FR2473514A2 - Cyano-alkanol ester(s) of phenoxy-propionic acids - having selective pre- and post- emergence herbicidal activity - Google Patents

Abstract

Phenoxy nitriles of formula (I) are new (where n is 1 or 2; R4 and R5 is H, 1-4C alkyl, or phenyl opt. substd. by 1-3 gps. selected from halogen, alkyl and 1-4C haloalkyl, or R4 and R5 together with the C atom to which they are attached form a 5, 6 or 7 membered polymethylene chain; R6 is Cl or CF3 but it is not p-CF3 when R4 and R5 are both H). Used as selective herbicides useful in crops of cereals and certain dicotyledons. This is an addition to FR79,01020.

Description

PHENOXY- AND THIOPHENOXYNITRILES AND THEIR APPLICATIONS
AS HERBICIDES
The present French patent application No. 79 01020 relates to phenoxy and thiophenoxynitriles.

 It also aims to apply these compounds as herbicides.

dans laquelle
- A est choisi dans le groupe constitué par

The main patent No. 79 01020 discloses phenoxy- and thiophenoxynitriles of the following general formula

in which
- A is chosen from the group consisting of

dans lequel X est choisi parmi -0-, -S- et CH2 - et R6 a les mêmes significations que R1 avec lequel il peut être identique,
R6 pouvant également représenter le groupe N02 ou CN;;
- Z est un atome de soufre et peut également représenter un atome d'oxygène lorsque Y représente le groupe

R1 represents a hydrogen atom, a halogen atom or an alkyl or haloalkyl radical having from 1 to 4 carbon atoms X
R 2, R 3, R 4 and R 5, which may be identical to or different from one another, are chosen from the group comprising hydrogen and alkyl radicals having 1 to 4 carbon atoms, the phenyl radical optionally substituted with (R 1) n the substituents R4 and R5 being able to form, with the carbon atom carrying them, a 5- or 6-membered polymethylene ring, it being understood moreover that, when one of the radicals R4 and R5 is a hydrogen atom, the other is different from CH3;
- Y has the same meanings as R1 or represents the group

wherein X is selected from -O-, -S- and CH2- and R6 has the same meanings as R1 with which it may be the same,
R6 may also represent the group NO2 or CN;
Z is a sulfur atom and may also represent an oxygen atom when Y represents the group

n and n, independently of each other, are integers from 0 to 3. -
Continuing its research, the Applicant Company has prepared other phenoxy- and thiophenoxynitriles corresponding to formula (I) in which A is an oxygen atom, Z is an oxygen atom and Y represents the group:

These compounds can be represented by the following formula:

in which
n1 is 1 or 2;
- R2, R4 and R5 which may be the same or different are selected from the group consisting of - hydrogen and alkyl radicals having 1 to 4 carbon atoms;
R4 and R5 can form with the carbon atom which carries them a polymethylenic ring with 5, 6 or 7 chain members, it being understood moreover that when one of the radicals R4 and R5 is a hydrogen atom, the other is different from CH3;
R1 represents a hydrogen atom, a halogen atom or an alkyl or haloalkyl radical having 1 to 4 carbon atoms and n is an integer of 0 to 3;
R6 is selected from the group consisting of C1 and CF3;
R6 is different from p-CF3 when R2 represents the radical CH3 and R4 and R5 simultaneously represent a hydrogen atom.

An advantageous group of compounds according to the invention consists of those of formula (III)

in which
- R4 and R5 which may be the same or different selected from the group consisting of hydrogen and alkyl radicals having 1 to 4 carbon atoms; the phenyl radical optionally substituted with (R1) n1, the substituents R4 and R5 being able to form, with the carbon atom carrying them, a 5-, 6- or 7-membered polymethylene ring, it being understood moreover that, when one of the radicals R4 and R5 is a hydrogen atom, the other is different from
CH3,
R1 represents a hydrogen atom, a halogen atom or an alkyl or haloalkyl radical having 1 to 4 carbon atoms and n is an integer of 0 to 3;
- R6 is selected from the group consisting of C1 and CF3, R6 being different from p-CF3 when R4 and R5 simultaneously represent a hydrogen atom.

A preferred group of compounds according to the invention have the formula (III) in which
- n1 is equal to 1 or 25
- R4 and R5, identical or different, are selected from the group consisting of hydrogen, -CH3, -C2H5 and -C6H5 radicals;
- R6 is selected from the group consisting of C1 and CF3, R6 being different from p-CF3 when R4 and R5 simultaneously represent a hydrogen atom.

Particularly preferred compounds corresponding to the aforesaid formula (III) are as follows
4-cyano-2-phenoxy-phenoxy-2-propanoate 2-pentanol (hereinafter referred to as Compound No. 34);
2-cyano-2-butanol 2 (hereinafter referred to as Compound No. 39) -: (2-trifluoromethyl-4'-phenoxy) phenoxy] -2-propanoate
4-cyano pentanol 3-tert-trifluoromethyl-4-phenoxy-4-phenoxy-2-propanoate (hereinafter referred to as # 40)
4-Cyano-benzyl alcohol (4-trifluoromethyl-4-phenoxy) -phenoxy-2-propanoate (hereinafter referred to as compound 41)
- [(3-dichloro-5'-phenoxy) -4-phenoxypropanoate 2-cyano propanol 2 (hereinafter referred to as compound No. 42)
Cyano-2-propanol 2-dichloro-2 ', 4'-phenoxy-4-phenoxy] propanoate 2 (hereinafter referred to as Compound No. 43);
- [(trifluoromethyl-3'-phenoxy) -4-phenoxy] -2-propanoate of cyanopropanol 2 (hereinafter referred to as Compound No. 44)
glycolonitrile [(trifluoromethyl 1 - 3 'phenoxy) - 4 phenoxy] - 2 propanoate (hereinafter referred to as compound 45) ::
- [(2-chlorophenyl-4'-phenoxy) -phenoxy] -2-propanoate of cyanopropanol 2 (hereinafter referred to as Compound No. 46)
1- (trifluoromethyl-4'-phenoxy) -4-phenoxy-2-propanoate of cyano-1-propanol (hereinafter referred to as Compound No. 48).

 In the following table I indicates for each of these compounds the melting point and / or the boiling point.

TABLE I (Compounds of formula III)

