DD217694A5 - HERBICIDAL COMPOSITION - Google Patents

Abstract

The invention relates to herbicidal compositions containing pyridinyl-phenoxy-alkansÄuren, pyridinyl-thiophenoxy-alkansÄuren, derivatives thereof and related compounds for the pre-eminent and post-environmental application in agriculture in the control of grassy weeds. The aim of the invention is the provision of new agents with a stronger herbicidal action. According to the invention, as active ingredient in the herbicidal compositions, novel pyridyl- (oxy / thio) -phenoxy-compounds of the formula in which, for example: X is CF3, CHF2, CClF2, Br or Cl; T O or S; Z is an organic moiety containing N, O or S atoms or is or may be a metallic, ammonium or organic amine cation and hydrolyzed in plants or the soil to a carboxy moiety which is present in undissociated and / or dissociated form is present. formula

Description

b) herbicidal compositions of these novel compounds and

c) Methods of using these compounds for the preemergence and post-interference control of grassy weeds both in non-cereal areas and in the presence of certain valuable cereals, crops such as soybeans, cotton and wheat.

Characteristic of the known technical solutions

The BE-PS 834 495, issued on 02 · 02 # 1976, as well as the! to DE-OS Nos., 2 546 251, which are equivalent to those on 29 *. 04, 1976, describe 2- (4-pyridinyl-2-oxy) -phenoxy) -alkanoic acids. Salts and esters having a halogen substitution in the 3 and / or 5-ring positions in the pyridine ring. Later references, for example, 2 026 865, disclose those compounds which are trifluoromethyl-substituted on the pyridine ring and EP-PS 0 002 800 describes the improved effect of the D-stereoisomers of these compounds,

63 257 18

A variety of herbicidal compounds containing substituted pyridyl and phenoxy moieties "linked via a divalent -O- and -S-" are described in the art. For example, US Pat. Nos. 4,046,531,4,317,913, 4,267,336; 4,213,774; 4,324,627 and 4,309,547 and EP-PS 483 such compounds ₈ Processes for their preparation and compositions containing them and methods of using these compositions In general, the proportions given to the corresponding -O- groups of the phenoxy radical are bonded in the herbicidal compounds "which are described in these references" also applicable "represented by Z in the formula for the up at ~ out new compounds as the monovalent organic residues, and these compounds may be ₈ when the corresponding Pyridinstartmaterial is given" prepared are prepared by methods described in the above-mentioned prior art and can be used in compositions as described in the prior art

Object of the invention

The aim of the invention is the provision of new compounds with stronger herbicidal activity *

Explanation of the nature of the invention

The invention is based on the object "new compounds with greater herbicidal activity, as they are present in known substances the same direction of action" /

63 257 18

According to the invention, the active compounds used in the herbicidal compositions are novel pyridyl (oxy / thio) -phenoxy compounds having herbicidal activity which have the following general formula

0 - Z

worxn X CF

₃ , CHF ₂ , CClF ₂ ,

Br or Cl means ι

T is O or S; and

Z is an organic moiety containing N, O, or S atoms, or is or may be a metallic, ammonium, or organic amine cation, and / or oxidizes in plants or the soil to a carboxy moiety which is in undissociated and / or dissociated form.

The invention is also directed to novel stereoisomers of these compounds, the β-isomers of exceptional activity.

Zr parts include, but are not limited to, among others:.

-C- (Y) _n R ²

  Λ; , , , , , :; , : .. Η ''

in which:

Y represents a saturated or unsaturated alkyl group having an even number of carbon atoms, preferably 2 to 18 carbon atoms,

η is 0 or 1, R is H or a C, to C -.- alkyl group and

R ^{2 represents} a group which corresponds to one of the following formulas:

CN,

NH -c

NH

/ A

Ii ' ^:

-C-X, wherein X is halogen or CN, 0

Il

-CO ^- M, in which

    - 5 - ...

M represents a metal cation, ammonium or organic amine cation which typically, but not exclusively, contains alkyl (saturated or unsaturated), alicyclic, heterocyclic or aromatic groups, all unsubstituted or substituted with various other groups which are not limited; but include halo, cyano, nitro and unsubstituted or substituted thiol, hydroxy, ¹ amino or carboxyl groups and additionally include alicyclic, heterocyclic and aromatic groups substituted with unsubstituted or substituted saturated or unsaturated alkyl groups, e.g. Trifluoromethyl, chloromethyl,. '

j.

