SE458683B - 2- (1- (3-TRANS-CHLOROYLYLOXIAMINO) PROPYLIDES) -5- (2-ETHYLTIOPROPYL) CYCLOHEXAN-1,3-DION AND COMPLIANT SALTS THEREOF, HERBICIDA COMPOSITIONS METALLOUS METERODE METERODE METERODE METERODE BEFORE PREPARING THEREOF - Google Patents

Description

Even in very low application applications with respect to broadleaf groves, the present invention is particularly useful for controlling grassy weeds in broadleaf crops and is particularly useful for controlling grassy weeds in soybean crops.

The compounds of the present invention may be represented by the following formula: scales and may be safely applied at such scales. Sa- Nox

The invention also relates to Compatible salts of compounds of formula I.

As will be appreciated, compounds of nature of formula (I) exist as tautomers.

The compounds also have two asymmetric carbon atoms and may also exist as optical isomers. The above formula is intended to include the respective tautomeric forms as well as the individual optical isomers as well as mixtures thereof and the respective tautomers and optical isomers as well as mixtures thereof are encompassed by the invention. In a further aspect, the invention provides a herbicidal composition comprising a compound active as a herbicide of the compound (or mixtures thereof).

The present invention also provides a method of controlling plant growth, comprising a method of controlling plant growth, which comprises treating growth. The medium and / or the foliage of such vegetation with a plant growth regulating effective amount of the compound (s) of the invention or mixtures thereof, effective to alter the normal growth pattern of such plants.

The present invention provides a process for the preparation of the compounds of the invention.

The invention will, further described below.

FURTHER DESCRIPTION OF THE INVENTION AND SUITABLE EMBODIMENTS The compound of formula (I) can usually be prepared by the following schematically represented procedure: \\ c, %% ï ° ~ ou + H Nonï .__ 2> I (B) H ca2cnsca2ca3 ) Wherein R1 represents 3-trans-chloroallyl.

This process can be conveniently carried out by introducing the pre-enzyme UU 1 hm fi acetic acid 3-trans-chloroallyloxyamine (B), conveniently into an inert organic solvent.

Typically, this process is carried out at temperatures in the range of from about 0 to 50 ° C, preferably from about 20 to 40 ° C, for about from 1 to 48 hours, preferably from about 4 to 12 hours, using from about 1 to 48 hours. 2, preferably 1.05 to 1.2 moles of 3-trans-chloroallyloxyamine (B) per mole of compound (A). Suitable inert organic solvents which may be used include, for example, lower alkanols, for example methanol, ethanol, ethers, for example ethyl ether, methylene chloride. Two phases, water and immiscible organic solvent (for example hexane), and the like. Compatible mixtures thereof can also be used.

Trans-chloroallyloxyamine is a known compound and can be prepared by known methods, as described in US-PS 4,440 S66.

Conveniently, a hydrochloride salt of trans-chloroallyloxyamine may be used by neutralizing the salt with an alkali metal alkoxide in situ.

The starting materials of formula (A) can be prepared by the general procedure described in U.S. Pat. No. 4,440,566.

The compatible salts of formula (I) may be prepared by conventional methods, for example by reacting compounds of formula I with a base such as sodium hydroxide, potassium hydroxide and the like, with the desired cation. Further variations in salt cations can also be effected via ion exchange with an ion exchange resin with the desired cation.

GENERAL COURSE CONDITIONS The reaction product can be recovered from the reaction product mixture thereof by any suitable separation and purification method, such as chromatography. Suitable separation and purification procedures are illustrated, for example, in the examples described below.

Reactions described above are usually carried out as liquid phase reaction and consequently the pressure is usually not significant except that it affects the temperature (boiling point) when the reaction is carried out at reflux.

Therefore, these reactions are usually carried out at pressures of about 300 to 3000 mm Hg and at about atmospheric or ambient pressures. It will also be appreciated, usually performed, that when typical or suitable process conditions (e.g., reaction temperature, times, molar ratio of reactants, solvents, etc.) have been given, that other process conditions may also be used. conditions (e.g., temperature, ratios, solvents, optimum reaction time, molar composition, etc.) may vary with the particular reagents or organic solvents employed, but may be determined by routine optimization procedures.

When optical isomer blisters are obtained, respective optical isomers can be obtained by conventional resolution methods. Geometric isomers can be separated by conventional separation procedures, which are due to differences in physical properties between the geometric isomers. However, it is usually convenient to use the desired isomeric starting material in the reaction.

