JPH0148260B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to the field of 2-haloacetanilides and their use in agricultural economic technology, for example as herbicides. Prior art relevant to the present invention includes unsubstituted or substituted substituents on the anilide nitrogen atom and/or on the anilide ring, including groups such as alkyl, alkoxy, alkoxyalkyl, haloalkyl, halogen, etc. contains numerous disclosures regarding 2-haloacetanilides. The compounds of the invention are characterized in that they have a hydrocarbyloxymethyl group in the anilide nitrogen, a trifluoromethyl group in one ortho position and a methyl group or, in special cases, an ethyl group or hydrogen in the other ortho position. More relevantly, the closest prior art known to the inventor is believed to be Belgian Patent No. 810,763. The most relevant disclosure in Belgian Patent No. 810763 is that one or more groups selected from various groups including halogen, alkyl, alkoxy or trifluoromethyl ( _-CF3 ) in the ortho and meta positions of the anilide ring General disclosure regarding N-alkoxyethyl- or alkyl-substituted alkoxyethyl-2-chloroacetanilides substituted with groups. For more details, the list of compounds in the table includes compounds that are substituted with a trifluoromethyl group at one ortho position and have no substituent at the other ortho position (compounds No. 37 to 48) and trifluoromethyl at the meta position. having a substituent, one ortho position is unsubstituted, and the other ortho position is substituted with a methoxy group (compounds No. 22 to 25) or a chlorine atom (compounds No. 33 to 36). Contains compounds such as However, Belgian patent no. 810763
This issue contains no specific disclosure or exemplary compounds regarding 2-haloacetanilides substituted with a trifluoromethyl group in one ortho position and with a methyl or ethyl group in the other ortho position as well as the compounds of the present invention. Not yet. Furthermore, the compound of Belgian Patent No. 810763 has an alkoxyalkyl group substituted on the anilide nitrogen atom (the alkylene moiety must have two or more carbon atoms between the nitrogen atom and the nitrogen atom of the alkoxy moiety). It is characterized by In contrast, the compounds of the present invention are further characterized somewhat by substitution at the anilide nitrogen atom with an alkoxymethyl group. The significance of the above-mentioned differences between the compounds of Belgian Patent No. 810,763 and the compounds of the present invention will become clear with reference to the comparison of the herbicidal data herein, which shows that the unit activity, selectivity, weed The superiority of the compounds of the invention in terms of control spectrum and crop safety has been clearly established. Other pertinent prior art that is less relevant than Belgian Patent No. 810,763 cited above includes U.S. Pat.
3966811 and 4152137, German Patent Application No. 2402983, British Patent Application No.
2013188 and South African Patent No. 74/
Specification No. 0767 is included. Although these references specifically contain general disclosures regarding 2-haloacetanilides in which the anilide ring is substituted with a trifluoromethyl substituent, all of these references do not discuss any type of such compounds. The only disclosures of this invention are found in US Pat. No. 3,966,811 and South African Patent No. 74/0767. Even so, neither U.S. Patent No. 3966811 nor South African Patent No. 74/0767 includes classes of compounds substituted with trifluoromethyl in the ortho position, either generally or more specifically. Nor does it include such compounds in which the other ortho position is further substituted with a methyl or ethyl group. The only types of trifluoromethyl substituted compounds disclosed in these patents are compounds substituted with trifluoromethyl at the meta position. Furthermore, the Belgian patent no.
Similar to '810763, US Pat. No. 3,966,811 and South African Patent No. 74/0767 both require two or more carbon atoms between the anilide nitrogen and the oxygen of the alkoxy moiety. This requirement is stated in all of the aforementioned prior art documents except US Pat. No. 4,152,137, which, as mentioned above, does not disclose any compounds substituted with trifluoromethyl. Among the most relevant prior art listed above are Belgian Patent No. 810763 and South African Patent No.
No. 74/0767 only discloses herbicidal data for N-alkoxyalkyl-2-haloacetanilides having a trifluoromethyl substituent on the anilide ring. Even so, such disclosures are vague, unclear, and incomplete. For example, Belgian Patent No. 810,763 contains only one compound substituted with trifluoromethyl, namely Compound No. 37 (which is the same compound as Example 2), i.e. 2-trifluoromethyl-N-(2'-methoxyethyl )-2-Chloro-acetanilide limited herbicidal data have been disclosed. In Table 3 of Belgian Patent No. 810763, compound No. 37 is Cuperus,
Setaria, Digitaria
It kills or seriously damages some unspecified species of Echinochloa and the weed oat [Avena spp.] in some crops.
It has been shown to cause little damage to unspecified species of Avena fatua and Lolium. Five of the six weeds tested were not specifically specified, which precludes meaningful evaluation of the effectiveness of Compound 37 as a herbicide. Similarly, South African Patent No. 74/0767 discloses only one compound substituted with a trifluoromethyl group, namely Compound No. 78, 2,6-dimethyl-
Limited herbicidal data have been disclosed for 3-trifluoromethyl-N-(2'-methoxyethyl)-N-2-chloroacetanilide. Compound No.
The only herbicidal data disclosed for 78 is shown in Example 5, where Compound No. 78
