DE3546928C2 - Selective herbicide for crops of soya - Google Patents

Abstract

Trans-2-(1-(3-chloro- allyloxy amino) propylidene-5-(2-ethylthio propyl) cyclohexane-1,3-dione (I), and its salts are new. R'=3-trans chloroallyl. To prepare (I) 2-propionyl-5-(2-methyl thio propyl) cyclohexane -1,3-dione (II) is contacted with 3-trans chloro allyloxyamine (III). This reaction is pref. effected in an inert organic solvent at 0-80 deg.C. (I) may be applied pre- or post-emergence, the application rate being 0.02-60 kg/ha, esp. 0.02-10 kg/ha. Suitable formulations may be solid, liq. or aerosols, contg. conventional adjuvants and diluents.

Description

The invention relates to the use of trans-2- [1- (3-chloroallyloxyamino) propy liden] -5- (2-ethylthiopropyl) cyclohexane-1,3-dione and salts thereof in herbicidal compositions for controlling certain, in claim 1 called grass species.

In my U.S. Patent 4,440,566, issued April 3, 1984, I disclose compounds of the formula

in which R is in particular alkyl having 1 to 6 carbon atoms, in particular ethyl or propyl,
R ^{1 is} in particular 3-trans-chloroallyl or 4-chlorobenzyl,
R ² and R ³ preferably each represent alkyl having 1 to 3 carbon atoms or one of the substituents R ² or R ^{3 is} hydrogen and the other alkylthioalkyl having 2 to 8 carbon atoms and in particular R ² and R ^{3 are} each methyl or one of the substituents R. ² or R ³ is hydrogen and the other consists of 2-ethylthiopropyl,
R ^{4 is} a hydrogen atom or carbalkoxy having 2 to 4 carbon atoms, and
R ^{5 is} a hydrogen atom, a cation or

wherein R ^{6 is} an alkyl of 1 to 6 carbon atoms or an aryl of 6 to 10 carbon atoms.

My patent also teaches that these compounds are one possess herbicidal activity against grasses and safe are regarding broad-leaved crops.  

It has now been found that one of the compounds (i.e. in the following formula I with R is ethyl) which of the U.S. Patent 4,440,566 is surprising superior herbicidal activity compared to other ver bonds including their homologue, in which R stands for propyl, shows. This is particularly surprising since such a homolog, in which R is propyl, is a is a very good herbicide.

The connection according to the invention not only shows a front casserole activity, but also an excellent after emergence herbicidal activity against Bermuda grass, fox tail, finger grass, wild corn, wild growing Sorghum, millet, broad-leaved signal grass, bedstraw, red rice, sprangletop, Johnsongrass seedlings and rhizone johnson grass.

The compound of formula I shows an excellent one Phytotoxicity to these grassers even at very low levels Application quantities and can be safely related broadleaf crops in such quantities appli be decorated. The connection according to the invention is therefore particularly valuable for combating grassy weeds tern in broad-leaved crops and is special valuable to control these grassy weeds in Soybean crops.

The compound used in the invention can be represented by the fol lowing formula

where R ^{1 is} 3-trans-chloroallyl.

The invention also relates to the use of compatible salts of ver Binding of formula I.

Compounds of the nature of the formula I are known to be found in Form of tautomers. The connections also have two asymmetric carbon atoms and can be opti isomers are present. The above formula is intended to both the respective tautomeric forms as well as the individual optical isomers and mixtures thereof, and the use of the respective tautomers and optical isomers and their Mixtures fall within the scope of the invention.  

The present invention relates to the use of the herbicidal composition to prevent or combat the growth of unwanted grassy vegetation and consists of the growth medium and / or the leaves of this Vegetation with a herbicidal amount of the compound to treat.

The invention is explained in more detail below:
The compound of formula (I) can be conveniently prepared by the process shown schematically below

where R ^{1 is} 3-trans-chloroallyl.

This method can be convenient in such a way be carried out so that the compound (A) with 3-trans Chlorallyloxyamine (B), preferably in an inert orga African solvent is contacted. In a typical way this method is used at temperatures in the range of 0 to 80 ° C and preferably 20 to 40 ° C rend 1 to 48 hours, preferably 4 to 12 hours, using 1 to 2 and preferably 1.05 to 1.2 moles of 3-trans-chloroallyloxyamine (B) per mole of Compound (A) performed. Suitable inert organic Solvents that can be used are included for example lower alkanols, for example methanol, Ethanol, ether, e.g. ethyl ether and methylene chloride. A 2-phase system made up of water and one unmixed organic solvent (e.g. hexane) or the like and compatible mixtures thereof can also be used.