DEFINITIONS As used herein, the following terms have the following meanings unless expressly stated otherwise: The term "compatible salts" refers to salts which do not. 20 years) 35 40 458 683 significantly adversely changes the herbicidal properties of the parent compound. Suitable salts include cationic salts, such as the cationic salts of lithium, sodium, potassium, alkaline earth metals, copper, zinc, ammonia, quaternary ammonium salts and the like.

The term "room temperature" or "ambient temperature" refers to about 20-25 ° C.

APPLICABILITY The compound of formula (I) and salts thereof exhibit both herbicidal action before and after germination and show particularly good herbicidal action against grasses. The compounds show particularly good phytotoxicity against foxtail, Bermuda grass, blood millet, "rhizon-Johnson grass" and wild maize, which are weed species that are usually very difficult to control.

For post-emergence applications, the herbicidal compounds are usually applied directly to the foliage or other plant parts.

For pre-emergence applications, the herbicidal compounds are applied to the growth medium or future growth medium of the plant. The optimal amount of herbicidal compound or composition will vary with the particular plant species and the degree of plant growth, if any, and the particular part of the plant being brought into contact and the degree of contact. The optimal dosage may also vary with the general location or environment (for example, protected areas, such as greenhouses, compared to exposed areas, such as fields) and the type and degree of control desired. Usually applied for both control before and after emergence of the present compounds in amounts of from about 0.02 to 60 kg / ha, preferably about from 0.02 to 10 kg / ha.

Although in theory the compounds may also be used undiluted, they are usually applied in the present practice as a composition or preparation comprising an effective amount of the compound (s) and an acceptable carrier. An acceptable and compatible carrier (agri-culturally acceptable carrier) is one which does not significantly adversely affect the desired biological effect achieved by the active compounds without diluting it. Typically, the composition contains about from 0.05 to 95% by weight of the compound of formula (I) or mixtures thereof. Concentrates can also be manufactured with high concentrations intended for dilution before use.

The carrier can be a solid, liquid or aerosol. The present compounds can take the form of granules, powders, dusts, solutions, emulsions, slurries, aerosols and the like. Suitable solid carriers which can be used for natural clays (such as kaolin, etc.), talc, pyrophyllite, include, for example, pulpite, montmorillonite, diatomaceous earth silica, synthetic fine silica, Calcium aluminum silicate, tricalcium phosphate and the like, such as walnut husk flour, cotton bark flour and the like are also suitable. Suitable liquid diluents include, for example, water (for example hydrocarbons such as benzene, toluene, dimethyl sulfoxide, kerosene, diesel fuel, diesel fuel). Suitable aerosol carriers, conventional aerosol carriers, etc. Organic materials may also be seed husks, wheat flour, wood flours, such as carriers, which may be used, organic solvents which may be used include cones such as halogenated alkanes, etc.

The composition may also contain various promoters and surfactants which increase the rate of transport of the active compound into the plant tissue, such as organic solvents, wetting agents and oils, and in the case of compositions intended prior to the emergence of excipients, such as reduces the association's leaching ability or otherwise increases soil stability. Harvest oils, such as soybean oils, paraffin oils and olefinic oils or advantageous as carriers increase phytotoxicity. , are specific or additives, in that they The composition may also contain various compatible adjuvants, stabilizers, conditioning agents, insecticides, fungicides and, if desired, other compounds active as herbicides.

A suitable concentrate preparation which can be used comprises 23-27% by weight of the active herbicide according to the invention, 2 to 4% by weight of an emulsifier, eg calcium alkylbenzene sulfonates, octylphenylethoxylate, etc. or mixtures thereof and about 70-75% organic solvent, to for example xylene, etc. The concentrate is mixed with water and applied and applied as a water emulsion containing about 0.5 to 2% of a crop oil, for example soybean oils, the herbicide containing about 0.02-0 6.6% by weight,% by weight of the herbicide according to the invention, one of an emulsifier, about 0.08-2.5% by weight. And paraffin oils and olefin oils, usually as water emulsion, preferably 0.07-0.15 and about 0.001-0.01% by weight. v 10 15 20 25 Un Lil \ l 458 683 1/4 to 1 / Z desired amount of water, then mix the harvest oil and then the remaining amount of water.If no harvest oil is used then simply mix together the water and the concentrate preparation.

A further understanding of the invention may be obtained in the following non-limiting preparations and examples, in which, unless expressly stated otherwise, all temperatures and temperature ranges refer to PC and the term "ambient" or "room temperature" refers to ca 20-BSOC. The term "percent" or "%" refers to weight percent and "moles" or "moles" refers to gram moles. The term "equivalent" refers to a quantity of reagent equal in moles to the moles of the previous or subsequent reactant, which are enumerated in this example in terms of final moles and final weight or volume. When given, the proton-magnetic resonance spectrum (p.m.r. or NHR) was determined at 60 mHz, signals are denoted as singlets (s), broad singlets (bs), doublets, (d), double dubbmtcr? (da), tripiettcr (t), doubles: repeats (at), quartets (q) and multiplets (ml: and cns refer to cycles per second, as well as repeated necessary examples to provide additional starting materials for subsequent examples .

