WO1996015667A2

WO1996015667A2 - Antidote composition and method for use of the composition

Info

Publication number: WO1996015667A2
Application number: PCT/HU1995/000060
Authority: WO
Inventors: Endre SEBESTYÉN; Sándor BÁLINT; Károly Henger; Jeno^' PELYVA; Csaba SÖPTEI; Lajos Nagy; Judit POLGÁRNÉ PATINSZKI; Géza SZABÓ; Gábor SZÚDY; Elemér TÖMÖRDI; Erzsébet GÉMES
Original assignee: Nitrokémia Rt.
Priority date: 1994-11-18
Filing date: 1995-11-16
Publication date: 1996-05-30
Also published as: HU222229B1; ZA959807B; BR9509735A; WO1996015667A3

Abstract

The invention relates to an antidote composition containing an N-phenylphthalimide derivative of formula (I), wherein R1, R2 and R3, which are the same or different, stand for hydrogen, halogen, C1-4alkyl or methoxycarbonyl group; and R4 and R5 together form an 1,2-phenylene, 1-cyclohexen-1,2-ylene or 4-cyclohexen-1,2-ylene group and, at least one herbicide from the class of chloro acetanilide, urea, uracil, thiolcarbamate, triazine sulfonylurea. N-phenyl phthalimide, pyridazinone and imidazolin derivates.

Description

ANTIDOTE COMPOSITION AND METHOD FOR USE OF THE COMPOSITION

The invention relates to selective herbicide compositions containing N-phenylphthalimide derivatives as well as a method for weed control and/or seed treatment (dressing) by using these compositions.

More particularly, the invention includes selective herbicide compositions comprising a mixture of at least one herbicide chosen from the types of derivatives of chloroacetanihde. urea, carbamate. uracil, thiolcarbamate, triazine, sulfonylurea, N-phenylphtiaalimide. pyridazinone, or imidazoline and 0.5 to 95% by weight of an N- phenylphthalimide derivative of formula (I)

0

⁽I)

wherein

Ri, R₂ and R₃, being the same or different, stand ior

drυccn halogen , C_M alkyl or methoxycarbonyl group;

R₄ and R_? taken together form an L2-phenylene or 1- cyclohexen-L2-ylene or 4-cyclohexen-1.2-ylene group in an admixture with at least one solid and/or liquid carrier, and if desired with surface active agent and additives (auxiliaries) commonly used in the formulation of plant protectives.

Furthermore, the invention relates to a method of selective weed control and seed dressing, wherein the above active compounds are used. A part of the compounds of formula (I) are new or, the utilization of their antidote action in the practice of plant protection is novel.

It is known from the literature and practice of plant protection that compositions containing a derivative of chloroacetanihde (US 3.442,945; US 3,547,620; HU 208,244; GB L438.311; GB L438,312), urea (GB 965,313; GB 914,779; DE 1,028.986), uracil (US 3,235,360), carbamate (GB 1,127,050), thiolcarbamate (US 2.913,327), sulfonylurea (US 4,127,405; US 4,514,212; US 4,789,393; US 4,420,325), pyrazone (DE 1,105,232), N-phenylphthalimide (EP 170,191; PCT Int. Appl. WO/9106216), triazine (GB 1,368,416; GB 814,947) or imidazoline as active ingredient, when preemergently and/or postemergenty sprayed or embedded into the soil, exert an excellent herbicidal effect on monocotyledonous and/or dicotyledonous weeds. Their use is stroπgh limited by the fact that these active compounds frequeniK damage aLso the cultivated plant to be protected.

Their damaging effects strongly depend on the s e.ie «n_ health state of the cultivated plant to be protected a. well as composition and water content of the soil and weather conditions.

Protective agents (antidotes) diminishing the phytotoxic effect of thiolcarbamate-type herbicides on cultivated plants are disclosed in the United States Patent Specification No. 3.13L509.

1,8-Napthtalenedicarboxylic acid and its derivatives such as anhydrides, esters and amides show a selective protecting effect on cultivated plants in addition to the retention (preservation) of herbicidal action. Antidotes containing N,N-d_substituted dichloroacetamides are described in the Hungarian patent specification No. D6,736. N- dichloroacetyl-l-oxa-4-azaspiro [4,5] decane and analogues disclosed in the Hungarian patent specification No. 176.784 are proposed to use as antidotes.

