# Patent

## Title
Herbicidal substituted triazolinones

## Abstract

This application is a continuation of application Ser. No. 07/336,085 filed on Apr. 11, 1989, now abandoned.

## Background
The present invention relates to a herbicidal composition. More particularly, it relates to a herbicidal composition comprising as the active ingredients (a) 2-[7-fluoro-3,4-dihydro-3-oxo-4-(2-propynyl)-2H-1,4-benzooxazin-6-yl]-4,5, 6,7-tetrahydro-1H-isoindol-1,3(2H)-dione (hereinafter referred to as "Compound (I)") of the formula: ##STR1## and (b) N-methoxymethyl-2',6'-diethyl-2-chloroacetanilide (hereinafter referred to as "alachlor") of the formula: ##STR2## or 2-chloro-6'-ethyl-N-(2-methoxy-1-methylethyl)acet-o-toluidide (hereinafter referred to as "metolachlor") of the formula: ##STR3## which exerts a highly enhanced herbicidal activity against a wide variety of weeds without causing any material phytotoxicity to crop plants, particularly to peanut and soybean crops.

In recent years, a great number of chemicals having herbicidal activity have been used to exterminate or control undesired weed vegetation. Since, however, weeds are diversified in kinds and their growth period extends over long period of time, the herbicidal effects of conventional herbicidal agents are quite restricted in general. Consequently, the appearance of any herbicidal agent which exerts a strong herbicidal activity against a wide variety of weeds without any material phytotoxicity to crop plants has been highly demanded.

As a result of the extensive study, it has now been found that the associated use of Compound (I) and alachlor or metolachlor as the active ingredients produces a highly enhanced herbicidal activity against a wide variety of weeds without causing any material phytotoxicity to crop plants, particularly peanut or soybean. In comparison with the sole use of each of the active ingredients, enhancement of the herbicidal potency on their associated use is remarkable so that the active ingredients may be applied in smaller dosages. Thus, a clear and definite synergistic effect is observed in the associated use.

The herbicidal composition of the invention which comprises Compound (I) and alachlor or metolachlor can exterminate or control a variety of weeds, e.g. dicotyledonus weeds such as wild buckwheat (Polygonum convolvulus), pale smartweed (Polygonum laphathifolium), Pennsylvania smartweed (Polygonum pensylvanicum), common purslane (Portulaca oleracea), common lambsquarters (Chenopodium album), redroot pigweed (Amaranthus retroflexus), wild mustard (Sinapis arvensis), hemp sesbania (Sesbania exaltata), sicklepod (Cassia obtusifolia), velvetleaf (Abutilon theophrasti), prickly sida (Sida spinosa), ivyleaf morningglory (Ipomoea hederacea), tall morningglory (Pharbitis purpurea), entireleaf morningglory (Ipomoea hederacea v. integriuscula), jimsonweed (Datura stramonium), black nightshade (Solanum nigrum), common cocklebur (Xanthium strumarium), common sunflower (Helianthus annuus), field bindweed (Convolvulus arvensis), sun spurge (Euphorbia nelioscopia) and devils beggarticks (Bidens frondosa); monocotyledonus weeds such as barnyardgrass (Echinochloa crus-galli), green foxtail (Setaria Viridis), giant foxtail (Setaria faberi), yellow foxtail (Setaria glauca), southern crabgrass (Digitaria ciliaris), goosegrass (Eleusine indica), johnsongrass (Sorghum halepense), quackgrass (Agropyron repens), shattercane (Sorghum bicolor) and purple nutsedge (Cyperus rotundus), etc.

Compound (I) is known to exert a herbicidal activity (U.S. Pat. No. 4,640,707). Alachlor and metolachlor are also known to be useful as a herbicide (The Pesticide Mannual 7th Ed. p. 3 and p. 377, The British Crop Council, 1983). However, the associated use of Compound (I) and alachlor or metolachlor has never been attempted, and the production of the synergistic effect on such combined use has never been expected.

The proportion of Compound (I) and alachlor or metolachlor as the active ingredients in the composition of the invention may vary within a considerable broad range. Generally, however, alachlor or metolachlor may be used in an amount of about 2 to 100 parts by weight, preferably of about 4 to 60 parts by weight, to one part by weight of Compound (I).

In addition to the above active ingredients, the composition may contain a solid or liquid carrier or diluent. Any surface active or auxiliary agent may be also incorporated therein. Thus, the composition may be formulated in any conventional preparation form such as emulsifiable concentrate, wettable powder, suspension or granules. The combined content of the active ingredients in the composition may be from about 0.5 to 90% by weight, preferably from about 1 to 80% by weight.

