triethylamine, DBU or potassium carbonate at a temperature between 0.degree. C. and 150.degree. C. for 0.5 to 24 hours. The described procedure in Scheme 4 can also be applied to the synthesis of thiobenzohydrazide analogs of formula (XVI) 9

[0079] The substituted derivatives represented by the formula (XVI) and (XVIII) in Scheme 5 can be prepared from formula (XVII) by treatment with an electrophile such as methyl iodide or acetyl chloride. The reaction can be carried out in the presence of base such as triethylamine or potassium carbonate in an inert solvent such as 2-butenone at a temperature between 0.degree. C. and 150.degree. C. for 0.5 to 24 hours. 10

[0080] The compound represented by formula (XXII) in Scheme 6 can be prepared from formula (XXI) by the reaction with hydrazine with or without base such as potassium carbonate. The reaction can be carried out in an inert solvent such as toluene at a temperature between -10.degree. C. to 150.degree. C. for 0.5 to 24 hours. Formula (XVII) can be prepared from formula (XXII) by condensation reaction with aldehyde or ketone in an inert solvent such as DMF with or without catalyst such as p-toluenesulfonic acid or potassium carbonate at a temperature between -10.degree. C. and 150.degree. C. for 0.5 to 24 hours. 11

[0081] The compound represented by formula (XXIII) in Scheme 7 can be prepared according to the literature procedure (EP 361114). Formula (XXIV) can be prepared according to the general procedure described in Scheme 1. Formula (XXIV) is then converted into the corresponding sulfur analogue represented by formula (XXV) by treating typical reagent such as Lawesson's reagent. Formula (XXVI) or (XXVII) can be prepared according to the general procedures described in Scheme 2. 12

[0082] The compound represented by formula (XI) and (XVI) in Scheme 8 can be prepared from formula (VIII) by a coupling reaction with corresponding hydrazine derivative in the presence of a dehydration reagent such as 1,3-dicyclohexylcarbodiimide (DCC). The reaction can be carried out with or without base such as N,N-dimethylaminopyridine (DMAP) in an inert solvent such as dichloromethane at a temperature between -10.degree. C. and 100.degree. C. for 0.5 to 24 hours. 13

[0083] The compound represented by formula (XXIX) in Scheme 9 can be prepared from formula (XXVIII). Nitration can be carried out by treatment with a nitrating reagent such as nitric acid at a temperature between -30.degree. C. and 60.degree. C. for 0.5 to 6 hours. Formula (I) is then converted into the corresponding aniline represented by formula (XXX) by typical reduction procedure e.g. iron in an acidic medium such as acetic acid or by catalytic hydrogenation. Uracil derivatives represented by formula (XXXII) can be prepared analogously by known method (U.S. Pat. No. 4,859,229). 14

EXAMPLE 1

Preparation of 2-chloro-5-(3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluorometh- yl)-1(2H)-pyrimidinyl)-N-[1-(1,1-dimethylethyl)-2,2-dimethylpropylidene]-4- -fluoro-benzenecarbohydrazonic acid methyl ester (Compound no. 5-6)

Step 1 Preparation of 2-chloro-5-(3,6-dihydro-3-methyl-2,6-dioxo-4-(triflu- oromethyl)-1(2H)-pyrimidinyl)-4-fluoro-benzoic acid

[0084] 2-Chloro-5-(3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H- )-pyrimidinyl)-4-fluoro-benzoic acid ethyl ester (5.2 g) was dissolved in methylenechloride (100 ml) and borontribromide (10 g) was added dropwise at ambient temperature. The reaction mixture was stirred for three hours at this temperature and poured into ice-water. The resulting mixture was extracted with ethyl acetate. The organic phase was washed with brine (.times.3) and dried over anhydrous Na.sub.2SO.sub.4. The solvent was removed under reduced pressure to give the titled compound (4.3 g) as a white solid.