<tb><SEP> E. <SEP> (mm)
<tb><SEP> Compound <SEP> R6 <SEP> R1 <SEP> R2 <SEP> A <SEP> R4 <SEP> R5 <SEP> and / or
<tb><SEP> PF (C)
<tb><SEP> 34 <SEP>: <SEP> p-CF3 <SEP>: <SEP> H <SEP>: <SEP> CH <SEP>: <SE> O <SEP>: <SEP> CH3 <SEP> CH3 <SEP>: <SEP> 135-140 <SEP>
<tb><SEP> (0.5 <SEP> mm)
<tb><SEP> 43-45
<tb><SEP> 39 <SEP> p-CF3 <SEP> H <SEP> CH3 <SEP> O <SEP> CH3 <SEP> C2H5 <SEP> 180-170
<tb><SEP> (0.03 <SEP> mm)
<tb><SEP> pasty
<tb><SEP> 40 <SEP>: <SEP> p-CF <SEP>: <SEP> H <SEP>: <SEP> CH3 <SEP>: <SEP> 0 <SEP>: <SEPARATE> C2H1 <SEP>:<SEP> C <SEP> H <SEP>: <SEP> 160-170 <SEP>
<tb><SEP> (0.04 <SEP> mm)
<tb><SEP> 41 <SEP> p-CF3 <SEP> H <SEP> CH3 <SEP> O <SEP> C6H5 <SEP> R <SEP> 140-145
<tb><SEP> (0.01 <SEP> mm)
<tb><SEP> pasty
<tb><SEP> 42 <SEP> di-Cl-3.5 <SEP> H <SEP> CH3 <SEP> O <SEP> CH3 <SEP> CH3 <SEP> 180-190
<tb><SEP> (0.06 <SEP> mm)
<tb><SEP>:<SEP>:<SEP> patty
<tb><SEP> 43 <SEP>: <SEP> di-Cl-2.4 <SEP>: <SEP> H <SEP>: <SEP> CH3 <SEP>: <SE> O <SEP>: <SEP> CH <SEP>: <SEP> CH3 <SEP>: <SEP> 2000
<tb><SEP> (0,01mm)
<tb> pasty
<tb><SEP> 44 <SEP> m-CF3 <SEP> H <SEP> CH3 <SEP> O <SEP> CH3 <SEP> CH3 <SEP> 160
<tb><SEP> (0, -5 <SEP> mm)
<tb><SEP> 45 <SEP>: <SEP> m-CF <SEP>: <SEP> H <SEP>: <SEP> CH3 <SEP>: <SEP> O <SEP>: <SEP> H <SEP>:<SEP> H <SEP>: <SEP> 1900
<tb><SEP> (0.1 <SEP> mm)
<tb><SEP> 46 <SEP> p -Cl <SEP> H <SEP> CH3 <SEP> O <SEP> CH3 <SEP> CH3 <SEP> 180-185
<tb><SEP> (0.04 <SEP> mm)
<tb><SEP> pasty
<tb><SEP> 48 <SEP>: <SEP> p-CF3 <SEP> H <SEP>: <SEP> CH3 <SEP>: <SEP> O <SEP>: <SEP> C2H5 <SEP>: <SEP> H <SEP>: <SEP> 1600
<tb><SEP> (0.02 <SEP> mm)
<tb><SEP> pasty
<Tb>
The compounds of formula (I) may be prepared by methods known per se, illustrated by the examples.

 As a reaction scheme, mention may be made of the following sequences.

les procédés peuvent être

Being admitted that

the processes can be

 The operating conditions clearly result from the following examples.

In the synthesis of compounds Nos. 34, 39, 40 and 48, [(trifluoromethyl-4'-phenoxy) -4-phenoxy] propionic acid is used, using the indications given in German Patent No. 2,433,067, 1976
EXAMPLE I - SYNTHESIS OF COMPOUND NO.
A particularly advantageous method of preparation of compound 34 is the following.

The acid chloride is first prepared
4-Ep-trifluoromethylphenoxy) phenoxy] -2-propionic acid
the following way
35 g of [(trifluoromethylphenoxy) - 4
2-phenoxypropionic are heated for 3 hours under reflux
with 35 g of thionyl chloride and a drop of
dimethylformamide. The excess of thionyl chloride is
then chased under vacuum. Acid chloride can be
distilled: Eb0.01 140O (33 g) or used raw.

A mixture of 0.03 moles of acid chloride
in 10 ml of chloroform, 0.03 mole of pyridine and
0.03 mole of commercial methyl-2-lactonitrile are then heated for 24 hours under reflux. After cooling, the mixture is washed successively with 5% hydrochloric acid and with molar sodium bicarbonate, and then distilled: Eb 0.5 = 135-140, F. 43-45 (Rt 40%).

EXAMPLE II - SYNTHESIS OF N-COMPOUND
2-Phenoxypropionic acid and its corresponding acid chloro acid are prepared as indicated in the synthesis of compound No. 34.

20 flans one bottle, 140 e of monopotassium phosphate is placed with 250 ml of water and then 80 g of methyl ethyl ketone are added. To this mixture, and poured into one
one time. 54 g of sodium cyanide are added
250 ml of water. Everything is stirred for 2 hours and the
product is extracted with ether; ethereal solutions
are washed with acidulated water. then rinsed with water.

 dried over anhydrous sodium sulphate and concentrated.

Eb 020 = 87/88 C Yld: 40
A benzene solution of 0.02 mole
acid chloride prepared in 10 is added with agita
and cooling to a mixture of 0.02 mole
cyanohydrin of methyl ethyl ketone prepared in 20 and
0.02 mole of triethylamine in 50 ml of benzene anhy
dre. The mixture is stirred for 2 hours at room temperature.
ambient, one chases the benzene, o takes again by the water and
the chloroform extract.

Eb 0.03 = 160/165 C, Yld: 54
EXAMPLE III - SYNTHESIS OF N-COMPOUND 40
Leacid (4-trifluoromethyl) is prepared.
noxy) -4-phenoxy-2-propionic (see German patent
No. 2,433,067, 1976) and its corresponding diacid chloride
as has been indicated in the synthesis of the
se n 34
Using the same procedure as that described in 2 of the preparation of compound No. 39, cyanohydrin is
diethylketone whose characteristics are
Eb 13 = 92 C.

The products obtained in 10 and 20 are reacted under the same conditions as those described in the preparation of compound No. 39 and the compound No. 40 obtained has the following characteristics:
Eb = 160 / 1650C, Yield: 53%.

EXAMPLE III - SYNTHESIS OF COMPOUND N 43
A solution of 0.12 moles of triethylamine and 0.12 moles of methyl-2-lactonitrile is mixed with 100 ml of anhydrous benzene. The mixture is cooled and a benzene solution of 0.12 moles of bromo-2-propionyl bromide is added dropwise.

The reaction mixture is stirred for 2 hours at room temperature, washed with water and concentrated
Eb020 = 1300C.

 0.03 mol of 4 [2,4-dichlorophenoxy] phenol, 0.03 mol of the product obtained in 10 and 0.06 mol of potassium carbonate in 200 ml of butanone are refluxed.

 Butanone is removed. It is taken up in water and then extracted with chloroform.

 Eb0 0.01 = 2000C, Yield: 50%.

EXAMPLE IV - SYNTHESIS OF THE N 45 COMPOUND
38 g of [meta-trifluoromethylphenoxy-4-phenol, 26 g of o-bromopropionic acid and 25 ml of water are mixed. Cool to 10 C and add drop to
37 @ drop of soda at 50. @@ let go back to tempe
ambient temperature and then heat for 2 hours
flow: it is taken up in 150 ml of acidified water, extracted with ether.

 Eb 0.05 = 185/190 C; Mp 63; Yield: 56%.

2 A mixture of 0.18 moles of paraformaldehyde,
0.5 mole of acetone cyanohydrin. 0.36 moles of carbonate
of anhydrous potassium and 12 moles of anhydrous methanol
dissolved in potassium carbonate, is stirred at 250 ° C. for
2 hours. It is acidified with hydrochloric acid to
@make the pH at around 6. The product is concentrated under
Reduced pr @ sso and the residue diluted with 100 ml of ether,
dried and concentrated.

24 g of crude glycolonitrile are obtained which is
directly reacts with the product obtained in 10.

The glycolonitrile obtained at 20 is added to
pyridine in chloroform and acid chloride
obtained in 10 is poured drop by drop while cooling.

The reaction mixture is left for 24 hours at
room temperature and then heated for 4 hours. We re
take by water and extract the product.

