NL8000264A - PHENOXY AND THIOPHENOXYNITRILLES AND THE USES THEREOF AS HERBICIDES. - Google Patents

Description

Γ

Phenoxy and thiophenoxynitriles and their use as herbicides.

The invention relates to phenoxy and thiophenoxynitriles.

The invention particularly relates to the use of these compounds as herbicides.

The phenoxy and thiophenoxynitriles of the invention have the general formula 1, wherein A is selected from -0-, -S-,

S, HH

t 3 ff -N- and -NN-, Rj represents a hydrogen atom, halogen atom or an alkyl radical or haloalkyl radical with 1-4 carbon atoms, R 1, R 8, R 1 and Rg, which may be the same or different, are selected from hydrogen and alkyl radicals of 1-4 carbon atoms, where when the phenyl radical is optionally substituted by (R ^) q the substituents R ^ and together with the carbon atom to which they are attached may form a 5, 6 or 7 membered polymethylene ring in addition, when one of the radicals R ^ and R ^ is a hydrogen atom the other has a meaning other than CH ^ 7 has the same meanings as R j or represents a group of the formula 2 wherein X is selected from -0-, -S- and -CH2 ~ and Rg have the same meanings as Rj, with which this group can be identical, where Rg can also represent the groups NO2 or CN, Z represents a sulfur atom and also represents an oxygen atom when 7 represents a group is of the formula 2, and n and n ^ are independent of represent integers from 0-3.

A first advantageous group of compounds of the general formula 1 are the compounds in which

800 0 2 M

* 2 Y and Rj, which are the same or different, represent hydrogen, chlorine or a haloalkyl group, A represents the group -NR 1 -, R 2 'R 5' or are different, 5 are selected from H, CH 3 and wherein one of the groups R ^ and R ^ have a meaning other than -CH ^ while the other is hydrogen and n represents an integer equal to 0 or 1.

A second group of advantageous compounds of the general formula 1 consists of compounds, wherein Y represents a group of the formula 3, wherein Rg is selected from Cl and CF ^, A is a group of the formula -N- and R3 nj equals 1 or 2,

Rj represents a hydrogen atom, Z represents a hydrogen atom, R2 ~ R5 'may be different, a hydrogen atom represents -CH ^ or where one of the groups R ^ and R ^ has a different meaning than -CH ^ when the other is hydrogen.

A third group of advantageous compounds of the general formula 1 is formed by the compounds wherein A represents a hydrogen atom, Y represents a group of formula 3 wherein Rg may be selected from Cl and CF 4, and Z represents a hydrogen atom.

Particularly advantageous compounds of the general formula 1 are the compounds of the formula 4 (hereinafter referred to as compound 11) and the formula 5 (hereinafter referred to as compound 12), as well as the compounds which are respectively referred to in the description below as Link 13, Link 35, Link 16, Link 19, Link 20, Link 34, Link 39, Link 40, Link 41, Link 43, Link 44, Link 45, Link 47 and Link 48.

80 0 0 2 64 * Λ 3

The compounds of the general formula 1 can be prepared by methods known per se, as illustrated in the examples below.

In connection with the preparation, reference is made to the general reaction schemes A and B. If the reaction is assumed to occur according to reaction scheme A, the processes will proceed according to reaction scheme B.

The working conditions are detailed in the examples below.

The compounds of the formula I are herbicides and in particular show an interesting herbicidal action against grassy crops.

They show an interesting selectivity to cereals and dicotyledons.

They can be applied after sowing before or after the plants emerge.

The amounts in which they are generally applied are, depending on the duration of the desired effect, the application technique, the nature of the soil, the cultivation techniques and the nature of the cultivated plants. active material per hectare or am / ha and preferably between 1000 and 5000 grams am / ha.

The invention encompasses the herbicidal treatments, in particular against grassy crops, which are selective over certain dicotyledons and more or less selective over cultivated cereals, using the acetamidonitriles of the invention.

The compounds according to the invention are used as herbicides and are applied before the emergence of the plants, with or without incorporation, or after the emergence of the plants, at the place where it is desired to ensure the control.

The compounds are in the form of preparations suitable for the intended uses; in addition to the active material, these compositions contain inert or active additives, vehicles or carrier materials. The herbicidal compounds 80 0 0 2 84 4 are generally formulated in the form of powders, wettable powders, granules, solutions, emulsifiable concentrates and aqueous or oily micronized dispersions.

Spreading is accomplished with the aid of devices suitable for use with any type of preparation.

Some examples of typical preparations are shown below.

(a) Example of wettable powders 10 for compounds 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12 described below.

52.6 parts of the compound with a purity of 95%, 41.4 parts of kaolin clay of the brand "Argirec B 24", 2 parts of wetting agent of the sodium 15 alkylnaphthalene sulfonate type (for example, of the brand Galoryl MT 701 from CFPI) and 4 parts of dispersant (e.g. sodium lignosulfonate).

The mixture is then passed through a Forplex grinder. A wettable powder with 50% active material is thus obtained, which has the properties usually exhibited by such preparations, namely an inferior wettability for 1 minute and a suspensivity of about 90% after 1 hour.

(b) Example of emulsifiable concentrates for compounds 3, 4, 5, 6, 7, 8, 9, 10, 11 and 12 described below.

253 g of the compound having a purity of 95%, 25 g / liter of calcium dodecylbenzene sulfonate in 70% solution in isobutyl alcohol, 35 g / liter of castor oil, condensed with 30 moles of ethylene oxide, and an amount sufficient to obtain 1 liter of a petroleum-type solvent, for example that of the Shellsol R brand (82% aromatics, "Pt. Eclair coupe fermee" 79 ° C). An emulsifiable concentrate with 240 g / liter of active material is thus obtained, which gives by dilution 35 emulsions which are stable for 8 hours.