The currency of known antidotes in the practice of plant protection is limited since they have brought only a partial success. Namely, the scope of herbicidally active agents with a damaging effect to be reduced is very wide. On the other hand, their phytotoxic effects are very different. It is also known that cultivated plants give different responses to the damaging effects of various herbicidally active agents. Thus, the possibility of reducing the toxic effect by a single known antidote is restricted.

The most important target of research on reducing the phytotoxicity and enhancing the selectivity* of herbicidally active agents is to prepare and utilize compounds which are useful in a wide range of cultivated plants and herbicidally active agents with an excellent effect; which are easily available and have favourable properties from the view of environmental protection.

N-(Dialι_yl)phenylphthah-nides as fungicides are known from the published Japanese patent applications Kokai 75 25736, 75 30868. 77 90626 and 77 122696. Tetrahydrophthalimides and N- acylphthalimides with complicated structures became known as herbicides or defoliants from the European Patent Specification No. EP 170.191 and the PCT application No. WO/910616. It has been recognized that the N-pheny-phthalimide type compounds described in the introduction possess an excellent and wide- ranging antidote action and decrease the phytotoxicity of several groups of herbicidally active agents without lessening the herbicidal effect.

Antidotes widespread in the practice of plant protection such as N-dιchloroacetyl-N ,N-diallylamιne, N-dichloroacetyl-1 -oxa- -4-azaspiro[ , 5Jde_ane or o — [( 1 , 3-dιoxolan-2-yl )- methoxyiniinojbenzylacetonitrile, respectively (European Patent Specification No. 0,011,047) and 4.6-dicUoro-2-phenylpyrimidine (European Patent Specification No. 0,055.693 and United States Patent Specification No. 4,493,726) exhibit a protecting effect only in the cases of herbicides inhibiting the sprouting of weeds (thiolcarbamates, chloroacetanihdes). In addition to the moderation of phytotoxicity of this type of herbicides, the protecting effect of antidotes of formula (I) is surprising. Namely, they decrease not only the phytotovicity of herbicides inhibiting the sprouting of weeds but al_o preserve the cultivated plants (e.g. sugar-beet) from the damaging effects of herbicides postemergently sprayed onto the foliage of cultivated plants (uracil or carbamate derivatives and the like) without weakening the herbicidal action.

Herbicidally active compounds, which may be mixed with the substances of formula (I) according to the invention are detailed in Table I. Table I Chloroacetanihde derivatives

Generic name Chemical name

Alachlor 2-chloro-2,6-diethyl-N-(methoxymethyl)aceta__i- lide,

Propachlor 2-chloro-N-isopropylacetan_ide, Metolachlor 2-chloro-2'-ethyl-6'-methyl-N-[(l-methyl-2- methoxy)ethyl]-acetanilide,

Acetochlor 2-chloro-2-e__yl-6-methyl-N-(ethoxymethyl)- acetanihde,

Butachlor 2-chloro-2,6-diethyl-N-(butoxymethyl)ace- tanihde,

Pretilachlor 2-chloro-2,6-diethyl-N-(2-propoxyethyl)ace- tanihde,

Propisochlor 2-chloro-2-ethyl-6-methyl-N-(isopropoxy- methyl)acetanihde.

Dimethenamide 2-chloro-N-(2,4-dimethyl-3-thienyl)-N-

(2-methoxy-l-methylethyl)acetanihde; Urea derivatives

Linuron N-(3,4-dichlorophenyl)-N'-methyl-N'-methoxy- urea,

Monolinuron N-(3-chlorophenyl)-N'-methyl-N'-methoxyurea, Chlorbromuron N-( 3 -chloro-4-bromophenyl)-N'-methyl-N'-me- thoxyurea,

Benzthiazuron N-(benzothiazol-2-yl)-N-methylurea, Chlortoluron N'-(3-chloro-4-methylphenyl)-N,N-dimethyl- urea,

Diuron N'-(3,4-dichlorophenyl)-N,N-dimethylurea, Fenuron N,N-dimethyl-N'-phenylurea, Isoproturon N'-(4-isopropylphenyl)-N,N-dimethylurea, _Metobromuron N'-(4-bromophenyl)-N-methoxy-N-phenylurea, Thiadiazuron N-Phenyl-N'-(l,2.3-thiadiazol-5-yl)urea;

Carbamate derivatives

Desmedipham 3-(ethoxycarbonylaπιino)phenyl-N-phenyl- carbamate, Phenmedipham 3-(memoxycarbony mino)phenyl-N-(3-methyl- phenyl)carbamate;

Uracil derivative

Lenacil 3-cyclohexyl-5,6-trimethyleneuracil Thiolcarbamate derivatives

EPTC S-ethyl N,N-d_propy___iolcarbamate,

Vemolate S-propyl N,N-dipropylt_iolcarbamate,

Butylate S-ethyl N,N-diisobutylthiolcarbamate,

Cycloate S-ethyl N-cyclohexyl-N-ethylthiolcarbamate,

Benthiocarb S-(4-chlorober__yl) N.N-diethylthiolcarbamate.