Eb 0.1 = 190 C; Yield: 36%.

EXAMPLE V - SYNTHESIS OF COMPOUND N 48
[(Trifluoromethyl-4 'phenoxy) 4-phenoxy] propionic acid is prepared
and its corresponding acid chloride, as indicated in the synthesis of compound No. 34.

2 In the same conditions as those described
in 30 of the preparation of compounds Nos. 39 and 40.
reacts with hydroxy-2-hutyronitrile (commercial product)
cial) with the product obtained in 10.

The compound n 48 obtained has the characteristics
following
Eh 02 = 160 C; Liked: 53
The compounds of formula (III) constitute
hertioides, including herbicides
interesting.

 There is an interesting selectivity on cereals and dicotyledons. A group of compounds also has an interesting selectivity on rice.

SELECTIVITY TO CEREALS AND DICOTYLEDONES
The compounds according to the invention can be applied post-sowing taken or post-emergence.

The doses that will generally be included are included
- 1 "'Jree the desired effect,
- the application technique,
- the nature of the soil,
- cultural techniques,
the nature of the cultures, between 500 g and 5000 g of active ingredient per hectare or ai / ha, preferably between 1000 and 5000 g ai / ha.

 The invention relates to herbicide treatments, mainly anti-grass, selective for certain dicotyledonous, and more or less selective for cultured cereals using the compounds according to the invention.

 The compounds according to the present invention are used as herbicides and are applied pre-emergence, with or without incorporation, or postemergence, at the place to be controlled.

 These compounds are in the form of formulations that are suitable for the intended applications: these formulations contain. in addition to the active ingredient, additives, vehicles or inert or active supports. The herbicidal compounds are generally formulated as a powder, wettable powder, granules, solution, emulsifiable concentrate and aqueous or oily micronized dispersion.

 Spreading is carried out using apparatus adapted to the use of each type of formulation.

Some typical formulations are
a) Example of wettable powders for the molecules corresponding to compounds 39 and 42.

In a ribbon blender, 52.6 parts of the molecule at 95% purity, 41.4 parts of "Argirec n 24" kaolinic clay and / or silica, 2 parts of wetting agent of the following type are mixed together. sodium alkylnaphthalene sulphonate (eg from the brand
GALORYL MT 701 from the FRENCH PRODUCTS COMPANY
INDUSTRIALS) and 4 parts of sodium tlignosulfonate dispersing agent, for example)
The mixture is then passed through a Forplex type mill. A wettable powder containing 50% of active material is thus obtained which exhibits the properties usually required of such formulations, namely wettability less than one minute and suspensivity equal to about 90% after one hour.

 b) Example of emulsifiable concentrates for the molecules corresponding to compounds 34, 40, 41, 43, 44, 45, 46 and 48.

 253 g of the molecule are mixed with 95% purity. 25 g / l of calcium dodecylbenzene sulfonate in a 70% solution in isobutyl alcohol, 35 g / l of castor oil condensed with 30 moles of ethylene oxide and the amount sufficient for one liter of a solvent oil tanker, for example that of the brand SHELLSOL R (62 -.

aromatics, Pt. light cut closed 790C). This gives an emulsifiable concentrate at 240 g / l of active material which provides emulsions per dilution stable for 8 hours.

 The interesting herbicidal properties and the selectivity of cultivated cereals and dicotyledonous compounds according to the invention have been demonstrated both by greenhouse experiments and by field experiments.

 The experiments on. The greenhouse tests are for Compounds Nos. 34, 39, 40, 41 and 43, and the field experiments are for Compound No. 34. The results for these tests are tabulated.

Systematic observations are made at regular intervals after treatment in a notation ranging from 0 to 10
- O indicating 0% destruction,
- 10 indicating 100% destruction, notes 1 to 9 representing intermediate values according to the table below
9 = 97.5%
8 = 95.0
7 = 65.0
6 = 70.0%
5 = 50.0
4 = 30.0%
3 = 15.0
2 = 5.0%
l = 2.5%
The products are applied
- either pre-planting with incorporation (hereinafter indicated by the abbreviation P @ SI)
- or post-emergence (hereinafter indicated by the abbreviation PL)
- or post-sowing pre-emergence (hereinafter referred to as PSPrL).

TEST N 1
Compound No. 34
PHYTOTRON TESTS
a) The test compound is applied at the rate of 5000 g / ai / ha in either PrSI or PL.

Species tested in this test Results
(PrSI) tPL) - Grasses:
. Agrostis spica venti ........... 10 10
. Alopecurus ..................... 10 10
. Avena .......................... 8 8
. Echinochloa .................... 10 2
. Lolium ......................... 10 6 - Dicotyledons:
.Atriplex. . . . . . . . . . . . . . . . . . . . . . . 2 10
Amarantus 2 6
. Chrysanthemum. . . . . . . . . . . . . . . . . . 6 6
. Daucus ......................... 0 2
. Medicago ....................... 0 0
. Raphanus ....................... 0 0
. Solanum ........................ 0 0
This test shows the anti-grass activity of the compound and its safety against cultivated dicotyledons.

 This compound No. 34 which has already been the subject of the patent No. 79 01020 has been subjected to a number of additional tests, as indicated below.

b) Following the previous test, the compound is then applied in PrSI at three doses
- 625.

- 250,
- and 2500 g / ai / ha.

 The results for these three doses are summarized in the table below.

 This test confirms the interest of the antigraminant action of the compound. The latter is aggressive on cultivated cereals.

 Following this study, a formulation of the compound in the form of an emulsifiable concentrate was prepared according to techniques well known to those skilled in the art, and the results obtained were compared by applying the compound according to the invention from 750 and 1500 g / ai / ha, to the results obtained with a reference product known as FERVIN, graminicide of Japanese origin, marketed in France by SCHERING and whose active ingredient is alloxydine.

The results for the 750 and 1500 g / ai / ha doses of compound 34 and the results obtained by applying the reference product at 750 and 1500 g / ai / ha are summarized in Table II. below.

TABLE II
RESULTS AND TESTS CARRIED OUT WITH CCMPOSE 34 IN PRSI

Compound <SEP> n <SEP> 34 <SEP> Product <SEP> of <SEP> reference
<tb> Species <SEP> tested <SEP>(<SEP> doses in <SEP> g / ai / ha) <SEP>(<SEP> doses in <SEP> g / ai / ha)
<tb> at the <SEP> course <SEP> of <SEP> the test
<tb> 625 <SEP> 750 <SEP> 1 <SEP> 250 <SEP> 1 <SEP> 500 <SEP> 2 <SEP> 500 <SEP> 750 <SEP> 1 <SEP> 500
<tb> Cultures <SEP>:
<tb> - <SEP> Oats <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 0 <SEP> 5 <SEP> 4 <SEP> 7 <SEP> 7 <SEP> 4 <SEP> 4
<tb> - <SEP> Wheat <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 4 <SEP> 7 <SEP> 5 <SEP> 9 <SEP> 9 <SEP> 7 <SEP> 7
<tb> - <SEP> Barley <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 4 <SEP> 4 <SEP> 5 <SEP> 5 <SEP> 7 <SEP> 5 <SEP> 5
<tb> - <SEP> Corn <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 7 <SEP> 7 <SEP> 7 <SEP> 9 <SEP> 9 <SEP> 4 <SEP> 5
<tb> Gramineae <SEP> winter <SEP>:
<tb> - <SEP> Agrostis <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 4 <SEP> 9 <SEP> 7 <SEP> 10 <SEP> 7 <SEP> 10 <SEP> 10
<tb> - <SEP> Alopecurus <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 0 <SEP> 7 <SEP> 5 <SEP> 9 <SEP> 9 <SEP> 9 <SEP> 10
<tb> - <SEP> Lolium <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 9 <SEP> 10 <SEP> 9 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10
<tb> - <SEP> Poa <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 7 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 9 <SEP> 9
<tb> Gramineae <SEP> summer <SEP>:
<tb> - <SEP> Echinochloa <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 10 <SEP> 9 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10
<tb> - <SEP> Setaria <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 9 <SEP> 10 <SEP> 9 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10
<tb> - <SEP> Festuca <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 0 <SEP> 9 <SEP> 7 <SEP> 9 <SEP> 9 <SEP> 10 <SEP> 10
<Tb>
c) Following the PrSI test, the following assay was performed in which the compound was applied in PSPrL at doses of 625, 1250 and 2500 g / ai / ha.