The invention is further explained but 80 0 0 2 64 5 α

# I

not limited by the following examples of the preparation of compounds of the first group of advantageous compounds.

Example I

Preparation of N- (1,1-dimethyl-cyanomethyl) -p-chlorothiophenoxy-5-acetamide (n = 1, Rj = p-Cl, »R ^ R ^ CH ^, Y * H) or compound 1.

7.25 g of p-chlorothiophenol, 8 g of the N-chloroacetyl derivative of α-aminoisobutyronitrile and 13.8 g of potassium carbonate are added in 120 ml of butanone and refluxed for 10 hours. It is filtered, the solvent is removed in vacuo, the residue is taken up in water, extracted with chloroform, dried and distilled. The residue is chromatographed on a silica column using ether as an eluent.

The compound 1 is obtained in a yield of 35% and has a melting point of 120-122 ° C.

Example II

Preparation of N— (1,1-dimethyl-cyanomethyl) -p-chlorothiophenoxy-2-propionamide (n 1, R 1 * p-Cl, R 2 * CH 2, R 1 = H, R 1 R 2 CH 1, Y = H) or compound 2.

98 g of 50% sodium hydroxide solution are added gradually and with stirring and cooling to a mixture of 59 g of p-chlorothiophenol, 73.2 g of α-bromopropionic acid and 70 ml of water. It is heated under reflux for 2 hours, acidified with concentrated HCl and extracted with ether. Iso-25 is thus taught to 87 g of p-chlorothiophenoxy-2-propionic acid with a melting point of 99-101 ° C.

42 g of this acid and 130 g of thionyl chloride are refluxed overnight. The excess thionyl chloride is removed in vacuo. A solution of the crude acid chloride in benzene is then added dropwise with stirring and cooling to a mixture of 16 g of α-aminoisobutyronitrile and 19 g of triethylamine in 100 ml of anhydrous benzene. After the addition is complete, stirring is continued for 2 hours at ambient temperature. The solvent is removed in vacuo, the residue is taken up in water, extracted with chloroform, dried and distilled. The residue is recrystallized from 800 0 2 64 6 from a mixture of ether and chloroform. The melting point of the product thus obtained is 115 ° C (yield 60%).

A number of other compounds of the first group of beneficial compounds of the invention were prepared in an analogous manner. These compounds are indicated in Table A through formulas and melting points. It is noted that for all compounds, H represents

Table A

Connection η Y Rj R2 R ^ R ^ ° F

10 3 0 Cl H C2H5 CH3 CH3 118-119 ° 4 2 H 2,5-Cl C2H5 CH3 CH3 110-112 ° 5 1 Cl 2-C1 H CH3 CH3 113-115 ° 6 1 Cl 2-C1 CH3 CH3 CH3 107 -109 ° 7 1 Cl 2-C1 C2H5 CH3 CH3 127-129 ° 15 8 2 H 2,5-Cl H CH3 CH3 136-138 ° 9 2 H 2,5-Cl CH3 CH3 CH3 120-122 ° 10 1 Cl 3-C1 H CH3 CH3 96-97 ° 11 1 Cl 3-C1 CH3 CH3 CH3 144 ° 12 1 Cl 3-Cl C2H5 CH3 'CH3 103-104 ° 20 13 1 Cl 3-Cl CH3 Η H 116-118 ° 14 1 Cl 3-Cl C2H5 Η H 96-98 °

Compounds of the second group of beneficial compounds were also prepared.

Example III

Preparation of N- (11-dimethyl-cyanomethyl) - / (4'-chlorophenoxy) -4-phenoxy / -2-propionamide (n ^ = 1, n = 0, R ^ = p-Cl, X = Z * 0, R2 = R ^ = R ^ = CH3, R3 = H) or compound 15.

To a solution of 0.19 mol of triethyl amine and 0.19 mol of α-aminoisobutyronitrile in 300 ml of benzene is added dropwise with stirring and cooling, 0.19 mol of a-chloropropionyl chloride. Stirring is then continued for 2 hours. The solvent is removed in vacuo, the residue is taken up in water, extracted with chloroform, dried and the solvent is removed. The Ν-α-chloropropamide of α-aminoisobutyronitrile 35 is isolated by distillation and obtained in a yield of 50%. Its boiling point is 120 ° C at 0.25 mm.

80 0 0 2 64 7

0.12 mol of the above product, 0.12 mol (4'-chlorophenoxy) -4-phenol and 0.24 mol potassium carbonate are added to 200 ml of butanone. The mixture is heated to reflux for 10 hours, filtered and the solvent is removed in vacuo. The residue is taken up in water, extracted with chloroform, dried and the solvent is removed. The residue is chromatographed on silica (ether and petroleum ether 60:40). A solid product with a melting point of 82-83 ° C is obtained.

Example IV

Preparation of N- (cyanomethyl) / (4'-chlorophenoxy) -4-phenoxy / -2-propionamide (nj = 1, n »0, Rg e p-Cl, X * Z = 0, * H, R2 e CH ^, R ^ = R = H) or compound 16.

12 g / (4 * -chlorophenoxy) -4-phenoxy / -2-propionic acid and 21 g thionyl chloride are heated under reflux for 10 hours. The excess thionyl chloride is removed in vacuo.

11 g of the thus obtained acid chloride are then added dropwise with stirring to a mixture of chloroform-water (50:50) containing 3.4 g of amino-20 acetonitrile hydrochloride and 6.2 g of sodium hydrogen carbonate. The organic phase is washed with water, dried and the solvent is removed in vacuo. The residue is chromatographed on a silica column using ether as the eluent. The desired product is obtained in a yield of 35% and has a melting point of 90-91 ° C.