Triallate S-(2,3,3-Trichloroallyl) N,N-di_sopropyl__iol- carbamate,

Molinate S-ethyl N,N-hexamethylenethiolcarbamate;

Sulfonylurea derivatives B e___sul_uronmethyl methyl 2- { [[[(4, 6-dimethoxypyrimidin-

-2-yl)amino] carbonyl] amino] sulfonyl} benzoate, Nicosulfuron 2- { [[[(4,6-d_memoxypyrimidin-2-yl)amino]

_-reido]amino]sulfonyl} -N,N-dimethyl-3- pyridinecarboxamide, Triasulfuron 3-(6-methoxy-4-methyl-L3,5-triazin-2-yl)-l-

[2-(2-chloroethoxy)phenylsulfonyl]urea, Clorsulfuron 2-chloro-N-[(4-methoxy-6-methyl-l,3,5-tria__n-

-2-yl)a___nocarbonyl]benzenesulfonamide;

N-phenylphthalimide derivatives

JFlumioxazine N-(7-fluoro-3,4-dihydro-3-oxo-4-prop-2- ynyl-2H-l,4-benzoxa__n-6-yl)cyclohex-l-ene-

1,2-dicarboximide,

Flumichlorac [2-chloro-4-fluoro-5-( 1,3,4,5, 6,7-hexahydro-

L,3-dioxo-2H-isoindol-2-yl)phenoxy]acetic acid;

Pyridazinone derivative Chloridazone 5-amino-4-chloro-2-phenyl-3(2H)-pyridazi- none; Imidazoline derivatives

Imazametabenmethyl methyl-2-(4-isopropyl-4-methyl-5-oxo-2- imidazo__ι-2-yl)-p- and -m-toluene Imazapyr 2-(4-_sopropyl-4-methyl-5-oxo-2-imi- dazo_m-2-yl)nicot__ic acid and Imazaquin 2-[4,5-dihydro-4-methyl-4-(l-methyl- ethyl)-5-oxo-.-N-imidazol-2-y_]-3- quinolinecarboxyhc acid. Some antidotes according to the invention and their physical characteristics are shown in Table II.

Table II.

The scope of protection of the invention includes also a method of select e weed control characterized by treating the soil before sowing, after sowing or simultaneously with sowing of the sprouted plant, respectively with a known herbicide as well as with a composition containing an N-phenylphthalimide derivative of formula (I), wherein the meanings of the substituents are as defined above, by using 5 to 10000 g per hectare of active agent, suitably O.l to 1000 g per hectare calculated for antidote active compound.

The invention furthermore relates to a method of seed dressing, which comprises treating the seeds of cultivated plants to be protected with an N-phenylphthahmide derivative of formula (I), wherein the meanings of the substituents are the same as defined above, together with or separately from other dressing agents

The treatment with the herbicide is carried out according to the method described in the art. The weight ratio of active ingredients of the composition containing the antidote and herbicide may be varied between 50 1 and 1.1, preferably between 20 1 and 10 1, this ratio depends on the structures of antidote and herbicidally ac e compound, the cultivated plant as well as other factors, which influence the use of active ingredients and are known to a person skilled in the art.

The employed amount of antidote is adapted to the required amount of herbicidally active agent by consideπn the above wciii - ratios On a simultaneous application, the total amount related to the active ingredient weight is in general 5 to 10000 g per hectare Wher used alone, the amount of composition containing the antidote may be usually 0.1 to 1000 g per hectare, suitably 2.5 to 250 g per hectare calculated for the antidote active ingredient.

