LU83227A1 - HYDROCARBYL OR HYDROCARBYLOXYALKYL-2-HALOACETANILIDE COMPOUNDS USEFUL FOR THE DESTRUCTION OF WEEDS ASSOCIATED WITH RICE, AND HERBICIDE COMPOSITIONS CONTAINING THEM - Google Patents

Description

· * - m ik i "1.

ί »*»

The present invention relates to the field of 2-haloacetanilides and to their use in agronomic techniques, for example as herbicides, particularly for use in transplanted rice.

The compounds of the present invention are characterized in that they are 2-chloroacetanilides having a specific combination of an n-butoxy radical in one ortho position, of an ethyl radical in the other ortho position, and , as a substituent on the anilide nitrogen atom, a radical chosen from the group consisting of allyl, chloroallyl, propargyl, 2-methoxyprop-2-yl radicals or of a radical having the formula -Ci ^ OR. ^ Where is an alkyl radical in

The prior art relating to the present invention includes numerous descriptions of 2-haloaceta-15 nilides which may be unsubstituted or substituted by a large number of substituents on the nitrogen atom anilide and / or on the anilide nucleus comprising alkyl, alkenyl, alkynyl, alkoxy, polyalkoxy, alkoxyalkyl, heterocyclic, halogen, etc. radicals The most interesting compounds of the prior art in this field seem to be those described in the following references: American Patents No. 3,268,584, No. 3,442,945, No. 3,547,620, No. 3,773,492 , No. 4,152,137 and Belgian Patent No. 810,763. However * 2.

However, none of these prior art references provide results for compounds of the type described herein, showing that they are useful herbicides for transplanted rice, nor do they describe or suggest the species particular features of the present invention.

The prior art 2-haloacetanilides, which are known to be useful as herbicides for transplanted rice, differ significantly in structure from those described here. Specifically, these herbicides from the technique. 10 anterior all contain lower alkyl radicals in the two positions ortho with respect to the anilide nitrogen atom and an alkoxyalkyl radical on this nitrogen atom.

Therefore, these prior art rice herbicides are not related to and do not suggest those described herein. However, to provide a basis for comparison, the relative herbicidal efficacy of the compounds according to the present invention is compared to the herbicide known under the registered trademark Machete (registered trademark of the company known as Monsanto Company) whose active ingredient is 2 ', 20 6'-diethyl-N- (n-butoxymethyl) -2-chloroacetanilide (common name "butachlor). Butachlor and its counterpart (" ethylbutachlor "here) are described as herbicides for rice in US Pat. In the prior art known for herbicides based on 2-haloacetanilide, only the herbicide known as Machete has hitherto obtained commercial status.

While herbicides have been found useful for

S

rice of the prior art, there is a continuing need for improved rice herbicides which control or control economically important resistant weeds at lower rates of application, which maintain control or control of these weeds weeds for longer periods of time, while maintaining safety for rice crops and improved toxicity compared to fish and mammals.

The prior art herbicides indicated above have been found to share one or more undesirable properties as herbicides for transplanted rice.

t. · I.

3.

Among some of the disadvantages of prior art herbicides for transplanted rice is their generally poor performance in controlling and / or suppressing economically important hardy perennial weeds consisting of Cyperus serotinus, Eleocharis kuroguwai and Sagittaria trifolia with a decrease in efficiency for the control or suppression of the annual weeds constituted by Echinochloa crus-galli and, in a lesser proportion, Monochoria vaginalis in a period _ 10 of 2 -6 weeks. These performance weaknesses appear particularly at lower application rates, that is to say, lowering to 0.19 kg / ha and even less. In fact, field tests have shown that in some treatments, some prior art herbicides could not selectively control Eleocharis kuroguwai at rates below 6 kg / ha or even 3 kg / ha for periods as short as 2 or 3 weeks. Similarly, in field tests, it was also found that certain prior art rice herbicides did not provide significant suppression of Sagittaria trifolia after 4 or 5 weeks.

It is therefore an object of the present invention to provide a class of herbicides which is particularly useful for transplanted rice.

Another object of the present invention is the provision of selected herbicides which: (1) are safe (i.e. do not produce more than about 15% damage) on the surface, transplanted rice at rates up to at least 2.24 kg / ha; (2) which selectively control Echinochloa crus-galli, Mono-30 choria vaginalis, Cyperus serotinus and Eleocharis kuroguwai, and (3) which provide increased suppression of Sagittaria trifolia.

Finally, it is an advantage of the herbicides of the present invention that they are safe and do not require special handling procedures.

The objects indicated above and other objects of the present invention will appear better from the description i 4.

detailed below.

The present invention relates to compounds with herbicidal activity, to herbicidal compositions containing these compounds as active ingredients and to the herbicidal method of using these compositions in various crops, particularly in transplanted rice.

We have now found that a selective group of 2-haloacetanilides, characterized by specific combinations of radicals on the nitrogen atom of anilide, of a specific alkoxy radical in an ortho position and of an ethyl radical in the other ortho position, has remarkable and unexpectedly superior selective herbicidal properties as herbicides for transplanted rice, compared to herbicides of the prior art with related structure, belonging to the most interesting prior art ^ including a commercial herbicide for rice.

A main feature of the herbicidal compositions of the present invention is their ability to control and / or control annual and perennial narrow-leaved weeds in transplanted rice, particularly the predominant and economically important annual weeds such as Echinochloa crus-galli, Monochoria vaginalis, and hardy perennials such as Cyperus serotinus, Eleocharis kuroguwai and '25 Sagittaria trifolia and other noxious weeds.

The compounds of the present invention are characterized by the formula: 30 2

C1CH0C R

n h O — n — C.H „- where R is allyl, chloroallyl, propargyl, 1-metho- 5.

xyprop-2-yl or a radical having the cumulated -CI ^ OR ^, where R ^ is a C ^ _ ^ alkyl group, preferably a C3_5 alkyl radical.

The preferred species of the present invention are those where, in the formula given above, R is the propargyl group, 1-methoxyprop-2-yl and species where is the allyl, n-propyl, sec-butyl group, 2-methylbutyl or isoamyl. Other species of the present inversion are those where R, in the formula above, is the allyl group, chloro-10 allyl or groups -CI ^ OR ^ where is the methyl group "isopropyl, n-butyl or isobutyl .

The usefulness of the compounds of the present invention, as active ingredients in the herbicidal compositions formulated with these compounds, and the process for their use will be described below.

The compounds of the present invention can be made in many ways. For example, these compounds can be prepared by N-alkylation of the anion of the appropriate secondary 2-haloacetanilide with an alkylating agent, 2o under basic conditions.

