DK142932B - PROCEDURE FOR THE PROTECTION OF A CROP WITH DAMAGE FROM A SUBSTITUTED SCETANILIDE HERBICIDE AND ACETANILIDE HERBICIDE FOR USING THE PROCEDURE - Google Patents

Description

in 142932

The present invention relates to a method of protecting a crop from damage resulting from a substituted acetanilide herbicide of formula 9 C-CH-C1 <° K.

Wherein R is ethyl or methyl and R is C1-6 alkoxyalkyl or O -CH2b-OC2H5.

It has been found that plants can be protected from damage caused by various herbicides of the substituted acetanilide type, alone or in admixture with other compounds, and / or that the tolerance of the plants to the active compounds can be substantially increased by The method according to the invention, characterized in that, at the planting site or on the plant seeds, prior to planting, respectively, feed or apply from approx. 0.01 to approx. 15 15 parts by weight per unit weight. by weight of acetanilide herbicide of an antidote compound of formula R -SR wherein R represents chloralkenyl of 3-6 carbon atoms or haloalkyl of 1-6 carbon atoms, 2 and R represents haloalkyl of 1-4 carbon atoms or chloro alkenyl of 3-6 carbon atoms.

The various substituent groups have the following meanings:

For Rx, chloralkenyl includes mono-, di-, tri- and tetrachloro substitution in alkenyl moieties having 3 to 6 carbon atoms inclusive.

2

For R, chloralkenyl comprises mono-, di-, tri- and tetrachloro-substitution in the alkenyl moiety having 3 to 6 carbon atoms inclusive. The term haloalkyl preferably includes such alkyl groups which are substituted by at least one halogen atom which may be chlorine or bromine and has from 1 to 4 carbon atoms.

2 142932

An embodiment of the process according to the invention is characterized in that the substituted acetanilide herbicide is 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) acetanilide. It has been found that the herbicidal effect of this herbicide is particularly well counteracted or modified by the antidotes of the method of the invention.

The antidotes added or applied to the process according to the invention may also affect the normal herbicidal action of the substituted acetanilide type compounds in order to make them selective in their effect. Regardless of the mode of action, the correspondingly useful and desirable effect is the continued herbicidal effect of the substituted acetanilide at the same time as the attendant diminished herbicidal effect on desired crop species. This advantage and usefulness will become more apparent in the following.

The invention further relates to acetanilide herbicides for use in carrying out the process of the invention.

The acetanilide herbicides are peculiar in that they comprise a mixture of an acetanilide herbicide of the formula

ISLAND

il R yC-CH-Cl

C

wherein R is ethyl or methyl and R3 is C1-4 alkoxyalkyl or -O4 CH2C-OC2H5; part by weight of the herbicide from approx. 0.01 to approx.

3 parts by weight of an antidote compound of the formula R -SR wherein R 2 -6 car-5 bon atoms.

The terms herbicide, antidote, or antidote should therefore describe the effect that tends to counteract the normal harmful herbicide response that the herbicide might otherwise elicit. Whether it should be referred to as an aid, honey, safeguard, safeguard or the like will depend on the particular mode of action in question. The mode of action varies, but the effect desired is the result of the method of treating plant seeds in the soil in which a crop plant is planted. To date, no system has existed that has been satisfactory for this purpose.

An antidote compound of the above purpose for use in the process of the invention can be prepared by several different methods depending on the starting materials.

General Procedure for Preparing Allyl Sulfides.

The active halide (of the allyl type) is dissolved in isopropyl = alcohol or another suitable solvent and sodium sulfide, nonahydrate, which has been coarsely ground, is added. Addition at reduced temperature, approx. 15 ° C.

At the end of the reaction, precipitated sodium chloride is removed by filtration and the solvent is removed in vacuo. The remaining residue is taken up in benzene and ether and washed with three portions of water. The solution is dried and the solvent is distilled off in vacuo.

General Procedure for Preparing Mixed Sulfides.