It is a general rule that the compositions containing both the herbicidally active compound and antidote include agriculturally acceptable additιve(s) compatible with both active ingredients. These compositions embrace both the compositions with high concentrations as well as the compositions prepared therefrom by dilution, which may be used directly. In these latter ones, the total content of active ingredient may be decreased even to a concentration of 0 01 g per litre The compositions prepared from the herbicide compositions and antidote composition mixed in a vessel or spraying device, or in some cases in the flooding water Optionally diluted compositions directly prior to use are also considered to be encompassed by the invention

A composition according to the invention may be any agriculturally acceptable solid or liquid composition, the preparation and effective use are possible on the basis of physical and chemical properties of the active ιngredιent(s) The composιtιon(s) contaιn(s) the active ιngredιent(s) together with agriculturally acceptable solid or liquid earners as well as surface active agents

The compositions may contain other additives, which favourably influence the properties of the compositions or promote their use

Any agriculturally acceptable organic or inorganic substance either of natural or man made oπgin may be used as earner The surface active additive may be an emulsifying or dispersing agent ionic and/or non-ionic in its character The presence of at least one surface active substance is required in the composition when the acme mgredιent(s) is (are) water-insoluble while using water as an adiu nt (additive) e g for dilution The liquid compositions, i c composition:_* used in liquid form may be solutions, emulsifiable concentrate, emulsions, concentrated suspensions, wettable powders or

powders or pastes The concentrated compositions may be powders, dusts or granules The compositions are prepared in a known way The application of compositions may be achieved optionally in an appropnately diluted form by employing the usual methods and devices, e g spraying, dusting, spreading or in a specific case by flooding or the like

The invention is illustrated in detail by the following non- hmiting Examples Example 1

Preparation of2,6-dιmethyI-N-phenyIphthalιmιde

To a mixture of 200 ml of acetic acid and 0 25 mol of phthalic anhydnde, 0 25 mol of 2,6-dιmethylanιhne were added while stimng, then it was heated to boil and boiled under reflux for 2 hours After evaporating to its half volume and cooling to room temperature, water was portionwise added The precipitate was filtered and dπed to obtain the title compound, m p 203 °C

Example 2

Preparation of N-[2-(methoxycarbonyl)phenyI]-l 2,3,6-tetra- hydrophthahmide

A mixture containing 152 15 g (1 mol) of 1,2,3,6- tetrahydrophthalic anhydπde in 800 ml of acetic acid was heated to the boiling point a coolable and heatable flask equipped with a stirrer, thermomether, feeder and reflux condenser, then 137 14 g (1 mol) of methyl 2-amιπobenzoate were portionwise added The reaction mixture was boiled under reflux for 2 hours, then 600 ml of acetic acid were distilled off After portionwise adding 300 ml of water and cooling, the crystalline precipitate was filtered and dπed to give 241 g (83% yield) of the title compound, m p 138 8°C

The compounds listed in Table II were prepared in an analogous way as descπbed above

The N-phenylphthahmide deπvatives of formula (I) can be formulated either alone or together with the herbicidally acme compound into powders or liquid compositions in the known and usual ways of the techniques of plant protectives

The compounds of formula (I) can be foπnulated to wettable powders by following e g the prescπption disclosed m Example 3 Example 3

70 parts by weight of compound No 10

17 parts by weight of kaolin

8 parts by weight of active silicic acid

2 5 parts by weight of fatty alcohol sulfonate

2 5 parts by weight of sodium hgninsulfonate are mixed m the above ratio m an Alpine type mill to obtain a ready-to- use wettable powder (a wettable powder suitable to use)

On formulating together with the herbicidally active agent, the above composition has to be modified in such a way that e g 60 parts by weight of herbicidally active agent and 10 parts by weight of the compound of formula (I) are mixed with the additives As additives, diluents of mineral oπgm, e g adhesion-promoting substances may be useful additives in wettable powder compositions When it is desired to reduce the phytotoxicity of known herbicidally compounds by treating the seed of the cultivated plant with the compound of formula (I) before sowing, the formulation is prepared by mixing 20 to 30 parts by weight of earner, suitably talc with 80-70 parts by weight active compound.

A few compounds of formula (I) can be formulated to emulsifiable concentrates

Emulsifiable concentrates may be of course prepared from crystalline compounds, as well This is especially preferred when the herbicidally active compounds are liquid, the damaging effect of which is to be decreased by the compound of formula (I)

Some characteπstic types of formulations of the compositions according to the invention are illustrated in the formulation Examples Example 4 Wettable powder 50 parts by weight of N-(3.4-dichlorophenyI)-N'- methyl-N-methoxyurea 1 parts by weight of compound No. 8 as antidote

5 parts by weight of fatty alcohol sulfonate (Arkopon T, Hoechst) as emulsifying agent

3 parts by weight of sodium ligninsulfonate as dispersing agent

41 parts by weight of kaolin

Example 5

Wettable powder

80 parts by weight of N-phenyl-N'-

(l,2,3-thiadιazol-5-yl)urea 1 parts by weight of compound No. 11 as antidote

4 parts by weight of polyoxyethylene alkyl aryl ether (Atlos 1960, Atlas Chemie) as emulsifying agent