Example 1 below illustrates the use of this N-alkylation to prepare a species of the present invention. A modified N-alkylation process is described in Example 2 to prepare another species of the present invention. The modified N-alkylation process described in Example 2 here involves the in situ preparation of halo ethers

S

methyl and alkyl or alkenyl, used as starting materials in the N-alkylation process.

EXAMPLE 1 2'-n-butoxy-6'-ethyl-2-chloroacetanilide, in an amount of 5.4 g (0.02 mole), propargyl bromide in an amount of 2.6 g (0.022 mole) and 2.0 g of benzyltriethylammonium chloride were mixed in 150 ml of methylene chloride and cooled. To the mixture at 15 ° C, 45 ml of 50% NaOH was added all at once and stirred for 5 minutes, then 150 ml of cold water was added. The layers were separated, washed with water, then dried over 6.

MgSO 4 and evaporated by the device called Kugelrohr to obtain 4.45 g (yield 73%) of yellow oil, at a boiling point of 118 ° C under 0.03 mm Hg.

Analysis calculated for C1 - C1N03 (%): C, 66.33; H, 7.20; 5 Cl, 11.52;

Found: C, 66.35; H, 7.21; 01.11.50

The product has been identified as N-propargyl-2'-n-butoxy-6'-ethyl-2-chloroacetanilide.

- 10 EXAMPLE 2

By following substantially the same procedure as that described in Example 1, but by substituting allyl bromide as alkylating agent, 4.9 g (yield 79%) of boiling yellow oil were obtained. at 128 ° C (device 15 known as Kugelrohr at 0.05 mm Hg).

Analysis calculated for C ^ H24C1N02 (%): C, 65.90; H, 7.81;

Cl, 11.44;

Found C, 65.89; H, 7.81;

Cl, 11.42 The product has been identified as N-allyl-2-n-butoxy-6'-ethyl1-2-chloroacetanil ide.

EXAMPLE 3

This example describes a modification of the N-alkylation process described in Example 1. In this exemplary embodiment of the process, the alkylating agent is formed in situ, thereby performing a more efficient, economical and simpler.

s- In a cooled mixture of 6.96 g (0.12 mole) of allyl al cool, 1.8 g (0.12 mole) of anhydrous para-formaldehyde and 150 ml of methylene chloride, added 4.71 g (0.06 mole) of acetyl chloride; the mixture was stirred for 90 minutes until all of the para-formaldehyde was dissolved. To the mixture was then added 5.4 g (0.02 mole) of 2'-n-butoxy-6'-ethyl-2-chloroacetanilide, 2.0 g of benzyltriethylammonium chloride and 50 ml of chlo

methylene rure. The mixture was cooled to 100 ° C

and 50 ml of 50% NaOH were added all at once and <........ Itllli · -.....-............... Γ -....., χ. r ... - inr-f- · ...................

7 ♦ stirred for 15 minutes. The layers were separated, washed with water, dried over MgSO 4 and evaporated by the device known as Kugelrohr to obtain 6.0 g (92% yield) of clear oil, at a boiling point of 122 ° C under 0.04 mm 5 Hg.

Analysis calculated for CjgH ^ CNNQ ^ (%) s C, 63.61; H, 7.71;

Cl, 10.43.

Found: C, 63.60; H, 7.74;

Cl, 10.42.

The product has been identified as N- (allyloxymethyl) -2'-n-butoxy-6'-ethyl-2-chloroacetanilide.

EXAMPLE 4

By following substantially the same procedure as that described in Example 3, but by substituting 2-15 butanol as the alkylating agent, 4.15 g (78% yield) of clear point oil were obtained. boiling 118 ° C under 0.02 mm Hg (device called Kugelrohr).

Analysis calculated for C19H3C) C1N03 (%): C, 64.12; H, 8.50;

Cl, 9.96; Found: C, 64.05; H, 8.52;

Cl, 9.90

The product has been identified as N ~ (sec-butoxymé-thyl) -2'-n-butoxy-6'-ethyl-2-chloroacetanilide.

The starting material consisting of secondary anilide, used in the above examples, is prepared according to known methods, for example by haloacetylation of the corresponding primary amine with haloacetylating agents such as a haloacetyl halide or a haloacetic acid anhydride. Typically, the appropriate amount of the appropriate primary amine is dissolved in a solvent, such as methylene chloride, containing a base, for example 10% NaOH, and stirred vigorously, while mixing with a halide solution. of haloacetyl, for example chloroacetyl chloride, with external cooling, for example 35 pie at 15-25 ° C. The layers are separated and the organic solvent layer washed with water, dried and evaporated in vacuo.

8 *

The primary amines used to prepare the secondary anilides can also be prepared by known means, for example by catalytic reduction of the correspondingly substituted nitro-benzene, for example a 2-alkoxy-6-alkylnitrobenzene, in a solvent such as an alcohol, for example ethanol, using a platinum oxide catalyst.

EXAMPLE 5

This example describes the preparation of N- (2-methoxy- "prop-2-yl) -2'-n-butoxy-6'-ethyl-2-chloroacetanilide.

In a cooled solution of N- (2-methoxyprop-2-yl) -2'-n-butoxy-6'-ethylaniline, in an amount of 4.42 g (0.016 mol) in 0.0176 mol of 10% NaOH and in 100 ml of C ^ C ^, 2 g (0.0176 mol) of chloro-acetyl chloride was added dropwise; the solution was stirred for 10 minutes, the layers thus formed were separated and the organic phase washed with water, dried over MgSO 4 and evaporated by the device known as Kugelrohr to give 3.5 g (yield 65%) d yellow oil, at a boiling point of 132 ° C under 0.07 mm Hg.

Analysis calculated for C ^ gl ^ gClNO ^ (%): C, 63.24; H, 8.26;

Cl, 10.37;

Find ; C, 63.16 H, 8.27 Cl, 10.36 The product was identified as in the first phase of this example.

The starting material consisting of secondary anilide used in Example 5 is obtained by known means (for example as in Belgian patent No. 810,763 mentioned above). Thus, 19.3 g (0.1 mole) of 2'-n-butoxy-6'-ethyl-aniline were heated to 50 ° C in 15 ml of ethanol and in 15 ml of glacial acetic acid, then 9.68 g (0.11 mole) of methoxyacetone and 0.1 g of were added and the mixture was hydrogenated at 50 ° C for 4 hours; the mixture was filtered, evaporated by the so-called Kugelrohr device at 100 ° C, under 0.07 mm Hg, to obtain a yellow oil.

Analysis calculated for (¾) * C, 72.41; H, 10.25; 9.

N, 5.28;

Found: C # 72.36; H, 10.27; N, 5.23

The product has been identified as N- (1-methoxyprop-2-5 yl) -2'-n-butoxy-6'-ethylaniline.

