NL8101322A - ALFA-HALOGENIC ACETANILIDS AND PREPARATIONS CONTAINING THEM. - Google Patents

Description

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α-haloacetanilides and preparations containing them.

This invention relates to α-haloacetanilides, preparations containing them, and their agricultural use, especially as herbicides.

The prior art includes many descriptions of α-haloacetanilides which can carry a wide variety of substituents on the nitrogen atom or on the phenyl nucleus, including alkyl, alkoxy, alkoxyalkyl and halogen.

For the present invention, which is concerned with compounds having a methyl or ethyl group on the nitrogen atom, an alkoxy group in one ortho position and a methyl group in the other ortho position, US Pat. Nos. 3,268,584 , 3,442,945, 3,773,492 and 4,152,137 are the most relevant. The last two disclose general formulas for herbicidal compounds which also include the compounds of the present invention, but the only N-alkyl-α-halo-acetoanilide mentioned therein is the N-isopropyl-α-chloroacetanilide or "propachlor" , a known commercial herbicide for which no herbicide figures are given. United States Patent 2,863,752 (Reissue 26,961) teaches us a group of compounds comprising the (unnamed) propachlor and homologs and analogs thereof; of the compounds described herein, propachlor was found to be most effective as a herbicide, and so this compound was further developed. In this US patent 2,863,752 it is stated that the compounds mentioned therein can be used in doses of only 1.12 kg / ha, but in example 4 it appears that one never went below 5.6 kg / ha or 28 kg / ha . In addition, U.S. Patent 2,863,752 specifically mentions N-ethyl-α-chloroacetanilide, but U.S. Patent 4,137,070 states that this compound (Example No. 406) is an antagonist of the herbicide EPTC. In contrast to said compounds of U.S. Pat. No. 2,863,752, the compounds of the present invention are highly active, selective herbicides 8101322-2-5. \ cid against weeds that are increasingly difficult to control, and that at doses clearly below 1 kg / ha, namely up to 0.07 kg / ha.

Structurally closer to the compounds of the invention than the propachlor and related compounds, the compounds are disclosed in U.S. Pat. Nos. 3,268,584 and 3,442,945. In particular, example 13 of patent 3,268,584 mentions the compound N-tert-butyl-2'-methoxy-a-chloroacetanilide and example 67 of patent 3,442,945 mentions the compound 2-methoxy- 6-tert-butyl-α-chloroacetanilide. Thus, propachlor differs from the compounds of the invention in the kind of substituents in two different places, namely both ortho positions of the benzene core and also in the kind of alkyl group on the nitrogen atom. The compound of Example 13 above differs in the type of substituent in one ortho position, the precise nature of the alkoxy group in the other ortho position and the exact nature of the alkyl group on the nitrogen atom. The compound of Example 67 above differs in the type of substituent on the nitrogen atom and the precise nature of alkyl and alkoxy groups in the ortho positions.

U.S. Pat. No. 4,146,387 teaches α-haloacetanilides which can bear alkyl groups on the nitrogen atom and on both ortho positions. The compounds according to this patent 4,146,387 are described as known herbicides of the type already mentioned in patents 3,442,945 and 2,863,752, including also propachlor.

The above-mentioned U.S. Pat. No. 3,268,584 mentions some herbicidal data concerning the above-mentioned compound that is most closely related in structure to the compounds of the invention, and for some other, somewhat less closely related in chemistry, homologs and analogs, some figures are also provided. given. More specifically, these pertinent literature references, while containing data on herbicidal activity on a number of weeds, teach nothing about compounds that additionally or simultaneously eradicate the difficult to exterminate annuals such as Texas hand grass, itch grass, Alexander grass, 8101322 a , ? - 3 - wild millet, allepo millet, red rice and brittle reed, which also control a wide spectrum of other harmful annuals and anniversaries such as yellow sedge, water pepper, goosefoot, foxtail, lobster grass and jack-of-all-trades.

5 A very useful and desirable property of herbicides is the ability to control weeds for long periods of time, the longer during the growing season the better. With many previously known herbicides, weeds are only held back for 2 to 3 weeks, and in some better cases x * el 4 to 10 6 weeks, but then these chemicals lose their effectiveness.

A drawback of most previously known herbicides is their relatively short life in the field.

Another drawback of some previously known herbicides, somewhat related to their longevity under normal weather conditions, is their sensitivity to leaching into deeper layers, so that a heavy downpour renders many herbicides ineffective.

Another drawback of many previously known herbicides is that their action is limited to certain types of soil, ie some herbicides are active on soils with little organic matter but ineffective on soils rich in organic matter, or vice versa. It is thus advantageous for a herbicide to be effective on all types of soil, from light humus to heavy clay.

Yet another drawback of many previously known herbicides is that they can only be administered in a particular manner, so either as a surface treatment before or as a treatment of the entire top layer, or as a treatment on already-weed. It is highly desirable to have a herbicide that can be applied to all possible types, however it may be.

And finally, a drawback of some herbicides is that they have to be applied in a very special way because of their toxicity. So safe handling is another wish for herbicides.

This invention provides a group of herbicides in which the above-mentioned drawbacks of previously known herbicides over-8101322 V? % - 4 - be won, and which offer a number of advantages as a group. The herbicides of this invention selectively control hard-to-eradicate annuals such as Texas hand grass, itch grass, alexander grass, wild millet, alpine millet, red rice and brittle reed, as well as suppress a broad spectrum of slightly less troublesome annuals and annuals, while safe for many useful crops such as soybeans, cotton, groundnuts, rapeseed, kidney beans, alfalfa and / or leafy vegetables. These herbicides are active in the soil for at least 12 weeks, and they are allowed to rinse and dilute under moist conditions such as with heavy rainfall. They also work on a wide variety of soils, such as on light humus-rich sandy soils such as on heavy clay and on well-fertilized soils. Another advantage of the herbicides according to the invention is that they can be used in very different ways, and that this does not involve any danger.