It has been described that it exhibits extremely strong growth inhibition against certain types of weeds. However, Belgian Patent No. 74/0767 does not explain what kind of crops Compound No. 78 has an effect on, or whether it selectively controls what weeds in what crops. No laboratory or field data on this issue have been disclosed. A meaningful evaluation of the compound based on such limited data is therefore not possible. Furthermore, the most relevant references mentioned above disclose herbicidal activity against various weeds, including the difficult-to-kill perennial weed Prunus japonicus in one or several crops;
Cyperus and trifolium and difficult-to-kill annual weeds such as seedling johnsongrass, shattercane, alexandergrass (Brachiaria plantaginea), and Texas panicum (Texas panicum). ) and wild millet, red rice and itchgrass, Raoulgrass, as well as other harmful Perennial and annual weeds, such as giant foxtail, willow knotweed, whiteweed, pigweed, and weeds (such as giant foxtail).
foxtail) and golden foxtail], crabgrass, cane millet, morning glory, croaker, Japanese snail, purslane, hempsesbania,
N- substituted with trifluoromethyl to control or suppress golden deer, etc.
No data are disclosed for alkoxy-alkyl compounds. A very useful and desirable property as a herbicide is the ability to maintain weed control over an extended period of time, the longer the duration of each crop's growing season the better. With many prior art herbicides, weed control may be adequate for as little as 2 or 3 weeks, and in some excellent cases perhaps 4 to 3 weeks.
Up to 6 weeks is suitable, after which the chemical loses its effective phytotoxic effect. Therefore, one disadvantage that most prior art herbicides have is their relatively short soil life. Another disadvantage that some prior art herbicides have is somewhat related to soil longevity under normal weather conditions, but weeds cannot survive under heavy rains, which inactivates many herbicides. This is a lack of sustainability of control. Another disadvantage of many prior art herbicides is their limited use in certain types of soil. That is, while some herbicides are effective in soils containing low amounts of organic matter, they are ineffective in other soils containing high amounts of organic matter, or vice versa. It is therefore advantageous for the herbicide to be useful in all types of soils ranging from light organic soils to heavy clays and composts. Yet another disadvantage of many prior art herbicides is that they are limited to specific effective application methods. That is, application methods are limited to pre-emergent surface application or incorporation into the soil before and/or after planting. The ability to apply herbicides by any application method, whether surface application or incorporation into the soil, is highly desirable. And finally, another disadvantage that some herbicides have is that, due to their toxicity, special handling procedures have to be applied and maintained. Therefore, another urgent requirement is that herbicides be safe to handle. It is therefore an object of the present invention to provide a family of herbicidal compounds which overcomes the above-mentioned disadvantages of the prior art herbicides and which offers a wide variety of advantages that have not been achievable to date with a single family of herbicides. It is to be. The purpose of the present invention is to maintain crop safety for a large number of crops, particularly corn and soybeans, and for other crops including cotton, peanuts, oilseed rape, small beans, wheat and/or sorghum. However, it is an object of the present invention to provide herbicides that control and/or suppress difficult-to-kill perennial and annual weeds, such as those mentioned above. Another object of the invention is to provide herbicide effectiveness in soil over a period of up to 12 weeks. Yet another object of the present invention is to provide a herbicide that resists dissolution and dilution due to humid conditions such as heavy rains. Yet another object of the present invention is to provide a herbicide that is effective over a wide range of soils, including light to normal organic soils to heavy clays and composts. Another advantage of the herbicides of the present invention is that they can be applied in a variety of ways: pre-emergent surface application or soil incorporation. Finally, it is an advantage of the herbicides of the invention that they are safe and do not require special handling methods. The above objects and other objects of the present invention will become more apparent from the detailed description below. The present invention relates to herbicidally active compounds, herbicidal compositions containing these compounds as active ingredients, and herbicidal methods using these compositions in specific crops. Now the selected compound is characterized by a special hydrocarbyloxymethyl group on the anilide nitrogen atom, a special combination of a trifluoromethyl (-CF ₃ ) group in one ortho position and a methyl or ethyl group or a hydrogen atom in the other ortho position. It has been found that a group of 2-haloacetanilides have significant herbicidal activity that is surprisingly superior to prior art herbicides, including the most related prior art congeners. The first feature of the herbicidal composition of the present invention is:
Especially corn and soybeans, but also other crops such as cotton, peanuts, oilseed rape, sorghum,