Cyanomethyl and vinyl,

-CH ₂ OR ³ , 4. R ⁴ \ 0 -CR ³ , R ³ 0 Il 0 / S Il -CH ₂ OCN CH ₂ OCR ⁶ , 0 Π. C-OR ³ , ο Il -C-SR ³ , 0 / S / R -C-N '

0 / S R "

-C-N

0 / S R ³ / CN, Il 0 / S -C-N \ it CH-O-C-N ". /

CN

-C = NR ³ ,

NC = NR ³ ,

0 H / alkyl -C-N0R · ³ ,

0 / S R- "» / -C N-

 n:

o / s

CN

0 / SR ⁴ R ⁵

Ν- Ν

0 / S R "

Il

-C-N

R ³ ;

OR

-C (SR ⁶ ).

H -C (OR ⁶

H -C (SR ⁶ ).

ρ o

^v 4

I ^ss

C-N = C

N (R ³ ).

N (R ³ )

N-R where X is S. or O.

where -W is halogen; R ³ is H or R; RH, an alkoxy group or R; RH, a metallic cation or R; and R is an alkyl group (saturated or unsaturated), an alicyclic, heterocyclic or aromatic group, unsubstituted or substituted with various other groups, which are not limited to, but include halo, cyano, nitro and unsubstituted or substituted thidl, hydroxy, amino or carboxyl groups and additionally alicyclic, heterocyclic and aromatic groups which are substituted by unsubstituted or substituted saturated or unsaturated alkyl groups, B. "trifluoromethyl, chloromethyl, cyanomethyl and vinyl,

-CN R ⁷ ,. , · I

o / s

-CH ₂ -OCN R ⁷ , «7

C = NR ³

  - ι:. ,

-C = N 'wherein A is 0, S or N, or: O / SR ⁴

Ν- Ν R ⁷ .-

wherein R completes an unsubstituted or substituted saturated heterocyclic ring system *,

The above derivatives can be prepared by methods generally known to those skilled in the art and described in the aforementioned patents. For example, the corresponding acid chlorides can be treated with a

Grignard reagent to produce the desired aldehydes or ketone derivatives. Likewise; the reaction of an acid chloride with KSH provide the desired thiol acids. Thioamides can be prepared from the corresponding amides by reaction with E * 2 ^S 5 ° ^ ^er 'when the hydrogen on the nitrogen atom, the carbonyl group can be converted, for example, in chloride with elimination of HCl, followed by reaction with hydrogen sulfide. Carbamoyl chlorides are available or can be prepared from the desired amines and phosgene or thiophosgene for use in the preparation of compounds containing

0 / SR ⁴ -

-C - N <^ T

^ - _R 3

Group included.

The reaction of an amine with a sulforiyl chloride, ζ. B. R ⁵ NH ₂ + R ⁶ SO ₂ Cl provides the group

HN

for use in the reaction with a corresponding acid chloride.

The reaction of an amine with BrCN provides z. B.

NC

which reacts with the corresponding acid chloride and provides compounds containing the

-C - N

CN

Share delivers. P _O S _C is applied to the corresponding

to produce the S-containing compounds.

/ '

>

The reaction of the above cyanoamine with phosgene or thiophosgene provides

R ³ O / S

- C - Cl

for use in the preparation of corresponding derivatives, The reaction of the compounds with the proportion

, - 'o · - .. ·'. ''^; -

  , 'Il. · · ".

', ^: -C-NHR3

with PCI leads to connections with the share

· '' · '·' Cl '-. ·' '. ;. '

-C = NR ³

The reaction of the corresponding acid chloride with RONH ₂ leads to compounds with the group _;

ο. η.

-C - N τ OR

Various hydrazine derivatives can be prepared, for. B. from trimethylhydrazine by reaction with the acid chlorides. The reaction of amides, ζ. B.

Il

C-NHR ³

with dicarboxylic anhydrides leads to compounds with the group.