Step 2 Preparation of 2-chloro-5-(3,6-dihydro-3-methyl-2,6-dioxo-4-(triflu- oromethyl)-1(2H)-pyrimidinyl)-4-fluoro-benzoyl chloride

[0085] To a stirred solution of 2-chloro-5-(3,6-dihydro-3-methyl-2,6-dioxo- -4-(trifluoromethyl)-1(2H)-pyrimidinyl)-4-fluoro-benzoic acid (4 g) in chloroform (100 ml) were added oxalyl chloride (1.8 g) and a few drops of N,N-dimethylformamide (DMF) at ambient temperature. The resulting mixture was stirred for three hours at same temperature and then filtered through Celite. The filtrate was concentrated under reduced pressure to give the titled compound (4.3 g) as a brown solid.

Step 3 Preparation of, 2-chloro-5-(3,6-dihydro-3-methyl-2,6-dioxo-4-(trifl- uoromethyl)-1(2H)-pyrimidinyl)-4-fluoro-benzoic acid, 2-[1-(1,1-dimethylethyl)-2,2-dimethylpropylidene]hydrazide (Compound No. 6-4)

[0086] 2-Chloro-5-(3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H- )-pyrimidinyl)-4-fluoro-benzoyl chloride (0.67 g) was dissolved in tetrahydrofuran (25 ml) and 3-pentanone, 2,2,4,4-tetramethyl-hydrazone (0.3 g) was added and the solution stirred overnight at ambient temperature. The reaction mixture was partitioned between ethyl acetate and brine. The organic phase was washed with brine (.times.3) and dried over anhydrous Na.sub.2SO.sub.4. The organic solvent was removed under reduced pressure and the residual oily product was purified by column chromatography on silica gel to give the titled compound (0.14 g).

Step 4

[0087] A mixed solution of 2-chloro-5-(3,6-dihydro-3-methyl-2,6-dioxo-4-(t- rifluoromethyl)-1(2H)-pyrimidinyl)-4-fluoro-benzoic acid, 2-[1-(1,1-dimethylethyl)-2,2-dimethylpropylidene]hydrazide (0.48 g), excess of methyl iodide and potassium carbonate (0.132 g) in acetonitrile (20 ml) was heated at reflux temperature overnight. The mixture was allowed to cool to ambient temperature and partitioned between ethyl acetate and brine. The organic phase was washed with brine (.times.3) and dried over anhydrous Na.sub.2SO.sub.4. The solvent was removed under reduced pressure and the residue was purified by column chromatography on silica gel eluted with a mixed solvent of ethyl acetate and hexane (1:4 to 1:2) to give the titled compound (0.25 g) along with its, 2-chloro-5-(3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyri- midinyl)-4-fluoro-benzoic acid, 2-[1-(1,1-dimethylethyl)-2,2-dimethylpropy- lidene]-1-methylhydrazide(0.1 g, Compound No. 6-8)

EXAMPLE 2

Preparation of 2-chloro-5-(3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluorometh- yl)-1(2H)-pyrimidinyl)-4-fluoro-benzoic acid, 2-(1,1-dimethylethyloxy)carb- onyl hydrazide (Compound No. 1-24)

[0088] To a solution of 2-chloro-5-(3,6-dihydro-3-methyl-2,6-dioxo-4-(trif- luoromethyl)-1(2H)-pyrimidinyl)-4-fluoro-benzoyl chloride (0.5 g) in tetrahydrofuran (20 ml) was added t-butylcarbazate (0.18 g) at ambient temperature. After 1 hour, the resulting mixture was concentrated under reduced pressure and the residue was subjected to column chromatography on silica gel eluted with a mixed solvent of ethyl acetate and hexane (2:3) to give the titled compound (0.48 g).

[0106] Dusts are admixtures of the active ingredient with finely ground materials such as clays (some examples include kaolin and montmorillonite clays), talc, granite dust or other organic or inorganic solids which act as dispersants and carriers for the active ingredient; these finely ground materials have an average particle size of less than 50 microns. A typical dust formulation will contain 1% active ingredient and 99% carrier.