Weeds that can be controlled by currently used herbicides while preserving crop safety for one or more of a number of crops, including wheat and beans, and one additional known herbicide. Their ability to control a broad spectrum of weeds, including many species of weeds that have not been individually and/or collectively controlled by some agents to date. While prior art herbicides are often useful in controlling a variety of weeds, including some resistant weeds, the unique herbicides of the present invention are useful in controlling a wide variety of resistant perennial and annual weeds, such as perennial cyperus, cyperus, and commonweed, annual broad-leaved weeds such as goldenrod, sesbania hemp, willow knotweed, whiteweed, pigweed, and annual weeds such as seedling Seiban sorghum, staghorn cane, Alexander grass, Texas panicum, wild millet, It has been found that rice, Japanese grass and other noxious weeds such as cane grass, grasshopper, cane millet, crabgrass, etc. can be controlled or greatly suppressed. Reductions in weed resistance have also been achieved in resistant weeds such as ragweed, croaker, morning glory, Japanese fir, and purslane. Compounds of the invention have the formula (wherein R is C _1-5 alkyl or alkoxyalkyl or alkenyl or alkynyl having up to 5 carbon atoms, R ₁ is hydrogen,
methyl or ethyl, except that when R ₁ is hydrogen, R is isopropyl, and when R ₁ is ethyl, R is ethyl, n-propyl or isopropyl) It is characterized by A preferred class of the invention is R ₁ in the above formula
is methyl or ethyl, and R is _{a C2-4} alkyl group. Individual preferred compounds of the invention are described below. N-(ethoxymethyl)-2'-trifluoromethyl-6'-ethyl-2-chloroacetanilide, N-(n-propoxymethyl)-2'-trifluoromethyl-6'-methyl-2-chloroacetanilide, N-(isopropoxymethyl)-2'-trifluoromethyl-6'-methyl-2-chloroacetanilide, N-(isobutoxymethyl)-2'-trifluoromethyl-6'-methyl-2-chloroacetanilide, N-(ethoxymethyl)-2'-trifluoromethyl-6'-ethyl-2-chloroacetanilide, N-(n-propoxymethyl)-2'-trifluoromethyl-6'-ethyl-2-chloroacetanilide, N-(isopropoxymethyl)-2'-trifluoromethyl-6'-ethyl-2-chloroacetanilide. Other compounds of the invention are described below. The utility of the compounds of the invention as active ingredients and their use in herbicidal compositions formulated using the compounds of the invention are described below. Compounds of the present invention can be prepared by N-alkylating the anion of a suitable secondary 2-haloacetanilide using an alkylating agent under basic conditions, as exemplified in Example 1 herein. Can be manufactured.
A modification of the N-alkylation process involves the in situ production of the halomethyl alkyl ether used as a starting material in the N-alkylation process described above, and is another modification of the present invention. Example 2 describes the production of two types. Example 1 This example describes the preparation of N-(ethoxymethyl)-2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. 2′-trifluoromethyl-
6′-Methyl-2-chloroacetanilide 4.02g
(0.016 mol), chloromethyl ethyl ether 3.02 g
(0.032 mol) and 2.0 g of benzyltriethylammonium bromide [phase transfer catalyst (phase
transfer catalyst)] in 75 ml of methylene chloride. When 15 ml of sodium hydroxide (50%) is added all at once with rapid stirring, it generates heat and reaches 26°C. Gas chromatography shows that the reaction is complete after about 5 minutes. After 15 minutes ice water is added, the layers are separated, the organic layer is washed with 2.5% sodium chloride, dried, filtered and the solvent is evaporated. The dark residue is distilled on a Kugelrohr and 3.4 g of a yellow oil boiling at 110-115°C (0.1 mm) is collected. This portion is dissolved in cyclohexane and purified by high performance liquid chromatography (HPLC) using 20% ethyl acetate in cyclohexane. Furthermore, when the main fraction was distilled using a Kugelrohr, 3.2g of colorless oil was obtained.
[Yield 65%, bp 100-110°C (0.1 mmHg)] is obtained, and when left to stand, it crystallizes to obtain a white solid (mp 41°C-43°C). Elemental analysis value (as C ₁₃ H ₁₅ ClF ₃ NO ₂ ) C H N theoretical value: 50.41 4.88 4.52 Actual value: 50.02 4.81 4.38 Example 2 This example describes another improved method by which the compound of the present invention can be produced. Explain the use of. A feature of the process of this example is that the alkylating agent is generated in situ, thus resulting in a more efficient, economical and simple operation. A slurry of 7.3 g (0.096 mole) of ethylene glycol monomethyl ether and 1.44 g (0.048 mole) of paraformaldehyde in 100 ml of methylene chloride solvent is cooled in an ice-water bath and 5.9 g (0.048 mole) of acetyl bromide is added. After stirring for about 45 minutes, 2'-trifluoromethyl-6'-methyl-2-
4.03 g (0.016 mol) of chloro-acetanilide and 2.0 g of benzyltriethylammonium chloride
Add. Add 50 ml of 50% sodium hydroxide all at once. Gas chromatography shows the reaction to be complete after about 5 minutes. Ice water is added to the mixture to separate the phases, then the organic phase is separated, dried, filtered and the solvent is distilled off. When the residue is vacuum distilled by short path distillation, it becomes a colorless and transparent oil.
4.2 g [yield 77%, bp 150-160°C (0.05 mmHg)] is obtained. Elemental analysis value (as C ₁₄ H ₁₇ ClF ₃ NO ₃ ) C H N theoretical value: 49.49 5.04 4.12 Actual value: 49.33 5.04 4.08 The product is N-(2-methoxyethoxymethyl)-2'-trifluoromethyl- 6′-methyl-2
-Identified as chloroacetanilide. If the above N-alkylation processes are carried out at extremely high or extremely low temperatures, various impurities can be formed, such as secondary anilides, the corresponding imidates, α-alkoxyamides or diketopiperazines. Such impurities can be removed by washing the organic layer with a dilute aqueous solution of acid containing salt, such as 2-3% sodium chloride or 5% hydrochloric acid. Examples 3-13 Following substantially the same procedures, amounts of reactants and general reaction conditions as described in Examples 1 or 2, but using the appropriate starting secondary anilide and alkylating agent, The final product or other compound according to the above formula is produced. These compounds are shown in the table.