Trans-chloroallyloxyamine is a known compound and can be prepared by known methods, for example wise the methods described in my US patent 4,440,566. Conveniently, can a hydrochloride salt of trans-chloroallyloxyamine Neutralization of the salt with an alkali metal alkoxide in be used in situ.

The starting materials of formula (A) can according to the general method that are produced in my U.S. Patent 4,440,566.

The compatible salts of the compound of formula (I) can be prepared are made using conventional methods, for example Reaction of the compound of formula (I) with a base, such as sodium hydroxide, potassium hydroxide or the like, with the desired cation. Other variations  in the salt cation can also by ion exchange with an ion exchange resin with the desired cation be performed.

General procedural conditions

The reaction product can be made from its reaction product by any suitable separation and cleaning method be obtained, for example by chromatography. Ge suitable separation and cleaning methods are for example explained in the following examples.

In general, the reactions described above performed as a liquid phase reaction, so that the pressure in is of no general importance, except that it is the Temperature (boiling point) at which the Reak tions are carried out under reflux. Therefore these reactions generally when you press 300 to 3000 mm Hg executed and in a convenient manner at atmospheric or ambient pressure guided.

It should also be noted that if typical or preferred process conditions (e.g., Reak tion temperature, reaction time, molar ratios of Reactants, solvents) are specified, others Process conditions can be met. optimal Reaction conditions (e.g. temperature, reaction time, molar ratios, solvents) can be found in Ab dependence on the respective reagents used or organic solvents vary, but can through routine optimization methods.

If optical isomer mixtures are obtained, then can the respective optical isomers according to conventional Separation methods can be obtained. Geometric isomers can can be separated using conventional separation methods,  those of different physical properties depend on the geometric isomers. However, it is in the generally preferred the desired isomeric starting use material in the reaction.

definitions

In the present case, the following terms have the following meanings, unless the opposite is indicated:
The term "compatible salts" refers to salts that do not significantly adversely affect the herbicidal properties of the parent compound. Suitable salts are cation salts, such as the cation salts of lithium, sodium, potassium, alkaline earth metals, copper, zinc, ammonium, quaternary ammonium salts.

The term "room temperature" or "ambient temperature" affects 20 to 25 ° C.

usability

The compound of formula (I) and its salts show one good pre-emergence and post-emergence herbicidal activity and be sit particularly good herbicidal activity against the above Grasses. The compounds have particularly good phyto Toxicity to foxtail grass, Bermuda grass, fingers grass, rhizone johnsongrass and wild corn where it is a weed species, which is generally very are difficult to combat.

In general, for post-emergence applications herbicidal compounds directly on the leaves or on plant parts applied. For pre-emergence applications  the herbicidal compounds on the growth medium or applied to the future growth medium of the plant introduced. The optimal amount of the herbicidal compound or of the herbicidal agent varies with the respective plants species and the extent of plant growth, if one such is present and the respective part of the plant, which is contacted, as well as the extent of the contact. The optimal dosage can also be with the general situation or Fluctuate around (for example depending on whether it is shielded areas, such as plants houses, compared to exposed areas, like fields), further depending on the type and the Extent of the desired control. Generally will for a pre-emergence and post-emergence control compounds used according to the invention in amounts of 0.02 to 60 kg / ha and preferably 0.02 to 10 kg / ha applied.

Although theoretically the compounds are undiluted Condition can be applied, they will be in practice generally as an agent or formulation applied an effective amount of the compound (s) and contains a compatible carrier. An acceptable one compatible carrier (for agricultural purposes ver carrier) is one that is not in signifi can disadvantageously adversely affect the desired biological effect, which is achieved by the active compounds flows, but only dilutes them. The agent contains 0.02 to <0.5% by weight of the compound of formula (I). Concentrates can also be produced that have high concentrations, which are designed for dilution before application. The carrier can be a solid, liquid or aero should be. The respective means can be in the form of granules laten, powders, dusts, solutions, emulsions, slurries or aerosols.  

Solid supports used that can be used are, for example, natural clays (kaolin, attapulgite, Montmonillonite etc.), talk, pyrophyllite, diatomaceous earth, synthetic fine silica, calcium aluminosilicate and tri calcium phosphate. Furthermore, organic Materials such as walnut shell flour, tree woolen husk, wheat flour, wood flour and wood bark flour can be used as a carrier. suitable liquid diluents that can be used are, for example, water and organic solvents (e.g. hydro substances such as benzene, toluene, dimethyl sulfoxide, kerosene, Diesel fuel, heating oil, petroleum naphtha). Suitable aerosol carriers that are used can be conventional aerosol carriers, such as halogenated Alkanes.