 The results for these three doses are summarized in the table below.

 This mode of application improves the selectivity towards cultivated cereals and the efficiency with respect to weeds.

 The procedure described in (b) is followed, applying compound No. 34 at doses of 750 and 1500 g / ai / ha and is compared with the FERVIN reference product under the same conditions as at comparative test described in bf. The results for the 750 and 1500 g / m ai / ha doses are summarized in Table III below.

TABLE III
RESULTS OF TESTS CARRIED OUT WITH COMPOUND 34 IN PSPrL

Compound <SEP> n <SEP> 34 <SEP> Product <SEP> of <SEP> reference
<tb> Species <SEP> tested <SEP>(<SEP> doses in <SEP> g / ai / ha) <SEP>(<SEP> doses in <SEP> g / ai / ha)
<tb> at the <SEP> course <SEP> of <SEP> the test
<tb> 625 <SEP> 750 <SEP> 1 <SEP> 250 <SEP> 1 <SEP> 500 <SEP> 2 <SEP> 500 <SEP> 750 <SEP> 1 <SEP> 500
<tb> Cultures <SEP>:
<tb> - <SEP> Oats <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 2 <SEP> 4 <SEP> 4 <SEP> 4 <SEP> 6 <SEP> 4 <SEP> 7
<tb> - <SEP> Wheat <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 0 <SEP> 4 <SEP> 4 <SEP> 7 <SEP> 5 <SEP> 5 <SEP> 9
<tb> - <SEP> Barley <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 2 <SEP> 4 <SEP> 4 <SEP> 7 <SEP> 7 <SEP> 5 <SEP> 7
<tb> - <SEP> Corn <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 5 <SEP> 5 <SEP> 7 <SEP> 7 <SEP> 9 <SEP> 7 <SEP> 9
<tb> Gramineae <SEP> winter <SEP>:
<tb> - <SEP> Agrostis <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 7 <SEP> 9 <SEP> 9 <SEP> 10 <SEP> 9 <SEP> 9 <SEP> 10
<tb> - <SEP> Alopecurus <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 7 <SEP> 7 <SEP> 9 <SEP> 9 <SEP> 9 <SEP> 9 <SEP> 10
<tb> - <SEP> Lolium <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 9 <SEP> 10 <SEP> 9 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10
<tb> - <SEP> Poa <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 7 <SEP> 9 <SEP> 9 <SEP> 10 <SEP> 10 <SEP> 9 <SEP> 10
<tb> Gramineae <SEP> summer <SEP>:
<tb> - <SEP> Echinochloa <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10
<tb> - <SEP> Setaria <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 10 <SEP> 9 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10
<tb> - <SEP> Festuca <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 5 <SEP> 7 <SEP> 7 <SEP> 10 <SEP> 9 <SEP> 10 <SEP> 10
<Tb>
dl In parallel with the PSPrL assay, the compound is applied in PL at doses of 625, 1250 and 2500 g / ai / ha.

 The results for the three doses are summarized in Table IV below.

 This last stage of application does not improve the selectivity on cultivated grasses, but the overall efficiency remains good.

 The procedure is then carried out as in the comparative tests described under (b) and (c) by applying Compound No. 34 at doses of 750 and 1500 g / ai / ha and is compared with the FERVIN reference product, under the same conditions as under B. ) and c). The results for 750 and 1500 g / m ai / ha are summarized in the table below.

TABLE IV
RESULTS OF TESTS CARRIED OUT WITH COMPOUND 34 HAS

Compound <SEP> n <SEP> 34 <SEP> Product <SEP> of <SEP> reference
<tb> Species <SEP> tested <SEP>(<SEP> doses in <SEP> g / ai / ha) <SEP>(<SEP> doses in <SEP> g / ai / ha)
<tb> at the <SEP> course <SEP> of <SEP> the test
<tb> 625 <SEP> 750 <SEP> 1 <SEP> 250 <SEP> 1 <SEP> 500 <SEP> 2 <SEP> 500 <SEP> 750 <SEP> 1 <SEP> 500
<tb> Gramineae <SEP> winter <SEP>:
<tb> - <SEP> Agrostis <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 5 <SEP> 9 <SEP> 5 <SEP> 9 <SEP> 9 <SEP> 9 <SEP> 10
<tb> - <SEP> Alopecurus <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 9 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 7 <SEP> 9
<tb> - <SEP> Lolium <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 9 <SEP> 10 <SEP> 9 <SEP> 10 <SEP> 10 <SEP> 9 <SEP> 10
<tb> - <SEP> Poa <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 4 <SEP> 7 <SEP> 7 <SEP> 9 <SEP> 10 <SEP> 7 <SEP> 7
<tb> Summer Grasses <SEP>:
<tb> - <SEP> Echinochloa <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10
<tb> - <SEP> Setaria <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 9 <SEP> 10
<tb> - <SEP> Festuca <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 5 <SEP> 7 <SEP> 9 <SEP> 7 <SEP> 10 <SEP> 7 <SEP> 9
<Tb>
The series of three PrSI, PSPrL, PL tests on the product placed under the emulsifiable concentrate formulation (applied at the respective doses of 750 and 1500 g / ai / ha) shows that the efficacy of compound 34 remains valid but confirms the differences in selectivity depending on the stage of application.

TESTS IN FULL FIELD
Given the interest shown by the compound in the above-mentioned phytotron assays, the experiment was continued in the field in comparison with various reference products. depending on the mode of application.

 The results obtained one month after treatment, in the field, with the compound No. 34 are combined in the following tables.