EXAMPLES 6-13

Following substantially the same procedure and conditions as described in Examples 1-4, using the same secondary anilide but substituting the appropriate alkylating agent as the starting material and the appropriate amounts, the corresponding products in Examples 7-13 corresponding to the formula in Table I were prepared. Thus, Examples 6-12 were prepared according to the N-alkylation process described in Examples 3 and 4 and the product of Example 13 was prepared by the N-alkylation process of Examples 1 and 2.

TABLE I

20 O

c1ch2c ^ CH ^ OR, \ n / 2 1

‘AToT" A

Example- R. P.E. ° C -Aüa.il £ e-- pie 1 (mm Hg) Calculated Element Found * _n ^ ___________ 6 i-Ct-H ,. 137 C 64.94 64.96 ολ D X (0.04) H 8.72 8.75

Cl 9.58 9.58 7 i “C.Hq 120 C 64.12 64.06 4 y (0.03) H 8.50 8.53

Cl 9.96 10.06 8 n-C-, Η 117 C 63.24 63.31 J 7 (0.02) H 8.26 8.27 35 Cl 10.37 10.42 CH. 3 9 -CH9CIICH0CH7 134 C 64.94 64.86 * 1 J (0.03) H 8.72 8.72

Cl 9.58 9.62 10.

TABLE I (Continued) 10 n-C. Hg 128 C 64.12 64.05 (0.03) H 8.50 8.49

Cl 9.96 9.91 H CH3 130 C 61.24 61.31 5 (0.04) H 7.71 7.71

Cl 10.30 10.33 12 i-C.H- 119 C 63.24 63.41 (0.02). H 8.26 8.31

Cl 10.37 10.46 13 Ç1 1Λ -CH C = CH 136 C 59.31 59.47 • 10 (0.1) H 6.73 6.78

Cl 20.60 20.52

As noted above, the compounds of the present invention have been found effective against major Asian weeds as herbicides for transplanted rice. However, the pre-emergence and post-emergence herbicidal activity against other weeds in other crops has also been shown. Tables II and III summarize the results of these tests conducted to determine the pre-emergence herbicidal activity of the compounds of the present invention.

Pre-emergence tests were carried out as follows:

Good top soil quality is placed in aluminum boxes and compacted to a depth of 9.5mm to 12.7mm from the top of the box. Above the ground, a number of seeds or vegetative pro-pagules of various plant species are placed. The soil required to fill the boxes, after sowing or adding vegetative propagules, is weighed in a box. The soil and a known amount of the active ingredient, applied in a solvent or in the form of a suspension of wettable powder, are completely mixed and used to coat the prepared dishes. After treatment, the boxes are sent to a greenhouse bench where they are humidified by irrigation from below, as necessary to give adequate humidity for germination and growth.

Approximately 2 weeks after seeding and IX.

the treatment, the plants were observed and the results recorded. Tables II and III below summarize these results. The herbicide rating was obtained using a fixed scale based on the percentage damage to each plant species. Evaluations are defined as follows:% of control Evaluation

0-24 O

25-49 1 10 50-74 2 75-100 3

Not determined 5

The plant species used in a series of tests, the results of which are presented in table II, 15 are identified by a letter according to the following legend: A Canada thistle E Quarter lamb I Johnson grass B Field nielle F Beautiful grass J Fluffy brome C Velvet leaf G Yellow sedge of K Bass grass- D Volubilis of the walnut gardens courtyard 20 H Charla tan grass 12.

TABLE II

Pre-emergence activity

Composed of Plant Species

example n ° kg / ha ABCDEFGHIJK

5 _ __ 3 2 ï 2 3 3 3 3 3 3 T

5.6 32123233033 2 11.2 32233333333 5.6 21111132033 3 11.2 50112233333 * 10 5.6 5 0 0 0 3 2 2 3 3 3 3 4 11.2 30002132033 5.6 30001223033 5 11.2 50103233533 5.6 50002313533 15 6 11.2 50000103033 5.6 50000030033 7 11.2 20323333133 5.6 31233323133 8 11.2 30002132133 20 5.6 31002132033 9 11.2 50000112033 5.6 50000000033 10 11.2 30111223333 5.6 10003111133 25 11 11.2 31233233233 * 5.6 00222132333 12 11.2 20133133233 5.6 10 111 132 133 13. 11.2 00102032033 30 5.6 00001001033

The compounds were further tested using the above procedure on the following plant species: L Soybean R Hemp Sesbania M Sugar beet E Quarter lamb N Wheat F Beautiful grass 0 Rice C Velvet leaf 35 13.

P Sorghum J Fluffy brome B Field nielle S Panicum Spp.

Q Wild buckwheat K Backyard grass D Garden volubilis T Wild grass 5 The results are summarized in Table III,

TABLE III

Pre-emergence activity

Composed of Plant Species

10 example n ° kg / ha LMNOPBQDREFCJSKT

ï 576 2 ~ 3 3 3 3 12333323335 1.12 0233302033203335 0.28 12322010333033 3 5 0.06 0011000000002135 0.01 000001000000002 5 2 5.6 0333302123303335 15 1.12 0323301013203335 0.28 0223100001003235 0.06 0101000000000000010 , 6 023303013335 1.12 5122101102103335 0.08 0112100001003335 20 0.56 000000000010003 5 4 5.6 0233301022203335 1.12 0011000010003235 0.28 0100000000002 135 0.06 0000000000000005 0,01 0000000000000005 25 5 5.6 0233301100 0.300 0000000000001025 0.01 0000000000001015 6 5.6 01200 100003335 1.12 0000000000003335 3Û 0.28 0000000003002035 0.06 0000000000000005 7 5.6 1323322333313333 1.12 0212301133103333 0.28 0101301020003333 0.06 01000000 1230 , 28 000 110 000 000 3335 0.06 000000000000103 5 0.01 0000000000001005

J

14.

TABLE III (Continued) 9 5.6 0111101011003 335 1.12 0100000023113 135 0.28 0000000000001 005 0.06 0000000000000 005 5 10 5.6 0122301011103335 1.12 0010100030003 235 0.28 0000000000002 135 0.06 0000000000000 025

Il 5.6 0333301333313 335 1.12 0323301112203 335 0.28 0202201022103 335 10 12 5.6 0333302122203 335 1.12 0223101012103 335 0.28 0102000000003 135 0.06 0000000000000 115 0.01 0000000000000 015 13 5.6 0233202123103. 0122102021003 335 0.28 0011000010003 135 0.06 0000000000000 005 0.01 0000000000000 005

The herbicides of the present invention have been found to possess unexpectedly superior properties as herbicides for transplanted rice, more particularly for the effective selective control of the economically important, resistant annual weeds of raw Echinochloa. -galli and Mono-choria vaginalis, and perennial weeds consisting of Cyperus serotinus (if not for one exception or Zb two) and Eleocharis kuroguwai, while in some cases suppressing the weed perennial Sagittaria trifolia, in greater proportion than the commercial herbicide called Machete, and, also by controlling or suppressing many other less resistant annual and perennial weeds.