EXAMPLES Example 1 Trans-2- [1- (3-chloroallyloxyamino) propylidene] -5- (Z-ethylthio-propyl] cyclohexane-1,3-dione II To this example was added 17.2 g (0.0636 mol 2-propionyl). -5-9 (2-ethylthiopropyl) -cyclohexane-1,3-dione, 0.9 g (0.0153 mol mol acetic acid and 10.9 g (0.0757 mol) 3-trans-chloroallyloxyamine in 35 ml water to 20 ml of hexane and stirred Aqueous 5% by weight sodium hydroxide was added slowly over about 15 minutes until 3.0 g (0.075 μm + small excess) of sodium hydroxide had been added - pH of the reaction mixture about 6. The mixture was deheated to And kept at 40 ° C in the Z-1/2 hours and then cooled to room temperature The organic (i.e. hexane) phase was separated and washed with 10 ml of aqueous 5% by weight hydrochloric acid and then aqueous 6,25% by weight sodium hydroxide was added. to pH 12. The aqueous phase was separated and mixed with 25 ml of hexane and the pH was adjusted to 5.4 by the dropwise addition of aqueous 36% by weight hydrochloric acid. ver an ice bath. The organic phase was separated, t0ïk fl dGS over magnesium sulphate and then concentrated by evaporation For 10 15 20 25 L! _11 ÄB 458 683 8 to give 18.0 g of a crude product. The crude product was purified by column chromatography on silica gel eluting with hexane methylene chloride to give the purified title compound as an oil. Elemental analysis: carbon calculated 56.73%, found 56.63%; hydrogen calculated 7.28%, found 7.55%; nitrogen 3.89%, found 3.55%.

Example 2 Sodium 2- [N- (3-trans-chloroallyloxyamino) propylidene-3-oxo-5- (2-ethylthiopropyl) -cyclohex-1-en-1-olate This example illustrates a process which can HDV produce the title association.

A solution containing 0.01 mol of sodium hydroxide dissolved in 2 ml of water is added to a solution containing 0.01 mol of Z- [4- (3-trans-chloroallyloxyamino) propylidene-5- (2-ethylthiopropyl) hexane-1,3-dione at room temperature. After the reaction is complete, the solvents are evaporated in vacuo to give the 1-hydroxy-sodium salt of 2- [N- (3-trans-chloroallyloxyamino) propylidene-3-oxo-5- (2-ethylthiopropyl) cyclohex-1- en-l-ol.

Example 3 In this example, the title compound of Example 1, i.e. 2-LW- (3-trans-chloroallyloxyamino) propylidene] -5- (2-ethylthiopropyl) -cyclohexane-1,5-dione, was tested, using the procedures , son1bC§k¿h @ 5 below, for Eytotoxic effect before germination and after germination against a variety of grasses and hrm fifl adíga D1ant0r including a grain harvest and a broadleaf harvest.

Pre-emergence herbicide test Pre-emergence herbicidal activity was determined as follows.

Test solutions of the respective compounds were prepared as follows: 355.5 mg of the test compound was dissolved in 15 ml of acetone. 2 ml of acetone containing 110 mg of a non-ionic active agent was added to the solution. 12 ml of this stock solution was then added to 47.7 ml of water containing the same nonionic surfactant at a concentration of 625 mg / l.

Seeds of the test vegetation were planted in a pot of soil and the test solution was sprayed uniformly on the soil surface at a test compound dose of 77 °. 2 _ _. _ __. _, 5 micrograms / cm unless otherwise stated in the following tables. The pot was watered and placed in a greenhouse. The pot was watered intermittently and observed for the germination of dilute plant, condition of germinating dilute plants, etc., for a 3-week period. At the end of this period, the herbicidal effect of the compound was graded on the physiological observations. A 0 to 100 scale was used, with 0 denoting no phytotoxicity, 100 denoting complete killing. The results of these experiments are summarized in Table 1.

