DK141711B - Process for controlling undesired plant growth in crops of useful plants and preparation for use in carrying out the process. - Google Patents

Description

(11) PRESENTATION 141711 DENMARK (61) Int el · 3 A 01 N 47/12 UMmvΙΜΠΓν A 01 Η 47/16 // C 07 c 149/16 § (21) Application No. 4625 /? 4 (22) Filed on JO. August 1974 (23) Live 50 Aug. 19? 4 (44). The application submitted and the submission paper published on 2. June 1 980

DIRECTORATE OF

THE PATENT AND TRADEMARK BASIS (30> requested from it

4. Bep. 1975, 594250, US

(71> STAUFFER CHEMICAL COMPANY, 1200 South 47th Street, Richmond, Cali * Tbrnia 94804, US.

i72) Inventor: Duane Randall Arneklev, Antelope, Montana 59211, US: Don Robert Baker, 15 Muth DrTve, Orinda, California 94565, US.

(74) Clerk of the Ego Process:

The company Chas. Hude.

(54) Procedure for controlling undesirable plant growth in crops of crops and preparation for use in carrying out the procedure *.

The present invention relates to a method for controlling undesirable plant growth in crops of utilitarian plants by means of a herbicide selected from S-ethyl-diprdyl pylthiocarbamate and S-ethyl-hexahydroazepine (1) -thiocarboxylate, and a composition for use in the process.

Among the many commercially available herbicidal compounds, the thio carbamates alone or in admixture with other herbicides such as the triazines have achieved a relatively high commercial success. These herbicides are immediately toxic to a large number of weeds at various concentrations, which vary with the resistance of the weeds. Some examples of these compounds are described in U.S.A. U.S. Patent Nos. 2,913,327, 3,037,853, 3,175,897, 3,185,720, 3,198,786 and 3,582,314. In practice, it has been found that the use of these thiocarbamates as herbicides for crops sometimes causes serious damage to the crop plant.

When used in the recommended amounts in the soil to control many broadleaf weeds and grasses, severe malformations and crippling of the crop plants occur. This abnormal growth of the crop plants results in loss of crop yield. Heretofore attempts to overcome this problem involve treating crop seeds with certain antagonistic agents before planting the seeds, see U.S.A. U.S. Patent Nos. 3,311,509 and 3,564,768. These antagonistic agents have not been very successful. Specifically, the aforementioned patents exemplify the treatment of seeds using compounds of another chemical class, which does not imply the present invention.

It has now been found that plants can be protected from damage from S-ethyl dipropylthiocarbamate and S-ethyl hexahydroazepine (1) thiocarboxylate, alone or in admixture with other compounds such as 2-chloro-2 ', 6' -diethyl-N- (methoxymethyl) acetanilide, and / or tolerance of the plants to the active compounds of the above-mentioned United States Patents can be substantially increased.

Thus, the present invention relates to a method of the kind set out in the preamble which is characterized by applying or applying an effective amount of the herbicide to the plant site or to the seed seeds before planting in random order or together. 0.01 to approx. 15 parts per weight part by weight of thiocarbamate = 12 liters of bicide of an antidote of formula R -SR wherein R represents alkenyl containing 3-6 carbon atoms, chloralkenyl containing 3-6 carbon atoms or haloalkyl containing 1-4 carbon = 2 atoms and R represents alkyl containing 1-4 carbon atoms, haloalkyl containing 1-4 carbon atoms, alkenyl containing 3-6 carbon atoms or chloralkenyl containing 3-6 carbon atoms.

The antidotes applied or applied to the method of the invention may also affect the normal herbicidal action of the thiocarbamate-type compounds and any additional herbicides, such as the substituted acetanilide type herbicides, to make them selective in effect. Regardless of the mode of action, the correspondingly useful and desirable effect is the continued herbicidal effect of thiocarbamate or an additional herbicide together with a concomitant diminished herbicidal effect on desired crop species. This advantage and usefulness will become more apparent in the following.