【table】

TABLE The secondary anilide starting materials used in the above examples to prepare the compounds of the invention are:
Suitably prepared by conventional chloroacetylation of a suitable primary amine as illustrated in Example 14 below. Example 14 This example describes the preparation of the secondary anilide starting material used to prepare the class of compounds of this example, namely the compound of Example 13. 2-trifluoromethyl-6-ethylaniline
6.0 g (0.03174 mol) dissolved in 75 ml toluene and 3.77 g (0.033 mol) chloroacetyl chloride
Add carefully. The resulting slurry is heated to reflux temperature and held for 4 hours. The mixture is then diluted with an equal volume of hexane and the mixture is allowed to stand. The product crystallizes. Filter the generated solids and air dry to form a product.
5.8 g (69% yield) is obtained. Concentrating the liquid yields an additional 2.7 g of white solid [mp 121-124°C (in a sealed tube)]. Elemental analysis value (as C ₁₁ H ₁₁ ClF ₃ NO) C H N theoretical value: 49.73 4.17 5.27 Actual value: 49.36 4.09 5.38 The product is fixed with 2'-trifluoromethyl-6'-ethyl-2-chloroacetanilide be done. Primary amines of the type used to prepare secondary anilides by haloacetylation as described above are known in the literature. See, for example, US Pat. No. 3,966,811 and UK Patent No. 2,013,188, cited above. As indicated above, the compounds of the present invention have been found to be effective as herbicides, and are particularly effective as pre-emergent herbicides, although post-emergence activity has also been demonstrated. The pre-emergence tests described herein include both greenhouse and field tests. In greenhouse tests, herbicides are applied surface-applied after sowing or after planting the plant propagules, or by incorporation into a volume of soil applied as a coating on the test seeds in the test container prior to sowing. Applicable. In field tests, herbicides were mixed into the soil before planting (pre-plant
(incorporated “PPI”). i.e. the herbicide is applied to the surface of the soil, incorporated into it by mixing means, and then the crop seeds are sown, or the crop seeds are sown and the herbicide is then applied to the surface (“SA” surface application). be able to. The surface application (SA) test method used in greenhouses is performed as follows. Typically 9.5″ x 5.25″ x 2.75″ (24.13cm x 13.34cm) with drainage holes in the bottom
x 6.99cm) aluminum pan or 3.75″ x
Fill a 3.75″ x 3″ (9.53 cm x 9.53 cm x 7.62 cm) plastic pot evenly with Ray Silt Loam soil, then fill it 0.5 inch (1.27 cm) from the top of the pot.
Pack it tightly to the level of . The pots are then sown with seeds of the type of plant to be tested and covered with a 0.5 inch layer of test soil. The herbicide is then applied to the soil surface using, for example, a belt sprayer.
Applied at 20gal/A, 30psi (187/ha, 2.11Kg/cm ² ). Water each pot with 0.25 inches (0.64 cm) using overhead irrigation, then place the pots on greenhouse benches for continued sub-irrigation as needed. Alternatively, top irrigation may be omitted. The effect of the herbicide is observed approximately 3 weeks after treatment. Contamination of soil used in greenhouse tests (S.
The herbicide treatment according to I.) is as follows. Fill an aluminum pan with good grade top soil and pack tightly to a depth of 3/8 to 1/2 inch from the top of the pan. A large number of seeds or plant propagules of many types of plants are placed on the soil surface. Weigh into the pans the soil needed to evenly fill the pans after sowing or adding plant propagation. The soil and a known amount of the active ingredient applied in a solvent or as a suspension in a wettable powder are thoroughly mixed and used to coat the prepared bread. After treatment, the pans are first top-irrigated with water equivalent to 1/4 inch (0.64 cm) of rainfall, then sub-irrigated as needed to provide adequate moisture for germination and growth. Water is supplied by Alternatively, top irrigation can be omitted. Observations are made approximately 2-3 weeks after sowing and treatment. Tables and Tables summarize the results of tests conducted to determine the pre-emergence herbicidal activity of compounds of the invention. In these trials the herbicides are applied by incorporation into the soil and watered only by sub-irrigation. Herbicide ratings are obtained on a fixed scale based on the damage rate of each plant species. The evaluation is determined as follows. Control rate (%) rating 0-24 0 25-49 1 50-74 2 75-100 3 Incalculable 5 The types of plants used in a set of tests are indicated in letters according to the legend below, and the data for them are Shown in the table. A. Ezono fox thistle G. Cyperus B. Japanese fir tree H. C. japonica C. I. Seiban sorghum D. Morning glory J. Japanese cyperus E. White-spotted herb K. Cane millet F. Willow knotweed