All this will emerge even better from the following, further description. It has been found that a selective group of C-haloacetanilides, characterized by certain combinations of alkyl groups on the nitrogen atom in one ortho position and a certain alkoxy group in the other ortho position, unexpectedly exhibits superior and excellent herbicidal properties, compared to the previously known herbicides and even compared to the most closely related compounds in structure.

A first aspect of the herbicidal compositions according to the invention is their ability to control a wide spectrum of weeds, including those that can be controlled well with the current herbicides and also a number of weeds that can be used individually or in combination up to 30 to the dance, while these preparations are safe for the useful crops, including soybeans, cotton, groundnuts, rapeseed, kidney beans, Lucerne and others. While previously known herbicides are useful for controlling various weeds, including some also known resistant weeds, the unique herbicides of this invention have been shown to be able to control a number of resistant weeds completely or completely. s currently largely controlled, most notably the annuals such as Texas handgrass, itch grass, wild millet (Panicum miliaceum), alexander grass, red rice, brittle reed and aleppo millet, while also other less resistant 5 year olds and stop perennial weeds.

The compounds of the invention are represented by the general formula 1, wherein R is methyl or ethyl, R 1 is an alkyl group having 1 to 6, preferably 3 to 5 carbon atoms, R 2 is methyl, ethyl or t-butyl (preferably methyl) and 10 Rg is hydrogen or methyl in the meta position (preferably hydrogen), with the limitation that if R 1 is ethyl and R 1 is n-butyl, R 2 is methyl and hydrogen, if R 1 is methyl, R and R 2 are also methyl and R 1 is isopropyl or n-butyl, if R 1 is hydrogen and R and R 2 are both methyl, R 1 is ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, 2- methyl butyl, 1-methylpentyl, 2-methylpentyl or 1,3-dimethylbutyl, when R 2 is ethyl, R is methyl and R 1 is isopropyl, and if R 2 is t-butyl, R and R 1 are both methyl. Preferred compounds of the invention are: N-methyl-2-isopentyloxy-6-methyl-a-chloroacetanilide N-methyl-2-n-propoxy-6-methyl-a-chloroacetanilide N-me thy1-2 -n-butoxy-6-methyl-a-chloro-30-acetanilide N-me thy1-2-s ec-but oxy-6-methyl-a-chloro-acetanilide N-ethyl-2-n-butoxy-6 -methyl-a-chloro-acetanilide 35 N-methyl-2-isopropoxy-6-methyl-a-chloro-acetanilide 81 01 322 t -6 - N-methyl-2-isobutoxy-6-methyl-a-chloro- acetanilide N-methyl-2-isopropoxy-6-ethyl-a-chloroacetanilide 5 N-ethyl-2-n-butoxy-6-methyl-a-chloroacetanilide.

The compounds of the invention can be prepared in various ways. For example, they can arise from H-alkylation of the anion of the appropriate secondary α-haloacetanilide, which will be described in Examples I and II.

Example I

4.9 g (20 mgmol) of 2-n-butoxy-6-methyl-α-chloroacetanilide, 2.6 g (20 mgmol) of dimethyl sulfate, 2.0 g of triethylbenzylammonium bromide and 250 ml of CH2 Cl2 were combined with cooling. mixed. Now 50 ml of 50% NaOH was added all at once at 15 ° C, and the whole was stirred for 2 hours. Then 1-0 ml of water was added and the whole was allowed to mix. The organic layer was separated, washed with water, dried over MgSO4 and evaporated to dryness.

Thus, 4.2 g (78% yield) of clear liquid with bp were obtained. 135 ° / 0.07 torr, which crystallized on standing to a colorless liquid with mp. 41-42 ° C.

Elemental analysis: C 62.34%, H 7.49%, Cl 13.16%

Calculated for C 62.33%, H 7.47%, Cl 13.14%.

This product was identified as N-methyl-2-n-butoxy-6-methyl-α-chloroacetanilide.

Example II

To a mixture of 5.6 g (22 mg mol) 2-n-butoxy-6-methyl-α-chloroacetanilide, 4.0 g (24-30 mgmol) diethyl sulfate, 2.2 g triethylbenzylammonium bromide and 250 ml cooled to 15 ° C methyl chloride was suddenly added 50 ml of 50% NaOH, and the whole was stirred for 5 minutes. 150 ml of water were now added and the whole was allowed to mix. The organic layer was washed with water, dried over MgSO4, and evaporated to dryness, yielding 4.1 g of 35 (66% yield) clear liquid with bp. 14 ° / 0.05 torr.

8101322 9 * - 7 -

Elemental analysis: C 63.50%, H 7.85%, Cl 12.48%

Calculated for C 4 H C 10 O C 63.48%, H 7.81%, Cl 12.49%.

This product was identified as N-ethyl-2-n-butoxy-6-methyl-α-chloroacetanilide.

Example III

In the same mode as described in Examples I and II, with the same conditions and essentially the same amounts, always starting from the appropriate secondary anilide, other N-methyl-α-haloacetanilides were prepared, as shown in Table A.

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The secondary anilides used as starting materials were prepared in known ways, for example by haloacetylation of the corresponding aniline. For example, the starting material for compound No. 15 used in Example I was prepared as follows:

A solution of 27.4 g (15.3 mgmol) of 2-n-butoxy-6-methylaniline in 250 ml of C 2 C 4 was stirred vigorously with 10% NaOH solution (250 mgmol) while applying a solution of 17 .4 g (15.4 mgmol) of chloroacetyl chloride in CE2C4 was added] Q, keeping the temperature between 15 ° and 25 ° C by external cooling. The mixture was then stirred for an additional 60 minutes and the whole was allowed to mix. The CH 2 Cl 2 layer was washed with water, dried and evaporated in vacuo to yield 28.3 g of white substance, m.p. 127-128 ° C was obtained.

J5 Elemental Analysis: C 61.04%, H 7.08%, Cl 13.86%

Calcd for C 21 H 18 ClNCl 3 C 61.05%, H 7.09 Z, Cl 13.86%.