3 parts by weight of sodium lauryl sulfate as dispersing agent 7 parts by weight of colloidal synthetic silicon dioxide

5 parts by weight of vermicuhte Example 6

Granular composition

1 parts by weight of 2-chloro-N-[(4-methoxy-6- methyl-l,3,5-tnazιn2yl)amιnocarbonyl]benzene- sulfonamide 1 parts by weight of compound No l as antidote

98 parts by weight of attapulgite Example 7

Aqueous colloidal suspension

45 parts by weight of 3-cyclohexyl 5,6-trimethylene uracil 5 parts by weight of compound No. 6 as antidote 4 parts by weight of fatty alcohol polyglycol ether as emulsifying agent (Emulsogen M, Hoechst)

3 parts by weight of sodium alkyl sulfate as dispersing agent

1 parts by weight of lecithin as protective colloid

4 parts by weight of colloidal synthetic silicon dioxide 38 parts by weight of water

Example 8

Aqueous colloidal suspension

5 parts by weight of 3-(methoxycarbonylamιno)phenyl N-(3-methylphenyl)carbamate

5 parts by weight of compound No 9 as antidote

5 parts by weight of polyoxyethylene alkyl phenyl ether

(Atlox 1690, Atlas Chemie) 3 parts by weight of potassium ligninsulfonate as dispersing agent 1 parts by weight of lecithin as protective colloid

81 parts by weight of water

Example 9

Colloidal suspension (oil)

50 parts by weight of 2-chloro-N-[(4-methoxy-6-methyl- l,3,5-tπazιn-2-yl)ammocarbonyl]benzenesulfonamide 5 parts by weight of compound No 5 as antidote 7 parts by weight of a mixture containing fatty alcohol polyglycol ether and polymerization product of ethyleneoxide with propylene oxide (Genapol PF 10, Hoechst) as emulsifying agent 38 parts by weight of paraffin oil

Example 0

Emulsifiable concentrate

84 parts by weight of 2-chloro-2'-ethyl-6'-methyl-N-

(isopropoxymethyl)acetanilide 4.2 parts by weight of compound No. 3 as antidote 5 parts by weight of polyoxyethylene sorbitan monolaurate (Tween 20, Atlas Che ie) as emulsifying agent 13.2 parts by weight of xylene Study of the biological effects

Example 11

Treatment of sowing seeds

After adding 10 g of maize sowing seeds to a mixture containing 50 mg of compound of formula (I) listed in Table II and 1 ml of acetone, the mixture was shaken in a closed glass bottle until the antidote uniformly coated the seeds

In a suitable stirπng equipment acetochlor, hnuron, chlorsulfijron as herbicidally active compounds were mixed each into

The herbicidally active compounds were applied onto or into the soil in the form of a suspension, emulsion or wettable powder prepared with 15 ml of water The soil pretreated was spread on a tray of 10 x 10 cm size; an area of 0 01 m- was investigated in each case The amount as kg/hectare (abbreviated: kg/ha) and name of herbicidally active compound are indicated in Table HI. On each tray, 6 pretreated maize seeds each were sown to a depth of 2,5 cm. In the series of comparative experiments, the same number of seeds but not treated with the antidote was sown into the soil pretreated with the herbicidally active compound. The trays were maintained in a phytotron at a temperature of 22 °C, 10 lux with a daily ihumination for 16 hours and a relative moisture content of 65%, and sprinkled suitably for the favourable growing of the plants. The state of sprouted plants was investigated after 3 weeks. The percentage of damage of the plants was determined in each case in comparison to the plants sprouted from seeds of natural origin (which were sown into a soil not treated with antidote and containing no herbicidally active compound). The results obtained are summarized ~ in Table HI, wherein

"A" means: seeds pretreated with antidote: "B" means: seeds left untreated.