0 0 -CNCR ³

R ² is preferably a carboxylic acid group, one of its alkali or alkaline earth salts, one of its ammonium or organic amine salts or a lower alkyl ester, wherein "lower alkyl" includes straight, branched or cyclic saturated or unsaturated alkyl groups having not more than 6 carbon atoms. Preferably, η = 0.

In the above formulas, the aliphatic groups preferably contain 1 to 6 carbon atoms, the alkenyl and alkynyl groups preferably contain 2 to 6 carbon atoms, the alicyclic groups preferably contain 3 to 6 carbon atoms, and the aromatic moiety is preferably phenyl, although other ring systems, including heterocyclic Ring systems, also can be applied, if desired.

In the formula for the above-mentioned novel compounds, T is preferably 0 and X is preferably CF ₃ , Cl or Br. Most preferred are those compounds in which X is CF ₃ or Cl, T is O and Z is

, , ·. , , - -. ·. CH-, .O · .. ' ".,.:.

_ fXl _ Γ · _ A _ Ό "'

wherein R "is a methyl, ethyl, propyl, isopropyl, isobutyl or n-butyl group.

The compounds of the above formula, referred to hereinafter as "active ingredients", have been found to be particularly active as herbicides for the control of native desired vegetation, e.g. B. grass or grassy weeds and they are unexpectedly much more effective than the compounds of the prior art. Particularly surprising is the finding that the unexpected activity of the claimed compounds is specifically related to the fluorine substitution in the 3-position of the pyridine ring; Fluorine substitution in other positions of the pyridine ring, .z. In the 5-position, do not lead to an unusually good activity. With the compounds of the invention, it is possible to use lower dose rates and still maintain effective control, thereby reducing plant residues and reducing any possible environmental contamination and / or toxicological effect on fish and warm-blooded animals. Accordingly, the present invention also encompasses herbicidal compositions' which contain one or more of these active ingredients both as a method of controlling undesired pöstemergenten präemergenten and plant growth, especially in the presence of valuable crops. Such methods include the use of a herbicidally effective amount of one or more of these active ingredients at the site of the undesired plants, that is, the seed, the tree cover, the rhizomes, stems and roots or other parts of the growing plants or soil in which the plants grow or can be found.

As used herein, the term "herbicidal" refers to an active ingredient that effectively controls or counteracts plant growth through phytotoxic or other effects to severely delay plant growth or damage the plant enough to kill the plant ,

By "growth control" or "herbicidally-effective" amount is meant an amount of active ingredient that has an affecting effect and includes deviations from natural development, killing, regulation, dehydration, slowing, and the like.

The term "plants" is intended to include germinating seeds, sprouting seedlings, rhizomes, stolons, and other subsurface and autonomous vegetation.

The active ingredients, ie the novel compounds of the present invention, are readily prepared by methods described in the above-cited prior art by selecting the appropriate starting material. The stereoisomers are readily separated as described in EU Patent 0002800 referred to above. ₍

Some of the pyridine reactants used to prepare the novel pyridinyl oxyphenoxy compounds of the invention are themselves novel compounds and such reactants can be prepared as generally described herein and as specifically set forth in the following examples or by analogy thereto, starting with known compounds becomes.

It has unexpectedly been found that the fluoratora in 3-chloro-2-fluoro-5- (trifluoromethyl) -pyridine can be readily replaced by a 2-cyano group by reacting the pyridine compound with an alkali cyanide, preferably potassium cyanide, in a polar aprotic solvent, preferably Pimethylsulfoxid, at a temperature of 10 to 50 ⁰ C, preferably 20 to 30 ⁰ C. It was further found that das.Chloratom in the resulting product, ie, 3-chloro-2-cyano-5- (trifluoromethyl) pyridine easily can be selectively replaced by fluorine by reaction with z. Example, cesium or potassium fluoride in a polar aprotic solvent, preferably dimethyl sulfoxide, at a temperature of 80 to 140 ⁰ C, preferably 90 to 100 ⁰ C. The cyano group in the resulting 2-cyano-3-fluoro-5- (trifluoromethyl) pyridine can be easily converted, by known methods, to the corresponding acid or amide as desired. The resulting acid can be readily converted to the corresponding bromo derivative by the Hunsdiecker reaction as shown in the following Example 4, or the amide can be converted to the corresponding amine and then into the hydroxy compound by the Hoffmann hypobromite. Reaction followed by diazotization and replacement of the hydroxide as known in the art. The latter is then treated with POCl ₃ and PCl ₅ , as known in the art, for. For example, 2-chloro-3-fluoro-5- (trifluoromethyl) -pyridine.