This product was identified as 2-n-butoxy-6-methyl-α-chloroacetanilide.

The starting materials used in Example III were prepared in corresponding ways.

The primary amines starting from the preparation of the above secondary anilides can be prepared in known ways, for example, by catalytic reduction of the corresponding 2-alkoxy-6-alkyl nitrobenzenes in ethanol with platinum oxide as catalyst.

As already mentioned, the compounds of the invention have proved to be very effective as herbicides, especially as pre-herbicides, although post-activity has also been demonstrated.

The tests demonstrating this effect beforehand were carried out in 30 greenhouses as well as in the field. When tested in greenhouses, the herbicide was applied over the soil surface or after a planting of seeds or cuttings or in a certain amount of soil to serve as a coating of pre-laid seeds. In the field trials, the planting herbicide was introduced (VPI), i.e. the herbicide was sprayed on the soil, then mixed through it, and then the seeds were planted therein.

8101322

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The superficial application of the herbicides in greenhouses was done as follows:

Suitable containers, usually aluminum pans measuring 24 cm x 13 cm x 7 cm or plastic containers measuring 9 cm x 9 cm x 7 | cm 5 with drainage holes in their bottoms were filled flat with sandy loam and then tamped to 13 mm below the rim. Then seeds of the kind to be tested were introduced and covered with a layer of 13 mm test soil. The herbicide was sprayed over the surface of this soil with a tire sprayer which gave 187 liters / ha under an atmospheric pressure of 2.1 atmospheres. All pots received 6.4 mm of water from above and were then placed on tables in greenhouses where they were supplied with water from below as required.

In an alternative embodiment, the watering can be omitted from above. The herbicidal effects were noted about 3 weeks after this treatment.

The greenhouse tests with soil-worked herbicides were carried out as follows:

A good quality covering soil was placed in aluminum pans and tamped to 10-13 mm below the edge. On top of that, a certain number of seeds or cuttings were laid. Enough soil to make the pans completely full again was weighed separately and mixed with a calculated amount of active substance in a solvent or as a wettable powder; after thorough mixing, this soil was used to fill the pans. Thereafter, the pans were first watered from above in an amount corresponding to 6.4 mm of rain, and then they received enough moisture for germination and growth from below. In an alternative embodiment, the watering can be omitted from above. The effect of the treatment is observed 2-3 weeks after seeding and treatment.

Tables B and C indicate the results of these tests; Herbicides had always been worked into the soil and the soil was only explored from below. The results are reported in figures 0 to 3, where 0 for 0-24% damage, 1 35 for 25-49% damage, 2 for 50-74% damage and 3 for 75-100% damage (relative to the blank). A - indicates that 8101322

7 C

- 13 - that combination of plant type and dosage was not tested.

The plant species are indicated with letters, as follows: A Akkerdistél E Goosefoot I Aleppo millet 5 3 Bolderik F Water pepper J Gentle dracik C Abutilon G Yellow sedge K Hanepoot 10 D Dayflower H Cultivated grass 8101322 -14-

Table B

Plant species

Dust no- kg / h ~ a ABCDEFGHIJK

1 11.2 33333333333 5.6 3 2 233333333 2 11.2 311233-3 333 5 * 6 301133-3133 3 11.2 32333333333 5.6 31323333233 4 11 * 2 32333333333 5 j 6 21323333333 5 11, 2 32333333333 5.6 323333333 6 11, 2 32233333333 5.6 32233333 233/7 11.2 3 3333333333 5.6 3i233333333 8 11.2 32333333133 5, 6 32223333333 9 11, 2 30333333333 5, 6 30233333333 1.12 20233123133 10 11, 2 2233333333 5.6 31323 2 2 3 233 11 11 32233333333 5, 6 222.23233333 12 11, 2 3 2 2 3 3 3 3 3 3 3 3 3 5.6 3113 3 233233 13 11, 2 -2223333-33 5.6 -1113323-33 14 11, 2 31333233333 5.6 00233233133 15 li, 2 11233333x30 5.6 20122132033 16 li, 2 3i ± 233333x8 5, 6 200 032 3 3333 81 01 3 2 2 ____

Continued from Table B.

- 15 -

Plant species

Substance no. Kg / ha ABCDEFGHIJK

5 17 11.2 31 102333333 5.6 30223233333 18 11, 2 32333333333 5.6 32233333333 30 19 11.2 31223333233 5.6 3 0 2 2 3 3 3 3 1 3 3

The compounds were further tested on the following 15 species: L Soybean R Hemp M Sugar beet E Goosefoot N Wheat F Water pepper 20 0 Rice C Abutilon P Millet J Dravik B Bolderik S Palm grass Q Wild buckwheat K Hanepoot D Day millet 25

The results are summarized in Table C.

8101322

Table C

ï -16-

Plant type_

Substance no.kcj / ha LMNOPBQDREFCJ SKT

1 5.6 333333333333333333 1) 12 2323312233313333 0,28 0213312123303333 0,06 0111312012203333 0,01 000000101110Ü133 0,006 00000-0011000232 2 5,6 123331123331333- 1.12 023330103330333- 0,28 012220003110333-00011 100113-00011 6 2333323333333333 1.12 1333322023323333 0.28 1223301003303333 0.06 0111000003100333 0.01 0000301000002333 0.006 0000000001100011 4 5.6 '2 333333333323333 1.12 0223313233223333 0.28 02333-0033 00000 0.06 0111333 006 00000 1.12 2333313333323333 0.28 0222311133323333 0.06 0112200033312333 0.01 0000000011100133 0.006 0100000021100012 '6 5.6 333332323333333- 1.12 233331222332333- 0.23 021330112322333- 0.06 01000000131033 2b 0232202223213333 0.06 0211110322111333 0.01 1101000110001023 0.006 0000000120001022 8101322 5

Continued from Table C.