A - PRE-SEMIS INCORPORE (effective on grasses)

Material <SEP> Dose <SEP> Agrostis <SEP> Festuca <SEP> Lolium <SEP> Poa <SEP> Poa <SEP> Digitaria
<tb> Oatmeal <SEP> Wheat <SEP> But <SEP> Barley
<tb> active <SEP> g / ha <SEP> tenuis <SEP> elatior <SEP> hybridum <SEP> annua <SEP> annua <SEP> sanguinalis
<tb> 250 <SEP> 5 <SEP> 500 <SEP> 5 <SEP>
Compound <SEP> 1 <SEP> 1000 <SEP> 5-6 <SEP> 9
<tb> n <SEP> 34
<tb> 1 <SEP> 250 <SEP> 9 <SEP> 10 <SEP> 10 <SEP> 7 <SEP> 10 <SEP> 9 <SEP> 10 <SEP> 10
<tb> 1 <SEP> 500 <SEP> 5-6 <SEP> 9
<tb> 2 <SEP> 500 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 9 <SEP> 10 <SEP> 10 <SEP> 10 <SEP> 10
<tb> B - POST-SEED PRE-LEVEE (grass efficiency)

Material <SEP> Dose <SEP> Agrostis <SEP> Festuca <SEP> Lolium <SEP> Poa <SEP> Poa <SEP> Digitaria
<tb> Oatmeal <SEP> Wheat <SEP> Corn <SEP> Barley
<tb> active <SEP> g / ha <SEP> tenuis <SEP> elatior <SEP> hybridum <SEP> annua <SEP> annua <SEP> sanguinalis
<tb> 250 <SEP> 7 <SEP> 9
<tb> 500 <SEP> 8 <SEP> 9
<tb> Compound <SEP> 1 <SEP> 000 <SEP> 9 <SEP> 9
<tb> n <SEP> 34
<tb> 1 <SEP> 250 <SEP> 3 <SEP> 9 <SEP> 2 <SEP> 2 <SEP> 10 <SEP> 7 <SEP> 3 <SEP> 8
<tb> 1 <SEP> 500 <SEP> 9 <SEP> 9
<tb> 2 <SEP> 500 <SEP> 3 <SEP> 9 <SEP> 5 <SEP> 3 <SEP> 10 <SEP> 8 <SEP> 9 <SEP> 9
<tb> C - POST-LEVEE 1 Annual grasses (young stage)

Material <SEP> Dose <SEP> Agrostis <SEP> Festuca <SEP> Lolium <SEP> Poa <SEP> Lolium
<tb> Oatmeal <SEP> Wheat <SEP> Corn <SEP> Barley
<tb> active <SEP> g / ha <SEP> tenuis <SEP> elatior <SEP> hybridum <SEP> annua <SEP> multiflorum
<tb> 250 <SEP> 5-6
<tb> 500 <SEP> 6-7
<tb> Compound
####
<tb> 1 <SEP> 000 <SEP> 8-9
<tb> 1 <SEP> 250 <SEP> 7 <SEP> 6 <SEP> 10 <SEP> 5 <SEP> 9 <SEP> 5 <SEP> 3 <SEP> 7
<tb> 2 perennial grasses a) with strains treated post-emergence

<tb><SEP> sn7eJde <SEP> t <SEP> rn
<tb><SEP> snllloJg
<tb><SEP> wnpTJqq
<tb><SEP>lun'lo7<SEP>:<SEP>)<SEP> Cb
<tb> Material <SEP>: <SEP> Dose <SEP>: <SEP> Obrtic <SEP>: <SEP>: <SEP><<SEP>'<SEP>:<SEP>:<SEP> E <SEP >'n<SEP>:<SEP> H <SEP>' n <SEP>: <SEP> H <SEP> .. <SEP> H <SEP>: <SEP> E <SEP> e <SEP>: <SEP> = <SEP>: <SEP> E <SEP> E <SEP>: <SEP>'n
<tb><SEP> u <SEP> o <SEP> u <SEP> tn <SEP><c<SEP> o <SEP><c<SEP> = <SEP> c <SEP> H <SEP>'n<SEP> c <SEP> =
<tb><SEP> unJor7nw <SEP> (
<tb><SEP> e <SEP> n <SEP> H <SEP> o <SEP> t = <SEP> E <SEP> O <SEP> e <SEP> H <SEP> e <SEP> H <SEP > H <SEP> H <SEP> E <SEP><O
<tb><SEP>wn'la7<SEP> Q)
<tb><SEP>:<SEP>:<SEP> LL <SEP> e <SEP> .. <SEP>: <SEP>: <SEQ> IL <SEP> t <SEP> CL <SEP> t <SEP > .. <SEP> o. <SEP> .. <SEP>: 0 <SEP><c
<tb><SEP> o <SEP> o. <September>
<Tb>

<SEP> auualad <SEP>'
<tb><SEP> mnrTo7 <SEP> CO <SEP> h
<tb><SEP> srsuaeJd
<tb><SEP> n0 <SEP> 34 <SEP>: <SEP>. <SEP>: <SEP> t <SEP> t <SEP>: <SEP> t <SEP> t <SEP> t <SEP> t, <SEP> t
<tb><SEP> 4 <SEP> 000 <SEP> 3 <SEP> months <SEP> t <SEP> 7 <SEP> t <SEP> 10 <SEP>: <SEP> 2 <SEP> t <SEP> 2 <SEP>: <SEP> 9 <SEP>: <SEP> 8 <SEP>: <SEP> 8 <SEP> t <SEP> 7 <SEP> t <SEP> 7 <SEP>: <SEP> 8 <SEP> t <SEP> 8 <SEP> 5
<tb><SEP> t <SEP> t <SEP>: <SEP>: <SEP> t <SEP>: <SEP>: <SEP>: <SEP>:
<tb><SEP> slnual
<tb><SEP> sFXs lsV <SEP> e <SEP> aM <SEP> tEt
<tb><SEP> ssualeld
<tb><SEP> I <SEP> o) <SEP> a)
<tb><SEP> wnalild
<tb><SEP> eulAo
<tb><SEP> I <SEP> 1% <SEP> N
<tb><SEP> esnRsaJ
<tb><SEP> elqnu <SEP> t
<tb><SEP> s <SEP> t
<tb><SEP> esnXSaJ <SEP> t
<tb><SEP> sTsuaXeld <SEP> j <SEP> s} <SEP> O
<tb><SEP> esn4SåJ <SEP> i,
<tb><SEP> .lollela
<tb><SEP> esnasaJ <SEP>'<SEP> N <SEP> N
<tb><SEP> C
<tb><SEP> O
<tb><SEP> t <SEP> I <SEP> ert <SEP> tst
<tb><SEP> I <SEP>, t <SEP> i
<tb><SEP> 111 <SEP> 1 <SEP> 0 <SEP> 0
<tb><SEP>><SEP> I <SEP> E <SEP> E
<tb><SEP> o
<tb><SEP>Q><SEP> s <SEP> r <SEP> n
<tb><SEP> Ct
<tb><SEP> D
<tb><SEP> O
<tb><SEP>,<SEP> O <SEP> O
<tb><SEP> tst <SEP> C <SEP> I <SE> O <SEP> O
<tb><SEP> OX
<tb><SEP> M <SEP><SEP> I <SEP><SEP>
<tb><SEP> X <SEP> Q]
<tb><SEP> C) <SEP> Q <SEP> sr
<tb><SEP> o <SEP>><SEP> I <SEP> O <SEP> te
<tb><SEP>, QM <SEP> H <SEP> I <SEP> a
<tb><SEP> v <SEP>&commat;<SEP> ~ <SEP> E
<tb><SEP> 4 <SEP> 0 <SEP> 1 <SEP> 0 <SEP> C
<tb><SEP> t <SEP> lU <SEP> S <SEP> Ct
<tb> 2 - Perennial grasses
b) rhizomes treated post-emergence

<tb><SEP>:<SEP>:<SEP> Paspalum <SEP> distichum
<tb> Material <SEP> active <SEP>: <SEP> Dosegram / hectare <SEP>: <SEP> one <SEP> month <SEP> and <SEP> half
<tb><SEP> after <SEP> treatment
<tb><SEP> 2 <SEP> 000 <SEP>: <SEP> 9
<tb><SEP> Compound <SEP> n <SEP> 34 <SEP>: <SEP> 3 <SEP> 000 <SEP> 9 <SEP><SEP> 9 <SEP>
<tb><SEP> 4 <SEP> 4 <SEP> 000 <SEP>: <SEP> 10
<Tb>
Confirmation of selective action on dicotyledons (continued)
B - PS PrL