The herbicidal compositions used can also be different promoters and limiters contain surface-active agents, which the Transportge increase the speed of the active ingredient in the plant tissue, for example organic solvents, wetting agents and oils, and in the case of funds used for a pre-emergence application are intended, means that the leachable reduce the connection or otherwise reduce the floor increase stability. Fruit oils such as soy bean oils, paraffin oils and olefinic oils are be particularly advantageous as carriers or additives, since they are the Increase phytotoxicity.

The agent used can also contain various compatible adjuvants, Stabilizers, conditioners, insecticides, Fungicides and possibly other herbicidally active Connections included.

A suitable concentrate formulation used to prepare the herbicidal agent used can consists of 23 to 27 wt .-% of the used according to the invention  active herbicide, 2 to 4% by weight of an emulsifier, for example calcium alkylbenzenesulfonates, octylphenol ethoxylate or mixtures thereof and 70 to 75% organic solvent, for example xylene. The concentrate is mixed with water and preferably one Fruit oil mixed before application and as a water emul sion applied, the 0.5 to 2% of a fruit oil, for example soybean oils and paraffin oils, and ole finish oils. In an expedient way, that will Herbicide applied as a water emulsion, the 0.02 to <0.5% by weight, preferably 0.07 to 0.15% by weight the herbicide, 0.001 to 0.01% by weight of an emulsifier, 0.08 to 2.5% by weight of an organic solvent and Contains 95 to 99 wt .-% water. Preferably the agent also contains 0.25 to 2% by weight of one Fruit oil. The application agent can be more convenient Ways are made by mixing the concentrate formulation with 1/4 to 1/2 of the desired Amount of water. Then the fruit oil is mixed in and then added the remaining amount of water. Will not be a fruit oil is used, then the water and the concentrate formulation simply mixed together.

The following serve to further understand the invention the non-limiting manufacturing examples and examples. Unless stated otherwise, refer to all temperatures and temperature ranges to Celsius system and the term "ambient temperature" or "room temperature "relates to 20 to 25 ° C. The term "Percent" or "%" refers to weight percent and the Be grabbed "moles" or "moles" of gramol. The term "equivalent" affects an amount of the reagent that corresponds to the moles of the above or subsequent reactants in this case play about the finite mole or finite ge weight or volume is equivalent. If specified,  the proton magnetic resonance spectrum (p. m. r. or NMR) determined at 60 mHz, the signals as singlets (S), broad singlets (bS), doublets (D), double doublets (dD), Triplets (T), double triplets (dT), quartets (Q) and Multiplets (M) are given; cps affects cycles per Second. If necessary, the examples will come back picks up more raw material for subsequent be win games.

Preparation example example 1 Trans-2- [1- (3-Chlorallyloxyamino) propylidene] -5- (2-ethyl thiopropyl) -cyclohexane-1,3-dione

In this example, 17.2 g (0.0636 mol) of 2-propionyl 5- (2-ethylthiopropyl) cyclohexane-1,3-dione, 0.9 g (0.0153 mol) Acetic acid and 10.9 g (0.0757 mol) of 3-trans chlorine allyloxyamine in 35 ml of water added to 20 ml of hexane and touched. Aqueous 5% by weight sodium hydroxide becomes long sam added over approximately 15 minutes to 3.0 g (0.0757M + a small excess) sodium hydroxide added have been set and the pH of the reaction mixture un has reached danger 6. The mixture is at 40 ° C heats and held there for 2½ hours and then cooled to room temperature. The organic phase (i.e. the hexane phase) is separated and treated with 10 ml an aqueous 5% by weight hydrochloric acid and then washed with aqueous 6.25% by weight sodium hydroxide, until the pH has reached 12. The aqueous phase is abge separates and mixed with 25 ml of hexane and the pH to 5.4 by dropwise addition of aqueous 36 wt .-% Hydrochloric acid adjusted on an ice bath. The organic phase is separated off over magnesium sulfate dried and then concentrated by evaporation, being 18.0 g of a crude product can be obtained. The raw product is purified by column chromatography on silica gel, with gelling with hexane: methylene chloride and thereby  the cleaned compound in the form of an oil will hold. Elemental analysis: carbon, calculated 56.73%, found 56.63%, hydrogen, calculated 7.28%, found 7.55%, nitrogen, calculated: 3.89%, found 3.55%.