Plant type -17-

Fabric no. Kg / ha L Μ PBQDRnFCJSKx N 0 e 5.6 12.1 2333312333333333 0223302223213333 0223301023203333 0.28 Q Ub G102301001001233 12:01 s 0100000013200133 3333323333333333 12.1 9 5.6 00:26 1233312223113333 0122201323212233 0121100020200233 0 ^ 06 0.01 10 5.6 0120000021100023 2233303333233333 0223311233223333 1'12 0.28 0213302223023333 0.06 0101200032023333 0.01 0100000010010003 11 5.6 1333313333313333 12 0123302223303333 0.28 01233-0113303333 O; 06 0012100023202233 O.üi OOOOOOOOOUOOOOui13 12 5.6 2233313. 12 0233313233313333 θ '. 28 0233300013203333 0 ", 06 0023302001203333 o'ül 0000000020001033 13 5.6 12323 23 33332333- 1.12 022331223331333- 0.23 0 2230011232 C 233- 0,06 011100001210033- 0,01 000000000010101- 14 5,6333331333332332322 0111001111000023

0.006 OLOOOOllIOOOOOO

15 5.6 2333313333323333 1. ^ .2 6233312113203333 0.28 0111101001103333 0.06 uiuüü 00061000236 0.01 0000000001100622 8101 322

Continued from Table C.

Plant type -18-

Substance nokg / ha LMNOPBQDREFCJ SKT

16 5.6 133331223331333- 1, 12 022330212230333- Ü j 28 021330001330233- 0.06 010100ϋ03100 323- 0.01 000000000000111- 17 5,6 033330113331333- 1.12 022330102220333- 0,28 0213200010 10333- 01 00000-000000001- 18 5.6 3333333333323333 1.12 0333303333323333 0.28 0223302023213333 0.06 0200202002303333 Q; Q1 0200000000-00033 8101322 - 19 -

The herbicides of the invention have unexpectedly proven to be superior pre-control herbicides, especially for the selective control of difficult-to-suppress seedlings such as Texas hand grass, alexander grass, aleppo-5 millet, wild millet, brittle reed, rice grass and itch grass. control other less resistant one year olds and perennial weeds.

Selective control of the above species has been identified among various useful crops such as soybeans, cotton, groundnuts, rapeseed and kidney beans. The selectivity has been shown at various doses in tests with sugar beet and broad beans, but some other crops (especially grasses) tolerate the herbicides according to the invention somewhat less well.

In order to demonstrate the unexpectedly superior properties of the compounds of the invention, both absolute and relative, comparative tests in greenhouses have been carried out with compounds of the prior art which are closest in chemical structure to that of the invention. These are carbon black in particular: A. N-tert-butyl-2-methoxy-α-chloroethyl ananide (Example 13 of U.S. Pat. No. 3,268,584) B. 2-t-butyl-6-methoxy-cr-chloroacetanilide (Example 67 of U.S. Pat.

(Cited in U.S. Pat. No. 2,863,752 and as a comparative also in U.S. Pat. Nos. 3,773,492 and 4,152,137).

In these comparisons, the dosages are named 30 ^ 15 and ®g5, these are the maximum dose in kg / ha respectively that inflicts less than 15% damage on the useful crop and the minimum dose to achieve 85% weed inhibition. GRj ,. and GRg; - are decisive for practical applicability, whereby it must of course be remembered that, within certain limits, commercial preparations can be somewhat more or less toxic.

8101 322 - 20 -

An additional measure of the effectiveness of a chemical as a selective herbicide is the selectivity factor, which is the fraction GRi / GRg, ie a comparative measure of effect on unresized and useful crops. In Table D, the selectivity factors are given in brackets behind the dosages in kg / ha in brackets. No or questionable selectivity is indicated by a -.

Since crop tolerance and weed control are interdependent, a brief discussion of this relationship is useful. In general, high safety for the crop is desirable, i.e. the crop needs a lot of herbicide, many for some reason higher concentrations and herbicide are often desirable. On the other hand, low tolerance of the weeds to the herbicide is desirable for both economic and environmental reasons, i.e. little herbicide has to do a lot. But low doses of a herbicide can sometimes be insufficient to control certain weeds and more is needed. The best herbicides are thus those that retain the largest numbers of species with the lowest doses and thereby provide the greatest safety for the useful crop. Therefore, the said selectivity factor has been introduced; the higher it is the better.

In a first greenhouse comparative test shown in Table D, Compound No. 1 (product of Example I) was compared with the aforementioned previously known herbicides A, B and C, on weeds commonly accompanying the soybean .

The results of Table D were obtained for all compounds under the same test conditions, i.e. test substance worked in soil and watering from above. Furthermore, the numbers 30 are the means of two duplicate experiments; from fabric No. 1, samples from two different lots were used. The time-tested weeds (with their abbreviations) were Texas hand grass, (TH), aleppo millet (ApG), brittle reed (BR), alexander grass (AxG), wild millet (WG), fall hand grass (HH), red rice (RR) and itch grass 35 (JG).

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From the figures in Table D, it is seen that none of the previously known herbicides withheld these weeds at the maximum dose of 1.12 kg / ha, with the only exception of substance C against autumn hand grass, and even here the selectivity factor 5 was lower than that of substance no. 1. In stark contrast, compound no. 1 selectively controlled all the tested weeds and even in extremely low doses, while the soybean slows down to 0.71 kg / ha. Particularly noteworthy is that compound no. 1 kept aleppo millet, brittle cane, alexander grass, autumn grass and itch grass completely under control in the lowest proven dose of 0.07 kg / ha, while the other species, Texas hand grass, wanted millet and red rice, at doses of only 0.10, 0.14 and 0.18 kg / ha were retained.

Additional experiments were carried out in greenhouses 15 in which the previously known herbicides A, B and C were compared with substances no. 1, 3, 4, 5 and 8 to 17. The substances were always worked through the soil and the dosages ranged from 0.07 to 1.12 kg / ha; there was a first watering from above and then watering from below as needed. The observations 20 happened 19 days after the treatment. The results are shown in table E, in which the plant species bear the same abbreviations as in table D. Behind the GR0 values of all weeds are the selectivity factors.