Alternatively, 2,3-difluoro-5- (trifluoromethyl) -pyridine can be prepared by reacting 2,3-dichloro-5- (trifluoromethyl) -pyridine or 3-chloro-2-fluoro-5- (trifluoromethyl) -pyridine in Connection brings with a fluorinating

63 257 18

The agent and the 2,3-difluoro-5- (trifluoromethyl) -pyridine can then be used directly to prepare 2- (4 - ((3-fluoro-5- (trifluoromethyl) -2-pyridinyl) oxy) -phenoxy). -Alkanoic acids and derivatives ·

Preferred compounds with favorable herbicidal activity are the following:

2- (4- (3-Fluoro-5- (trifluoromethyl) -2-pyridinyloxy) -phenoxy) -propanoic acid and its agriculturally acceptable salts and esters, for example methyl-2- (4- (3-fluoro-5- (trifluoromethyl ) -2-pyridinyloxy) phenoxy) -propanoate or the R-enantiomer of this compound;

2- (4- (3-fluoro-5-chloro-2-pyridinyloxy) -phenoxy) -propanoic acid and its agriculturally acceptable salts and esters, for example 2- (4- (3-fluoro-5-chloro-2-pyridinyioxy) phenoxy) -propanoic acid methyl ester or the R-enantiomer of this compound;

2- (4- (5-bromo-3-fluoro-2-pyridinyloxy) -phenoxy) -propanoic acid and its agriculturally acceptable salts and esters;

2- (4- ((3-fluoro-5- (trifluoromethyl-2-pyridinyl) -oxy) -phenoxy) -propionitrile «

embodiment

The following examples further illustrate the invention.

62 257 18

, / '

Example 1 . '' ·. , '. _. · · · .- Preparation of 3-chloro-2-cyano-5- (trifluoromethyl) -pyridine

3-Chloro-2-fluoro-5- (trifluoromethyl-1-pyridine (obtainable as a by-product of the fluorine exchange reaction in the conversion of 2,3-dichloro-5-trichloromethylpyridine to 2V3-dichloro-5- (trifluoromethyl) -pyridine) (4O ₁ O g of "0.2" oil) was added to 270 ml of dimethylsulfoxide and stirred while potassium cyanide (14.4 g "0.221 mol) was spooned in over a period of 20 minutes." The mixture was then stirred for a further 20 minutes. The temperature was maintained between 23 and 28 ^° C. during the reaction. The mixture was poured into 600 ml of ice-water and the product was extracted into hexane The hexane was removed on a rotary evaporator The product was treated with charcoal and distilled on a Vigreaux. Claisen at 108 to 110 ⁰ C and 30 mm Hg with a yield of 31.45 g of a colorless oil with the following analysis in% by weight

calculated: C = 40.70; H = 0.98; N = 13.56 found; C = 40.42; H = 0.99; N = 13.66 ·

• Example '' 2

Preparation of 3-fluoro-2-cyano-5- (trifluoromethyl) -pyridine.

A flask equipped with an air stirrer and a puller was attached. Casium fluoride (45.6 g, 0.3 mol), potassium carbonate (1.2 g) and 350 ml of dimethylsulfoxide were added to the flask and heated and stirred under vacuum (30 mm). 120 ml of dimethyl sulfoxide was distilled off to dry the system. The Reaktionsmxschuhg was cooled to 8O ⁰ C, the vacuum was released and 3-chloro-2-cyano-5- (trifluoromethyl) pyridine (41.6 g - 0.201 mol) were added over a ^ Ζθί 3μΐη of 7 minutes. The reaction mixture was then heated to 93 ^° C. and held at 93 to 111 ^° C. for 20 minutes. The mixture was then cooled to 54 ° C, poured over ice and extracted twice with hexane and once with methylene chloride. The solvents were removed and the product was distilled at about 30 mm Hg at 90 to 94 ° C to give a yield of 29.6 g of a colorless oil which had the following analysis in wt%:

calculated: C = 44.22; H = I, 06; N = 14.74. Found: C = 43.53; H = I, 11; N = 14.44. .