Example 2 Sodium 2- [1- (3-trans-chloroallyloxyamino) propylidene] -3- oxo-5- (2-ethylthiopropyl) cyclohex-1-en-1-olate

This example shows a procedure that leads to Her position of the searched connection can be used.

A solution, the 0.01 mole of sodium hydroxide, dissolved in 2 ml Water, is added to a solution containing 0.01 mol 2- [1- (3-Trans-Chlorallyloxyamino) propylidene-5- (2- ethylthiopropyl) cyclohexane-1,3-dione at room temperature contains. After the reaction is over, the Solvent evaporated under vacuum, the 1-hydroxy sodium salt of 2- / 1- (3-trans-chloroallyoxyamino) propylidene- 3-oxo-5- (2-ethylthiopropyl) cyclohex-1-en-1-ol is obtained.

Example 3

In this example, the connection of example 1, namely 2- [1- (3-trans-chloroallyoxyamino) propylidene] -5- (2-ethylthiopropyl) cyclohexane-1,3-dione tested, where the methods described below are used, namely on the phytotoxic pre-emergence and post-emergence activity on a variety of grasses and wide leafy plants including a grain crop and a broad-leaved crop.

Vorauflaufherbizidtest

The pre-emergence herbicidal activity is shown in the following Determined way.  

Test solutions of the respective compounds are as follows manufactured.

355.5 mg of the test compound are applied in 15 ml acetone solves. 2 ml of acetone containing 110 mg of a nonionic surfactants are added to the solution. 12 ml of this stock solution then become 47.7 ml of water added that the same nonionic interfacial acti ve contains agents at a concentration of 625 mg / l.

Seed of the test vegetation is placed in a pot filled with soil and the test solution is sprayed evenly onto the surface of the soil in a dose of the test compound of 27.5 micrograms / cm ² , unless otherwise stated in the following tables. The pot is poured and placed in a greenhouse. The pot is watered at intervals and observed for the emergence of the seedlings, the health of the emerging seedlings, etc. during a 3-week period. At the end of this period, the herbicidal activity of the compound is evaluated based on physiological observations. A scale from 0 to 100 is used, with 0 meaning no phytotoxicity and 100 reflecting complete killing. The results of these tests are summarized in Table 1.

Nachauflaufherbizidtest

The test compound is formulated in the same manner as described in connection with the pre-emergence test. This formulation is evenly applied to two similar pots containing plants 50 to 75 mm high (except for wild oats, soybeans and water grass, although the height is 75 to 100 mm) (approximately 15 to 25 plants per pot) sprayed at a dose of the test compound of 27.5 micrograms / cm ² unless otherwise specified in the following tables. After the plants have dried, they are placed in a greenhouse and then, if necessary, watered at intervals on their lower parts. The plants are observed periodically for phytotoxic effects and for their physiological and morphological response to the treatment. After 3 weeks, the herbicidal activity of the compound is evaluated based on these observations. A scale from 0 to 100 is used, where 0 means no phytotoxicity and 100 represents complete killing. The results of these tests are summarized in Table 2.

Example 4

In this example, the connection of example 1 according to the present invention ("1") on the post-emergence herbicidal activity with moderately low dosage amounts ne ben its butylidene homologue, namely trans-2- [1- (3- Chlorallyloxyamino) butylidene] -5- (2-ethylthiopropyl) -cyclo hexane-1,3-dione, tested.

The tests are carried out in the same way as in Example 3 described performed, with the exception that the in The application rates specified in Table 3 were observed and four attempts per test instead of two be performed. The average result of the four again The tests obtained are summarized in Table 3 below summarizes, where 0 means no phytotoxicity and 100 one represents complete mortality. Generally will Phytotoxicity less than about 20 to 30% regarded as insignificant, since the plants in typical Way can grow despite this level of injury.  

As can be seen from Table 3, the compound is 1 the comparative compound C-1 versus millet clearly superior at moderately low doses. The Superiority of compound 1 becomes even clearer at the small ones observed in Example 4 below Dosages.

Example 5

In this example the connection ("1") to the Nach emergence herbicidal activity at very low dosage levels gene in addition to trans-2- [1- (3-chloroallyloxyamino) butylidene] -5- (2-ethylthiopropyl) cyclohexane-1,3-dione ("C-1") and the commercially available herbicide sethoxydim ("C-2") (i.e. 2- [1- (ethoxyamino) butylidene] -5- (2-ethylthiopropyl) -cyclo hexane-1,3-dione) against a larger list of Un herb grass tested.