<tb><SEP> Compound <SEP> n <SEP> 34
<tb><SEP>: 1 <SEP> 250 <SEP>: <SEP> 2 <SEP> 500
<tb><SEP> Cultures <SEP>: <SEP>
<tb><SEP> Beet ..................... <SEP> 3 <SEP>: <SEP> 5
<tb><SEP> Carrot ....................... <SEP> 1 <SEP>: <SEP> 2
<tb><SEP> Chicory ...................... <SEP> 2 <SEP>: <SEP> 2
<tb><SEP> Cabbage .......................... <SEP> 4 <SEP>: <SEP> 4
<tb><SEP> Bean ....................... <SEP> 2 <SEP>: <SEP> 2
<tb><SEP> Lin ........................... <SEP> 0 <SEP>: <SEP> 0
<tb><SEP> Alfalfa <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 0 <SEP> 3
<tb><SEP> Peas <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 0 <SEP> 2
<tb><SEP> Bad <SEP> Herbs
<tb> Morelle <SEP>: <SEP><SEP> O <SEP> 0 <SEP>: <SEP> 0
<tb><SEP> Chenopode <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 0 <SEP> 0
<tb><SEP> Fumitory <SEP>: <SEP> O <SEP>
<tb><SEP> Knotty <SEP> of <SEP> birds <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 0 <SEP> 0
<tb> Mouron <SEP> of <SEP> birds <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 0 <SEP> 0
<Tb>
Confirmation of selective action on dicotyledons (continued)
C - Post-emergence

<tb><SEP> Compound <SEP> n <SEP> 34
<tb><SEP> 625 <SEP> 1 <SEP> 250 <SEP> 2 <SEP> 500
<tb> Cultures <SEP>:
<tb> Beet ........................ <SEP> 2 <SEP>: <SEP> 3 <SEP>: <SEP> 3
<tb> Carrot .......................... <SEP> 2 <SEP>: <SEP><SEP> 2 <SEP>: <SEP> 2
<tb> Chicory ......................... <SEP> 0 <SEP>: <SEP> 0 <SEP>: <SEP> 0
<tb> Cabbage ............................. <SEP> 2 <SEP>: <SEP> 2 <SEP>: <SEP> 2
<tb> Bean .......................... <SEP> 0 <SEP>: <SEP> 1 <SEP>: <SEP> 2
<tb> Lin .............................. <SEP> 2 <SEP>: <SEP> 2 <SEP>: <SEP> 2
<tb> Alfalfa <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 0 <SEP> O <SEP>: <SEP> O
<tb> Peas <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 2 <SEP> 2 <SEP> 2
<tb> Bad <SEP> Herbs <SEP>:
<tb> Morelle .......................... <SEP> 0 <SEP>: <SEP><SEP> 0 <SEP>: <SEP> 0
<tb> Chenopodium ........................ <SEP> 0 <SEP>: <SEP> 0 <SEP>: <SEP> 0
<tb> Fumitory <SEP>: <SEP> 0 <SEP>: <SEP> 0 <SEP> 0 <SEP>
<tb> Knotty <SEP> of <SEP> birds <SEP>: <SEP> O <SEP>: <SEP> 0 <SEP>: <SEP> O
<tb> Mouron <SEP> of <SEP> birds <SEP>: <SEP> O <SEP>: <SEP> O <SEP>: <SEP> 0
<Tb>
CONCLUSIONS
The molecule No. 34 according to the invention, proves to be a remarkable graminicidal compound active on many species of grasses whether they are cultivated or that they are annual or perennial weeds.

The similarity of the reactions that exist between cultivated or wild grasses of the same species makes it possible to appreciate the interest of this molecule to obtain in particular the destruction on the one hand, the autumn or winter lifts of the cultivated grasses such as
- barley,
- corn,
- oats, etc.

on the other hand, for the destruction of weeds such as
- wild oats,
- alep sorghum, summer grasses such as
- panic,
- to shut up,
- crabgrass, etc.

or perennial grasses with spring, summer or fall vegetation, such as
- cynodon dactylon,
- paspalum distioum,
- agropyrum repens.

Destruction methods may vary and be undertaken in
- pre-planting with incorporation,
- post-sowing pre-emergence,
- post-emergence.

The doses to be used may, depending on the species, the desired goal (vegetation braking or total destruction), and treatment, vary from
- less than 500 g ai / ha to more than 5 kg ai / ha.

This molecule according to the doses used and the techniques of use a) has performances on annual grasses:
in PrSI: near or above the diallate
in pre-emergent post-sowing: performance similar to that of atrazine, sometimes with differences depending on grass species
post-emergence: performances close to alloxydim.

 However, variations in efficiency are recorded according to the species.

b) has performance on perennial grasses, stems and rhizomes
close to glyphosate (with variations depending on the species) and even superior to aminotriazole X
on cultivated dicots or weeds, according to the species and the modes of use, this compound has a selectivity close to the other graminicidal herbicides already used in this field.

 The transient depreciations that may be encountered are normal in all cultures, when using such graminicidal compounds. They come from among others, formulating agents and possibly competition from surrounding weeds, cultivated plants and dicots.

TEST N 2 (PHYTOTRON)
Compound No. 39
a) The compound is applied at the rate of 5000 g / ai / ha, either in PrSI or in PL.

Species tested in this test Results
(PrSI) (PL) - Grasses
. Avena. . . . . . . . . . . . . . . . . . . . . . . . . 7 10
. Agrostis 10 9
. Alopecurus 10 10
. Echinochloa. . . . . . . . . . . . . . . . . . . . . 10 10
. Lolium. . . . . . . . . . . . . . . . . . . . . . . . . . 10 10 - Dicotyledons:
. Medicago 0 9
. Raphanus 0 10
.Daucus. . . . . . . . . . . . . . . . . . . . . . . . . . 2 9
. Amarantus 0 5
. Atriplex. . . . . . . . . . . . . . . . . . . . . . . . . 0 10
. Solanum. . . . . . . . . . . . . . . . . . . . . . . . . 0 2
There is good anti-grass activity, regardless of the mode of application.

 b) Following the previous test, the compound is applied in PrSI at two doses: 1250 and 2500 g / m.a / ha.

Species tested in this test Results
Anti-grass action 1,250 2,500 - Crops
. Oats. . . . . . . . . . . . . . . . . . . . . . . . . . 4 5
. Andropogon. . . . . . . . . . . . . . . . . . . . . . 9 10
. Triticum. . . . . . . . . . . . . . . . . . . . . . . . 5 7
. Ordeum. . . . . . . . . . . . . . . . . . . . . . . . . . 4 4
. Zea. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 9 - Winter grasses
. Agrostis. . . . . . . . . . . . . . . . . . . . . . . . 7 10
. Alopecurus 9 9
. Poa. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 10 - Summer grasses
. Echinochloa 9 10
. Setarie. . . . . . . . . . . . . . . . . . . . . . . . . 9 10
. Festuca 9 9
This test confirms the anti-gramaceous activity of the compound because of the aggressivity on cultivated cereals.

the following test was undertaken.