To illustrate the unexpectedly superior properties of the compounds according to the present invention, both on an absolute basis and on a relative basis, comparative tests were conducted in the greenhouse. In these tests, the herbicide known as Machete (the only common commercial herbicide for rice, consisting of 2-haloacetanilide) was tested in 15.

comparative goals.

In the discussion of experimental results below, occasionally, reference is made to the rates of herbicide application symbolized by "GR ^ g" and "GRgg", these rates are given in kilograms per hectare (kg / Ha). The GR rate ^ defines the maximum rate of herbicide required to produce 15% or less damage to the crop and the GRg rate defines the minimum rate required to obtain 85% weed inhibition. g and GR85 are used as measures of potential commercial performance, it being understood of course that suitable commercial herbicides may show more or less damage to plants within reasonable limits.

Another guide to the effectiveness of a chemical as a selective herbicide is the "selectivity factor" ("FS") for a herbicide in given crop plants and in given weeds. The selectivity factor is a measure of the relative degree of safety for the plants to be harvested and of damage to weeds, and is expressed as a function of the ratio GR- ^ g / GRgg, i.e. the Gr15 rate for the plant to be harvested divided by the GRgg rate for the weed, these two rates being in kg / ha.

Since tolerance for crops and weed control are interrelated, a brief discussion of this relationship as a function of selectivity factors is significant. In general, it is desirable that the safety factors for the plants to be harvested, i.e. the herbicide tolerance values, be high, since higher concentrations of herbicide are frequently desired for some reason or another. Conversely, it is desirable that the weed control rates be low, that is to say that the herbicide has a high unit activity for economic and possibly ecological reasons. However, low rates of herbicide application may not be adequate for controlling certain weeds and a higher rate may be required. Therefore, the best her- 16.

Bicides are the ones that control the greatest number of weeds with the least amount of herbicide and provide the greatest degree of safety for the plants to harvest # ie tolerance to the plants to be harvested. Therefore # on, use selectivity factors (defined above) to quantify the relationship between safety for the plants to be harvested and weed control; the higher the numerical value # the greater the selectivity of the herbicide for weed control in a given crop.

In a comparative test in the greenhouse # results of herbicidal activity were obtained and are presented in Table IV # comparing the relative efficacy of the compounds of Examples 1 # 3-6, 8 and 9 # which are representative compounds % jL5 tifs of the present invention # with tubachlor (active ingredient in the product known as Machete # which is a commercial herbicide for rice) as selective herbicides against economically important Asian weeds # commonly associated with transplanted rice.

2o The operating method used in this test in the greenhouse is as follows: upper soil made up of silty so-called Ray soil containing about 0.05% by weight of Krillium is sieved through a 0.6 cm sieve and subjected to fumigation for approximately 5-LO days before use. Pots are then filled with the soil constituted by the silty loam known as Ray up to a level to allow a drowning depth * of 2.54 cm. Rice plants (Bluebelle) 2 to 3 weeks old are transplanted into the pots and bulbs or seeds of experimental weeds also planted in the 3q pots. The pots are then drowned and the experimental chemical applied to the surface of the flooding water. The drowning water is reduced to allow the seed of Echinochloa crus-galli (backyard grass) to germinate and the pots are subsequently drowned again and kept in this state. Observations of the percentage inhibition using a 0-100% scale are made approximately 3 weeks after treatment (SAT).

17.

The experimental results presented in Table IV below represent the percentage of inhibition of the plants within the limits of the experimental rates of 0.28 kg / ha to 2.24 kg / ha. The results are expressed in terms of the GR. ^ And GRg ^ rates, respectively, for rice and weeds, as explained above; selectivity factors are shown in parentheses below each weed; "NS" means non-selective within the limits of experimental rates. The degree of control of 10 Sagittaria trifolia, one of the most commercially significant weeds, and the most 2-haloacetamide-resistant perennial weed among experimental weeds, is presented in the final column of Table IV; the percentage of control presented is indicated for the maximum experimental rate of 2.24 kg / ha. Weed species are identified as follows: Echinochloa crus-galli (EC), Monochoria vaginalis (MV), Cyperus Serotinus (CS), Eleocharis kuroguwai (EK) and Sagittaria trifolia (ST).

20 TABLE IV

fr “aux GRTT] ~ GR rate“ - Control (kg / ha) ____ (kg / ha) __ of the ST for

Compo- Rice ÊC 7 Μ \ ΓΊ CS EK ST 2.24 kg / ha) se _________________ (%] _

Buta- chlor 2.24 <0.23 <0.25 <0.25 0.4> 2.24 15 (> 8.0) (> 8.0) (> 8.0) (5.0) (NS); Ex. 1.24 <0.28 <0.28 <0.28 <0.28> 2.24 65 (> 8.0) (> 8.0) (> 8.0) (> 8.0 ) (NS)

Ex. 3> 2.24 <0.28 <0.28. <0.28 <0.28> 2.24 30 (> 8.0) (> 8.0) (> 8.0) (> 8.0) (NS) 30 Ex. 4> 2.24 <0 , 28 <0.28 <0.28 <0.28> 2.24 20 (> 8.0) 08.0) 08.0) 08.0) (NS)

Ex. 5> 2.24 <0.28 <0.28 <0.28 <0.28> 2.24 10 (> 8.0) 08.0) 08.0) (> 8.0) (NS )

Ex. 6> 2.0 <0.28 <0.28 <0.28 0.43> 2.24 10 (> 8.0) 08.0) (> 8.0) 04.7) (NS) 35 Ex. 8 1.96 <0.28 <0.28 <0.28 <0.28 <2.24 70 (> 7) 07.0) (> 7.0) 07.0) (NS)

Ex. 9 1.87 <0.28 <0.28 0.31 0.86> 2.24 25 ____) ___ [(> 6.7) 106.7) 1 (5.4) (1.9) 1 (NS) 1_ 18.

Referring to the results in Table IV, several important advantages of the compounds of the present invention will be seen over butachlor as follows; (1) Examples 3-6 had higher safety factors for rice; (2) Examples 1, 3-5 and 8 had higher selectivity factors against EK and (3) Examples 1, 3, 4f 8 and 9 all showed ST control with a higher percentage than butachlor. The overall superiority of the compounds according to the present invention, particularly those of Examples 1 1 and 3-6, compared to the commercial herbicide, is clearly presented by the results in Table IV.