【table】

[Table] Additionally, the compounds are tested against the following plant species by using the method described above. L Soybean R Sesbania hemp M Sugar beet E White radish N Wheat F Salix spp. O Rice C Japanese sorghum P Sorghum J Sorghum B. Japanese staghorn S. Fiscus Q. Buckwheat K. Corn millet D. Morning glory T. The results are summarized in the table.

【table】

【table】

[Table] The herbicide of the present invention can be used as a pre-emergence herbicide, more specifically, perennial and annual weeds that are difficult to kill, including perennial cyperus, cyperus, and cyperus, annual broad-leaved weeds, such as golden deer, Sesbania hemp, fireweed, whiteweed, greenweed, and annual weeds such as staghorn cane, alexandergrass, seiban sorghum, Texas panicum, wild millet, rice, yutsigrass,
Rottboellia exaltata
It has been found that the present invention has a surprisingly good effect in the selective control of Sparrow grasses (for example, Foxtail, Golden foxtail and Giant Foxtail), Japanese millet and crabgrass. Selective control and increased suppression of the above-mentioned weeds by the herbicides of the present invention is found in a large number of crops, of particular interest in corn and soybean, but in other crops such as cotton. , peanuts, oilseed rape, beans (small kidney beans), wheat and sorghum. However, the latter two crops are usually less tolerant of the herbicides of the invention than the other crops described. Such reduced tolerability can be improved by using safeners or antidotes to the herbicide. In discussing the data below, and in the tables containing those data, the herbicide application ratios designated by the symbols "GR ₁₅ " and "GR ₈₅ " are used for reference. These ratios are given in kg per hectare (Kg/ha),
It is converted to pounds per acre (lbs/A) by dividing the Kg/ha ratio by 1.12.
GR ₁₅ is defined as the maximum application rate of herbicide required to achieve 15% or less crop damage, and GR ₈₅ is defined as the minimum application rate required to achieve 85% control of weeds. Ru. GR ₁₅ and GR ₈₅ are used as a measure of possible commercial utility. It is, of course, understood that appropriate commercial herbicides may cause some crop damage within reasonable limits. Another measure of a chemical's effectiveness as a selective herbicide is the herbicide's "selection factor" (SF) for a given crop and weed. The selection factor is a measure of the relative extent of crop safety and weed damage, and is determined by the ratio GR ₁₅ /GR ₈₅ , i.e. the ratio of GR ₁₅ to crop to weeds.
GR ₈₅ (both ratios are expressed in kg/ha (lb/A)). In the table below, selection factors are indicated in brackets next to the proportion of GR ₈₅ for each weed. The symbol "NS" stands for "non-selective." Marginal or undetermined selectivity is indicated by a dash (-). Since crop tolerance and weed control are interrelated, it is worthwhile to briefly discuss this relationship in terms of selective factors. In general, it is desirable for the crop to have a high safety factor, ie, a high tolerance value to the herbicide. This is because higher herbicide concentrations are often desirable for one reason or another. Conversely, it is economical to have a low weed control ratio, that is, a high unit activity of the herbicide.
And perhaps desirable for ecological reasons. However, low application rates of herbicides may not be suitable for controlling some weeds, and larger rates may be required. Therefore, the best herbicide is one that controls the maximum number of weeds with the least amount of herbicide and provides the highest crop safety or crop tolerance. Selection factors (as defined above) are therefore used to quantify the relationship between crop safety and weed control. For the selection factors listed in the table, the higher the number, the more selective the herbicide is for weed control in a given crop. In order to explain the unexpectedly superior action of the compounds of the invention on both an absolute and relative basis, comparative studies with prior art compounds whose chemical structure is most closely related to the compounds of the invention were carried out in the greenhouse. It will be held in The above prior art compound is represented as (using the same nomenclature as the compounds of the present invention) A N-(methoxyethyl)-2'-trifluoromethyl-2-chloroacetanilide, B N- (Ethoxyethyl)-2'-trifluoromethyl-2-chloroacetanilide. Tables and Tables Compare the Relative Efficiency of the Compounds of the Invention and the Prior Art Compounds Listed Above as Selective Herbicides Against the Resistant and Troublesome Perennial Weeds Cyperus and Cyperus in Soybean and Corn, respectively. Previous herbicidal activity data are shown. These weeds are commonly associated with major crops such as corn and soybeans. The test data in Tables and Tables were obtained under the same conditions and represent the average of two duplicate tests (with the exception of Example 13, which represents the results of one comparative test). The test procedure is similar to that described in Tables and for, except that an initial top irrigation equivalent to 1/4 inch (0.64 cm) of rainfall is applied. Subsequent water supply will be provided by underground irrigation.
"NS" means non-selective within the test range.