 (c) The compound is applied in PSPrL at 1,250 and 2,500 g / m.a./ha.

Species tested in this test Results
Anti-grass action 1,250 2,500 - Crops
.Avoine. . . . . . . . . . . . . . . . . . . . . . . . . 0 0
. Andropogon 10 10
. Triticum. . . . . . . . . . . . . . . . . . . . . . 0 0
. Ordeum. . . . . . . . . . . . . . . . . . . . . . . . 0 0
. Zea. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 4 - Winter grasses
Agrostis 7 9
. Alopecurus 9 10
. Poa. . . . . . . . . . . . . . . . . . . . . . . . . . . 7 9
. Lolium. . . . . . . . . . . . . . . . . . . . . . . . 9 9 - Summer grasses
. Echinochloa 10 10
. Setaria 10 10
. Festuca 7 9
This mode of application very clearly improves the selectivity on cultivated cereals, except on sorghum, without noticeably reducing the anti-grass activity.

 d) Parallel to the previous test. the compound is applied in PL at 1,250 and 2,500 g / m 2 / ha.

Species tested in this test Results
Anti-grass action 1,250 2,500 - Crops
. Oats. . . . . . . . . . . . . . . . . . . . . . . . 9 10
. Andropogon 10 10
. Triticum 9 10
. Ordeum. . . . . . . . . . . . . . . . . . . . . . . . 9 10
. Zea. . . . . . . . . . . . . . . . . . . . . . . . . . . 10 10 - Winter Grasses
. Agrostis 7 10
. Alopecurus 9 10
. Poa. . . . . . . . . . . . . . . . . . . . . . . . . . . 4 5
. Lolium. . . . . . . . . . . . . . . . . . . . . . . . 9 9 - Summer grasses
. Echinochloa 10 10
. Setaria. . . . . . . . . . . . . . . . . . . . . . . . . . 10 10
Festuca 4 7
By this mode of application, the selectivity is lost on cultivated cereals, but the anti-graminaceous activity of the compound is confirmed.

TEST N 3 (PHYTOTRON)
Compound No. 40
a) The test compound is applied at the rate of 5000 g / ai / ha, either in PrSI or PL.

Species tested in this test Results
(PrSI) (PL) - Grasses
. Avena. . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 10
. Agrostis 10 7
. Alopecurus 10 10. Echinochloa, 10 9
. Lolium. . . . . . . . . . . . . . . . . . . . . . . . . . . 10 10 - Dicotyledonous
. Medicago. . . . . . . . . . . . . . . . . . . . . . . . . 0 4
. Raphanus 0 9. Daucus; 2 5
. Amarantus. . . . . . . . . . . . . . . . . . . . . . . . 0 9
. Atriplex 0 7
. Chrysanthemum 0 7
. Solanum. . . . . . . . . . . . . . . . . . . . . . . . . . 0 0
There is good anti-grass activity.

whatever the mode of application.

 b) Following the previous test, the compound is applied in two-dose PrSI 1250 and 2500 g / m.a / ha.

Species tested in this test Results
Action against grasses i 250 2,500 - Crops
Oats S 7
. Andropogon. . . . . . . . . . . . . . . . . . . . . . . 9 10
. Triticum. . . . . . . . . . . . . . . . . . . . . . . . . 9 10 33
. Ordeum. . . . . . . . . . . . . . . . . . . . . . 5 7
. Zea. . . . . . . . . . . . . . . . . . . . . . . . . 9 9 - Winter Grasses
. Agrostis 10 10
. Alopecurus 9 9
. Poa. . . . . . . . . . . . . . . . . . . . . . . . . 10 10
. Festuca. . . . . . . . . . . . . . . . . . . . . 10 10 - Summer grasses
. Echinochloa 10 10
. Setaria 9 10
. Lolium. . . . . . . . . . . . . . . . . . . . .. 10 10
This test confirms the anti-grasses activity of the compound, given its aggressiveness on cultivated cereals, the following test was undertaken.

 c) The compound is applied in PSPrL at the same doses.

Species tested in this test Results
Anti-grass action 1,250 2,500 - Crops
. Oats. . . . . . . . . . . . . . . . . . . . . . 2 2
. Andropogon 10 10
. Triticum. . . . . . . . . . . . . . . . . . . . 0 4
. Ordeum. . . . . . . . . . . . . . . . . . . . . . 0 2
. Zea. . . . . . . . . . . . . . . . . . . . . . . . . 4 6 - Winter Grasses
. Agrostis 7 10
. Alopecurus. . . . . . . . . . . . . . . . . . 9 10
. Poa. . . . . . . . . . . . . . . . . . . . . . . . . 7 10
. Festuca 7 9 - Summer grasses
. Echinochloa 10 10
. Setaria 7 9
. Lolium. . . . . . . . . . . . . . . . . . . . . . 9 10
Selectivity on cultivated cereals is significantly improved compared to the test. B) the anti-grass action remains good.

 d) In parallel with the above test, the compound is applied PL at the same doses.

Species tested in this test Results
Anti-grass action 1,250 2,500 - Crops
Oats 10 10
. Andropogon. . . . . . . . . . . . . . . . . . . . . . 10 10
. Triticum 10 10
. Ordeum. . . . . . . . . . . . . . . . . . . . . . . . . . 10 10
Zea 10 10 - Winter grasses
Agrostis 9 10
. Alopecurus 9 9
. Poa. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 9
. Festuca. . . . . . . . . . . . . . . . . . . . . . . . . 7 10 - Summer grasses
. Echinochloa 10 10
. Sataria. . . . . . . . . . . . . . . . . . . . . . . . . 10 10
. Lolium. . . . . . . . . . . . . . . . . . . . . . . . . . 10 10
This mode of application causes the disappearance of any selectivity, but confirms the anti-grease action of the compound.

TEST N 4 (IN PHYTOTRON)
Compound No. 41
The test compound is applied at a rate of 5000 g / ai / ha, either in PrSI or PL.

Species tested in this test Results
(PrSI) (PI) - Grasses
. Avena. . . . . . . . . . . . . . . . . . . . . . . . . . . 7 10
. Agrostis 10 4
. Alopecurus 10 10
. Echinochloa. . . . . . . . . . . . . . . . . . . . . 10 10
. Lolium. . . . . . . . . . . . . . . . . . . . . . . . . . 10 10 - Dicotyledons:
. Medicago OO
. Raphanus O 0
. Daucus. . . . . . . . . . . . . . . . . . . . . . . . . 0 4
. Amarantus 2 4
. Atriplex 0 5
. Chrysanthemum OO
Solanum OO
This test shows that the compound is active against grasses and appears to be selective for some cultivated dicotyledons.

TEST N 5 (IN PHYTOTRON)
Compound No. 43
The test compound is applied at the dose of
S 000 g / ai / ha, either in PrSI or in PL.

Species tested in this trial Results - Grasses: tPrSI) (PL)
.Avena. . . . . . . . . . . . . . . . . . . . . . . . . . 4 7
. Agrostis 10 0
. Alopecurus. . . . . . . . . . . . . . . . . . . . . 7 4
. Echinochloa 9 10
. Lolium. . . . . . . . . . . . . . . . . . . . . . . . . 10 9 - Dicotyledonous
. Medicago OO
. Raphanus OO
. Daucus. . . . . . . . . . . . . . . . . . . . . . . . . 0 0
. Amarantus 4 0
. Atriplex. . . . . . . . . . . . . . . . . . . . . . . 0 9
. Chrysanthemum OO
. Matricaria OO
. Solanum. . . . . . . . . . . . . . . . . . . . . . . . . 0 0
The compound shows an anti-microbial efficacy and a good selectivity on some cultivated dicotyledons.