* In another comparative greenhouse test, other compounds according to the present invention were also compared to butachlor as a standard herbicide for transplanted rice. The compounds of Examples 2, 7 and 10-13 and butachlor were tested according to the procedure described above; the experimental results are presented in table V.

TABLE V

Rate ~ GR, _ / Rate GR7T 'Oontrô-

20 (kg / hary ______ (kg / ha) the SI

Compo- Rice f EC T MV CS EK ST 'for se 2 „24kg / __________________ha (%)

Buta- 1.68 0.99 1.3> 2.24 0.71> 2.24 25 chlor (1.7) (1.3) (NS) (2.4) (NS) _ Ex. 2 1 , 8 <0.28 <0.25 0.78 <0.28> 2.24 10 25 07.2) 07.2) (2.6) 07.2) (NS)

Ex. 7> 2.24 <0.28 <0.43 <0.52 0.47> 2.24 0 08.0) (> 5.3) (4.3) (4.8) (NS)

Ex. 10> 2.24 <0.28 <0.28> 2.24 <0.28> 2.24 O

(> 8.0) (> 8.0) (NS) (> 8.0) (NS), Ex. 11 1.12 <0.28 <0.28 0.95 <0.28> 2.24 10 30 (4.0) 04.0) (1.2) (> 4.0) (NS)

Ex. 12 0.75 <0.28 <0.28 1.8 <0.28> 2.24 15 (> 2.7) 02.7) (NS) 02.7) (NS)

Ex. 13 1.12 <0.28 <0.28 1.0 <0.28> 2.24 20 (> 4.0) (> 4.0) (1.1) 04.0) (NS)

Referring to the experimental results in Table V, it is again noted that each of the compounds of the present invention had one or more advantages over butachlor as follows: (1) Examples 2, 7 and 10 13 had factors higher safety levels in rice and (2) each compound of the invention had selectivity factors against EC, MV, CS (except Example 10) and EK higher than butachlor. Although butachlor has higher safety factors than Examples 11-13 and a higher ST control percentage than the compounds of the present invention, these benefits are offset by significantly lower selectivity factors in most of the weeds in the test. It should be mentioned that, although field and greenhouse tests vary from test to test (more in the greenhouse than in the field usually), the comparative results presented in the tables here have been provided in identical conditions compared to all herbicides in the test.

In other comparative tests in the greenhouse, one at a maximum experimental rate of 1.12 kg / ha and another at a maximum experimental rate of 2.24 kg / ha, the compound of Example 3 and the butachlor were tested in rice sown in mountainous terrain. It was found that, as an average of 2o of two tests, the compound of Example 3 selectively controlled Echinochloa crus-galli (backyard grass) at 0.31 kg / ha while maintaining safety for rice at a rate> 1.443 kg / ha, providing a selectivity factor of at least 4.6. In contrast, butachlor (25 tiz commercial herbicide) required 0.7 kg / ha to selectively control the same weed, with rice safety maintained at> 1.68 kg / ha, providing a selectivity factor of at least 2.4, that is to say approximately half that of the compound of Example 3.

In other greenhouse tests, the compound of Example 3 was tested for activity against annual weeds in sugar beets, at experimental rates in the range of 0.07 to 1, 12 kg / ha. The rates and GRg ^ for sugar beets and various weeds are presented in Table VI? the selectivity factors for the weed herbicide in sugar beets are shown in brackets under the weeds; "NS" means 20.

not selective within the experimental limits. The following abbreviations 9Dit used in the table: backyard grass (BYG), wild oats (WO), downy bromegrass (DB), red-rooted anserine (RRP), black grass (BG), large wild grass 5 (LCG ) and yellow fox tail (YFT).

TABLE VI

GR rate ς GRß rate (kg / ha) (kg / ha) ΰ ~ * _, _

Bettera- BYG Γ WO Γ DB "T RRP BG I LCG YFT

sugar cubes *> 1.12 <0.07 0.28 0.21 "> 1.12 0.14 0.14 0.14 016) (> 4) (> 5.3) (NS) 08 ) (> 8) 08) ♦ The results in Table VI show that the compound of Example 3 selectively controlled each weed in the test, except the red root anserine, at levels well below 1.12 kg / ha, thereby proving the general character of this compound as an effective herbicide in important crops.

The compounds of the present invention can be used safely with the normal degree of care required to handle the herbicidal compounds; no special precautions are required.

Accordingly, it will be appreciated from the foregoing detailed description that the compounds according to the present invention have shown unexpectedly and remarkably superior herbicidal properties, both absolutely and relatively to compounds of interest. structure in the prior art, one of which (butachlor) is the active ingredient in a commercial herbicide. More particularly, the compounds of the present invention have been shown to be remarkable selective herbicides, particularly for the control of economically important Asian annual and perennial weeds in transplanted rice.

More particularly, compounds according to the present invention exhibit remarkable control of the annual grasses constituted by Echinochloa crus-galli, and "i 21.

Monochoria vaginalis and perennial weeds such as Cyperus serotinus, Eleocharis kuroguwai, and some members are particularly effective against Sagit-taria trifolia, while controlling and / or suppressing at-5 very annual herbs and other less resistant perennial weeds, including those listed in Tables II, III and VI above, and others.

The herbicidal compositions of the present invention comprising concentrates which require dilution before application, contain at least one active ingredient and an adjuvant in solid or liquid form. The compositions are prepared by mixing the active ingredient with an adjuvant, comprising diluents, extenders (fillers), carriers and conditioning agents to provide compositions in the form of finely divided particulate solids, granules, pellets, solutions, dispersions or emulsions. Thus, the active ingredient can be used with an adjuvant such as a finely divided solid, a liquid of organic origin, water, a wetting agent, a dispersing agent, an emulsifying agent or any suitable combination. of these products.

The compositions of the present invention, particularly wettable liquids and powders, preferably contain as conditioning agents one or more surfactants in amounts sufficient to make a given composition readily dispersible in water or in water. 'oil. The incorporation of a surfactant in the compositions greatly enhances their effectiveness. By the term "surfactants" it is understood that wetting agents, dispersing agents, suspending agents and emulsifying agents are included.

Anionic, cationic and nonionic agents can be used with equal ease.

Preferred wetting agents are alkylben-zene- and alkylnaphthalenesulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isethionate, sodium sulfosuceinate esters *, esters 22.

sulphated or sulphonated fatty acids, petroleum sulphonates, sulphonated vegetable oils, acetylenic glycols, polyoxyethylene derivatives of alkylphenols (particularly isooctylphenol and nonylphenol) and polyoxyethylene derivatives of esters of higher monocarboxylic fatty acids of hexitol anhydrides (for example sor-bitan). Preferred dispersion products are methyl cellulose, polyvinyl alcohol, sodium lignin sulfonates, polymeric alkylnaphthalenesulfonates, sodium naphthalene sulfonate and polymethylenylene bisnaphthalenesulfonates.