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From the data in Table E it can be seen that within the limits of the tested dosages of substance A none of the weeds occurring between soybeans stopped, substance B only autumn hand grass (no yard difficult case) and then just, and substance C only autumn -hand grass and but not Texas hand grass, alexander grass and red rice. However, with the exception of dust C against autumn hand grass and dust B against autumn hand grass and alexander grass, none of these previously known compounds stopped all these weeds at a dosage of less than 1.12 kg / ha.

In sharp contrast, all compounds of the invention suppressed all weeds between soybeans except for a few isolated cases. Those few exceptions are compounds no. 8 and 17 against red rice, dust no. 9 against wild millet and red rice, dust no. 14 against wild millet 15 and dust no. 15 against brittle reed. In addition, and again contrary to the experience with the previously known compounds (and with the exceptions mentioned above), the compounds of the invention all stopped the weeds at very low dosages ranging from no more than 0.56 kg / ha to just 20 0.07 kg / ha, in absolute terms a remarkable performance in view of the high resistance of the tested weeds (with the exception of autumn hand grass) and especially in view of the inability of the best comparable compounds according to the state of the art to test the tested weeds to fight.

Preferred compounds of the invention were further investigated in field trials for selective activity against the one-year-old Texas hand grass (TH), prick nose (Pn), and Florida posterium (FP). The fabrics were applied to the surface of the soil, which was a Dothan type sandy loan with just 1.3% organic matter. Effects were noted at 4, 8 and 12 weeks; these results (always the averages of three tests) are shown in table F.

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It can be seen from Table F that Compound No. 2 controlled all three groundnut weeds at doses between 2.24 and 4.48 kg / ha, up to 12 weeks after application. Selective control of one or more weeds also occurred to a lesser extent that compounds No. 1 and 3 to 12 weeks after application showed that under these three under these test conditions had the highest selectivity factor over groundnuts.

Still other field trials were conducted to verify the relative efficacy of compounds No. 1, 3 and 4 against wild millet in soybeans for 12 weeks after application, with the herbicides applied both over the surface (00A) or before planting ( VPI). The soil was sandy loam again with 1.7% organic matter. Two days after the treatment there was a line of 63.5 mm. The results (averages of three tests) are shown in Table G.

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From the figures of Table G, it is seen that 3.36 kg / ha of each of the three tested compounds retained wild millet between soybeans for up to 12 weeks after application. Thus, with a single treatment of the field, wild millet is kept under control for a whole season 5, as the germination and growth of this species progresses with the season. The greater degree of damage to the soybeans upon insertion before planting has been attributed to excessively deep and uneven harrowing and heavy rainfall two days after application. In this case, superficial application was found to give better results.

In yet another field trial, compounds No. 1, 3 and 4 were tested on the highly resistant aleppo millet (one year old), with both surface application and planting through and through. The soil in this case was clayey (58% clay 35 and 3.1% organic matter). The results (averages from three trials) were recorded 4 and 8 weeks after treatment; these are shown in table H.

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When pre-introduced, compound 4 already stopped aleppo millet at a dose of 2.24 kg / ha for 8 weeks and when applied over the surface in doses of 3.36 and 4.48 kg / ha. Compound No. 1 repressed after application 5 over the ground aleppo millet for at least 4 weeks at a dose of 3.36 kg / ha.

As can be seen from the figures in the preceding tables, the compounds according to the invention are excellently suitable, both in the case of pre-introduction into the soil and afterwards introduction over the soil, the choice of the method of administration being dependent on various factors such as soil type, climate, etc. In general, however, application over the surface is preferable to insertion into the ground.

In laboratory tests to check the resistance of the herbicide to leaching from the soil and the consequences thereof on its herbicidal action) the compound No. 1 (of Example I) was dissolved in acetone and sprayed in various concentrations on weighed amounts of sandy loam type "Ray", which was in jars whose leak holes in the bottom were covered with 20 filter paper. The pots with treated soil were exposed to leaching by placing them on a turntable that passed under two nozzles set so that each pot received 25 mm of water per hour (simulation of rain). The degree of leaching was varied by different times on the turntable. After the pots were sprinkled with soil, they were allowed to stand at room temperature for three days, after which the soil was taken out of the pots, crumbled and coated on top of the soil in other pots with the same type of sandy loam that was already seeded with coot. The pots were now placed on tables in 30 greenhouses, watered from below and thus left for 2-3 weeks. The rate of growth inhibition relative to untreated blanks was judged by eye, and grass weight was measured and noted after 18 days. The results of this are shown in Table I.

35 8101322 - 32 -

Table I

_Hanepoot_

Herbicide Regen% inhibition Fresh% relative to

(kg / ha) (cm) _ weight blank_ 5 2.24 0 100 0 0 0.64 100 0 0 1.27 100 0 0 2.54 100 0 0 5.08 100 0 0 10 10.16 95 0 0 0.56 0 100 0 0 0.64 100 0 0 1.27 100 0 0 2.54 100 0 0 15 5.08 95 0 0 10.16 95 0 0 0.14 0 100 0 0 0.64 100 0 0 1.27 100 0 0 20 2.54 95 0 0 5.08 95 0.20 3.3 10.16 90 0.83 14.1

It can be seen from this that the N-methyl-2-n-butoxy-6-methyl-α-chloroacetanilide, representative of the compounds of the invention, is highly resistant to leaching even under heavy rainfall conditions; even at a dosage of only 0.14 kg / ha and 30 cm of rain, no less than 90% of the cocks' leg is stopped.

A clear advantage of the herbicides according to the invention is that they act on a wide variety of soil types. Data are collected in Table J regarding the herbicidal effect of compounds No. 1 and 3 on alexander grass and soot bean coot, on a variety of soils. The herbicides were applied to the soil surface with overhead watering as previously described.

The state of affairs was noted 13 days after the treatment; the GR ^ and GRg ^ values given are averages from two duplicates. The selectivity factors are given in brackets behind the GRg ^ values.