Example V

Preparation of N- (11-dimethylcyanomethyl) - / (4, -trifluoromethyl-phenoxy) -4-phenoxy / -2-propionamide (n = 0, nj 1, Rg = p-CF ^, X = Y = 0, Rg = H, Rj * Rj 'CH3) or compound 17.

19 g / (4-trifluoromethylphenoxy) -4-phenoxy / -2-propionic acid and 40 g thionyl chloride are refluxed for 12 hours. The excess thionyl chloride is removed in vacuo. A solution of the crude acid chloride in benzene is then added dropwise, with stirring and cooling, to a solution of 5 g of α-aminoisobutyronitrile and 6 g of triethylamine in 200 ml of benzene. After the 800 0 2 64 8 addition is complete, the mixture is stirred for 2 hours at ambient temperature. The benzene is removed in vacuo, the residue is taken up in water, extracted with chloroform, dried, the solvent is removed and the residue is chromatographed.

The desired end product is obtained in a yield of 35% and has a melting point of 68-70 ° C.

Using analogous methods, a number of other derivatives of the second group of the beneficial compounds of the invention were prepared.

These other compounds, where n = 0, are indicated by their formulas and their melting points in Table B below.

Table B

Verb in- n, R, X Z R „R„ R. Rc ° F

15 ding_ 18 1 p-Cl 0 0 Η H CH3 CH3 98-100 ° 19 1 p-CF3 0 0 Η H CH3 CH3 104-105 ° 20 1 p-CF3 0 OH C2H5 CH3 CH3 92-94 ° 21 1 p- CF3 0 0 CH3 CH3 Η H 102-104 ° 20 22 1 p-CF3 0 0 H CH3 Η H 74-76 ° 23 1 p-CF3 0 0 Η Η Η H 93-94 ° 24 1 m-CF3 0 0 Η H CH3 CH3 90-92 ° 25 1 m-CF0 0 0 H CH „CH„ CH, 114-116 ° ó ó ó ó 26 1 m-CF3 O OH CH3 CH3 91-92 ° 25 27 2 2,4-Cl OO Η H CH3 CH3 102-103 ° 28 1 p-Gl S 0 Η H CH3 CH3 93 ° 29 1 p-Cl CH2 0 Η H CH3 CHg 108-110 ° 30 1 p-Cl CH2 OH CH3 CH3 CH3 98-100 ° 31 2 2.4-C1 CH2 0 Η H CH3 CH3 121-123 ° 30 In the tables T 'and B "below, a number of other compounds according to the invention are indicated together with their melting points.

These compounds were prepared according to the procedures described above.

35 800 0 2 64 r «9

Table B '(Compounds of formula 1 with Y = -0- and Z - 0) (V',

Verbin- R, R, R "A R. R. Smp. (° C) j. O 1 Z ho ding_ 32 p-Cl H CH3 N-CH3 CH3 CH3 44-46 33 p-CF „H CH- N-CH_ CH_ CH, 56-58 c 3 3 3 3 3 35 p -CF »H CH„ NH C0H, C_H_ 76-78 3 3 Su Su 36 p-CF3 H CH3 NH CH3 58-60 37 3.4-C1 H CH3 NH CH3 CH3 109-111 38 p-CF3 H CH3 NH H 105- 107 800 0 2 64 10 t & £ / yyy * / ^ s

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Compound 34 has a refractive index of 1.5125 and a boiling point of 135-140 ° C at 0.5 mm Hg.

The interesting herbicidal properties over grassy crops and the selectivity with respect to cultivated cereals and dicotyledons of the compounds of the invention have been demonstrated by both greenhouse and open field experiments.

These tests were performed on compounds 11 and 12 of the first group, on compounds 35, 17, 10, 21, 22 and 30 of the second group, as well as on compounds 34, 35, 36, 39, 40, 41 and 43 of the second group, where n is 0.

First, the tests performed in phytotron, and then the tests conducted in the open field will be described, the results of which are shown in the tables below.

Systematic observations were made at regular intervals after treatment, with the ratings indicated with numbers from 0 to 10, where 0 means 0% destruction and 10 means 100% destruction, while the 20 numbers represent 1-9 intermediate values, as indicated in the table below.

9 - 97.5 2 8 = 95.0 2

7 = 85.0 Z

25 = 70.02

5 = 50.0 Z

4 - 30.0 2 3 = 15.0 2 2 = 5.0 2 30 1 * 2.5 µ

The products are applied either before sowing with inclusion (indicated below with the abbreviation PrSI), or after emergence (indicated below with the abbreviation PL) or after sowing and before emerging 800 0 2 64 12 (indicated below with PsPrL ).

Test group I: Connection 12.

The tested compound is applied in an amount of 5000 g / a.m. / ha, either before seeding with incorporation (referred to below as PrS1) or after emergence (referred to below as PL).

Plant species examined Results

Grassy crops: (PrSI) (PL)

Agrostis spica venti 10 2 10 Alopecurus 8 0

Avena 8 0

Echinochloa 10 0

Lolium 10 0

Dicotyledons: 15 Atriplex 0 0

Amaranthus 0 0

Chenopodium 0 0

Chrysanthemum 2 0

Daucus 2 0 20 Hedicago 0 0

Raphanus 0 0

Solanum 2 0

The results of this test show the activity against grassy crops of this compound and its harmlessness against dicotyledons.

Test group II: Connection 11.

The tested compound is applied in an amount of 5000 g / a.m. / ha, either by PrSI or by 30 PL.

80 0 0 2 64 «« 13

Plant species examined Results

Grassy crops: (PrSI) (PL)

Agrostis spica venti 10 4

Alopecurus 8 0 5 Avena 8 0

Echinochloa 10 2

Dicotyledons:

Atriplex 0 0

Amaranthus 0 0 10 Chenopodium 0 0

Chrysanthemum 2 0

Daucus 2 2

Medicago 0 0

Raphanus 2 0 15 Solanum 20

The results of this test indicate the activity against grassy crops at PrSI of the compound and its harmlessness to dicotyledons.