[0107] Wettable powders are composed of finely ground particles which disperse rapidly in water or other spray carriers. Typical carriers include kaolin clays, Fullers earth, silicas and other absorbent, wettable inorganic materials. Wettable powders can be prepared to contain from 1 to 90% active ingredient, depending on the desired use pattern and the absorbability of the carrier. Wettable powders typically contain wetting or dispersing agents to assist dispersion in water or other carriers.

[0108] Water dispersible granules are granulated solids that freely disperse when mixed in water. This formulation typically consists of the active ingredient (0.1% to 95% active ingredient), a wetting agent (1-15% by weight), a dispersing agent (1 to 15% by weight) and an inert carrier (1-95% by weight). Water dispersible granules can be formed by mixing the ingredients intimately then adding a small amount of water on a rotating disc (said mechanism is commercially available) and collecting the agglomerated granules. Alternatively, the mixture of ingredients may be mixed with an optimal amount of liquid (water or other liquid) and passed through an extruder (said mechanism is commercially available) equipped with passages which allow for the formation of small extruded granules. Alternatively, the mixture of ingredients can be granulated using a high speed mixer (said mechanism is commercially available) by adding a small amount of liquid and mixing at high speeds to affect agglomeration. Alternatively, the mixture of ingredients can be dispersed in water and dried by spraying the dispersion through a heated nozzle in a process known as spray drying (spray drying equipment is commercially available). After granulation the moisture content of granules is adjusted to an optimal level (generally less than 5%) and the product is sized to the desired mesh size.

[0109] Granules are granulated solids that do not disperse readily in water, but instead maintain their physical structure when applied to the soil using a dry granule applicator. These granulated solids may be made of clay, vegetable material such as corn cob grits, agglomerated silicas or other agglomerated organic or inorganic materials or compounds such as calcium sulfate. The formulation typically consists of the active ingredient (1 to 20%) dispersed on or absorbed into the granule. The granule may be produced by intimately mixing the active ingredient with the granules with or without a sticking agent to facilitate adhesion of the active ingredient to the granule surface, or by dissolving the active ingredient in a solvent, spraying the dissolved active ingredient and solvent onto the granule then drying to remove the solvent. Granular formulations are useful where infurrow or banded application is desired.

[0110] Emulsifiable concentrates (EC) are homogeneous liquids composed of a solvent or mixture of solvents such as xylenes, heavy aromatic naphthas, isophorone or other proprietary commercial compositions derived from petroleum distillates, the active ingredient and an emulsifying agent or agents. For herbicidal use, the EC is added to water (or other spray carrier) and applied as a spray to the target area. The composition of an EC formulation can contain 0.1% to 95% active ingredient, 5 to 95% solvent or solvent mixture and 1 to 20% emulsifying agent or mixture of emulsifying agents.

[0111] Suspension concentrate (also known as flowable) formulations are liquid formulations consisting of a finely ground suspension of the active ingredient in a carrier, typically water or a non-aqueous carrier such as an oil. Suspension concentrates typically contain the active ingredient (5 to 50% by weight), carrier, wetting agent, dispersing agent, anti-freeze, viscosity modifiers and pH modifiers. For application, suspension concentrates are typically diluted with water and sprayed on the target area.

[0112] Solution concentrates are solutions of the active ingredient (1 to 70%) in solvents which have sufficient solvency to dissolve the desired amount of active ingredient. Because they are simple solutions without other inert ingredients such as wetting agents, additional additives are usually added to the spray tank mix before spraying to facilitate proper application.

[0113] Microemulsions are solutions consisting of the active ingredient (1 to 30%) dissolved in a surfactant or emulsifier, without any additional solvents. There are no additional solvents added to this formulation. Microemulsions are particularly useful when a low odor formulation is required such as in residential turfgrass applications.

[0114] Suspoemulsions are combinations of two active ingredients. One active ingredient is made as a suspension concentrate (1-50% active ingredient) and the second active is made as an emulsifiable concentrate (0.1 to 20%). A reason for making this kind of formulation is the inability to make an EC formulation of the first ingredient due to poor solubility in organic solvents. The suspoemulsion formulation allows for the combination of the two active ingredients to be packaged in one container, thereby minimizing packaging waste and giving greater convenience to the product user.