The composition for use in carrying out the process of the invention in which herbicide and antidote are applied together is peculiar in that it comprises S-ethyl dipropylthiocarbamate or S-ethylhexahydroazepine (1) -thiocarboxylate and pr. part by weight of herbicide compound from ca. 0.01 to approx. 15 parts by weight of an antidote compound 12 of formula R -SR wherein R represents alkenyl containing 3-6 carbon atoms or chloralkenyl containing 3-6 carbon atoms or haloalkyl containing 1-4 carbon atoms and R represents alkyl containing 1-4 carbon atoms, haloalkyl containing 1-4 carbon = atoms, alkenyl containing 3-6 carbon atoms or chloralkenyl containing 3-6 carbon atoms.

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

The compounds of the invention of the above formula used in the process of the invention can be prepared by several different methods depending on the starting materials.

General Procedure for Preparation of Allyl Sulfides.

The active halide (of the allyl type) is dissolved in isopropyl alcohol or another suitable solvent and sodium sulfide, nonahydrate, sqm has been coarsely ground. The addition takes place 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 is 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 elucidated in the following example. Following the preparation example is a table of compounds which can be prepared in accordance with the procedure described. The compounds have been assigned numbers which are used to identify the compounds for the remainder of the specification.

Example

Preparation of bis (3,3-dichloroallyl) sulfide 1,1,3-trichloropropene-1 (1100 g, 7.5 mol) was dissolved in one liter of iso-propanol and sodium sulfide, nonahydrate (900 g, 3 75 mol), which had been coarsely powdered, was added over an hour at 15 ° C. The mixture was stirred at 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 400 ml portions of water. The solution was dried over magnesium sulfate and the solvent removed in vacuo. The remaining solvent was removed at ca. 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.

5 141711

Table 1 in τ Boiling point R -S-R oc or in 2 "ifl

Compound No. R-1- R * 1 CC12 = CHCH2 CC12 = CHCH2 75-77 / 35 mm Hg 2 CC12 = CC1CH2 CH2CH3 1.5325 3 CH3CC1 = CHCH2 CH3CC1-CHCH2 1.5387 4 CHC1 = CHCH2 CHC1 * CHCH2 1, 5270 5 CH2-CHCH2 CH2 * CHCai2 1.4850 6 CC12 = CC1CH2 CC12 = CC1CH2 1.5810 7 C1CH2CH2CH2 CH2CH2CH2c1 1.4828 8 C1-CH = CC1-CH, CH-CC1 * CSC1 red / broken liquid

The antidotes were used in effective herbicidal antidotes containing the thiocarbamates in combination with the antidotes described above. They were tested as follows.

Procedure; Multlafgrøde-modgiftbeskyttelse.

Plant boxes were filled with Felton clay mixed sandy soil. A variety of grasses and broadleaf crops were used for these experiments.

EPTAM ® (EPTC) was incorporated at 0.56, 3.36 or 5.6 kg / ha using a constant amount of 5.6 kg / ha of the antidote.

EPTAM® (EPTC) or ORDRAM® (S-ethylhexahydroazepine (1) -thiocarb = oxylate) and the relevant herbicide antidote were now applied separately by pipetting metered amounts of the appropriate stock solutions to the soil while introducing it into a 20 liter rotary cement mixer.

The stock solutions were prepared as follows: A. 0.56 kg / ha: Dilute 670 mg of EPTC 6E (75.5% a.i.) with 500 ml of deionized water so that 2 ml corresponds to 0.56 kg / ha of plant box.

B. 5.6 kg / ha: Dilute 6700 mg of EPTC 6E (75.5% a.i.) with 500 ml of deionized water so that 2 ml corresponds to 5.6 kg / ha of plant box.

C. 6.72 kg / ha: 4312 mg of ORDRAM 6E (71.3% a.i.) was diluted with 500 ml of deionized water so that 4 ml of the stock solution corresponds to 6.72 kg / ha when applied to a plant box.

141711 6

Antidote stock solutions are prepared by diluting 102 mg of technical material with 10 ml of acetone with 1% Tween 20 ® (polyoxyethylene sorbitan monolaurate) to 2 ml corresponding to 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 plant box for retention and use to cover the seeds after planting. Then. the soil is leveled and 6 mm deep grooves are produced in each plant box. Plant boxes treated with 5.6 kg / ha EPTAM are sown with maize (Zea maize) and sunflower (Helianthus annus). Plant boxes treated with 0.56 kg / ha EPTAM are sown with sorghum (Sorghum vulgare), r ^ s (Dryaa sativa) and barley (Hordeum vulgare). The seeds are then covered with the approximately half liter of soil sample that has been removed before sowing.