Table The data in the table shows that all the compounds of the present invention exhibit significantly higher selectivity factors (values in brackets) than the prior art compounds for both Cyperus and Cyperus in soybean.
More particularly, the compounds of the present invention can have significantly higher unit activity (relative phytotoxicity per unit of herbicide) against cyperus and cyperus than that of the prior art compounds while retaining crop safety. Recognize. Particularly noteworthy is that the selectivity factors of the compounds of Examples 1 and 13 are significantly higher. Additional comparative data is provided in the table showing the relative effectiveness of the compounds of the present invention as compared to the prior art compounds described above against cyperus and cyperus in corn.

TABLE The data in the table shows that all compounds of the present invention exhibit significantly higher selection factors than the prior art compounds for both cyperus and cyperus in corn. Once again, it can be seen that the unit activity of the compounds of the invention against cyperus and cyperus is significantly higher than that of the prior art compounds, and at the same time crop safety is preserved. Of particular note is the large selectivity of the compounds of Examples 3, 5 and 13, especially compared to the selectivity of the prior art compounds. From the comparative data presented in the table and in Table 1, the compounds of the present invention are shown to be effective against the most closely related prior art compounds against the herbicidally resistant perennial weeds Cyperus and Cyperus in two major crops, namely soybean and corn. That is, compound A
It is clear that the efficacy as a herbicide is significantly higher and unexpectedly superior to that of B and B. Further pre-emergence herbicidal data from other tests have shown that the compounds of the invention also have been shown to be effective against cyperus and cyperus in one or more crops of cotton, peanuts, small beans, wheat, sorghum and/or canola. and/or other weeds. For example, the table shows the compounds of Examples 1 and 3,
Data are provided demonstrating herbicidal selectivity for snail beetles in field beans, sorghum, and wheat. Unless otherwise noted, greenhouse trials in the table and other tables below include herbicide treatment by incorporation into the soil as described above, initial top irrigation followed by sub-irrigation.

[Table] The compound of Example 1 was also found in a wide variety of crops, such as Sparrow (genus), cane millet, and white millet.
tested in the field to determine pre-emergence selectivity for the plant (prosomillet). Data (representing three replicates) are shown in the table for both surface application (SA) and soil incorporation (PPI, ie pre-plant incorporation) of the herbicide. It is sown in a bed of fine silty loam soil with moderate moisture.
Seeds are sown 2 inches (5.08 cm) deep. First rain the day after treatment (0.2 inches, 0.51 cm)
It rained a second time on the second day after treatment (0.25″, 0.64
cm), and the total rainfall during the 22 days after treatment was 1.8 inches (4.57 cm). Observations are made 6 weeks after treatment.