B ei ρ i el 3

    · '.

Preparation of 3-fluoro-5- ('trifluoromethyl) -picolinic acid

F ₃ C

2 "cyano-3-fluoro-5- (trifluoromethyl) -pyridine (11.1 g, 0,0584InOl) was immersed in 87 ml of 90% sulfuric acid placed in a beaker. The mixture was stirred and heated to 100-112 ⁰ C. The reaction mixture was then cooled, poured over ice and the precipitated solids were filtered off The solids were dissolved in a dilute solution of

V. '·.' · '.- ·

NaOH. Any material that did not go into solution

was filtered off and the filtrate was acidified with aqueous HCl and the precipitate was filtered off and dried. This gave a yield of 6.47 g of a solid product with the analysis in wt.%:

calculated: C = 40.20; H = I, 45; N = 6.70. found: C = 39.29; H = I, 35; N = 6.98.

1.05 g of a second amount of solids was obtained on standing, which showed the same IR spectrum as that of the first solids. These were combined and used to prepare the following sample compound. ¹ ; - '·. "

- 18 -

Example 4.

Preparation of 2-bromo-3-fluoro-5- (trifluoromethyl) -pyri

din ·. ..; .. ·. , '-. .. ·. ν ^: '...

The 3-fluoro-5- (trifluoromethyl) -picolinic acid (7.35 g, 0.035 mol) as the starting material was added to 150 ml of dry carbon tetrachloride and then red mercuric oxide (9.1 g, 0.042 mol) was added and the _; The mixture was stirred and refluxed for one hour and 25 minutes. A solution of bromine (6.7 g, 0.042 mol) in 20 mL of dry carbon tetrachloride was added slowly, with the mixture remaining at reflux for the next 2 1/3 hours. Light from a UV lamp was directed to the reaction mixture during the addition and the reaction mixture was refluxed for an additional 1 hour. An additional 25 ml of dry carbon tetrachloride was added and reflux was continued for about 16 more hours, with UV light. Irradiation was applied. The reaction was then filtered through GELITE diatomaceous earth to remove the mercury salt. The carbon tetrachloride was removed from a still and the product was distilled over with a yield of 2.45 g of a yellow oil with the following analysis in wt%.

calculated: C = 29.53; H = O, 83; N = 5.74. found: C = 29.36; H = 0.77; N = 5.82.

The gas chromatograph showed that the oil was a 99% pure compound.

Be i s ρ i e 1

Preparation of 2- (4- (3-fluoro-S- (trifluoromethyl) -2-pyridinyl) oxy) phenoxy) propane acid

CH-I. -V

QV-OCHCO ₂ H

2- (4-hydroxyphenoxy) -propanoic acid (1.80 g, 0.00988 mol) was dissolved in 15 ml of dimethyl sulfoxide. A solution of sodium hydroxide (0.8 g, 0.02 mol in 1 ml of water) was added and the reaction mixture was heated and the nitrogen heated to 48 ° C over a period of 27 minutes. Pyridine (2.40 g, 0.00984 mol) dissolved in 5 ml of dimethyl 2-bromo-3-fluoro-5- (trifluoromethyl) was added and the reaction mixture was heated to 75 to 78 ⁰ C for 40 minutes. The mixture was poured into 150 ml of cold water and acidified with aqueous HCl. A resinous residue fell out. During workup and purification, a fraction (0.45 g) was obtained which had an elemental analysis in wt% of:

calculated: found:

C = 52.18; H = 3.21; N = 4.06, C = 51.89; H = 3.19; N = 4.02,

This material had a melting point of 130 to 130 ° C. :. . ' - .. ^;

Example 6

Preparation of 2- (4 - ((3-fluoro-5-trifluoromethyl) -2-pyridinyl) oxy) phenoxy) -propionamide