An organic mercaptan is dissolved in a suitable solvent such as dioxane, isopropyl alcohol or the like. Sodium hydroxide solution is added and the reaction mixture heated. An active organic halide is added and the mixture is heated at reflux. The work-up is done by normal procedures in the form of extraction, solvent removal, distillation or crystallisation.

The antidotes used in the process of the invention and their preparation are further elucidated by the following examples. Following the preparation examples are a table of compounds which can be prepared in accordance with the procedures described. The compounds have been assigned numbers which are used to identify the compounds for the remainder of the description.

Example 20 Preparation of bis (3,3-dichloroallyl) sulfide.

1,1,3-trichloropropene-1 (1100 g, 7.5 M) was dissolved in one liter of isopropanol and sodium sulfide, nonahydrate (900 g, 3.75 M), which had been coarsely pulverized, was added over for one hour at 15 ° C. The mixture was stirred at 25-25 30 ° C for 3 hours and at 50 ° C for 2 hours. It was allowed to stand overnight at room temperature. The precipitated sodium chloride was filtered off and the solvent removed in vacuo. The remaining oil was taken up in a mixture of one liter of benzene and one liter of ether and washed with three 30 400 ml portions of water. The solution was dried over magnesium sulfate and the solvent removed in vacuo. The remaining solvent was removed at about 0.5 mm Hg. A reddish brown liquid was obtained, yield 853 g (90%).

The formula was confirmed by NMR spectroscopy. The product distilled at boiling point 75-77 ° C / 35 mm Hg.

Table 1.

r1-s-r2 · mp ° C

or

Compound 9 "30 No. R ~ ET _D_ 1 CC12 = CHCH2 CC12 = CHCH2 75-77 / 35 mm Hg 10 2 CH3CC1 = CHCH2 CH3CC1 = CHCH2 1.5387 3 CHC1 = CHCH2 CHC1 = CHCH2 1.5270 4 CC12 = CC1CH2 CC12 = CC1CH2 1.5810 5 C1CH2CH2CH2 CH2CH2CH2C1 1.4528 6 C1-CH = CC1-CII2 CH2CC1 = CHC1 red / brown liquid The antidote compounds were used in effective herbicidal antidotes containing substituted acetanilides in combination with the antidotes described above.

They were tested as follows.

Procedure: Multi-crop antidote protection.

20 seed boxes were filled with Felton clay-mixed sandy soil. A variety of grass and broadleaf crops were used for this experiment. LASSO ® and the relevant herbicide antidote were now applied separately by pipetting measured amounts of the relevant stock solutions to the soil during introduction into a 20 liter rotary cement mixer. The stock solutions were prepared as follows:

Herbicide stock solution, 2.24 kg / ha: Dilute 427 mg of LASSO 4E with 100 ml of deionized water so that 1 ml corresponds to 5 2.05 mg (ai) and 4 ml corresponds to 8.2 mg equivalent to 2.24 kg / ha plant box.

Antidote stock solutions are prepared by diluting 102 mg of technical material with 10 ml of acetone with 1% Ttoeen 20® (polyoxyethylene sorbitan monolaurate) so that 2 ml corresponds to 10 5.6 kg / ha plant box.

After treating the soil with both herbicide and additive, the soil is transferred from the mixer to the plant box where it is prepared for sowing. The initial step in the preparation consists of removing approx. 1/2 liter soil sample from each 15 plant boxes for retention and use to cover the seeds after planting. The soil is then leveled and 6 mm deep grooves are produced in each plant box. Plant boxes treated with the herbicide and additive were sown with corn (Zea maize), sugar beet (Beta vulgare), 20 sunflowers (Helianthus annus), cotton (Gossypium hirsutum), soybean (Glycine max) and oilseed rape (Brassica napus). Plant boxes treated with 2.24 kg / ha LASSO were sown with maize (Zea maize), wheat (Triticum aestivum), rice (Oryza sativa), sorghum (Sorghum vulgare) and barley (Hordeum vulgare).

The seeds are then covered with the approx. half a liter of soil sample which has been removed before sowing.

The seed boxes are then placed on greenhouse benches where the temperatures are kept between approx. 21 ° C and approx. 32 ° C. The soil is watered by spraying to ensure good plant growth.