Post-emergence herbicide test The test compound was prepared in the same manner as described above for the pre-emergence test. This preparation was uniformly sprayed on 2 similar pots containing plants 2 to 3 inches long (excluding wild oats, soybeans and water grasses which were 3 to 4 inches long) (approximately 15 to 20 plants per pot) at a test dose of 27. 5 micrograms / cm: unless otherwise indicated in the following tables. After the plants had dried, they were placed in a greenhouse and then irrigated with their bases as needed. The plants were periodically observed for phytotoxic effects and physiological and morphological responses to the treatment. After 3 weeks, the herbicidal activity of the compound was evaluated based on these observations. A 0- to 100-scale was used, with 0 denoting no phytotoxicity, 100 denoting complete killing. The results of these tests are summarized in Table 2. 10 458 683 oow QQP oo ~ oo fi about m ~ about mm mmm. o »> w: flfi H> m» «: øoHz mmhuuo fi wcnßw fi om nHHoE: fi> w Qmcow zëzm fi w azwwozocøzuz ~ m ~ fi u fl xopo ~>% W maka pou: æ ~ cn: fl ws ~ @ wonn ~ @ ~ H> woman umccm øwc fl aw fl> mw .NEu \ Emhmo »x« E m.ßN Uposmwpwmzwmc fi pwçqm ~ o1 ::; ~: w2z: w; w; :: x »o> wwu fi sguz Pxwšmšr _ hc wcwcohæu 11 458 685 oo_ oo" cor cor of av mw om _ m fi u o »> m: wH«> wh fi swo fi s mmwuuo fl mcmßnwow m ~ fi oE: W> m aøwzu uz zemz ø puu fi u fi zouopwu 6 mmßc I popcn fi n mwwwm fi ßvohm mo> Hw: c umccm opc fl mvH> æw. Eu Emumoh fi e _ npwlïummfmïähø m.. M.. N x. ßw Q _ _. In this example, the title compound of Example 1 of the present invention, ("1"), was tested for herbicidal action after germination at moderately low dosage rates side by side with its butylidene homologue, i.e. trans-2- / 1- (3-chloroalyloxyamino) butylidene / - 5- (2-ethylthiopropyl) -cyclohexane-1,3-dione.

The tests were performed in the same manner as described in Example 2 above except that the loading rates, indicated in Table 3, were used and 4 replica pots were used per test instead of 2. Mean results of the 4 replica experiments are reported in Table 3 below, where 0 indicates no phytotoxicity and 100 indicates complete killing. Usually phytotoxicities below about 20-50% are not considered significant because the plant can typically grow out of this amount of damage. 458 683 wøä hoxmm Umu fi cz cm cou fifi cukncowcocmcëmc cm wa mæ ma wc ».» O ~ oE «U: uu ~ = c = n> 4 ca: accuocxmë n: o fl w« mc |: axo: oHx> uxc ~ Aaouco fi p ~> uø | ~ c «m | \ do® fi H> ~: ß ~ oc fi Em @ xoH> HHøø» o fi z | mc1fm | ~ | m: = c ~: o ~ fi | mc | ccxø: oHx> u | ^ ~% co »co «UH% wm | Nvlmaxcow fi Hznowanoc fi ëm fi xo fi h fl HwoHoHx | wunrwnwnmnmpu mHOS & mHm fl Sw fi CHhUwOU WCCQÜ ¶w $ hOC®Qß @ Om GQ NU§0Üw> G Üwm cmc. c? Z så ... ccc cJ cc E: ci N cccc _ c cc E: E: ccmc c .. oc> c: c ~ «> wmcuuo fl muczïo fi z zcwzamom = ~ _oE: W> w: ucuz Ezs fl a« «qEu \ u : E: mvo: c: o: u mcwpowøn u0PHUwKOHOP> uw UWw_U @ ZOuOu%; c ._ wmnc Loccccc zuwsscs fi apm Hopmoummmcpuwmw.Mma fi ßwm flfl mumz wo cnhccwczs cow o ::.> ø> cuñcco v _ c 4. . m .SMEÉ nzvïwïw Pnu cum _10 F P * Hc ucmcopßu 10 15 458 683 14 As can be seen from Table 3, compound 1 was substantially superior in comparison with compound C-1 against h1Qdhir5 ,, even at moderately low dosages. The superiority of compound 1 will become more apparent at low doses, as used in Example 4 below.

Example 4 In this example, the title compound ("1") was tested for herbicidal action after germination at a very low dose rate side by side with trans-2- [1- (3-chloroallyloxyamino) butylidene] -5- (2-ethylthiopropyl) - cyclohexane-1,3-dione ("C-1") and the commercial herbicide Sethoxdm ("C-2"] (i.e. Z- [1- (ethoxyamino) butylidene] -S- (2-ethylthiopropyl) -cyclohexane-1,3-dione against an expanded list of weeds.