Table HI

Percentage of herbicide-induced damage of maize plants sprouted from seeds pretreated (A) or not pretreated (B), with antidote resp

Antidote Herbicide Damage of cultivated plants after 3 weeks (%) No Amount Name *g,kg/ha A B m /lO

Based on the result summarized in Table III it can be established that plants sprouted from seeds treated with the dressing agent according to the invention were essentially less damaged than were the plants sprouted from untreated seeds

Example 12

Investigation of the effect of soil treatment a / Herbicidally active compounds and antidotes shown in Table III were mixed into 1000 ml of soil each in a suitable mixing equipment A suspension, emulsion or wettable powder of a herbicidally active compound m 50 to 100 ml of water, whereas those of antidotes in 5 to 10 ml of water were applied into the soil, which was then spread on trays of 10 x 10 cm size . Thus , the area

2 observed was 0.01 m in each case . The amount of herbicidally active compounds and antidotes expressed in kg/hectare are shown in Table IV. Six seeds were sown in each tray to a depth of 2.5 cm b./ Six seeds were sown to a depth of 2.5 cm in each tray of 10 x 10 cm size containing untreated soil. The herbicidally active compound(s) and antιdote(s) were applied as suspensions, emulsions or wettable powders onto the surface of the soil.

The cultivated plants are shown in Table IV. Two comparative series of experiments were earned out: in the first series the soil was treated only with the herbicidally active compound; in the second one neither herbicidal nor antidoting treatment were employed.

The trays were maintained under laboratory conditions described for the seed treatment test and sprinkled according to the favourable growth of the plants. The plants were observed after 4 weeks. The percentage values of the protective effect exerted by the antidotes against the herbicides according to method a./ or method b /, respectively are indicated in Table IV.

The percentage of protective effect was calculated by the following equation

A - E

Protective effect %= x 100

Q - E wherein

A means the average shoot length of plants growing on a soil pretreated with herbicidally active compound and antidote,

E means the average shoot length of plants growing on a soil pretreated with herbicidally active compound; and

Q means the average shoot length of plants growάng on a soil left untreated. 7 -

21 Table IV

Percentage of protective effect of antidotes against the herbicide- induced damage of cultivated plants

It can be stated from Table IV that a wide range of cultivated plants were protected by the compounds of formula (I) against many types of herbicides

Example 13

FIELD TRIALS

Field tnals were earned out on pea, sunflower, maize, sorghum, πce, cotton, peanut, soy and sugar-beet in 4 repetitions on lots (land parcels) of 20 m- each, except nee The compositions according to the invention or commercial compositions containing the same active ingredient without protective agent were sprayed with an amount of water corresponding to 300 1/ha onto the soil after sowing the plant seeds

In the case of πce, the herbicides were applied onto the field

dropping them into the flooding water after 3 days following the sowing of πce The size of πce-producing lots was 10 x 30 m-, the treatments with herbicides were earned out in one repetition in the case of rice Sample areas of 4 x 2 m- were labelled in the lots as models in the vegetative peπod

The effects of compositions were evaluated on πce. sorghum and sunflower in the 18th week and at the pea and rice on the 8th week following the sowing In addition to the damaging effect, the percentage of sprouting and herbicidal effect were evaluated The evaluation of both the damaging and herbicidal effects was earned out according to the internationally accepted EWRC scale based on visual observation The meanings of scores are as follows 7

23

On evaluation of the percentage of sprouting, the number of plants sprouted under treatments without antidote was considered to be 100% and the number of plants sprouted in the lots treated with herbicide compositions containing antidote was compared with it. In order to prove the protective effect, the compositions were sprayed out in twofold doses compared to the approved doses.

Table V

Herbicidal effects of herbicide compositions with or without, respectively antidote

Name or label Dose W e e d s of kg ha Echmochloa Setaria Cheno- Amaranthus composition crus-galli viπdis podium retroflexus

Example (Ex ) album

50 WP of Ex 4 5,0 7 8 1 1 Afalone 50 WP (Agrevo) 5,0 7 8 1

50 FW of Ex 7 5,0 7 7

Adol 80 WP

(G Richter pic) 3,0 7 7

50 FW of Ex 9 0,075 8 7 5

Glean 75 DF

(DuPont 0,050 8 7 5

840 EC of Ex 10 4,0

Proponit 840 EC (Nitrokemia pic) 4,0 1

5 WSC* ofEx 8 20.0 9 9 Betanal 6 9 9 (Agrevo Peremarton. Hungary))

* The composition was postemergently spread in the one to two-leaf state of the weeds

It appears from the above Table that the herbicidal effect of herbicides was not lessened by the use of antidotes- Table VI

Damaging effects on cultivated plants of herbicide composit ons with or without antidote

The composition was sprayed in the 2-leaf state of plants. It has been shown that the herbicide compositions containing the antidotes according to the invention were not or essentially less phytotoxic to culπvated plants than were the compositions containing no antidote.