TABLE The data in the table generally indicate that the compound of Example 1 works better as a selective herbicide in surface application than when incorporated into soil. More specifically, in surface application tests, the herbicide was tested at application rates of 0.58 Kg/ha (0.5 lb/A) or higher.
Seed Testing Selective control of weeds while in forage corn (field corn) and soybean
Retain crop safety (i.e. losses up to about 15%) up to 4.48 Kg/ha (4.0 lb/A), and
2.24 Kg/ha (2.0 lb/A) or more in sugar sorghum, groundnut and oilseed rape, and exactly 2.24
Remains safe in cotton, sorghum and small beans below Kg/ha. In the PPI test, the compound of Example 1 was applied to feed corn, peanuts and oilseed rape at a rate of up to 2.24 kg/ha.
and 1.12Kg/ha while retaining crop safety at a rate slightly lower than 2.24Kg/ha for soybeans.
(1.0 lb/A) or less to selectively control passerine and cane millet. Other field test data for the compound of Example 1 include other weeds in soybean, corn, cotton, and/or peanuts, such as sedge, giant foxtail, goldenrod, white locust, morning glory, Japanese snail, Japanese radish, and other weeds in soybean, corn, cotton, and/or peanuts.
Pre-emergence selective for Pennsylvania smartweed, golden deer, purslane, crabgrass, porcupine, Texas panicum, Florida pusley and/or bristly starbur Shows control. It is understood by those skilled in the art that not all described weeds may be selectively controlled in all described crops under all conditions including climate, soil, moisture and/or herbicide application method. will be understood. Data on selectivity for the control of the said weeds in the crops soybean, corn, cotton and groundnut from numerous field trials at different locations under different conditions of soil, moisture, etc. are collected in Tables XI, respectively. is shown. In the table, "WAT" means "weeks after treatment" of plants with herbicides by surface application (SA) or pre-plant soil incorporation (PPI). The application ratio data for each crop/weed combination is represented by the ratio of GR ₁₅ and GR ₈₅ (as defined above), where the ratio GR ₁₅ /GR ₈₅ represents the selection factor (SF). "NS" indicates non-selective and dash (-) for example because the actual GR ₁₅ and GR ₈₅ ratio is greater or less than the maximum or minimum ratio used in the indicated test; Represents limited or undetermined selectivity. Blank spaces in Tables XI indicate that the plant type was not used in the particular test, or the data were not available, or are less significant than other data present. For example, 3WAT observations are omitted in favor of 6WAT data, or
This indicates that 6WAT data is omitted because 3WAT data is definitive.

[Table] Smartweed The data in the table indicates that the compound of Example 1 is SA or
The PPI application method has been shown to selectively control giant foxtail, white locust, and Pennsylvania smartweed in soybean between 6 and 8 WAT.

[Table] The data in the table indicates that the compound of Example 1 is SA or
The PPI application method is shown to selectively control giant hockstail in maize between 6 and 6.5 WAT. Although selectivity for morning glory and Japanese fir is not determined in the test ratios, suppression of these weeds is demonstrated.

TABLE The data in the table show that the compound of Example 1 selectively controls common grass and purslane up to 9 WAT, golden deer up to 6 WAT, and crabgrass up to 7 WAT. Control of staghorn grass is limited or undetermined. Table XI lists three resistant annual weeds in groundnuts for up to 12WAT, namely Texas panicum;
Pre-emergence activity data for the compound of Example 1 against B. bristolii starbur and F. pasulei are shown. The data in Table XI is 1.3% organic;
Represents the average of three replicate tests with surface application of the herbicide in a sandy loam soil containing 79.2% sand and 10% clay.

TABLE The data in Table XI show that the compound of Example 1 selectively controlled Texas panicum in peanuts for up to 8 weeks and at approximately 4.48 Kg/ha (4.0 lb/A).
Showing a high degree of control even at 12WAT, the selective control of Bristoly Starbur is 3.36
Kg/ha (3.0lb/A) was achieved for 8 weeks, complete control was maintained for 12WAT at 4.48Kg/ha (4.0lb/A), and selective control of Florida Paslay was
It can be seen that control was achieved for 8WAT at 2.24Kg/ha or less, and 95% control was achieved at 12WAT at 4.48Kg/ha. In other greenhouse tests the compounds according to the invention show selective control over various annual and perennial weeds in various crops. To explain in more detail, the compound of Example 1 selectively controls Porites in corn and soybean, and
Weed GR ₁₅ /GR ₈₅ ratio (expressed in Kg/ha)
is 0.67/0.25 (SF = 2.7) in corn and 1.12/0.25 (SF = 4.5) in soybean. The compound of Example 11 exhibits selective control over Cyperus and Cyperus in corn and soybeans. The ratio of each crop/cyperus GR ₁₅ /GR ₈₅ in corn>
2.24/0.95 (SF=2.4), 2.24/0.5 (SF=
4.5), and for corn and soybean, the respective GR ₁₅ /
The ratio of GR ₈₅ is >2.24/0.5 (SF=>4.5). GR ₁₅ / in the test against Cyperus in cotton
The ratio of GR ₈₅ (average of two repeated tests) is 1.96/0.95
(SF=2.1). Similarly, the compound of Example 13 showed selective control of Cyperus japonica in cotton and Cyperus japonica in wheat, and each
The ratio of GR ₁₅ /GR ₈₅ is 0.7/0.47 (SF=1.7) in cotton,
and 0.58/0.47 (SF=1.2) in wheat. In one multi-crop test in a greenhouse, the compounds of Examples 1, 13, 14 and 15 are tested against Cyperus in cotton, soybean, corn and rice. Each compound is non-selective for Cyperus in rice. However, significantly higher selectivity for Cyperus in cotton, soybean and corn was demonstrated for each compound in the test. The respective GR ₁₅ and GR ₈₅ ratios for these compounds are shown in Table XII, with selection factors indicated in brackets after each crop.