Wettable powders are water dispersible compositions containing one or more active ingredients, an inert solid extender (filler) and one or more wetting and dispersing agents. Inert solid extension products are ordinarily of mineral origin, such as natural clays, diatomaceous earth and synthetic minerals from silica and the like. Examples of these extension products include kaolinites, so-called attapulgite clay and synthetic magnesium silicate. The wettable powder compositions of the present invention ordinarily contain about 0.5 to 60 parts (preferably 5-20 parts) of active ingredient, about 0.25 to 25 parts (preferably 1-15 parts) of agent wetting, about 0.25 to 25 parts (preferably 1.0-15 parts) of dispersion product and 5 to about 95 parts © ((preferably 5-50 parts) of inert solid extension product B, all the parts being by weight relative to the total composition. When required, about 0.1 to 2.0 parts of the solid inert extender can be replaced with a corrosion inhibitor or an anti-foaming agent or both.

Other formulations include dust concentrates comprising 0.1 to 60% by weight of the active ingredient on a suitable extender; this dust can be diluted for application at concentrations * in the range of about 0.1-10% by weight.

23.

The aqueous suspensions or emulsions can be prepared by stirring an aqueous mixture of a water-insoluble active ingredient and an emulsifying agent until they are uniform and then homogeni-5 to give an emulsion of very finely divided particles. The resulting concentrated aqueous suspension is characterized by its extremely small particle size, so that, when diluted and sprayed, the coating is very uniform. Suitable concentrations of these XO formulations contain about 0.1-60%, preferably 5-50%, by weight of active ingredient, the upper limit being determined by the solubility limit of the active ingredient in the solvent.

In another form of aqueous suspension, a water immiscible herbicide is encapsulated to form a microencapsulated phase dispersed in an aqueous phase. In an exemplary embodiment, tiny capsules are formed by bringing together an aqueous phase containing an emulsifier formed from ligninesulfonate, a water immiscible chemical and polyethylene polyphenylisocyanate, by dispersing the immiscible phase with water in the aqueous phase, followed by addition of a polyfunctional amine. The isocyanate and amine compounds react to form a solid urea shell wall around the particles of the water immiscible chemical, thereby forming microcapsules. Generally, the concentration of the microencapsulated material will range from about 480 to 700 g / l of total composition, preferably 480 to 600 g / l.

Concentrates are ordinarily solutions of active ingredient in water-immiscible or partially water-immiscible solvents, with a surfactant. Suitable solvents for the active ingredient of the present invention include dimethylformamide, dime-thylsulfoxide, N-methylpyrrolidone, hydrocarbons and ethers, esters or ketones immiscible with water. However, other high concentration liquid concentrates can be formulated by dissolving the active ingredient in a 24.

solvent, then diluting, for example with kerosene, to the spray concentration.

The concentrate compositions herein generally contain about 0.1 to 95 parts (preferably 5-60 parts) of active ingredient, about 0.25 to 50 parts (preferably 1-25 parts) of surfactant and , when required, about 4 to 94 parts of solvent, all parts being by weight based on the total weight of the emulsion oil.

The granules are physically stable particulate compositions comprising the active ingredient adhering to or distributed through a base matrix of an inert, finely divided particulate extension product. To assist the leaching of the active ingredient from the particulate product, a surfactant, such as those indicated above, may be present in the composition. Natural clays, pyrophyllites, illite and vermiculite are examples of well-functioning classes of particulate mineral extension products. Preferred extension products are 2o porous, absorbent, preformed particles, such as preformed and sieved particulate attapulgite or thermally expanded particulate vermiculite and finely divided clays such as kaolin clays, hydrated attapulgite or clays bentonitics. These ex-tension products are sprayed or mixed with the active ingredient * to form the herbicidal granules.

The granular compositions of the present invention may contain about 0.1 to about 30 parts, preferably about 3 to 20 parts, by weight of active ingredient 30 per 100 parts by weight of clay and 0 to about 5 parts by weight of surfactant per 100 parts by weight of particulate clay.

The compositions of the present invention may also contain other additives, for example, fertilizers, other herbicides, other pesticides, safety products and the like, used as adjuvants or in combination with one any of the adjuvants described above.

Ht 25.

Other herbicidal compounds useful in combination with the active ingredients of the present invention, particularly for use in transplanted rice include, for example, methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate (name common "bifenox", active ingredient in the herbicide known under the registered trademark Modown), 1,3-dimethyl-4- (2,4-dichlorobenzoyl) -5-pyrazolyl paratoluenesulfonate (code designation "SW 751") , 1'a- (ß-naphthoxy) propionanilide (code designation "MT-101"), 2,4-dichloro-3'-metho-10 xy-4'-nitrodiphenyl ether (code designation "W -52 "), 3,4-, dichloropropionanilide (common name" propanil "), etc. For use in other crops other than rice, other herbicidal compounds can also be combined with the compounds according to the present invention. For example, these other compounds include triazines, ureas, carbamates , acetamides, acetanilides, uracils, acetic acid or phenol derivatives, thiolcarbamates, triazines, benzoic acids, nitriles, biphenyl ethers and the like such as: Nitrogen / sulfur heterocyclic derivatives 2 -chloro-4-ethylamino-6-isopropylamino-s-triazine 2-chloro-4,6-bis (isopropylamino) -s-triazine la 2-chloro-4,6-bis (ethylamino) -s-triazine t le 3-isopropyl-1H-2,1,3-dioxide-benzothiadia-25 zin-4- (3H) -one 3-amino-1,2,4-triazole 6,7-dihydrodipyrido salt (l, 2-a: 2 ', l'-c) -pyrazi-dinium i 5-bromo-3-isopropyl.-6-methyluracil 30 1,1'-dimethyl-4,4'-bipyridinium la 5 -t-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazol-2-one

Urea N '- (4-chlorophenoxy) phenyl-N, N-dimethylurea 35 N, N-dimethyl-N' - (3-chloro-4-methylphenyl) urea 3- (3,4-dichlorophenyl) -1 , 1-dimethylurea 1, 3-dimethyl-3- (2-benzothiazolyl) urea 26.