[0115] The herbicidal compounds of this invention may be formulated or applied with insecticides, fungicides, acaricides, nematicides, fertilizers, plant growth regulators or other agricultural chemicals. Certain tank mix additives, such as spreader stickers, penetration aids, wetting agents, surfactants, emulsifiers, humectants and UV protectants may be added in amounts of 0.01% to 5% to enhance the biological activity, stability, wetting, spreading on foliage or uptake of the active ingredients on the target area or to improve the suspensibility, dispersion, redispersion, emulsifiability, UV stability or other physical or physico-chemical property of the active ingredient in the spray tank, spray system or target area.

[0116] The compositions of the present invention may be used in admixture with or in combination with other agricultural chemicals, fertilizers or phytotoxicity-reducing agents. In such a case, they may exhibit even better effects or activities. As other agricultural chemicals, herbicides, fungicides, antibiotics, plant hormones, insecticides, or acaricides may, for example, be mentioned. Especially with herbicidal compositions having the compounds of the present invention used in admixture with or in combination with one or more active ingredients of other herbicides, it is possible to improve the herbicidal activities, the range of application time(s) and the range of applicable weed types. Further, the compounds of the present invention and an active ingredient of another herbicide may be separately formulated so they may be mixed for use at the time of application, or both may be formulated together. The present invention covers such herbicidal compositions.

[0117] The blend ratio of the compounds of the present invention with the active ingredient of other herbicides can not generally be defined, since it varies depending on the time and method of application, weather conditions, soil type and type of formulation. However one active ingredient of other herbicide may be incorporated usually in an amount of 0.01 to 100 parts by weight, per one part by weight of the compounds of the present invention. Further, the total dose of all of the active ingredients is usually from 1 to 10000 g/ha, preferably from 5 to 500 g/ha. The present invention covers such herbicidal compositions.

[0118] As the active ingredients of other herbicides, the following (common name) may be mentioned. Herbicidal compositions having the compounds of the present invention used in combination with other herbicides, may occasionally exhibit a synergistic effect.

[0119] 1. Those that are believed to exhibit herbicidal effects by disturbing auxin activities of plants, including a phenoxy acetic acid type such as 2,4-D, 2,4-DB, 2,4-DP, MCPA, MCPP, MCPB or naproanilide (including the free acids, esters or salts thereof), an aromatic carboxylic type such as 2,3,6 TBA, dicamba, dichlobenil, a pyridine type such as picloram (including free acids and salts thereof), triclopyr or clopyralid and others such as naptalam, benazolin or quinclorac.

[0120] 2. Those that are believed to exhibit herbicidal effects by inhibiting photosynthesis of plants including a urea type such as diuron, linuron, isoproturon, chlorotoluron, metobenzuron, tebuthiuron or fluometuron, a triazine type such as simazine, atrazine, cyanazine, propazine, terbuthylazine, atraton, hexazinone, metribuzin, metamitron, simetryn, triazaflam, terbutryn, ametryn, prometryn or dimethametryn, a uracil type such as bromacil, terbacil or lenacil, an anilide type such as propanil or cypromid, a carbamate type such as desmedipham or phenmedipham, a hydroxybenzonitrile type such as bromoxynil or ioxynil, and others such as pyridate, bentazon and methazole.

[0121] 3. A quaternary ammonium salt type such as paraquat, diquat or difenzoquat, which is believed to be converted to free radicals by itself to form active oxygen in the plant and thus to exhibit quick herbicidal effects.

[0122] 4. Those which are believed to exhibit herbicidal effects by inhibiting chlorophyll biosynthesis in plants and abnormally accumulating a photosensitizing peroxide substance in the plant body, including a diphenyl ether type such as nitrofen, lactofen, acifluorfen-sodium, oxyfluorfen, fomesafen, bifenox, or chlomethoxyfen, a cyclic amide type such as chlorphthalim, flumioxadine, flumiclorac-pentyl, flumioxazine, or cinidon-ethyl, and others such as fluthiacet-methyl, pyraflufenethyl, pentoxazone, azafenidin, oxadiargyl, oxadiazon, carfentrazone, sulfentrazone, fluazolate, butafenacil, or thidiazimin.