TABLE Compounds of Examples 1 and 13-15 are further tested against Physcomitrella sinensis in wheat, soybean and corn. Each compound was found to be non-selective in wheat. The selectivity data for the above compounds against Physcomitrella in soybean and corn are shown in the table.

Table: In other greenhouse tests for herbicide efficacy, the compounds of Examples 1 and 3 were tested against resistant weeds such as Texas panicum, Seiban sorghum, Shatter cane, Alexander grass, and wild millet (Panicum myricaeum). , Akaine (red
It is tested against a number of annual weeds, including rice (Japanese rice, red rice) and Japanese grass. The results of these tests are shown in the table. The selection factor is indicated by brackets, and the dash represents marginal or undetermined selectivity.

【table】

TABLE The data in the table shows that the compound of Example 1 selectively controls all annual weeds in the test in soybean. The compound of Example 3 shows reliable selective control against all weeds except Texas panicum, wild millet and yutsigrass at the maximum test rate of 1.12 Kg/ha. A higher ratio is required to determine the selectivity of the compound against these three weed species that do not show selective control at this test ratio. A distinct advantage of herbicides is their ability to act in a wide range of soil types. Therefore, in a wide range of soil types with different organic and clay contents, Example 1
Data showing the herbicidal activity of the compounds are provided in the table. Herbicide treatment is done by soil incorporation, seeding to a depth of 0.375 inches (0.95 cm) and watering by top irrigation to 0.25 inches (0.64 cm). Observations are made approximately 3 weeks after treatment. Selection factors are indicated by brackets.

【table】

[Table] Organic matter
clay

Claims (1)

[Claims] 1 formula (In the formula, R is C _1-5 alkyl, or C 5
alkoxyalkyl, alkenyl or alkynyl, and R ₁ is hydrogen, methyl or ethyl group. However, when R ₁ is hydrogen, R is isopropyl, and when R ₁ is ethyl, R is ethyl, n-propyl or isopropyl. ). 2. The compound according to claim 1, wherein R is _C2-4 alkyl. 3. A compound according to claim 2, wherein R ₁ is methyl. 4. The compound according to claim 3, which is N-(ethoxymethyl)-2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. 5. The compound according to claim 3, which is N-(n-propoxymethyl)-2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. The compound according to claim 3, which is 6 N-(isopropoxymethyl)-2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. 7. The compound according to claim 3, which is N-(isobutoxymethyl)-2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. 8. A compound according to claim 2, wherein R ₁ is ethyl. 9. The compound according to claim 8, which is N-(ethoxymethyl)-2'-trifluoromethyl-6'-ethyl-2-chloroacetanilide. 10 The compound according to claim 8, which is N-(n-propoxymethyl)-2'-trifluoromethyl-6'-ethyl-2-chloroacetanilide. 11. The compound according to claim 8, which is N-(isopropoxymethyl)-2'-trifluoromethyl-6'-ethyl-2-chloroacetanilide. 12. The compound according to claim 2, wherein R ₁ is hydrogen. 13. The compound according to claim 12, which is N-(isopropoxymethyl)-2'-trifluoromethyl-2-chloroacetanilide. 14. The compound according to claim 1, wherein R is a _C3-5 alkenyl group. 15. The compound according to claim 14, which is N-(allyloxymethyl)-2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. 16. The compound according to claim 1, wherein 16R is a _C3-5 alkynyl group. 17. The compound according to claim 16, which is N-(propargyloxymethyl)-2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. 18. A compound according to claim 1, wherein 18R is an alkoxyalkyl group having up to 5 carbon atoms. 19. The compound according to claim 18, which is N-(methoxyethoxymethyl)-2'-trifluoromethyl-6'-methyl-2-chloroacetanilide. 20 Formulas for adjuvants and herbicidal effective amounts (In the formula, R is C _1-5 alkyl, or C 5
alkoxyalkyl, alkenyl or alkynyl, and R ₁ is hydrogen, methyl or ethyl group. However, when R ₁ is hydrogen, R is isopropyl, and when R ₁ is ethyl, R is ethyl, n-propyl or isopropyl. ) A herbicidal composition containing a compound represented by: 21 The above compound is N-(ethoxymethyl)-
Claim 20, which is 2'-trifluoromethyl-6'-methyl-2-chloroacetanilide.
Compositions as described in Section.