The tests were performed in the same manner as described in Example 5 above except that the dosages given in Table 4 were used.

The results of this test are summarized in Table 4, where 0 indicates no phytotoxicity and 100 indicates complete killing. Usually phytotoxicities below about 20-30% are not considered meaningful because the plant can typically grow out with this amount of damage. 15 458 683 o or Fe mo cv cv oß æß F vw mw ma 0 QOOQQO Ncào NU CQ o_ OQ om o_ m @ “@ Nqu QC w fl _m @_ wø @_ __. @ NU QQ wø wß øm om mm wN.O ~ -UOQQQO w Q ~ @. @ ~ -UQQ cv _N @ ~ oq mv m @. @ PU QQ mm mq mg Qß mN _ ~. @ ~ -U QQQ »wø oø. Qm mm wN. @ _-UOQ _ ~ _N Q mm ~ @. @ _ OC mø mø 0 GQ O * m @. @ FOQ Nm NG øq co mo __. @ _ QO aa aa @@ ma _ß w ~. @ _ mwm ncwnn fl om w> øw: »oc> um: => m> mp: mm; m |: øm o @> :: w ~ m> wm> amo; wpwzvo fi m «NEu \ @:« Hc fi = c - = L @ w- = oNM fi wr pop fi u fi xouopæw b n po »fl u @ xopow> @ w wc fl pomoo wc fi coamm wmhc powcw fi z Eäsn fi nnøuæ uvpmwp; wmvcnwmnmccs Houwø cwMhæ> v fi u fi nwmï «| mmmm« H 10 15 20 458 ess W As can be seen from Table 4 with the exception of wild oats and Cyprus species, compound 1 was superior to compound C-1 in the doctrine of the other tested the weed species. Compounds 1 and C-1 were approximately equivalent to wild oats and both compounds were inactive at these dosing rates against Cynerus species. Compounds 1 and C-1 were both superior to compound C-2.

The term dosages required to elicit equivalent responses was an application rate of compound 1 of 0.11 g / cm 2 approximately equivalent to an application rate of compound C-1 of 0.28 g / cm 2 to control blood millet and An application rate of compound 1 of 0.05 g / cm 2 was approximately equivalent to an application rate of C-1 of 0.28 g / cm 2 to control yellow fox tail and an application rate of compound 1 of 0, 11 g / cm 2 was superior to an application rate of compound C-1 of 0.28 g / cm 2 to control "Johnson grass".

Obviously, many modifications and variations of the invention, which are described above and below, may depart from the nature and scope thereof. done without

Claims (6)

A compound of the formula cngcsz Non 1 v C33 H H2 CHS CH2CH3 wherein R1 represents 3-trans-chloroallyl, and compatible salts thereof. 2. A compound according to claim 1, characterized in that the compound is 2-E1- (3-trans-chloroallyloxyamino) propylidene-5 - (2-ethylthiopropyl) -cyclohexane-1,3-dione. Herbioid composition, characterized in that it comprises 0.02-0.6% by weight of a compound according to claim 1, 0.001-0.15% by weight of an emulsifier, 0.08-2.5% by weight of an organic solvent and about 95 to 99 weight percent water. Herbicidal composition, characterized in that it comprises 0.02-0.6% by weight of a compound according to claim 2, 0.001-0.15% by weight of an emulsifier, 0.08-2.5% by weight of an organic solvent and about 95 to 99 weight percent water. Herbicidal composition, characterized in that it comprises an amount of active herbicide of the compound according to claim 1 and about 0.25-2% by weight of a crop oil selected from soybean oils, paraffin oil and olefin oils. Method for controlling grassy plants, characterized in that a herbicidal amount is applied in the range from about 0.02 to 10 kg / ha of a compound according to claim 1 to the foliage or plant habitat. 458 683 19 2 Method for controlling grassy plants, characterized in that a herbicidal amount is applied in the range from about 0.02 to 10 kg / ha of a compound according to claim 2, to the foliage or plant habitat. Method for controlling foxtail, bermuda grass, wild sorghum, broadleaf signal grass, oryza rutipogon ("red rice"), gooseberry, Scholochloa testucacca ("Sprangletop"), "Johnson grass" or wild maize, derived therefrom - A herbicidal effective amount in the range of from about 0.02 to 10 kg / ha of a compound according to claim 1 is applied to the grass species or their habitat 9. A method of preparing a compound according to claim 1, characterized by the step , contacting 1 mole of 2-propionyl-5- (2-methyl-thiopropyl) -cyclohexane-1,S-dione with 1 to 2 moles of 3-transchloroallyloxyamine under reactive conditions at temperatures in the range of about 0 to BÜOC.