SELECTIVITY WITH RICE
TEST N 6
The invention also relates to the herbicide treatments, mainly anti-grass, selective for rice and using a group of compounds according to the invention.

 The interesting herbicidal properties and rice selectivity have been demonstrated by experiments on the group of compounds comprising compounds Nos. 39, 40, 41, 43 and 45.

 These compounds are applied at the respective doses of 250 and 500 g of active ingredient per hectare, or 500 and 1000 g of active ingredient per hectare, pre-plant incorporated and post-emergent. The crop tested in this test is rice, the grass tested being Echinochloa, an important weed in rice cultivation.

 With regard to formulations, reference may be made to what has been said in the context of the paragraph on selectivity for cereals and dicotyledons.

The test results are summarized in the table below.

<Tb>

<SEP> PrSI <SEP> PL
<tb><SEP>: 250 <SEP> 500 <SEP> 1000 <SEP>: <SEP> 250 <SEP> 500 <SEP> 1000
<tb> Compound <SEP> n <SEP> 39 <SEP> - <SEP> Rice <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 5 <SEP> 3
<tb><SEP> Echinochloa .. <SEP>: <SEP> 7 <SEP>. <SEP> 10 <SEP>
<tb> Compound <SEP> n <SEP> 40 <SEP> - <SEP> Rice <SEP>: <SEP> 3 <SEP> 6 <SEP>: <SEP> 3 <SEP> 5
<tb><SEP> Echinochloa .. <SEP>: <SEP> 5 <SEP> 8 <SEP> 8 <SEP> 8
<tb> Compound <SEP> n <SEP> 41 <SEP> - <SEP> Rice <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 1 <SEP> 5
<tb><SEP> Echinochloa .. <SEP>: <SEP>: <SEP> 8 <SEP> 10
<tb> Compound <SEP> 43 <SEP> - <SEP> Rice <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 2 <SEP> 3
<tb><SEP> Echinochloa <SEP>. <SEP>. <SEP> 10 <SEP> 10
<tb> Compound <SEP> n <SEP> 45 <SEP> - <SEP> Rice <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP>. <SEP> 5 <SEP>: <SEP> 3
<tb><SEP> Echinochloa <SEP>. <SEP>. <SEP> 6 <SEP> 10
<Tb>
This table shows the graminicide activity differentiated according to the species and modes of applicaticn.

 In the context of this study, the low activity of compounds Nos. 39, 41, 43 and 45 with regard to rice and the destruction that it operates on Echinochloa, highlight the interest of the implementation of of these compounds in rice cultivation.

 Compound No. 40 also has rice selective activity but is slightly less marked than compounds Nos. 39, 41, 43 and 45.

The tests carried out on rice show that
the amount of product of group 39, 40, 41, 43 and 45 to be used pre-planted with incorporation or post-emergence, should be chosen between about 50 and about 2000, more particularly between about 100 and 700 g / ha of active material, the preferred doses being from about 250 to about 500 g / ha of active ingredient.

Claims (12)

1. Phenoxy- and Thiophenoxynitriles of Formula

 in which  n1 is 1 or 2;  R 4 and R 5, which may be identical or different, are chosen from the group comprising hydrogen and the alkyl radicals having from 1 to 4 carbon atoms, the phenyl radical optionally substituted with (R 1) n, the substituents R 4 and R 5 being able to form with the carbon atom carrying them a 5-, 6- or 7-membered polymethylene ring, it being understood furthermore that when one of the radicals R4 or R5 is a hydrogen atom, the other is different from CH3;  R1 represents a hydrogen atom, a halogen atom or an alkyl or haloalkyl radical having from 1 to 4 carbon atoms and n is an integer of from 0 to 3;  R6 is selected from the group consisting of Cl and CF3, R6 is different from p-CF3 when R4 and R5 simultaneously represent a hydrogen atom.  2. Phenoxy- and Thiophenoxynitriles of Formula III) in which  n1 is 1 or 2;  R 4 and R 5, which are identical or different, are chosen from the group comprising hydrogen, the radicals -CH 3, C H and -C 6 H 5;  R8 is selected from the group consisting of Cl and CF3, R6 is different from p-CF3 when R4 and R5 simultaneously represent a hydrogen atom.  3. The compounds  2-cyano-2-butanol 2-tetrifluoromethyl-4-phenoxy-4-phenoxy] propanoate (compound No. 39);  - [(trifluoromethyl-4'-phenoxy) -4-phenoxy-2-propanoate cyano pentanol 3 (compound No. 40);  - [(trifluoromethyl-4'-phenoxy) phenoxy] -2-propanoate of cyano-benzyl alcohol (compound No. 41)  2- (2-dichloro-phenoxy) -4-phenoxy-2-propanoate of cyanopropanol 2 (compound No. 43)  2 - [(trifluoromethyl - 3 'phenoxy) - 4 phenoxy] - 2 propanoate of cyanopropanol 2 (compound No. 44)  - [(trifluoromethyl - 3 'phenoxy) - 4 phenoxy] - 2 propanoate glycolonitrile (compound No. 45)  - [(2-chlorophenyl) -1-phenoxy) phenoxy-2 propanoate 2-cyano propanol (compound No. 46)  4- (trifluoromethyl-4'-phenoxy) -4-phenoxy-2-propanoate of cyanopropanol (compound No. 48).  4. Herbicide characterized in that it contains an effective amount of a compound according to any one of claims 1 to 3.  5. An anti-grass selective agent for dicotyledonous and cultivated cereals and comprises, as an active ingredient, an effective amount of compounds according to one of claims 1 to 3.  6. A selective anti-grass treatment for broadleaf weeds and cultivated cereals consisting in applying in PrSI or PL, an effective amount of a compound according to one of claims 1 to 3.  7. Selective weed-control treatment for broadleaf weeds and cultivated cereals consisting in applying to PSPrL an effective amount of a compound according to one of claims 1 to 3.  The treatment of any one of claims 3 to 7 of applying a dose of 500 to 5,000 g of active ingredient per hectare.  9. The treatment according to claim 7, comprising applying a dose of 1,000 to 5,000 g of active treare per hectare.  10. Wettable anti-grass powder with 50% active ingredient. selective method for cultivated dicotyledons and cereals, consisting of a mixture of 52.6 parts of substance according to one of claims 1 to 3 at 95% purity, 41.4 parts of kaolin clay and / or silica, 2 parts of sodium alkylnaphthalene sulfonate wetting agent and 4 parts of dispersing agent.  11. An emulsifiable anti-graminaceous emulsifiable concentrate, selective for broadleaf weeds and cultivated cereals, consisting of a mixture of 253 g of substance according to one of claims 1 to 3, at 95% purity. 25 g / l of calcium dodecylbenzene sulfonate in 70% solution in isobutyl alcohol, 35 g / l of castor oil condensed with -30 moles of ethylene oxide and the amount sufficient for one liter of a petroleum solvent.  A rice selective anti-grass treatment comprising applying in PrSI or PL an effective amount of a compound selected from the group consisting of compounds 39, 40, 41, 43, 44, 45, 46 and 48, according to claim 3, preferably at a dose of 50 to 2,000, and advantageously from 100 to 700 g of active ingredient per hectare.