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It can be seen from Table J that the action of the compounds of the invention is substantially insensitive to the type of soil. More specifically, compound No. 1 shows a clear selective effect on alexander grass and jack-of-all 5 between soybeans on all soils with percent organic matter between 150 and 22.1. This also applies to compound No. 3, except in Florida sand and manure. There compound no. 3 on Drummer type sandy loam, with the same organic material content as the Florida sand but with much more clay (37%) as on soils with more organic material and more clay, for example on the clayey loam from Brazil, which controlled both alexander grass and coot, it is believed that the low clay content (1.8%) of the Florida sand contributed to the non-selective effect on coot in that sand.

The main application of the compounds of the invention will be on soybeans and groundnuts. But the selective control of weeds has been established in a variety of other crops, as can be seen from Table C.

In still other tests, compound No. 1 has also been found to be useful between kidney beans and broad beans in doses up to 1.12 kg / ha and between cotton, rapeseed, carrots and beets in doses up to 0.56 kg / ha or more, and between Lucerne, flax and cabbage at doses of 0.28-0.56 kg / ha.

A study of the toxicology of compounds 25 no. 1, 3 and 4 showed the following:

Connection no.

1 3_ 4_ LD50, mg / kg 3370 2300 2400 DLD, mg / kg> 2000> 1000 <1260> 3100 <5010 30 eye irritation mild heavy moderate skin irritation none corrosive corrosive

The corrosive nature of compound No. 3 may be due to an impurity, dimethyl sulfate, which was subsequently found in the sample with which the toxicology study was conducted. From the above it is clear that the compounds with normal precautions can safely be used with such compounds 8101322-35. The degree of safety of these three seems to be: substance no. 1> substance no. 4> substance no. 3.

From the foregoing, it will be apparent that the compounds of this invention exhibit unexpected superior herbicidal properties, both absolute and relative to the most closely structurally related compounds, one of which (substance G) is a commercial herbicide. More particularly, the compounds of the invention have been found to be excellent selective herbicides, especially for killing annuals that are difficult to control among soybeans, groundnuts and other useful crops. In particular, the compounds of the invention are particularly good at texas grass, itch grass, alexander grass, wild millet, aleppo millet, brittle reed and red rice and are also very good at other weeds such as lamprey, Florida. poster slate, etc.

This invention also relates to herbicidal preparations, which are characterized in that they contain one or more compounds according to the invention, including concentrates which still have to be diluted for flat feed use. These preparations are prepared by mixing the active substances with one or more auxiliaries, including carriers and diluents (also water and organic liquids), wetting agents, dispersants, emulsifiers and others; they can be in the form of powders, granules, tablets, solutions, dispersions and emulsions.

The compositions of the invention, especially the liquids and wettable powders, preferably contain enough of one or more surfactants to make the whole easily dispersible in water or oil. This surfactant greatly enhances their efficacy; for this purpose, anionic and cationic and nonionic substances may equally well be used.

Preferred humectants are alkylbenzene and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines and acid amides, esters of higher alcohols with sodium isethionic acid 35 or sodium sulfosuccinic acid, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated-polyoxyethylene-ethylene-8-phenyl-ethylene-8-101-322- - derivatives of alkylphenols (especially isoctylphenol and nonylphenol) and polyoxyethylene derivatives of monoesters of hexitol anhydrides (such as sorbitan). Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonate, sodium (polymer alkyl) naphthalene sulfonate, and polymethylene bisnaphthalene sulfonates.

Wettable powders are water-dispersible preparations containing one or more active substances, solid diluents and one or more wetting agents and dispersants. The inert solid diluents are usually inorganic such as clay, diatomaceous earth, silicic acid, etc. Examples of these are kaolin, attapulgite and synthetic magnesium silicate. They usually contain 0.5 to 60% (preferably 5-20%) active, 0.25 to 25% (preferably 1-15%) humectant, 0.25 to 15 25% (preferably 1.0- 15%) dispersant and 5 to 95% (preferably 5-50%) inert diluent. If necessary, 0.1 to 2.0% diluent can be replaced with a corro-decorative bucket and / or anti-foaming agent.

Other formulations are dusting powders containing 0.1 to 60% by weight of active ingredient which are diluted to 0.1-10% by weight of active agent as needed.

Aqueous suspensions or emulsions can be prepared by mixing well a mixture of a water-insoluble active agent and an emulsifier and then homogenizing to a stable emulsion of very fine particles. The concentrated aqueous suspension thus obtained is characterized by its extremely small particle size, so that the coverage after dilution and spraying is very uniform. Suitable concentrations in these formulations are between 0.1 and 60%, preferably between 5 and 50% by weight of active substance; the upper limit thereof is determined by the solubility of the active substance in the solvent.

In another form of aqueous suspensions, a water-immiscible herbicide is encapsulated into microcapsules dispersed in the water phase. In one embodiment, tiny capsules are made by combining a water phase containing a lignin sulfonate, a water-immiscible 8101322-37 chemical, and a polymethylene polyphenyl isocyanate, dispersing the water-immiscible phase, and then a adding polyfunctional amine. The isocyanate and amine react to form a urea condensate which surrounds the fine particles of the water-immiscible chemical as a solid wall. Generally, the concentration of the encapsulated material will be between 480 and 700 g / l, usually between 480 and 600 g / l.

Concentrates are usually solutions of the active agent and a surfactant in a water-immiscible or partially miscible solvent. Suitable solvents are dimethyl formamide, dimethyl sulfoxide, N-methylpyrrolidone, hydrocarbons and water-immiscible ethers, esters and ketones. However, other strong liquid preparations can be prepared by incorporating the active substance in a solvent and then diluting it to practical concentration with, for example, kerosene.

These concentrates usually contain 0.1 to 95% (preferably 5-60%) active substance, 0.25 to 50% (preferably 1-25%) surfactant and, if necessary, 4 to 94% solvent.