Table VII Effects on the percentage of sprouting of herbicide compositions with or without antidote

Table VII (continued^')

5 WSC^H ofEx 8 20 0 105 102 98 100 - 102

Betanal 6 0 100 100 100 100 - 100

(Agrevo)

^* = The composition was postemergently used

Example 14

For investigating the effect of antidotes of formula (I) according to the invention an expenment was arranged, wherein the individually formulated antidote of formula (I) according to the invention and Acetochlor as a chloroacetani de-type herbicide, were separately sprayed out

As antidote 70 WP of Example 3, as herbicide composition Acenit 50 EC (Nitrokemia Ltd ) containing Acetochlor as active ingredient were used in this expenment

The soil was first treated with the antidote in such a way that, after diluting with 400 1/ha of water, 1 44 kg/ha of wettable powder composition of Example 3 containing 70 parts by weight of antidote as active ingredient (I e 1 0 kg of active ingredient) were sprayed onto the expeπmental lot and embedded in the soil to a depth of 5 cm by using a cultivator Subsequently, the expeπmental lot was sown with maize One week after sowing the lots were sprayed with the doses of Acenit 50 EC indicated in Table VIII by using 300 Lha of water The effects of treatments were evaluated by 18 weeks following the sowing. Both the. damaging effect exerted on maize as well as the herbicidal action were studied. The evaluation was based on the internationally accepted EWRC scale including visual observation. The experiment was carried out in 4 repetitions.

As comparative control, treatment with the herbicide alone was performed by one week following the sowing as described above, except that the soil was not treated with the antidote composition according to Example 3

Table VIII

Name or label of Dose Weeds composition kg/ha

According to our experimental results, the damaging phytotoxic effect exerted on maize by the herbicide employed was successfully prevented by the antidote of the invention even in the case when the herbicide and antidote compositions, respectively were separately applied onto the soil at different times.

Example 15

The EC composition of Example 10 was investigated on cotton, peanut, soy and sugar-beet in a field trial with the same arrangement and evaluation as described in Example 14.

Table IX

The damaging effect on cultivated plants of herbicide compositions with or without antidote

It has been proven by our results that the herbicide composition containing an antidote according to the invention is not or essentially less phytotoxic to cultivated plants than compositions without antidote

Example 16

The phytotoxic activities of two herbicide compositions namely, Adol 80 WP containing lenacil as active ingredient and Betanal containing phenmedipham as active ingredient, respectively alone or supplemented with an antidote according to the invention were postemergently investigated on sugar-beet in field tπal This expenment was earned out on lots of 5 m² each in 4 repetitions The compositions were sprayed in 400 1 of water each in the 2 to 4-leaf state of sugar-beet The effects of compositions were evaluated based on the scores orf EWRC scale in the 21st and 42nd days following the spraying

Table X Damaging effect of cultivated plants of herbicide compositions w r*. or without antidote

Table X (continued)

Adol 80 WP + 70 WP 1.5 of Example 3 0.14_

Betanal (Agrevo) 9.0

Betanal + 70 WP 9.0 of Example 3 0.07

Betanal + 70 WP 9.0 of Example 3 0.14

70 WP of Example 3 0.14

It can be established on the basis of above expeπments that the antidotes according to the invention protected the cultivated plants against damages induced even by post-emergent herbicides

Claims

L Selective herbicide composition, which comprisesa N- phenylphthalimide derivative of formula (I),

wherein

Ri, R₂ and R₃. being the same or different, stand for hydrogen- halogen. Ci-talkyl or methoxycarbonyl group;

R» and R? together form an 1,2-phenylene, l-cyclohexen-L2- ylene or 4-cyclohexen-L2-ylene group, and at least one herbicide chosen from the types of chloroacetanihde derivatives; urea derivatives; carbamate deπvatnes. uracil deπvatives. thiolcarbamate derivatives; triazine derivatives; sulfonylurea derivatives; N-phenylphthalimide derivatives; pyridazinone derivatives or imidazoline derivatives in an admixture with a solid or hquid carrier, if desired with surface active agents and additives commonly used in the formulation of plant protectives.