The tests are carried out in the same way as in Example 3 described performed, with the exception that the in doses specified in Table 4 are observed. The results of this testing are shown in Table 4 before, where 0 means no phytotoxicity and 100 means represents complete mortality. Generally will Phytotoxicity below about 20 to 30% as not considered significant since the plant is in a typical Way can grow despite this level of damage.  

As can be seen from Table 4, with the exception of wild oats and yellow cypress grass the connection 1 of the Comparative Compound C-1 for each of the ge tested superior to other weed species. The connections 1 and C-1 are approximately the same with respect to wild oats and both compounds are opposed to these doses inactive over yellow grass. Compounds 1 and C-1 are both superior to compound C-2.

As for the dosages required to effect equivalent response, an application amount of compound 1 of 0.11 g / cm ^{2 is} approximately equivalent to an application amount of compound C-1 of 0.28 g / cm ² for controlling white Goose foot and finger grass. An application amount of compound 1 of 0.05 g / cm ² is approximately equivalent to an application amount of compound C-1 of 0.28 g / cm ² for combating yellow foxtail and an application amount of compound 1 of 0.11 g / cm ² is superior to an application amount of the compound C-1 of 0.28 g / cm ² for controlling Johnson grass.

comparison

In Table 5 below, the herbicide shown in Table 4 is shown Effect of the compound of formula (I) defined in claim 1 in a herbicides used in the present invention with respect to some grasses the herbicidal activity of this compound in one disclosed in DE 31 46 309 C2 Herbicidal agents are compared, the herbicidal activity in DE 31 46 309 C2 is shown in Table VI.

In Table 5, "Table 4, Note" means Table 4 of the present application and "Tab. VI, DE" means Table VI of DE 31 46 309 C2.

Table 5

comparison test

In the comparative test described below, the herbicidal activity of the Compound of formula (I) defined in claim 1 with the herbicidal action some structurally very similar compounds disclosed in US-A-4,440,566 are compared.

First, the compounds of the general formula given in Table A below

manufactured:

Table A

Compound No. 1 in Table A corresponds to that in claim 1 of the present Invention defined compound of formula (I).

Afterwards, a post-emergence herbicidal test was carried out in the following manner:
An acetone solution of the test compound was prepared by mixing 500 mg of the compound, 158 mg of a nonionic surfactant and 20 ml of acetone. 20 ml of this solution was added to 80 ml of water to provide the test solution.

This formulation was sprayed evenly onto 2 similar pots of 24-day-old plants (about 15 to 25 plants per pot) at a dose of 27.5 µg / cm ² . After the plants had dried, they were planted in a greenhouse and then watered at intervals, if necessary. The plants were examined at regular intervals with regard to the phytotoxic effect and the physiological and morphological response to the treatment. After 3 weeks, the herbicidal activity of the compound was rated based on these observations. A rating scale of 0 to 100 was used, with 0 indicating no phytotoxicity and 100 completely killing.

The results of the comparative test are shown in Table 6.

Table 6

Post-emergence (post-emergence) herbicidal activity - percent control tests with low dosage

Claims (5)

1. Use of a herbicidal composition comprising a compound of the formula (I)
wherein R ^{1 is} 3-trans-chlorallyl, and compatible salts thereof, and a compatible carrier, for combating the grass species of foxtail, Bermuda grass, wild sorghum, broad-leaved signal grass, bedstraw, red rice, Sprangletop, Johnson grass or wild corn, where the herbicidal agent 0.02 to <0.5 wt .-% of a compound according to formula (I), 0.001 to 0.15 wt .-% of an emulsifier, 0.08 to 2.5 wt .-% of an organic solvent and contains 95 to 99% by weight of water. 2. Use according to claim 1, wherein the herbicidal agent ent a fruit oil holds. 3. Use according to claim 2, wherein the herbicidal agent 0.25 to 2 wt .-% contains a fruit oil. 4. Use according to any one of claims 1 to 3, wherein the herbicidal agent applied to the leaves or to the growth site of the plants becomes.   5. Use according to one of the preceding claims, wherein the herbi zide agent from a herbicidal concentrate preparation, containing 23 to 27% by weight of a compound according to formula (I), 2 to 4% by weight of one Emulsifier and 70 to 75% by weight of an organic solvent, was obtained.