Granules are particulate preparations with the active substance on or through a base matrix of inert, finely divided filler. In order to promote the draining of the active substance from the matrix, one of the aforementioned surfactants may be present. Clay, pyrophyllite, illite and vermiculite are examples of suitable particulate carriers. The preferred carriers are porous, absorbent preformed particles such as screened attapulgite or heat-set vermiculite, and further finely divided clay such as kaolin, attapulgite or bentonite. The active substance is sprayed on or mixed with these diluents to form herbicidal granules.

These granulating compositions according to the invention usually contain 0.1 to 30 parts (preferably 3 to 20 parts by weight) of active substance and 0 to 5 parts of surfactant per 100 parts by weight of clay.

8101322 - 38 -

The preparations according to the invention may also contain other active substances, for example fertilizers or other herbicides, pesticides, substances for safer use, etc. In combination with the active substances according to this invention, other useful substances include the triazines, urea-deri barrels, carbamates, acetamides, acetanilides, uracils, acetic and phenol derivatives, thiocarbamates, triazoles, benzoic acids, nitriles, biphenyl ethers, and the like such as:

Heterocyclic substances 10 2-chloro-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4,6-bis (isopropylamino) -s-triazine 2-chloro-4,6-bis (ethylamino) -s-triazine 3- isopropyl-1H-2,1,3-benzothiadiazinone-4- (3H) -2,2-dioxide 3-amino-1,2,4-triazole 15 6,7-dihydrodipyrido (1,2-a: 2 1'-c) -pyrazidinium salt 5-bromo-3-isopropyl-6-methyluracil 1,1, -dimethyl-4,4'-bipyridinium salt Ureas N '- (4-chlorophenoxy) phenyl- N, N-dimethyl urea 20 N, N-dimethy1-N'- (3-chloro-4-methylphenyl) urea 3- (3,4-dichlorophenyl) ~ 1,1-dimethyl-urea-1,3-dimethyl-3- (2-benzothiazolyl) urea 3- (p-chlorophenyl) -1,1-dimethyl urea 1-butyl-3- (3,4-dichlorophenyl) -1-methyl urea 25 'Carbamates and thiocarbamates 2-chlorallyldiethyl dithiocarbamate S- (4-chlorobenzyl) ) -N, N-diethylthiol carbamate Isopropyl-N- (3-chlorophenyl) carbamate S-2,3-dichloroallyl-N, N-diisopropylthiol carbamate 30 Ethyl-N, N-dipropylthiol carbamate S-propyl dipropylthiol carbamilide, Acetamides, Aceetamides Amides 2-chloro-N, N-diallylacetamide N, N-dimethy1-2, 2-diphenylacetamide 35 N- (2,4-dimethyl-5 - // (trifluoromethyl) sulfonyl / amino / phenyl) acetamide N-isopropyl-2-chloroacetanilide 81013 2 2 - 39 - 2 ', diethyl-N- methoxymethyl-chloroacetanilide 2 * -methyl-6'-ethyl-N- (2-methoxypropyl-2) -2-chloroacetanilide α, α, α-trifluoro-2,6-dinitro-N, N-dipropyl-p-toluidine N- (1,1-dimethylpropynyl) -3,5-dichlorobenzamide 5 Acids, esters and alcohols 2,2-dichloropropionic acid 2-methyl-4-chlorophenoxyacetic acid 2,4-dicloro-phenoxyacetic acid methyl-2- / 4- (2,4- dichlorophenoxy) phenoxy / propionate 10 3-amino-2,5-di-chlorobenzoic acid 2-methoxy-3,6-dichlorobenzoic acid 2,3,6-trichlorophenylacetic acid sodium-5- / 2-chloro-4- (trifluoromethyl) phenoxy / -2- nitrobenzoate 4.6-dinitro-o-sec-butylphenol 15 N- (phosphonomethyl) glycine and its monoalkylammonium and arkali metal salts and combinations thereof.

Ethers 2,4-dichlorophenyl-4-nitrophenyl ether 2-chlorophenyl-4-trifluoro-p-tolyl-3-ethoxy-4-nitrodiphenyl ether 20 Miscellaneous 2.6-dichlorobenzonitrile Monosodium ethanesaronate Disodium methanesarsonate.

Fertilizers useful in combination with the aforementioned active substances include ammonium nitrate, urea, potassium salts and superphosphate. Other useful additives are materials in which the plants can root and grow, such as compost, stable dust, humus, sand, etc.

Some examples of the indicated types of herbicidal preparations 3Q now follow.

I. Emulsifiable concentrates. „„ ------- Gbw · /? A. Connection No. 1 35.6

Calcium dodecylbenzene sulfonate / polyoxyethylene ether mixture (such as Atlox 3437F) 5.0 35 Monochlorobenzene 29.7 (L-aromatics hydrocarbons 29.7 y 100.00 8101322 - 40 - B. Compound No. 3 85.0

Calcium dodecyl benzene sulfonate / alkyl aryl polyether / alcohol mixture 4.0 C-aromatic hydrocarbons 11.0 y - 5 100.0 C. Compound No. 4 5.0

Calcium dodecylbenzene sulfonate / polyoxyethylene ether mixture (e.g.

Atlox 3437F) 1.0 1 o Xylene 94.0 100.0 II. Liquid concentrates.

---- Wt. % A. Compound No. 5 10.0 15 Xylene 90.0 100.0 B. Compound No. 6 85.0

Dimethyl sulfoxide 15.0 20 100.0 C. Compound No. 18 50.0 N-methylpyrrolidone 50.0 100.0 25 D. Compound No. 19 5.0

Ethoxylated Kastor Oil 20.0

Rhodamine B 0.5

Dimethylformamide '74.5 30 100.0 III. Emulsions.

A. Connection No. 7 40.0

Polyoxyethylene polyoxypropylene block copolymer with butanol (eg.