Test group III: Compound 15.

(A) The tested compound is applied in an amount of 5000 g / a.m. / ha, either by PrSI or by PL.

Plant species examined Results

Grassy crops: (PrSI) (PL) 25 Agrostis spica venti 10 0

Alopecurus 8 - (not sown)

Avena sativa 10 2

Lolium 10 2 2Q Dicotyledons:

Atriplex 0 6

Chrysanthemum 0 4

Daucus 2 0

Medicago 0 4 2 ^ Rumex acetosa 0 4

Solanum nigrum 0 2 80 0 0 2 64 14

The results of this test demonstrate the beneficial activity against grassy crops when applied by PrSI and the harmlessness to dicotyledons under the same conditions.

(B) According to the previous test, the compound is applied by PrSI in three doses, namely 1250, 2500 and 5000 g / a.m. / ha.

Plant species examined Results

Operation against grassy crops: 1250 2500 5000 10 Grassy winter crops:

Agrostis spica venti 4 66

Agropyrum 4 6 10

Poa 10 10 10 15 Lolium 8 10 10

Alopecurus 8 10 10

Grassy summer crops:

Andropogon 888

Digitaria · 10 10 10 20 Effect against dicotyledons:

Rapeseed 0

Raphanus 2

Bite root 0

Chicory 2 25 Tomato 2

Caterpillar 0

Carrots 0

Flax 2

Allium cepa 0 30

The results of this test confirm its efficacy against grassy crops of the test compound as well as its harmlessness to dicotyledone plants, 800 0 2 64 15

Test group IV: Connection 17.

(a) The tested compound is applied in an amount of 5000 g / a.m. / ha by PrSI or PL. Plant species examined Results 5 Grassy crops: (PrSI) (PL)

Agrostis spica venti 10 10

Alopecurus 10 8

Andropogon 10 4

Avena sativa 10 2 10 Lolium 10 6

Dicotyledons:

Atriplex 4 0

Amaranthus 0 not sown

Chrysanthemum 2 0 15 Daucus 0. 4

Medicagp 0 0

Raphanus 0 0

Rumex 0 0

Solanum 0 0 20

The results of this test demonstrate the interesting activity against grassy crops, particularly when applied by PrSI, as well as good selectivity to dicotyledone plants.

(B) According to the previous test, the same compound is applied by PrSI in three amounts, namely 1250, 2500 and 5000 g / a.m. / ha.

30 800 0 2 64 16

Plant species examined Results

Effect against grassy crops: 1250 2500 5000

Grassy winter crops:

Agrostis 10 10 10 5 Poa 10 10 10

Lolium 10 10 10

Alopecurus 10 10 10

Grassy summer crops:

Andropogon 8 10 10 10 Digitaria 10 10 10

Echinochloa 10 10 10

Setaria 10 10 10

Action against dicotyledons:

Rapeseed 000 15 Raphanus 000

Atriplex 002

Chrysanthemum 0 0 0

Taraxacum 000

Tomato 000 20 Solanum 000

Medicago 000

Daucus 000

Amaranthus 000

Allium Cepa 0 0 0 25 Poppy 000

Flax 000

This test shows the interesting action against grassy crops of the compound in question, as well as the perfect selectivity to dicotyledons. (C) The same compound is applied after seeding and before emergence (abbreviated by PSPrL). The same amounts as in (b) are used.

80 0 0 2 64 17

Plant species examined Results

Effect against grassy crops: 1250 2500 5000

Cultivated crops:

Oats 002 5 Wheat 0 0 0

Maize 246

Barley 2 0 2

Grassy winter crops:

Agrostis 10 10 10 10 Poa 10 10 10

Lolium 468

Alopecurus 10 10 10

Grassy summer crops:

Andropogon 8 8 10 15 Digitaria 10 10 10

Echinochloa 8 10 10

Setaria 10 10 10

This method of application allows the use of the compound on cultivated grassy crops, in particular oats, wheat and barley. The test also confirms its effectiveness against accidental grass-like crops. Test group V: Connection 21.

(a) The tested compound is applied in an amount of 5000 g / a.m. / ha, either by PrSI or by PL.

Plant species examined Results

Grassy crops: (PrSI) (PL)

Agrostis spica venti 8 2

Alopecurus 10 4 30 Echinochloa 10 8

Lolium 10 6

Dicotyledons:

Amaranthus 0 2

Chenopodium 0 0 35 Chrysanthemum 2 2

Daucus 0 0

Medicago 20

Raphanus 2 0

Solanum nigrum 0 0 800 0 2 64 18

The results of this test show good activity against grassy crops when applied by PrSI (and also a specific activity against Echinochloa when applied by PL) and a satisfactory selectivity to dicotyledons.

(b) According to the previous test, the compound is applied by PrSI in three doses, namely 1250, 2500 and 5000 g / a.m. / ha.

Plant species examined Results 10 Effect against grassy crops: 1250 2500 5000

Cultural crops and:

Oats 468

Wheat 8 10 10

Corn 10 10 10 15 Barley 688

Grassy winter crops:

Agrostis 10 10 10

Poa 10 10 10

Lolium10 10 10 20 Alopecurus 10 10 10

Grassy summer crops:

Andropogon 10 10 10

Digitaria 10 10 10

Echinochloa 10 10 10 25 Setaria 8 10 10

This test confirms the good effect against grassy crops of the compound. On the other hand, due to the aggressiveness of the compound towards grassy cultivated plants, the following test (c) was performed.

(C) The compound is applied by PSPrL at the same doses as indicated above.