3- (p-chlorophenyl) -1,1-dimethylurea l-butyl-3- (3,4-dichlorophenyl) -1-methylurea Carbamates / thiolcarbamates 2-chloroallyl diethyldithiocarbamate 5 Ν, Ν-diethylthiolcarbamate - (4-chlorobenzyl) isopropyl N- (3-chlorophenyl) carbaraate Ν, Ν-diisopropylthiolcarbamate S-2,3-dichloro-allyl Ν, ethyl propylthiolcarbamate am, dipropylthiolcarbamate

Acetamides / acetanilides / anilines / amides la 2-chloro-N, N-diallylacetamide la N, N-dimethyl-2,2-diphenylacetamide la N- (2,4-dimethyl-5 - [[(trifluoromethyl) sulfonyl] 15 amino ] phenyl) acetamide le. N-isopropyl-2-chloroacetanilide 1e. 2 ', 6'-diethyl-N-methoxymethyl-2-chloroacetanilide 2'-methyl-6'-ethyl-N- (2-methoxyprop-2-yl) -2- chloroacetanilide 20 1'α, α, α- trifluoro-2,6-dinitro-N, N-dipropyl-p-toluidine N- (1,1-dimethylpropynyl) -3,5-dichlorobenzamide Acids / esters / alcohols 2,2-dichloropropionic acid 25 l 2-methyl-4-chlorophenoxyacetic acid 2,4-dichlorophenoxyacetic acid, methyl 2- [4- (2,4-dichlorophenoxy) phenoxy] propionate * 3-amino-2,5-dichlorobenzoic acid 30 sodium 2-methoxy-3,6-dichlorobenzoic acid 2,3,6-trichlorophenylacetic acid Nl-naphthylphthalamic acid 5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzoate 4,6-dinitro-o-sec-butylphenol N- (phosphonomethyl) glycine, its monoalkyl salts (C, c) amines, its alkali metal salts and their lb j 27.

combinations.

Ethers 2,4-dichlorophenyl-4-nitrophenyl ether 2-chloro-a, a, a-trifluoro-p-tolyl-3-ethoxy-5 4-nitrodiphenyl ether

Various Products 2,6-Dichlorobenzonitrile Methanearsonate Monosodium Acid Disodium Methanearsonate The herbicides of the present invention can be used individually or as mixtures with other herbicides and can be used sequentially with other herbicides. other herbicides. For example, treatments of a crop plant consisting of rice repi-15 that with the herbicides of the present invention can be followed by treatments with other herbicides or with mixtures such as S-4-chlorobenzyediethylthiocarbamate. the (common name "benthiocarb") plus 2-chloro-4,6-di (ethyl-mino) -1,3,5-triazine (common name "simazine") or 2,2-dio-20 xyde 3-isopropyl- (1H) -benzo-2, l, 3-thiadiazin-4-one (common name "bentazone") or 4- (4-chloro-2-methylphenoxy) butyric acid (common name "MCPB" ).

The compounds of the present invention have their main use in transplanted rice. However, as indicated by the experimental results for the compound of Example 3 in Table V, at least some members of this class can also be used in directly seeded rice. However, due to the high unit activity of the compounds according to the present invention, the directly sown rice may be less tolerant towards certain members of the compounds of the present invention. Accordingly, it is within the protection field of the present invention to combine these herbicides with safety products or antidotes to enhance the tolerance of both repi-35 and directly seeded rice. Examples of safety products intended to be useful with the herbicides of the present invention include cyanomeric ether.

thyl of phenylglyoxylonitrile 2-oxime described in US Patent No. 4,152,137, 2,4-disubstituted 5-thiazolecarboxylic acids and their derivatives, as described in US Patent No. 4,199,506, and others known safety products for 2-haloacetanilides in rice.

Useful fertilizers in combination with the active ingredients include, for example, ammonium nitrate, urea, potassium carbonate and superphosphate. Other useful additives include materials in which plant organisms take root and grow, such as compost, fertilizer, humus, sand and the like.

Herbicidal formulations of the types described above are given by way of examples in several illustrative embodiments below.

15 I. Emulsifiable concentrates% by weight A. Compound of Example 1 50.0

Ester consisting of phosphate of ethoxylated alcohols (for example product known under mar-2o that deposited GAFAC RE-610) 4,125

Ethoxylated tertiary amine from fatty oils such as palm oil (for example product known under the trademark Ethomeen C / 12) 0.875 25 Monochlorobenzene 13.5

Aromatic solvent C ^ (T-400) 31.5 100.00 B. Compound of Example 3. 46.45

Product called GAFAC RE-610 4,125 * 30 Product known under the registered trademark

Ethomeen C / 12 0.875 MCB 48.55 100.00 C. Compound of Example 4 5.0 35 Mixture of calcium dodecylbenzenesulfonate / polyoxyethylene ethers (for example product known as Atlox 3437F) 1.0 29.

Xylene 94.0 100.00 II. Liquid concentrates% by weight 5 A. Compound of example 5 5,0

Xylene 90.0 100.00 B. Compound of Example 6 85.0

Dimethylsulfoxide 15.0 10 100.00 C. Compound of Example No. 7 50.0 - N-methylpyrrolidone 50.0 - 100.00 * D. Compound of Example No. 8 5.0 15 castor ethoxylated 20.0

Product called Rhodamine B 0.5

Dimethylformamide 74.5 100.00 III. Emulsions 20% by weight A. Compound of Example 9 40.0

Polyoxyethylene / polyoxypropylene block copolymer with butanol (for example product known under the trademark 25 Tergitol XH) 4.0

Water 56.0 100.00 ”B. Compound of Example 10 5.0

Polyoxyethy-lene / polyoxypropylene block copolymer with butanol 3.5

Water 91.5 100.00 IV. Wettable powders% by weight 35 A. Compound of Example 1 25.0

Sodium lignosulfonate 3.0 N-methyl-N-oleyl-taurate sodium 1.0 30.

"

Amorphous silica (synthetic) 71.0 100.00 B. Compound of Example 3 80.0

Sodium dioctylsulfosuccinate 1.25 5 Calcium lignosulfonate 2.75

Amorphous silica (synthetic) 16/00 100.00 C. Compound of Example 4 10.0

Sodium lignosulfonate 3.0 10 N-methyl-N-oleyl-taurate * sodium 1/0

Clay called kaolinite 86.0 '100.00 V. Dust 15% by weight A. Compound of example n ° 10 2.0

Attapulgite 98.0 100.00 B. Compound of Example No. 11 60.0 20 Jfontmorillonite 40.0 100.00 C. Compound of Example No. 12 30.0

Bentonite 70.0 100.00 25 D. Compound of Example 13 1.0

Diatomaceous earth 99.0, 100.00 VI. Granules *% by weight 30 A. Compound of Example 1 15.0

Granular attapulgite (passing through a sieve with a mesh opening of between 0.841 mm and 0.420 mm, i.e. 20-40 mesh) 85.0 100.00 35 B. Compound of Example 3 30.0