Tergitol XE) 4.0

Water 56.0 100.0 8101322 - 41 -. Wt% B. Compound No. δ 5.0

Polyoxyethylene polyoxypropylene block copolymer with butanol 3.5 5 Water 91.5 100.0 IV. Wettable powders A. Compound No. 9 25.0 j q Sodium lignin sulfonate 3.0

Sodium N-methyl-N-oleyl taurate 1.0

Amorphous silica (synthetic) 71.0 100.0 15 B. Compound No. 10 80.0

Sodium dioctyl sulfosuccinate 1.25

Calcium lignin sulfonate 2.75

Amorphous silica (synthetic) 16.00 100.00 20 C. Compound no. 11 10.0

Sodium lignin sulfonate 3.0

Sodium X-methyl-N-oleyl taurate 1.0

Kaolin 86.0 25 100.0 V. Dusting powders.

A. Connection No. 12 2.0

Attapux cast 93.0 30 100.0 B. Compound No. 13 60.0

Montmorillonite 40.0 100.0 35 81 01 3 2 2 - 42 -

Wt% C. Compound No. 14 30.0

Bentonite 70.0 100.0 5 D. Compound No. 15 1.0

Diatomaceous earth 99.0 100.0 1 o VI. Granules.

A. Compound No. 16 15.0

Granular attapulgite (0.4-0.8 mm) 85.0 100.0 35 B. Compound no. 17 30.0

Diatomaceous earth (0.4-0.8 mm) 70.0 100.0 C. Compound no. 18 0.5 20 Bentonite (0.4-0.8. Mm) 99.5 100.0 D. Compound no. 19 5.0

Pyrophyllite (0.4-0.4 mm) 95.0 25 100.0 VII. Microeapsules A. Compound No. 1 49.2 encapsulated in polyurea 30 Sodium lignin sulfonate (e.g.

Reax 88B) 0.9

Water 49.9 100.0 35 81 013 2 2 - 43 -

Wt% B. Compound No. 3 10.0 encapsulated in polyurea Potassium lignin sulfonate (e.g.

Rexas C-21) 0.5 5 Water 89.5 100.0 C. Compound No. 4 encapsulated 80.0 in polyurea 10 L magnesium Lignin Sulfate (Treax LTM) 2.0

Water 18.0 100.0 When using the compositions of the invention, refrigerated amounts of acetanilides are appropriately introduced into or onto the soil containing plants or into an aqueous medium. The application of liquid or solid preparations to the ground can be done in the usual manner, with 20 nozzles operated by hand or by motors. These preparations can also be sprayed from airplanes because they are already active at such low concentrations. The application of herbicidal preparations to aquatic plants is usually done by adding the preparation to the water in which control of aquatic plants is desired.

The application of an effective amount of one or more compounds of the invention to the site of undesirable herbs is an essential part of this invention. How much active substance is used depends on various factors, including the plant species and the stage of its development, the type of soil and how the soil is arranged, the amount of rain, and the choice of acetanilide. With selective ex ante control, a dose of 0.02 to 11.2 kg / ha will be applied, preferably between 0.04 and 5.6 kg / ha and most preferably between 1.12 and 5.6 kg / ha. In some cases, higher or lower dosages may be required. In the individual case, a person skilled in the art can easily find the optimum dosage, also in view of the examples given.

The words "soil" and "soil" are applied to beer in its broadest sense, including everything that is referred to as "soils" in 5 Webster's New International Dictionary (second edition, 1961). This therefore includes any substance or medium in or on which plants can grow, so not just soil, but also compost, farmyard manure, stable dust, humus, sand, etc.

10 8101322

Claims (18)

A compound according to claim 1, characterized in that R 1 is an alkyl group with 3-5 carbon atoms and R 1 and R 2 are both methyl. Compound according to claim 2, characterized in that it is N-methyl-2-isopentyloxy-6-methyl-α-chloroacetanilide, Compound according to claim 2, characterized in that it is N-methyl-2-n-propoxy-6-methyl-α-chloroacetanilide. Compound according to claim 2, characterized in that the X-methyl-2-n-butoxy-6-methyl-α-chloroacetanilide. 6. A compound according to claim 2, characterized in that it is N-methyl-2-sec-butoxy-6-methyl-α-chloroacetanilide. A compound according to claim 2, characterized in that it is N-methyl-2-isopropoxy-6-methyl-α-chloroacetanilide. A compound according to claim 2, characterized in that it is X-aathy1-2-isobutoxy-6-methyl-α-chloroacetanilide. A compound according to claim 1, characterized in that it is N-ethyl-2-n-butoxy-6-methyl-α-chloroacetanilide. A compound according to claim 1, characterized in that it is N-methyl-2-isopropoxy-6-ethyl-α-chloroacetanilide. 11. Herbicidal composition containing one or more excipients and an effective amount of a compound of the formula 3, wherein R, R 1, R 2 and R 2 have the aforementioned meanings, with the int claims 1. Herbicidal composition according to claim 11, characterized in that it contains as active substance a compound according to formula 1 in which R 1 is an alkyl group with 3-5 carbon atoms and R and R 1 are both methyl groups. Herbicidal composition according to claim 12, characterized in that the active substance therein is a compound according to any one of claims 3 to 8. Herbicidal composition according to claim 11, 10, characterized in that the active substance therein is a compound according to claim 9 or 10. 15. Method for controlling unwanted plants between useful species, whereby an effective amount of α-chloroacetanilide is introduced on site, characterized in that the α-chloroacetanilide is a compound according to formula 1, wherein R, Rj, Rl and R have the meanings set forth in claim 1 and with the limitations set forth in claim 1. 16. Process according to claim 15, characterized in that a compound according to formula 1 is applied in situ, in which R1 is an alkyl group with 3-5 carbon atoms and R and R1 are both methyl groups. Method according to claim 16, characterized in that an active substance according to any one of claims 3 to 8 is introduced on site. Method according to claim 35, characterized in that an active agent according to claim 9 or 10 is applied on site. 19. Method mainly according to description and / or examples. 30 8101322 o CUCH-C R n 0R1 MONSANTO COMPANY, St. Louis, Missouri, USA America 8101322