800 0 2 64 19

Plant species examined Results

Effect against grassy crops: 1250 2500 5000

Cultivated crops:

Oats 222 5 Wheat 2 4 4

Maize 2 2 4

Barley 244

Grassy winter crops:

Agrostis 10 10 10 10 Poa 8 8 10

Lolium 10 10 10

Alopecurus 8 10 10

Grassy summer crops:

Andropogon 488 15 Digitaria 10 10 10

Echinochloa 8 10 10

Setaria 8 10 10

The application by PSPrL significantly reduces the aggressiveness of the compound towards grassy cultivated plants, but does not diminish, or only slightly, its action against accidental grassy crops.

Test group VI: Connection 22.

(a) The tested compound is applied in an amount of 5000 g / a.m. / ha, either by PrSI or by PL.

Plant species examined Results

Grassy crops: (PrSI) (PL)

Agrostis 10 4 30 Alopecurus 108

Avena 10 6

Echinochloa 10 10

Lolium 10 8

Dicotyledons: 35 Amaranthus 4 2

Chenopodium 0 0 80 0 0 2 84 20 (PrSI) (PL)

Chrysanthemus 4 2

Medicago 0 0

Raphanus 2 2 5 Solanum 0 0

Daucus 0 2

The results of this test demonstrate good activity against grassy crops when applied by PrSI (and a specific activity against Echinochloa when applied by PL), as well as a satisfactory selectivity to dicotyledone cultivated crops.

(b) According to the previous test, the compound is applied by PrSI in three doses, namely 1250, 2500 and 5000 g / a.m. / ha.

15 Plant species examined Results

Effect against grassy crops: 1250 2500 5000

Cultural crops and:

Oats 8 10 10

Wheat 10 10 10 20 Corn 10 10 10

Barley 8 8 10

Grassy winter crops:

Agrostis 10 10 10

Poa 10 10 10 25 Lolium 10 10 10

Alopecurus 10 10 10

Grassy summer crops:

Adropogon 10 10 10

Digitaria 10 10 10 30 Echinochloa 10 10 10

Setaria 10 10 10

This test confirms the compound's interesting action against grassy crops. Because the compound is aggressive towards cultivated cereals, the following test was performed.

80 0 0 2 64 21 (c) The compound was applied after sowing and before emerging at rates of 1250, 2500 and 5000 g / a.m. / ha.

Plant species examined Results

Effect against grassy crops: 1250 2500 5000

Cultivated crops:

Oats 6 10 10

Wheat 10 10 10

Corn 10 10 10 10 Barley 6 10 10

Grassy winter crops:

Alopecurus 10 10 10

Lolium 10 10 10

Poa 10 10 10 15 Grassy summer crops:

Andropogon 10 10 10

Digitaria 10 10 10

Echinochloa 10 10 10

Setaria 10 10 10 20 This test confirms the interesting action against grassy crops of compound 20, but it also appears that the selectivity to cereals has not improved.

Experiment group Vil: Compound 34, 25 Experiments in phytotron.

(a) The tested compound is applied at a dose of 5000 g / a.m. / ha, either by PrSI or by PL.

Plant species examined: Results 30 Grassy crops: (PrSI) (PL)

Agrostis spica venti 10 10

Alopecurus 10 10

Avena 88

Echinochloa 10 2 35 Lolium 10 8

Dicotyledons: 800 0 2 84 22

Atriplex 2 10

Amarantus 2 6

Chrysanthemum 6 6

Daucus 0 2 5 Medicago 0 0

Raphanus 0 0

Solanum 0 0

The results of this test show the activity against grassy crops of the compound and its harmlessness to dicotyledone cultivated crops.

(b) According to the previous test, the compound is applied by PrSI in three doses, namely 625, 1250 and 2500 g / a.m, / ha.

The results obtained with these three doses are shown in Table F below.

This test confirms the interesting action against grassy crops of the compound in question. This compound is aggressive toward cultured grain 20 waxes.

Subsequently, a preparation of the compound was prepared in the form of an emulsifiable concentrate using methods known in the art and the results obtained upon application of the compound of the invention in amounts of 750 and 1500 g / m / m. ha, are indicated in table F below, 80 0 0 2 64 23 Η

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The results obtained with these three doses are shown in Table G below.

This method of application improves selectivity over cultivated cereals and effectiveness over casual weeds.

Then, the same experiment as described under (b) is carried out applying compound 34 at doses of 750 and 1500 g / a.m. / ha. The results obtained at doses of 750 and 1500 g / a.m. / ha are shown in Table G below.

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The results obtained with these three doses are shown in Table H below.

The overall operation of the connection remains good.

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The results obtained at doses of 750 and 1500 g / a.m. / ha are shown in Table H below.

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Tasting in the open field.

Due to the interesting action of the compound in the phytotron tests described above, the study was continued in the open field using various methods of application.

The results obtained one month after treatment in the open field with compound 34 are shown in the tables below.

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Inferences.

The compound 34 of the invention has been found to be a remarkably active graminicide compound for numerous accidental annual or perennial grassy crops.

5 The analogy of the reactions between the cultivated grassy crops and the wild forms of the same species shows the importance of this compound in obtaining, in particular, the destruction of the emerging autumn or winter plants of cultivated grassy crops, such as wild oats. , aleppo millet, grassy summer crops, such as finger grass, coniferous nature, foxglove, etc., or of perennial grassy crops with spring, summer, or fall vegetation, such as cynodon dactylon, paspalum disticum, and agropyrum repens.

The destruction methods can vary and are performed before seeding with inclusion, after seeding before emergence and after emergence.

The doses used may vary from at least 500 g a.m./ha to more than 5 kg a.m./ha depending on the species, the desired purpose (vegetation inhibition or total destruction).