[0123] 5. Those which are believed to exhibit herbicidal effects characterized by whitening activities by inhibiting chromogenesis of plants such as carotenoids including a pyridazinone type such as norflurazon, chloridazon or metflurazon, a pyrazol type such as pyrazolate, pyrazoxyfen or benzofenap, and others such as fluridone, fluramone, diflufenican, methoxyphenone, clomazone, amitrole, sulcotrione, mesotrione, isoxaflutole and isoxachlortole.

[0124] 6. Those which exhibit herbicidal effects specifically to gramineous plants including an aryloxyphenoxypropionic acid type such as diclofop-methyl, pyrofenop-sodium, fluazifop-butyl, haloxyfop-methyl, quizalofop-ethyl, fenoxaprop ethyl, or cyhalofop-butyl and a cyclohexanedione type such as alloxydim-sodium, sethoxydim, clethodim, tepraloxydim, clefoxydim butroxydim, or tralkoxydim.

[0125] 7. Those which are believed to exhibit herbicidal effects by inhibiting amino acid biosynthesis of plants, including a sulfonylurea type such as chlorimuron-ethyl, nicosulfuron, metsulfuron-methyl, triasulfuron, primisulfuron, tribenuron-methyl, chlorosulfuron, bensulfuron-methyl, sulfometuron-methyl, prosulfuron, halosulfuron-methyl, thifensulfuron-methyl, triflusulfuron-methyl, rimsulfuron, azimsulfuron, flazasulfuron, imazosulfuron, cyclosulfamuron, oxasulfuron, flupyrsulfuron, sulfosulfuron, amidosulfuron, ethyoxysulfuron, foramsulfuron, iodosulfuron, cinosulfuron, a triazolopyrimidinesulfonamide type such as chlorasulam-methyl, flumetsulam, diclosulam, florasulam or metosulam, an imidazolinone type such as imazapyr, imazethapyr, imazaquin, imazamox, imazapic, imazameth, imazamethabenz methyl, a pyrimidinesalicylic acid type such as pyrithiobac-sodium, bispyribac-sodium or pyriminobac-methyl, and others such as glyphosate, and its' salts such as glyphosate-ammonium, glyphosate-isopropylamine or sulfosate.

[0126] 8. Those which are believed to exhibit herbicidal effects by interfering with the normal metabolism of inorganic nitrogen assimilation such as glufosinate, glufosinate-ammonium, phosphinothricin or bialophos.

[0127] 9. Those which are believed to exhibit herbicidal effects by inhibiting cell division of plant cells, including a dinitroaniline type such as trifluralin, oryzalin, nitralin, pendamethalin, ethafluralin, benefin and prodiamine, an amide type such as bensulide, napronamide, and pronamide, a carbamate type such as propham, chlorpropham, barban, and asulam, an organophosphorous type such as amiprofos-methyl or butamifos, an oxyacetamide type such as mefenacet or flufenacet, a carboxamide type such as fentrazamide or cafenstrole and others such as DCPA, thiazopyr and dithiopyr.

[0128] 10. Those which are believed to exhibit herbicidal effects by inhibiting protein synthesis or long chain fatty acid synthesis of plant cells, including a chloroacetanilide type such as alachlor, metolachor, propachlor, butachlor, pretilachlor, thenylchlor, propisochlor, betenachlor, acetochlor (including combinations with herbicide safeners) and dimethenamid.

[0129] 11. Those in which the mode of action causing the herbicidal effects are not well understood including the dithiocarbamates such as thiobencarb, pyributacarb, EPTC, diallate, triallate, molinate, dimepiperate, pebulate, cycloate, butylate, vernolate or prosulfocarb and miscellaneous herbicides such as MSMA, DSMA, endothall, ethofumesate, sodium chlorate, pelargonic acid, indanofan, fosamine, cafenstrole, amicarbazone, propoxycarbazone, flucarbazone, isoxaben, quinchlorac, quinmerac, cinmethylin, diflufenzopyr-sodium, napropamide.