As the solid carrier or diluent, there may be used kaolin clay, attapulgite clay, bentonite, terra alba, pyrophyllite, talc, diatomaceous earth, calcite, wallnut-shell powder, urea, ammonium sulfate, synthetic hydrated silica, etc. Examples of the liquid carrier or diluent are aromatic hydrocarbons (e.g. xylene, methylnaphthalene), alcohols (e.g. isopropanol, ethylene glycol, cellosolve), ketones (e.g. acetone, cyclohexanone, isophorone), vegetable oils (e.g. soybean oil, cotton-seed oil), dimethylsulfoxide, acetonitrile, water, etc.

The surface active agent used for emulsification, dispersion or spreading may be any of the anionic and nonionic type of agents. Examples of the surface active agent include alkylsulfates, alkylarylsulfonates, dialkylsulfosuccinates, phosphates of polyoxyethylenealkylaryl ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. Examples of the auxiliary agents include ligninsulfonates, sodium alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate), etc.

Practical embodiments for preparation of the composition are illustratively shown in the following Formulation Examples wherein part(s) are by weight.

Two parts of Compound (I), 50 parts of alachlor, 3 parts of calcium ligninsulfonate, 2 parts of sodium laurylsulfate and 43 parts of synthetic hydrated silica are well mixed while being powdered to obtain a wettable powder.

0.5 part of Compound (I), 20 parts of alachlor or metolachlor, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 73.5 parts of water are mixed and pulverized until the particle size of the composition become less than 5 microns to obtain a suspension.

0.5 part of Compound (I), 10 parts of metolachlor, one part of synthetic hydrated silica, 2 parts of calcium ligninsulfonate, 30 parts of bentonite and 56.5 parts of kaolin clay are well mixed and pulverized. The resulting powder is admixed with water and dried to obtain granules.

A composition comprising Compound (I) and alachlor or metolachlor thus formulated is useful for pre-emergence control of undesired weeds by soil treatment. The soil treatment includes application to the soil surface prior to or after seeding or transplanting of the crop or incorporation into the soil before seeding. The direct application may be also adopted.

In order to improve the herbicidal activity, the composition may be used together with other herbicides. Besides, it may be used in combination with insecticides, acaricides, nematocides, fungicides, plant growth regulators, fertilizers, soil improvers, etc.

The dosage of the active ingredients may vary depending on prevailing weather conditions, soil involved, formulation used, mixing proportion of each active ingredient, crop and weed species, etc. In general, however, the total amount of Compound (I) and alachlor or metolachlor is favored to be within a range of about 50 to 4000 grams per hectare, preferably of about 200 to 2500 grams per hectare.

In case of the composition being formulated into an emulsifiable concentrate, a wettable powder or a suspension, it is normally diluted with water and applied over the top at a volume of about 10 to 1000 liters per hectare to the foliage of the crop plants or weeds which germinate or have germinated. The dilution may contain, in addition to the above mentioned surface active agent, any spreading or auxiliary agent such as polyoxyethylene resin acid esters, ligninsulfonates, abietic acid, dinaphthylmethanedisulfonates, paraffin and the like.

The practical herbicidal activity of the system of the invention will be explained in further detail with reference to the following Test Examples wherein the growth controlling percentage (%) was determined by weighing the aerial parts of the test plants (fresh weight) and making calculation according to the following equation: ##EQU1##

The phytotoxicity to crop plants was visually observed.

Seeds of soybean, peanut, green foxtail, southern crabgrass, barnyardgrass, redroot pigweed, black nightshade, velvetleaf and sicklepod were sowed in a vat (area, 17.times.24 cm.sup.2 ; height, 7 cm) filled with upland field soil. A designated amount of the composition in the form of a wettable powder formulated according to Formulation Example 1 was diluted with water and sprayed to the soil at a spray volume of 1000 liters per hectare by the aid of a small hand sprayer. After 20 days' cultivation outdoors, the phytotoxicity and growth controlling percentage were observed. The results are shown in Table 1. __________________________________________________________________________ Mixing Phyto-  Growth controlling percentage (%) ratio toxicity Green Southern        Black Active  Dosage (by  Soy-    fox- crab- Barnyard- Redroot night- Velvet Sickle- ingredient (g/ha) weight) bean Peanut tail grass grass pigweed shade leaf pod __________________________________________________________________________ Alachlor 250  --   None None 55  45   80    41   10  0   5 500  --   None None 88  70   95    68   16  0  10 Metolachlor 250  --   None None 65  60   85    93   18  0  12 500  --   None None 88  78   97   100   25  0  16 Compound (I) 25  --   None None 66  50   10    93   96  73 21 50  --   None None 85  63   58   100  100  95 40 Compound (I) 25 + 1:10 None None 100 100  100   100  100 100 83 +     25 + 500 1:20 None None 100 100  100   100  100 100 94 Alachlor 50 + 250 1:5  None None 100 100   98   100  100 100 95 50 + 500 1:10 None None 100 100  100   100  100 100 100 Compound (I) 25 + 250 1:10 None None 100 100  100   100  100 100 87 +     25 + 500 1:20 None None 100 100  100   100  100 100 96 Metolachlor 50 + 250 1:5  None None 100 100  100   100  100 100 98 50 + 500 1:10 None None 100 100  100   100  100 100 100 __________________________________________________________________________