30 Damage assessments are made 2, 3 or 4 weeks after the treatments are completed. Soil treated with herbicides - only in amounts of 0.56, 2.24, 3.36, 5.6 or 6.72 kg / ha 7 has been included to provide a basis for determining the extent of damage reduction provided by using the herbicide antidote. The percentage protection is determined by a comparison with plant boxes not treated with the antidote concerned, but with the herbicide alone. The results are listed in Table 2.

Table 2.

Multi crop protection results Percent protection

Antidote- Herbicide Antidote% Compound Amount Amount of Protection No._ kg / ha kg / ha Crop (4 weeks) 1 LASSOC 2.24 5.6 Wheat 39 LASSO 2.24 5.6 sorghum 100 c = 2-chloro-2 ' , 6'-diethyl-N- (methoxymethyl) acetanilide.

In addition, the following test was carried out for the purpose of assessing compounds Nos. 1, 4 and 8 as herbicide antidotes to acetanilide herbicides. The 15 crops used were wheat and dried grains.

The antidotes were applied by a 0.5% seed treatment and by a surface treatment before germination at 5.6 kg / ha (tank mixture).

"Dual 6E" and "Antor 4E" were applied at 3.36 and 4.48 kg / ha in a surface treatment before germination (tank mix).

20 Antidotes;

No. in ci2 = chch2-s-ch2ch = cci2

No. 3 CH2CH = CHC1-S-CHC1 = CHCH2

No. 6 CHC1 = CC1CH2-S-CH2CC1 = CHC1 142932 8

Herbicides: "Dual": / CH 3

"Antor": / C2H5 / 5-ch2Cl5 ("^ CH2C0c2H5

Nc2H5 o N-chloroacetyl-2,6-diethyl-anilinoacetacetic acid ethyl ester.

5 The tested crops were wheat (Wh) grains (mil) (Ml)

Weeds: Watergrass (WG) Fox Tail (FT) 9 142932 (O o G, β O O Cso loo \ S TP * P H ID \ D t— -

tn— '....... G

Oh O <D

Eh i I II I I o>

CO fa H

^ ---- p = * · o a η h u i i i i i i o m «·! s r-l 0

--- D

£ ° 4J

O H CO O II I I O G

P a cn σι H o β ... χ <D rtj Λ 03 s G ooooooo Ό H <d 2 "tn« pm m vo 10 m OJ Λ ---> CT \ o H tn Eh II II IIO c 'ΰ Η η φ S --- 03 r- * r ^ DO (—i 03 CO OII II II o <0 s * £ i — I t7>

Λ 00___H

-P η 00 O II I m O G tn

R goo o o G G

_____H_ 03 H

O Λ I O O I I I Ο X3 c P (d S 00 00 o (0

Λ G ---—-— ---- tf H

\ O φ X)

'tPf4 11 1 I 1 1 o g G

H X H H c H --- tn! O H 00 OH +) ^ P I I II I I O r-l

H s »jg H

dl H tP ........ ~ 1 -. - t, c S co o ro φ 5, dOLO lin 110> tn

E "l r- | g CD H IO r-l C

2 G. ^

3 o O) 03 P

QrGOO 10 OOO tOO-H

s S t- * 3 · ID 00 00 H H 0) & (0 --- <U 4J 03 h „o t n 03

\ E-) I I II I I O Η M

i? · * Η Ό Η Φ X-- (0 H ih

O M 4J

10 P l I II I I ο oi t n

^ s _ H d) P G

GO) Ή cn oh

H O m 11 I I O »4J H

2, ^ Η H d) IM C · I- 11- ..........— - - - ...... ..... W · Η «~ _ rH * j> yes c

S 2 2 <13 tf <33 H

Εί H E ^ -P O Λ H

• PS O) Tf

QJ + iWEo WEH toti>,> g G

Tdypqco Hen Hen g G rd £

21¾¾ H CU 03 Q) H G

β -g 00 OP dp ΦίηΉΦ

WMlOfN CD fN CD (N J3 C H G

s g · \ - X - \ Η φ φ.

inHinHUOH G> H

—————————__ _. . (DM O H

® OO

H β> II II

<y η h g tS 02

5 PUB

Si HH ro n COlD-P

ti 2 β -. one

.P O I H EH

LÉJ ___— Λ and 142932 10

The protection was shown for damage to durra and wheat at different application rates. The damage is caused by acetanilide herbicides. Seed treatment and application before germination (tank mix) was used.