[0130] A few formulation examples of the present invention are given as follows.

FORMULATION EXAMPLE 1

Emulsifiable Concentrate

[0131]

13 Ingredient Chemical % Trade Name Name Supplier Function wt./wt. Compound 1-9 Active 5.0 Ingredient Toximul H-A Calcium Stepan Co. Emulsifier 2.5 sulfonate and nonionic surfactant blend Toximul D-A Calcium Stepan Co. Emulsifier 7.5 sulfonate and nonionic surfactant blend Aromatic 200 Aromatic Exxon Solvent QS to hydrocarbon Chemical Co. 100%

FORMULATION EXAMPLE 2

Suspensions Concentrate

[0132]

14 Ingredient Chemical % Trade Name Name Supplier Function wt./wt. Compound Active 10.00 1-15 Ingredient Proylene Anti-freeze 5.00 gylcol Antifoam Silicone Dow Corning Anti-foam 0.50 1530 defoamer Rhodopol Xanthan gum Rhone-Poulenc Suspending 0.25 23 Aid Morwet Napthalene Witco Corp. Dispersant 3.00 D-425 formaldehyde condensate Igepal Octylphenol Rhone-Poulenc Wetting 3.00 CA-720 ethoxylate agent Proxel GXL 1,2 benziso- ICI Americas Preservative 0.25 thiazolin- 3-one Water Diluent 68.00

FORMULATION EXAMPLE 3

Wettable Powder

[0133]

15 Ingredient Chemical % Trade Name Name Supplier Function wt./wt. Compound Active 50.00 1-29 Ingredient Geropon T-77 Sodium-N- Rhone-Poulenc Wetting 3.00 methyl-N- agent oleoyl taurate Lomar PW Napthalene Henkel Corp. Dispersant 5.00 Sulfonate Kaolin clay Kaolin clay J. M. Huber Filler 42.00

FORMULATION EXAMPLE 4

Water Dispersible Granule

[0134]

16 Ingredient Chemical % Trade Name Name Supplier Function wt./wt. Compound Active 50.00 4-9 or 6-4 Ingredient Morwet EFW Witco Corp. Wetting 2.00 agent Morwet D-425 Napthalene Witco Corp. Dispersant 10.00 formaldehyde condensate ASP 400 Kaolin Clay Engelhard Filler 38.00 Corp.

TEST EXAMPLE

[0135] A standard greenhouse herbicide activity screening system was used to evaluate the herbicidal efficacy and crop safety of these test compounds. Seven broadleaf weed species including redroot pigweed (Amaranthus retroflexus, AMARE), velvetleaf (Abutilon theophrasti, ABUTH), sicklepod (Cassia obtusifolia, CASOB), ivyleaf morningglory (Ipomoea hederacea, IPOHE), lambsquarters (Chenopodium album, CHEAL), common ragweed (Ambrosia artemisiifolia L., AMBEL), and cocklebur (Xanthium strumarium, XANST) were used as test species. Four grass weed species including green foxtail (Setaria viridis, SETVI), barnyardgrass (Echinochloa crus-galli, ECHCG), johnsongrass (Sorghum halepense, SORHA), and large crabgrass (Digitaria sanguinalis, DIGSA) were also used. In addition, four crop species, field corn (Zea mays L., var. Dekalb 535, CORN), soybean (Glycine max L., var. Pella 86, SOY), upland rice (Oryza sp., var.Cocodrie, RICE) and wheat (Triticum aestivum L.) were included.

[0136] All plants were grown in 10 cm square plastic pots which were filled with a sandy loam soil mix. For pre-emerge tests, seeds were planted one day prior to application of the test compounds. For post-emerge tests, seeds were planted 8-21 days prior to the test to allow emergence and good foliage development prior to application of the test substances. At the time of the post-emerge application, plants of all species were usually at the 2-3 leaf stage of development.