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

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

η 1-4171 1

Table 2

Multi crop protection results Percent protection

Herbicide Antidote% Protect-

Connection quantity quantity quantity no. kg / ha kg / ha Crop (4 weeks) 1 EPTCa 0.56 5.6 durra X00 EPTC 0.56 5.6 rice 30 EPTC, 3.36 5.6 corn 100 ORANGE 6.72 5.6 rice 72 2 EPTC 3.36 5.6 mustard 100 3 EPTC 0.56 5.6 sorghum 50 EPTC 0.56 5.6 rice 30 EPTC 3.36 5.6. corn 6/4 eptc 5.6 5.6 sunflower 67 *) 5 EPTC 0.56 5.6 rice 100 *) ORDRAM 6.72 5.6 rice 30 6 EPTC 0.56 1.12 'rice 11 7 EPTC 0 , 56 5.6 barley 45 8 EPTC 5.6 5.6 corn 15 a = S-Ethyl dipropylthiocarbamate b = S-Ethylhexahydroazepine (1) -thiocarbpxylate (t) percent protection for 3 weeks.

The antidotes and compositions of the invention can be used in any suitable form. The antidote compounds 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 prior to planting the seeds. However, it is to be understood that the betbicides can be incorporated into the soil and that the antidote 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 soil that has been treated with herbicides or that has been treated with herbicide and then treated with the herbicide. The addition of the antidote compound U1711 8 does not affect the herbicidal effect of the herbicides on the undesired plant growth.

0.01 and approx. 15 parts by weight of antidote as described herein. part by weight of herbicide. The exact amount of antidote will usually be determined by economic conditions for the most effective amount of use. It is to be understood that a non-phytotoxic amount of the antidote will be used in the herbicidal compositions described herein.

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

It is to be understood that the herbicidal agents described and illustrated herein are characterized as effective herbicides which exhibit such activity. The degree of this herbicidal activity is different for the compounds and varies between combinations in terms of the compounds. Thus, the choice of the herbicidal compound or herbicidal combination to control undesirable plant species can be readily accomplished. Within the scope of the present invention, prevention of damage to a particular crop species can be achieved. in the presence of a particular compound or combination.

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 combating 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 two active herbicidal compounds are selected from

Claims (2)

9 U1711 EPTC and S-ethylhexahydroazepine (1) -tipcarboxylate. 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, blotting, desiccation, regulation, 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. 1. A method for controlling undesirable plant growth in crops of crops using a herbicide selected from S-ethyl dipropylthiocarbamate and S-ethylhexahydroazepine (1) -thiocarbo; cyl = », characterized by planting or on the plant seeds before planting in random order or collectively apply or apply an effective amount of the herbicide and from ca. 0.01 to approx. 15 parts per weight by weight of thiocarbamate herbicide 12 1 of an antidote compound of formula R -SR wherein R represents alkenyl containing 3-6 carbon atoms, chloralkenyl containing 3-6 carbon atoms or haloalkyl containing 1-4 carbon atoms, and R represents alkyl containing 1-4 carbon atoms, haloalkyl containing 1-4 carbon atoms, alkenyl containing 3-6 carbon = atoms or chloralkenyl containing 3-6 carbon atoms. A composition for use in carrying out the method according to claim 1, wherein the herbicide and antidote are applied together, characterized in that it comprises a mixture of S-ethyl dipropylthiocarbamate or S-ethylhexahydrpazepine- (1) - thio = carboxylate and per. part by weight of herbicide compound from ca. 0.01 to 1 2 approx. 15 parts by weight of an antidote compound of formula R -SR wherein R 1 represents alkenyl containing 3-6 carbon atoms, chloro = alkenyl containing 3-6 carbon atoms or haloalkyl containing 1-4 carbon atoms, and R represents alkyl containing 1-4 carbon atoms , haloalkyl containing 1-4 carbon atoms, alkenyl containing 3-6 carbon atoms or chloralkenyl containing