Depending on the doses used and the application techniques (a), this compound may exhibit an effect on annual grassy crops and perennial grassy crops emerging from stumps and rhizomes: near or better than the action of the hitherto Herbicides used against grassy crops, while this compound exhibits a selectivity on cultivated dicotyledons and weeds depending on the species and the mode of use similar to other graminicidal herbicides already used in this field. Test group VIII: Compound 35.

The compound is applied in an amount of 5000 g / a.m. / ha, either by PrSI or by PL.

80 0 0 2 84 38

Plant species examined Results

Grassy Crops (PrSI) (PL)

Agrostis spica venti 10 10

Alopecurus 10 10 5 Avena 8 10

Echinochloa 10 10

Lolium 10 8

Dicotyledons:

Atriplex 0 4 10 Amarantus 2 8

Chrysanthemum 0 6

Daucus 0 4

Medicago 4 4

Raphanus 0 8 15 Solanum 0 0

This test shows the activity against grassy crops of the compound regardless of the mode of application and its harmlessness to dicotyledons when applied by PrSI.

20 Test group IX: Compound 36.

The compound is applied in an amount of 5000 g / a.m. / ha, either by PrSI or by PL.

Plant species examined Results

Grassy crops: (PrSI) (PL) 25 Agrostis spica venti 10 10

Alopecurus 10 8

Avena 8 4

Echinochloa 10 10

Lolium 10 6 30 Dicotyledons:

Atriplex 2 6

Amarantus 0 6

Chrysanthemum 0 2

Daucus 2 0 35 Medicago 2 6

Raphanus 0 6

Solanum 0 0 80 0 0 2 84 39

This test shows the activity against grassy crops of the compound and its harmlessness to dicotyledons when applied by PrSI.

5 Test group X: Connection 39.

(a) The compound is applied in an amount of 5000 g / a.m. / ha, either by PrSI or by PL.

Plant species examined Results

Grassy Crops: PrSI PL

10 Agrostis 10 9

Alopecurus 10 10

Echinochloa 10 10

Lolium 10 10

Dicotyledons: 15 Medicago 0 9

Raphanus 0 10

Daucus 2 9

Amarantus 0 5

Atriplex 0 10 20 Solanum 0 2 The results show good activity against grassy crops, regardless of the application method.

(b) According to the previous test, the compound is applied by PrSI in two doses, namely 1250 and 2500 g / a.m. / ha.

Plant species examined: Results

Effect against grassy crops 1250 2500

Cultures:

Oats 4 5 30 Triticum 57

Order 44

Grassy winter crops:

Agrostis 7 10

Alopecurus 9 10 35 Poa 10 9 80 0 0 2 64 40

Grassy summer crops:

Echinochloa 9 10

Setaria 9 10

Festuca 9 9 5 This test confirms the activity against grassy crops of the compound in question. The next test was also carried out.

(c) The compound is applied by PSPrL in amounts of 1250 and 2500 g / a.m. / ha.

10 Plant species examined: Results

Effect against grassy crops 1250 2500

Cultures:

Oats 0 0

Triticum 0 0 15 Order 0 0

Zea 2 4

Grassy winter crops:

Agrostis 7 9

Alopecurus 9 10 20 Po a 7 9

Lolium 9 9

Grassy summer crops:

Echinochloa 10 10

Setaria 10 10 25 Festuca 7 9

This method of application very clearly improves selectivity to cultivated cereals, except for sorghum, without significantly reducing the activity against grassy crops.

(D) Parallel to the previous test, the compound is applied by PL at doses of 1250 and 2500 g / a.m. / ha.

35 800 0 2 64 i '»41

Plant species examined Results

Effect against grassy crops 1250 2500

Grassy winter crops:

Agrostis 7 10 5 Alopecurus 9 10

Poa 4 5

Lolium 99

Grassy summer crops:

Echinochloa 10 10 10 Setaria 10 10

Festuca 47

In this application method, the activity of the compound against grassy crops is confirmed. Test group XI: Link 40.

(A) The tested compound is applied in an amount of 5000 g / a.m. / ha, either by PrSI or by PL.

Plant species examined Results

Grassy Crops: PrSI PL

20 Agrostis 10 7

Alopecurus 10 10

Echinochloa 10 9

Lolium 10 10

Dicotyledons: 25 Medicago 0 4

Raphanus 0 9

Daucus 2 5

Amarantus 09

Atriplex 0 7 30 Chrysanthemum 0 7

Solanum 0 0

The results of this test show good activity against grassy crops regardless of the method of application.

(B) According to the previous test, the compound is applied by PrSI in two doses, namely 1250 and 800 0 2 64 42 2500 g / a.m. / ha.

Plant species examined Results

Effect against grassy crops 1250 2500

Cultures: 5 Oats 5 7

Order 5 7

Grassy winter crops:

Agrostis 10 10

Alopecurus 9 9 10 Poa 10 10

Festuca 10 10

Grassy summer crops:

Echinochloa 10 10

Setaria 9 10 15 Lolium 10 10

This test confirms the activity against grassy crops of the compound. The next test was also carried out.

(c) The compound is applied by 20 PSPrL in the same doses.

Plant species examined Results

Effect against grassy crops 1250 2500

Cultures:

Oats 2 2 25 Triticum 0 4

Order 0 2

Zea 4 6

Grassy winter crops:

Agrostis 7 10 30 Alopecurus 9 10

Poa 7 10

Festuca 7 9

Grassy summer crops:

Echinochloa 10 10 35 Setaria 7 9

Lolium 9 10 800 0 2 64 »1. '43

The selectivity to cultivated cereals is significantly improved compared to test (b); the good effect against gtas-like crops is maintained.

(D) Parallel to the above test, the compound is applied by PL in the same doses.