2. A selective herbicide composition as claimed in claim L which comprises an N-phenylphthalimide derivative of formula (I), wherein Rj, R₂. R₃. j and R5 are the same as defined in claim L and at least one herbicidally active compound chosen from 2-chloro- 2,6-diethyl-N-(methoxymethyl)acetanihde, 2-chloro-N-ιsopr opylacetani de, 2-chloro-2'-ethyl-6'-methyl-N-[( 1 - -methyl-2-methoxy)ethyl]-acetanihde, 2-chloro-2-ethyl-6-methyl-N- -(ethoxymethyl)acetamhde, 2-chloro-2, 6-dιethyl-N-(butoxymethyl)- acetani de, 2-chloro-2,6-dιethyl-N-(2-propoxyethyl)acetanιhde, 2- chloro-2-ethyl-6-methyl-N-(ιsopropoxymethyl)acetanιlιde, 2-chloro- -N-(2,4-dιmethyI-3-thιenyl)-N-(2-methoxy- 1 -methylethyl)acetanιhde, N-(3 ,4-dιchlorophenyl)-N-methyl-N-methoxyurea, N-(3-chlorophe- nyl)-N-methyl-N-methoxyurea, N-(3-chloro-4-bromophenyl)-N- methyl-N-methoxyurea, N-(benzothιazol-2-yl)-N-methylurea, N-(3- -chloro-4-methylphenyl)-N,N-dιmethylurea, N-(3 ,4-dιchlorophen> 1)- -N,N-dιmethylurea, N,N-dιmethyl-N-phenylurea, N-(4-ιsopropylphe- nyl)-N,N-dιmethylurea, N-(4-bromophenyl)-N-methoxy-N-phenylurea N-ρhenyl-N-( 1 ,2.3-thιdιazol-5-yl)urea,

3-(ethoxycarbonylamιno)phenyl-N-phenylcarbamate, 3-(methoxycar- bonylamιno)phenyl-N-(3-methylphenyl)carbamate, 3-cyclohexyl-5,6-tπmethyleneuracιl,

S-ethyl N,N-dιpropylthιolcarbamate, S-propyl N,N-dιpropvlthιolcarba- mate, S-ethyl N.N-diisobutylthiolcarbamate, S-ethyl N-cyclohexyl-V -ethylthiolcarbamate, S-(4-chlorobenzyl) N,N-dιethylthιolcarbamate S-(2,3,3-tπchloroallyl) N,N-dnsopropylthiolcarbamate, S-ethyl N,N- -hexamethylenethiolcarbamate,

2-chloro-4-ethylamιno-6-ιsopropylamιno-s-tnazιne, 2-chloro-4,6-bιs- (ethylamιno)-s-tπazme, 2-chloro-4-ethylamιno-6-cyanopropylammo- -s-tπazine, 2-methylrnercapto-4,6-bιs(ιsopropylamιno)-s-tπazιne, 2- -methylmercapto-4-ethylamιno-6-tert-butylamιno-s-tπazιne, 2-meth- oxy-4-ethylamιno-6-tert-butylamιno-s-tπazιne, 4-amιno-4, 5-dιhydro- -3-methyl-6-phenvl-l,2,4-tπazιn-5-one, methyl 2- { [[[(4, 6-dimethoxypyrintidin-2-yl)amino]carbonyl]amino]- sulfonyl}-benzoate, 2-{ [[[(4,6-dime_hoxypyrir din-2-yl)arnino]ureido] amino]sulfonyl}-N,N-dimethyl-3-pyridinecarboxamide, 3-(6-methoxy- -4-methyl-l,3,5-triazin-2-yl)-l-[2-(2-chloroethoxy)phenylsulfonyl]urea 2-chloro-N-[(4-methoxy-6-methyl-l,3,5-triazin-2-yl)aminocarbonyl]- benzenesulfonamide;

N-(7-fluoro-3 ,4-dihydro-3-oxo-4-prop-2-ynyl-2H- 1 ,4-benzoxazin-6- yl)cyclohex-l-ene-l,2-dicarboximide, [2-chloro-4-fluoro-5-(l,3,4,5,6,7 -hexahydro-l,3-dιoxo-2H-isoindol-2-yl)phenoxy]acetic acid; 5-amino-4-chloro-2-phenyl-3(2H)-pyridazinone; methyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-p- and -m- -toluene, 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid and 2-[4,5-dihydro-4-methyl-4-(l-methylethyl)-5-oxo-l-N-imida- zol-2-yl]-3-quinolinecarboxylic acid.

3. Method for the selective killing (control) of harmful plants, c h a r a c t e r i z e d by simultaneously or successively applying a herbicide composition containing a compound of formula (I), wherein Ri, R₂, R₃, R-» and R< are the same as defined in claim L onto the soil or locus of growth or foliage of the cultivated plant.

4. A seed treatment method c h a r a c t e r i z e d by treating the seeds of the plants to be protected with a selective herbicide composition containing an N-phenylphthalimide derivative of formula (I), wherein R., R;. R₃, R» and R are the same as defined in claim L