Seeds of geen foxtail were sowed in a vat (area, 10.times.16 cm.sup.2 ; height, 6 cm) filled with upland field soil. A designated amount of the composition in the form of a wettable powder formulated according to Formulation Example 1 was diluted with water and sprayed to the soil at a spray volume of 1000 liters per hectare by the aid of a small hand sprayer. After 20 days' cultivation outdoors, the growth controlling percentage was observed. The results are shown in Tables 2 and 3. ______________________________________ Growth controlling percentage of green foxtail (%) Compound (I) (g/ha) 0    6.3    12.5     25   50     100 ______________________________________ Alachlor 0       0     21   45     66    85     97 (g/ha)  63     12     43   55     85    98    100 125     35     64   84     96   100    100 250     58     83   98     100  100    100 500     88     97   100    100  100    100 1000    99     100  100    100  100    100 ______________________________________ ______________________________________ Growth controlling percentage of green foxtail (%) Compound (I) (g/ha) 0     6.3    12.5     25   50   100 ______________________________________ Meto-    0       0      21   45     66    85   97 alachlor 63     13      45   75     88    97  100 (g/ha)  125     45      70   86     95   100  100 250     63      85   96     100  100  100 500     88      95   100    100  100  100 1000    98      100  100    100  100  100 ______________________________________

The results in Test Example 2 were analyzed according to the isobole (i.e. equivalent efficacy line) method [Vol. 3, Herbicides, pages 109-111 (1981) in "Noyaku Jikkenho" (Methods in Pesticide Science) edited by Junichi Fukami et al., Soft Science Inc., Tokyo] based on the Tammes's method [Tammes, P. M. L.: Neth. J. Plant Path., 70, 73-80 (1964)]. Namely, several combinations of the compositions having different mixing ratios of Compound (I) and alachlor or metolachlor but exerting the same level of growth control effect, for example, 90% growth control, were plotted in a graph so as to readily determine a synergistic effect, an arithmetic effect or a competitive effect. In case of exhibiting the synergistic effect, the equivalent efficacy line as plotted is shown below the arithmetic efficacy line.

Explaining further in detail with reference to the accompanying drawings, FIG. 1 wherein the ordinate indicates the dosage of Compound (I) and the abscissa indicates the dosage of alachlor shows that the equivalent efficacy line (i.e. solid line) of 90% growth control of green foxtail is located below the arithmetic efficacy line (i.e. dotted line), from which it is understood that the associated use of Compound (I) and alachlor in a certain mixing ratio produces a synergistic effect; and FIG. 2 wherein the ordinate indicates the dosage of compound (I) and the abscissa indicates the dosage of metolachlor shows that the equivalent efficacy line (i.e. solid line) of 90% growth control of green foxtail is located below the arithmetic efficacy line (i.e. dotted line), from which it is understood that the associated use of Compound (I) and metolachlor in a certain mixing ratio produces a synergistic effect.

## Claims

1. A herbicidal composition which comprises a herbicidally effective and synergistic amount of the combination of (a) 2-{7-fluoro-3,4-dihydro-3-oxo-4-(2-propynyl)-2H-1,4-benzoxazin-6-yl}-4,5,6 ,7-tetrahydro-1H-isoindol-1,3(2H)-dione of the formula: ##STR4## and (b) N-methoxymethyl-2',6'-diethyl-2-chloroacetanilide of the formula: ##STR5## as the active ingredients in a quantity capable of producing a synergistic herbicidal effect, and an inert carrier or diluent, wherein the weight proportion of the components (a) and (b) is from 1:5 to 60.

2. The composition according to claim 1, wherein the weight proportion of the components (a) and (b) is from 1:5 to 40.

3. The composition according to claim 1, wherein the weight proportion of the components (a) and (b) is from 1:10 to 40.

4. The composition according to claim 1, wherein the weight proportion of the components (a) and (b) is from 1:20 to 40.

5. A method for controlling weeds which comprises applying a herbicidally effective and synergistic amount of the composition according to claim 1 to the weeds.

6. The method according to claim 5, wherein the weeds are those germinated in a field of soybean or peanut crops.

7. The method according to claim 5, wherein the total amount of the components (a) and (b) is from 200 to 2500 grams per hectare.

8. The method according to claim 5, wherein the total amount of the components (a) and (b) is from 200 to 1000 grams per hectare.