Plant species examined Results

Effect against grassy crops 1250 2500

Grassy winter crops: 10 Agrostis 9 10

Alopecurus 9 9

Poa 7 9

Festuca 7 10

Grassy summer crops: 15 Echinochloa 10 10

Setaria 10 10

Lolium 10 10

This method of application leads to the disappearance of any selectivity, but confirms the action against grassy crops of the compound.

Test group XII: Link 41.

The tested compound is applied at a dose of 5000 g / a.m. / ha, either by PrSI or by PL.

25 Plant species examined Results

Grassy Crops: PrSI PL

Agrostis 10 4

Alopecurus 10 10

Echinochloa 10 10 30 Lolium 10 10

Dicotyledons:

Medicago 00

Raphanus 0 0

Daucus 0 4 35 Amarantus 2 4

Atriplex 0 5 80 0 0 2 64 ft 44

Chrysanthemum 0 0

Solanum 0 0

This test shows that the compound is active against grassy crops and is selective with respect to certain cultured dicotyledons.

Test group XIII; Connection 43.

The tested compound is applied at a dose of 5000 g / a.m. / ha, either by PrSI or by PL.

10 Examined plant species Results

Grassy Crops: PrSI PL

Avena 4 7

Agrostis 10 0

Alopecurus 7 4 15 Echinochloa 9 10

Lolium 10 9

Dicotyledons:

Medicago 0 0

Raphanus 0 0 20 Daucus 0 0

Amarantus 4 0

Atriplex 0 9

Chrysanthemum 0 0

Matricaria 0 0 25 Solanum 0 0

The compound exhibits activity against grassy crops and good selectivity to certain cultivated dicotyledons.

30 Tests in the open field.

The open field tests are carried out on 5 m plots.

The application methods used are those described above, namely PrSI, PSPrL and PL.

The observations were made 15 days, 1 month and 2 months after the treatment for the two first application methods and 15 days and 1 month after the treatment for the third application method.

The results obtained after the treatment by PrSI are shown in Table C below, in which the 5 columns 1, 2 and 3 for each treated plant report the observations at 15 days, 1 month and 2 months, respectively.

The valuations are mentioned above.

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The results obtained after the treatment by PSPrL are shown in Table D 'below, in which columns 1, 2 and 3 under each said plant have the same meanings as indicated for Table C'.

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This method of application significantly improves selectivity to cereals; good selectivity towards cultured dicotyledons is maintained.

The action against grassy crops is generally more specific and more variable than when using the previous application technique, except for compound 22, for which this action remains significant.

The results obtained after the treatment by PL are shown in Table E 'below, in which columns 1 and 2 under each treated plant report the observations 15 days and 1 month after the treatment, respectively.

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The post-emergence application gives a selectivity to cereals, which varies with the nature of the cereals. The selectivity to cultured dicotyledons remains good.

The action against grassy crops is more specific and more variable, except for compound 22, for which this action remains good.

It will be understood that the invention is not limited to the above-described methods of application and embodiments and includes all possible variants thereof.

80 0 0 2 64

Claims (15)