A) A fresh sample of 2- (4 - ((3-fluoro-5- (trifluoromethyl) -2-pyridinyl) oxy) phenoxy-propanoic acid was prepared by reaction of 2,3-difluoro-5- (trifluoromethyl) -pyridine with 2- (4-hydroxyphenoxy) -propanoic acid in the presence of 2 moles of sodium hydroxide,

w as described above and 9.0 g (0.026 mol)

boiled under reflux in excess SOCl ₂ for about 1/2 hour to prepare the corresponding acid chloride ^ The excess SOCl ^ was removed by heating at 115 ⁰ C under an aspirator vacuum. The resulting acid chloride was added to a mixture of concentrated ammonium hydroxide (30 ml) and methanol (60 ml). The flask was rinsed with an additional 15 ml of ammonium hydroxide mixed with about 25 ml of methanol and the two fractions were combined. The acid amide was formed as a solid which was filtered off, washed with water, suspended in water

V was filtered, dried and analyzed.

Melting point 140 to 141 ⁰ C.

Analysis: calculated: % C 3 %H 8.14 found: 52.33 3 , 51 8, 09 52.54 , 46

B) Other propionamides of the invention, as previously stated, were prepared using similar procedures: V

A enamel calc. : 55 % C analysis % N 7, 80 point ⁰ C ge f. : 55 7, 70 45 % H '. 16 -H , 88 11 -N Cl 142-143.5 3.32 6, 3.34 6,

B e i s ρ i e 1

Preparation of 2- (4 - ((3-fluoro-5- (trifluoromethyl) -2-pyridinyl) oxy) phenoxy) -propionitrile

A portion of the amide prepared in Example 6A) (5.68 g, 0.0165 mol) was refluxed with an excess of POCl ₃ for about 2 hours, after which the excess of POCl was removed by distillation under a suction vacuum. The reaction mixture was poured over ice and extracted with methylene chloride. The methylene chloride was removed on a rotary evaporator and the crude material was taken up in hexane and decolorized with charcoal. A rubbery material formed, which was returned to the evaporator, leaving an oil which was recovered and analyzed. .

Analysis:. calculated: % c 3 %H 8th % N found: 55.22 3 , 09 8th , 59 55.64 00 , 81

Refractive index = 1.5067 at 25 ° C.

Example 8

Preparation of 2- (4 - ((3-fluoro-5- (trifluoromethyl) -2-pyridinyl) oxy) phenoxy) -methyl-propanoate

Following the procedure of Example 6A), the acid chloride was prepared by boiling a portion of the acid of Example 6A) with thionyl chloride at reflux. The resulting acid chloride (3.45 g, 0.01 mol) was then reacted with methanol (1.0 g, 0.0312 MpI) in the presence of triethylamine (2.0 g, 0.02 mol) in 20 mL of toluene 80 to 88 ° C. The salt was removed by filtration, then washed with hexane, the filtrate was combined, and the solvent was removed by evaporation. The crude product was taken up in hexane, some solids were removed by filtration, and the solution was decolorized with charcoal and the solvents removed under vacuum. The product was gradually solidified, recovered and analyzed. Melting point 50 to 52 ⁰ C.

Analysis: calculated: % C 3 %H 3 % N found: "53.49 3 , 63 3 90 53.82 , 68 , 87

According to the above procedure, except that other alcohols or thioalcohols were used as the esterifying agent, the following compounds were prepared having the general formula:

<KO

• ν .-.

-OC ₄ H ₉

Properties oil

calculated: found: percent composition CHNS

56.86 4.77 3.49 56.85 4.77 3.51

OCH ₂ CH ₂ OCH ₂ CH ₃

oil, R.I. = 1.4944 a 25 ° C

calculated found;

Oil, R.I. = 1.5164 calculated a 25 ° C found:

54.68 4.59 3.36 7 , 68 54,74 4.44 3.42 7 , 59 54.67 4.59 3.36 54.87 4.54 3.39

R.I. = Refractive index corrected for 25 ° C.