The antidotes and compositions of the invention can be used in any suitable form. The antidotes may thus be contained in emulsifiable liquids or concentrates and may be in the form of liquids, wettable powders, powders, granular masses or any other suitable form. In its preferred form, a non-phytotoxic amount of a herbicide antidote is mixed with a selected herbicide and incorporated into the soil before or after planting the seeds. However, it is to be understood that the herbicides can be incorporated into the soil and that the antifungal compound can then be incorporated into the soil. Furthermore, the crop seeds themselves can be treated with a non-phytotoxic amount of the compound and planted in the soil which has been treated with herbicides or which has been treated with herbicide and then treated with the herbicide. The addition of the antidote does not affect the herbicidal action of the herbicides.

The amount of antidote present may be between about. 0.01 and approx. 15 parts by weight of antidote as described herein. part by weight of herbicide. The exact amount of antidote compound will usually be determined by economic conditions for the most effective usable amount.

It is to be understood that a non-phytotoxic amount of the antidote will be used in the herbicidal materials described herein.

The herbicides listed in the tables and elsewhere are used in amounts which will produce an effective control of undesirable vegetation. The quantities are within the recommended quantities specified by the supplier. The weed control is therefore in each case commercially acceptable within the desired or recommended range.

It is to be understood that the classes of herbicides described and illustrated herein are characterized as effective herbicides which exhibit such activity. The degree of this herbicidal activity varies between certain compounds and between combinations of certain compounds. Similarly, the degree of activity varies to some extent among the species of plants to which a particular herbicide compound or herbicide combination may be used. Thus, selection of a particular herbicide compound or herbicide combination to control undesirable plant species can be made. Within the scope of the present invention, prevention of damage to a particular crop species can be achieved by the presence of a particular compound or combination. The utilitarian plant species which can be protected by this method are not intended to be limited to the particular crops used in the examples.

The herbicidal compounds used in the practice of the invention are active herbicides of a general type. That is, they are herbicidal effective against a wide variety of plant species, without distinguishing between desired and undesirable species. The method of controlling vegetation comprises applying a herbicidal effective amount of the herbicidal compounds described herein to the area or plant site where control is desired. The compositions of the invention include those wherein the preferred active herbicidal compound is selected from 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) acetanilide, 2-chloro-N-isopropylacetanilide and N, N-diallyl-2 chloroacetanilide and combinations thereof.

By a herbicide as used herein is meant a compound which fights or modifies the growth of vegetation or plants. Such combating or modifying effects include all deviations from natural evolution, such as e.g. killing, retarding, flaking, drying, regulating

Claims (3)

142932 clay, crippling, firing, stimulation, dwarf growth induction and the like. By plants is meant germinating seeds, emergent sprouts as well as established vegetation including roots and plant parts above ground. 5 Patent claims. A process for protecting a crop from damage resulting from a substituted acetanilide herbicide of formula 0 in C-CHCl <° C <C2 H5 V 3 10 wherein R is ethyl or methyl and R is C 2 -alkoxyalkyl or 0-O ^ fc-OCjHg, characterized in that, at the planting site or on the plant seeds before planting, respectively, feed or apply from approx. 0.01 to approx. 15 parts per weight by weight of acetanilide herbicide of an antidote of formula R -SR wherein R represents chloralkenyl of 3-6 carbon atoms or haloalkyl of 1-6 carbon atoms and R represents haloalkyl of 1-4 carbon atoms or chloralkenyl of 3-6 carbon atoms. Process according to claim 1, characterized in that the substituted acetanilide herbicide is 2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) acetanilide. Acetanilide herbicide for use in carrying out the method according to claim 1 or 2, characterized