1. Phenoxy and triphenoxynitriles of the general formula 1, wherein A is selected from -0-, -S-, R, Η H f I Phenoxy and thiophenoxynitriles of the general formula 1 according to claim 1, characterized in that Y and R 1, which are the same or different, represent a hydrogen atom, a chlorine atom, or a haloalkyl group, A represents the group -NR 2 - , R 2, R 2 j, which are the same or different, are selected from H, CH 5 and wherein one of these groups R 1 and R 1 has a different meaning than -CH 2 when the other represents hydrogen, and n is an integer equal is 0 or 1. 3. Phenoxy and thiophenoxynitriles of the general formula 1 according to claim 1, characterized in that Y represents a group of the formula 3, wherein Rg is selected from Cl and CF-, A represents the group -N- and n, equals 1 or 2, r3 Rj represents a hydrogen atom, Z represents an oxygen atom and R2 represents "R ^" which are the same or different, represent a hydrogen atom, -CH ^ or where one of the groups R ^ and R ^ is an 80 0 0 2 64 * has a different meaning than -CH 3 when the other is hydrogen. Phenoxy and thiophenoxynitriles of the general formula 1 according to claim I, characterized in that A represents an oxygen atom, Y represents a group of the formula 5, where there is a choice of Cl and CF 4, and Z represents an oxygen atom . 5. N- (1,1-dimethylcyanomethyl) (3,4-dichloro-thiophenoxy) -2-propionamide (compound 11), N- (1,1-dimethylcyanomethyl) (3,4-dichloro-10 thiophenoxy) -2-butyramide (compound 12) , N— (1,1-dimethylcyanomethyl) - / 4- (4 * - chlorophenoxy) -phenoxy / -2-propionamide (compound 15), N- (cyanomethyl) / 4- (4'-chlorophenoxy) -phenoxy / -2-propionamide ( compound 16), 15 N- (1,1-dimethylcyanomethyl) / 4- (4'-trifluoromethyl-phenoxy) -phenoxy / -2-propionamide (compound 17), N- (cyanomethyl) -N-methyl / 4- (4, - trifluoro-methyl-phenoxy) -phenoxy / -2-propionamide (compound 21), N- (cyanomethyl) / 4- (4 * -trifluoromethyl-20-phenoxy) -phenoxy / -2-propionamide (compound 22), (4- ( 4'-trifluoromethylphenoxy) -phenoxy) -2 propanovate of 2-cyanopropanol-2 (compound 34), (4- (4'-trifluoromethylphenoxy) -phenoxy) -2 propanoate of 2-cyanobutanol-2 (compound 39), (4- (4'-Trifluoromethylphenoxy) -phenoxy) -2-propanoate of 3-cyanopentanol-3 (Compound 40), (4- (4'-trifluoromethylphenoxy) -phenoxy) -2-propanoate of α-cyanobenzyl alcohol (compound 41), (4- (2'4'-dichlorophenoxy) -phenoxy) -2-30 propanoate of 2-cyanopropanol-2 (compound 43), (4- (3'-trifluoromethylphenoxy) -phenoxy- 2 propanoate of 2-cyanopropanol-2 (compound 44), / 4- (3-trifluoromethyl-phenoxy) -phenoxy / -2-propano-ayan glycolonitrile (compound 45), 35/4- (4'-trifluoromethyl-phenoxy) phenoxy / -2 propanoate of glycolonitrile (compound 47) and 80 0 0 2 84 / 4- (4'-trifluoromethyl-phenoxy) -phenoxy / -2-propanoate of 1-cyanopropanol (compound 48). 5 -N- and -NN-, R 1 represents a hydrogen atom, halogen atom or an alkyl radical or haloalkyl radical having 1 to 4 carbon atoms, R 2, R 1, R 1, and R 1, which may be the same or different, are selected from hydrogen and alkyl radicals of 1-4 carbon atoms, the phenyl radical being optionally substituted by (Rj) n and the substituents R 1 and R 1. together with the carbon atom to which they are attached can form a 5, 6 or 7 membered polymethylene ring, in addition, where one of the radicals R 1 and R 1 is a hydrogen atom, the other has a meaning other than CH 1, Y has the same meanings when R} represents a group of the formula 2, wherein X is selected from -O-, -S- and -CI ^ - and Rg has the same meanings as Rj, with which it may be identical, Rg also being the group NO2 or CN may represent, Z represents a sulfur atom and also may represent an oxygen atom when Y represents a group of the formula 2, and n and n ^ are independently integers of 0-3. Herbicidal composition, characterized in that it contains an effective amount of one or more compounds 5 as defined in claims 1-5. Grass-crop control agent, selective with respect to dicotyledons and cultivated cereals, characterized in that it contains, as active substance, an effective amount of one or more compounds 10 as defined in claims 1-5. A method for controlling grassy crops, which is selective with respect to dicotyledons, characterized in that an effective amount of one or more compounds according to claims 1-5 is applied by PrSI. Process for controlling grassy crops, which is selective with respect to dicotyledons and cultivated cereals, characterized in that an effective amount of one or more compounds according to claims 1-5 is applied by PSPrL. A method of controlling grassy crops, which is selective with respect to dicotyledons, characterized in that an effective amount of one or more compounds according to claims 1-5 is applied by PL. 11. Method according to claims 5-10, characterized in that 500-5000 g of active material are applied per hectare. Method according to claim 9, characterized in that 1000-5000 g of active material are applied per hectare. Moisturizable powder for the control of grassy crops with 50% active material, which is selective with respect to dicotyledons and cultivated cereals, characterized in that it comprises a mixture of 52.6 parts of compounds according to claims 1-5 with a purity of 95%, 41.4 parts of kaolin clay, 2 parts of wetting agent of the sodium alkylnaphthalene sulfonate type and 4 parts of dispersing agent. 800 02 64 • m Emulsifiable concentrate for controlling grassy crops, which is selective with respect to dicotyledons and cultivated cereals, characterized in that it comprises a mixture of 253 g of one or more compounds according to claims 1-5 with a purity of 95%, 25 g / l calcium dodecylbenzene sulfonate in 70% solution in isobutyl alcohol, 35 g / l castor oil condensed with 30 moles ethylene oxide, and an amount sufficient to make up to 1 liter of a petroleum-type solvent. 15. Compounds, preparations and methods as described in the description and / or examples. 15 800 02 84 Λ -? τ Υ - (\ /) - 2- CH-C — A - C —ΟξΝ ψ I! I 1 (Rl) n ° * 0-χ- ζ ^ ~ ° ~ (%, 2 3 I CH * Η CHj I II Cl — Γ y ~ S— CH - C— N - C— C = N, O CHj L_ C / Hs ^ Cl — fV-S-CH - C — N —C —CSN 5 \ = / ii lo ch3 -A- R »Ri ^ HN — C - C = N + Cl —CH - C - Cl - yCl - CH— CNC — C = N • II II 'Ry OO Rf 80 0 0 2 64 COMPAGNIE FRANCAISE DE PRODUITS INDUSTRIELS, SA Gennevilliers, France B Rj.r3 R-, Π) Y- ^ V-SH + CICH-C -N-C-C = NK; CO2> + / II I 0 Rs ^ Rl) * R. R, R4 _ jc Γ I Y — u V_ s - CH-C-N-C-C ^ N \ == / il I. . 0 Rg. K. ^ ¢ 2) i_y SH Br-CH-C-OH NaOH Y-f y-S — CH— C - OH ψ j x * (»,), (Bi)« f? £ Rj Row S0CU. Y_ / ~ Vs-CH-C-Cl + NH — CC = N Vj = / »IN„ _ _ 14 13 14 Y— / Vs-CH-CNC- C = N \ 4 = / ii II 0 Rs · (Ri ) “R * Λ-k / —y (3) Cl — CH — CNC-C = N + \ l / X— \ | V ° H" R5 (*) ", N * * i RS R4 _ / ~ Λ_χ_ / ^ - 0 — CH-C — N — C — CSN “δ 4 N“. (R'k Rj. Ri. —V / r ~ \ i soc1i / Γ \ Γ ~ \ I (4) <ry_X ^ Vz -CH-C-OH-I ^ yZ-CH-jl-Cl (¾) ^ 0 (R ^, (R ') «Rs iu HN — C — C = N, 1 * Ri R ^ i / V_x_i \ - 2 —CH - C - N — C - C = N -? £ - ^ W \ = fc / "^ 80 0 0 2 84 (Rl \ ifcV. *