[0137] All test compounds were dissolved in acetone and applied to the test units in a volume of 187 l/ha. Test materials were applied at rates ranging from 15 g ai/ha to 1000 g ai/ha using a track sprayer equipped with a TJ8001E even flow flat fan spray nozzle. Plants were arranged on a shelf so that the top of the canopy (post-emerge) or top of the soil surface (pre-emerge) was 40-45 cm below the nozzle. Pressurized air was used to force the test solution through the nozzle as it was mechanically advanced (via electrically driven chain drive) over the top of all test plants/pots. This application simulates a typical commercial field herbicide application.

[0138] Pre-emergence tests were top watered immediately after treatment to incorporate the test materials, then routinely top-watered for normal growth. Post-emerge test units were always bottom-watered.

[0139] At 14 days after application of the test materials, phytotoxicity ratings were recorded. A rating scale of 0-100 was used as previously described in Research Methods in Weed Science, 2nd edition, B. Truelove, Ed., Southern Weed Science Society, Auburn University, Auburn, Alabama, 1977. Briefly, "0" corresponds to no damage and "100" corresponds to complete death of all plants in the test unit. This scale was used both to determine efficacy against weed species and damage to crop species. Herbicide activity data for various compounds of this invention, which are shown by compound No. in Tables 1-12, are shown in Tables 13 and 14. The data demonstrate significant differences between compounds for both efficacy against weeds and selectivity for crop species. For selected compounds, excellent activity against a majority of the weed species was observed with minimal damage to at least one of the crop species.

SECOND TEST EXAMPLE

[0141] Paddy field soil was put into a 1/1,000,000 ha pot, and seeds of barnyardgrass (Echinochloa oryzicola: ECHOR) and japanese bulrush(Scirpus juncoides: SCPJO) were sown and slightly covered with soil. Then the pot was left to stand still in a greenhouse in a state where the depth of flooding water was from 0.5 to 1 cm, and one day later, tubers of japanese ribbon wapato(Sagittaria pygmaea: SAGPY) were planted. Thereafter, the depth of flooding water was maintained at a level of from 3 to 4 cm, and when bamyardgrass and japanese bulrush reached a 0.5 leaf stage, an aqueous diluted solution of a wettable powder or emulsifiable concentrate having the compound of the present invention formulated in accordance with a usual formulation method, was uniformly applied under submerged condition by a pipette so that the dose of the active ingredient would be at a predetermined level. On the other hand, paddy filed soil was put into a 1/1,000,000 ha pot and puddled and leveled, and the depth of flooding water was from 3 to 4 cm. One day later, rice(Oryza sativa L.: ORYSA) of 2 leaf stage was transplanted in a depth of 3 cm. On the 4.sup.th day after the transplantation, the compound of the present invention was applied in the same manner as described above. On the 14.sup.th day after the application of the herbicide, the growth of bamyardgrass, japanese burlush and japanese ribbon wapato was visually observed and on the 21.sup.st day after the application of the herbicide, the growth of rice was visually observed, arid the herbicidal effects were evaluated by growth controlling degrees(%) ranging from 0 (equivalent to the untreated control) to 100 (complete kill), whereby the results shown in Table 15, were obtained. Compound Nos. in Table 15 correspond to Compound Nos. in Table 1 to 12 given hereinbefore.

19TABLE 15 Water Application Herbicidal Activity Compound Rate No. g a.i./ha ECHOR SCPJO SAGPY ORYSA 1-9 125 90 98 100 70 1-11 125 95 100 100 35 1-15 63 100 50 98 30 1-16 63 60 20 90 30 1-24 125 50 98 100 40 1-25 125 20 90 100 35 1-29 125 95 98 100 20 4-4 125 70 -- -- 20 4-8 125 100 -- -- 30 4-9 63 100 70 80 30 5-2 63 100 40 100 35 5-4 63 98 70 100 35 5-6 125 95 98 100 70 5-7 125 98 98 100 30 6-4 125 100 100 100 50 6-5 63 70 40 100 60 6-8 125 70 90 100 50 6-15 125 70 98 100 35

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