Diatomaceous earth (passing through a sieve with a mesh opening between 31 * 0 | 841 mm and 0.420 mm) 70.0 100.00 C. Compound of example n ° 4 0.5

Bentonite (passing through a sieve with a mesh opening between 0.841 mm and 0.420 mm) 70.0 100.00 D. Compound of Example 5 5.0

Pyrophyllite (passing through a sieve with a mesh opening of between 0.841 mm and • 0.420 mm) 95.0 100.00 ‘VII. Microcapsules A. Compound of Example No. 1 Encapsulated in a Polyurea Envelope Wall 49.2

Sodium lignosulfonate (for example product known under the trademark Reax 88 B) 0.9

Water 49.9 20 100.00 B. Composed of example n ° 3 encapsulated in a polyurea envelope wall 10.0

Potassium lignosulfonate (e.g. product known under the trademark 25 Reax C-21) 0.5

Water 89.5 100.00 * C. Composed of example n ° 4 encapsulated in a polyurea shell wall 80.0 3o Magnesium salt of lignosulfate (product known under the registered trademark

Treax LTM) 2.0

Water 18/0 100.00 35 When operating according to the present invention, effective amounts of the acetanilides of the present invention are applied to the soil containing the plants, or are incorporated

J

* 32.

in aquatic environments, in any suitable manner. The application of liquid compositions and particulate solid compositions to the soil can be carried out by conventional methods, for example with mechanical dust-forming devices, telescopic and hand-held spraying devices and dust-forming devices by spray. The compositions can also be applied from aircraft in the form of a dust or a spray, owing to their effectiveness at low doses. The application of herbicidal compositions to aquatic plants is usually accomplished by adding the compositions to aquatic environments in the area where control of aquatic plants is desired.

The application of an effective amount of the compounds of the present invention to the place where the unwanted weeds are found is essential and critical to the practice of the present invention. The exact amount of active ingredient to be used depends on a variety of factors, including use in aqueous or soil media, the species of plant and its stage of development, the type and condition of the soil. , the amount of rainfall and the specific anilide used. In a selective pre-emergence application to plants or soil, a dose of 0.02 to approximately 11.2 kg / ha, preferably approximately 0.04 to approximately 5.60 kg / ha, or suitably 25 of 1, 12 to 5.6 kg / ha of acetanilide is commonly used.

Higher or lower rates may suffice or be required in some cases. For example, in some tests on rice seeded in mountainous terrain, compounds according to the present invention have shown measurable damage to backyard grass at extremely low rates. Thus, the compound of Example 3 had a control of 5% of backyard grass at a rate of 0.035 kg / ha and the compound of Example 5 had a control of 5% of lowland grass yard at the rate of 0.0175 kg / ha. A person skilled in the art can readily determine from this description, including the example above, the optimum rate to be applied in any particular case.

* i '• y *' 33.

The term "soil" is used in its broadest sense to include all conventional "soils", as defined in the New International Dictionary of Webster, 2nd edition, unabridged (1961). Thus, the term refers to any substance or medium in which vegetation can take root and grow and includes not only soil, but also compost, fertilizer, manure (garbage), manure. * mus, sand and the like adapted to maintain the growth of plants.

The present invention is not limited to the exemplary embodiments which have just been described, it is on the contrary liable to variants and modifications which will appear to those skilled in the art.

$ e r t <

Claims (14)

1. Compounds, characterized in that they have the formula: 5? ClCh2C ^ ^ R N C2H5 ^ | Γ jl 0-n-C4H9 10 where R is the allyl, chloroallyl, propargyl, e-methoxy-prop-2-yl group, or a hydrocarbyloxymethyl radical * having the formula -Cf ^ OR ^ where R ^ is the group, a C ^ _ ^ alkyl radical. 2. Compound according to claim 1, characterized in that it is formed by N-propargy1-2'-n-butoxy-6'-ethyl-2-chloroacetanilide. 3. Compound according to claim 1, characterized in that it is formed by N- (l-methoxyprop-2-y1) -2'-n-butoxy- 6 '-ethyl-2-chloroacetanilide. 4. Compounds according to claim 1, characterized in that R ^ is an alkyl radical in ^ - ^ - 5 ' 5. Compound according to claim 4, characterized in that it is formed by N- (sec-butoxymethyl) -2'-n-butoxy-6'- ethyl-2-chloroacetanilide. 6. Compound according to claim 4, characterized in that it is formed by N- (2-methylbutyl) -2'-n-butoxy-6'- ê ethyl-2-chloroacetanilide. * 7. Compound according to claim 4, characterized in that it is formed by N- (isoamyloxymethyl) -2'-n-butoxy-6’-éthy1-2-chloroacétanilide. 35 Μ *! 35 ‘V 8. Compound according to Claim 4, characterized in that it is formed by N- (isobutoxyméLhyl) -2 * -n-butoxy-61-ethyl-2-chloroacetanilide, ^ - Compound according to Claim 4, characterized 5 in what it is formed by N- (n-butoxymethyl) -2'-n-butoxy- '6'-ethyl-2-chloroacetanilide. 10. Herbicidal compositions, characterized in that they comprise an adjuvant and a herbicidally effective amount of a compound having the formula 10 O * cich2c R "\ N / C2H5 ----- 0-n-C4H9 where R is the allyl, chloroallyl, propargyl, 1-methoxy-prop-2-yl group or a hydrocarbyloxymethyl radical having the formula -Cl ^ OR ^, where is the allyl group or an alkyl radical 20 en. 11. Composition according to claim 10, characterized in that the provisions of any one of claims 2 to 9 are applied. 12. Method for combating undesirable plants in plants to be harvested, characterized in that it consists in applying to the place where these undesirable plants are found a quantity, herbicide effective, of a compound having the formula; t 30 O I »ClCH ~ C R 2 35 C2h5 A on-c4., 9 where R is allyl, chloroallylo, propargyl, 1-methoxy-prop-2-yl or a hydrocarbyloxymethyl radical having the formula 36. tfi * * the -Ci ^ QR ^, where Had an allyl group or an alkyl radical. l3 - Process according to reveidication l2, characterized in that the plant to be harvested is transplanted rice. 14. Method according to claim 13, characterized in that the provisions of any one of claims 2 to 9 are applied. · 15. Method for combating weeds in transplanted rice, characterized in that it consists in * applying to the place where these weeds are found a * quantity, herbicide-effective, of N- (allyloxy- * methyl ) -2'-n-butoxy-6'-ethyl-2-chloroacetanilide or N-propargyl-2'-n-butoxy-6'-ethyl-2-chloroacetanilide or N- (l-methoxyprop-2-yl) ) -2'-n-butoxy-6'-ethyl-2-chloroacetanili-15 from. / fi "/