Example 9; , '

Preparation of 2- (4 - ((3-fluoro-5- (trifluoromethyl) -2-pyridinyl) oxy) phenoxy-1-propanol

The methyl ester of Example 8 (5.7 g, 0.0159 mol) was dissolved in methanol (75 ml) and a solution of sodium borohydride. (3.5 g, 0.0954 mol) was added dropwise to the cooled (19 ° C) solution, the temperature was maintained at about 25 ⁰ C. The mixture was stirred for about 1 1/2 hours, after which the temperature had dropped to 18 ° C. At the 30-minute standing, the temperature rose to 23.5 ° C, and the reaction mixture was heated to 42 ⁰ C (30 minutes), stirring was continued without heat for 30 minutes, it was poured into a beaker and added ice water (200 ml ). It was extracted with hexane and then twice with methylene chloride. The extracts were combined, the solvent removed and 4.94 g of the product indicated above were obtained as a light yellow oil. RI = 1.5144 25 ° C.

Analysis: 54 % C 3 %H 4 % N calculated: 54 , 38 3 96 4 , 23 found: 25 , 98 , 44

Example 10

Preparation of the R-enantiomer of 2- (4 - ((3-fluoro-5- (trifluoromethyl) -2-pyridinyl) oxy) phenoxy) -propionic acid methyl ester

A mixture of 2.11 g (7.72 mmol) of 4- (3-fluoro)

5- (trifluoromethyl)) -2-pyridyloxyphenol (prepared as in Example 12), 1 ^ 07 g (7.72 mmol) of anhydrous

_ 25 -

K ₂ GO ₃ and 1-4.1 g (77.2 mmol) of methanesulfonate of the methyl ester of L - '(+) - lactic acid in 16 ml of dry dimethylsulfoxide (DMSO) were stirred at room temperature for 43 hours. The reaction mixture was partitioned between diethyl ether and water. The organic phase was separated, dried (Na ₂ SO ₄ ) and evaporated at reduced pressure to give a colorless liquid. Purify by high pressure liquid chromatography on silica gel, eluting with ethyl acetate.

Hexane ¹ (3:22; V / V) gave 2.15 g (78%) of the R-enantiomer

• 25 of the desired product as a colorless oil: U ^ J _n +

31.4 ° (CH 2 Cl 2, C 0.0110 g / ml); IR (CCl ') 1766 and 1741

- 1 T cm; H NMR (CDCl ₃ CI 8.0-8.2 (IH, m), 7.5-7.8 (IH, m))

6.7-7.2 (4H, m), 4.71 (IH, q), 3.73 (3H, s) and 1.59

(3H, d); ¹⁹ F NMR (CDCl ₃ , ppm field up from CgFg)

102.1 (s) and 26.3 (d). Analysis:

calculated for C ₁₆ H ₁₃ F ₄ NO _4: C, 53.49; H, 3.65; N, 3,90.

found: C, 53.61; H, 3.53; N, 3:86. The optical purity of the sample was determined with

90% eu (tfc)

90% ee by H NMR analysis in the presence of

3 *

Example 11

Preparation of the R-enantiomer of 2- (4 - ((3-fluoro-5-chloro-2-pyridinyl) -oxy) phenoxy) -propionic acid methyl ester

A mixture of 1.80 g (7.50 mmol) of 4- (3-fluoro-5-chloro) 2-pyridyloxyphenol, 1.04 g (7.50 mmol) of anhydrous K ₃ CO ₃ and 13.7 g (75 , 0 mmol) of methanesulfonate of the methyl ester of L - (+) - lactic acid in 16 ml of dry DMSO were stirred at room temperature for 42 hours. The

Reaction mixture was partitioned between diethyl ether and water. The organic phase was separated, dried (Na ₂ SO ₄ ) and evaporated at reduced pressure to give a colorless liquid. Purification by high pressure liquid chromatography on silica gel eluting with ethyl acetate-hexane (1: 9, v / v) gave 1.82 g (75%) of the R-enantiomer of the desired product as a colorless oil: J kI + 34.4 ° (CHCl ₃ ,

0.0112 g / ml); IR (CCl ₄ ) 1762 and 1740 cm ^-1 , ¹ H NMR

_(CDCl3) i7 _f 82 (IH, d), 7.43 (IH, d of d), 6.7 to 7.3

(4H, m), 4.69 (IH, q), 3.72 (3H, s), and 1.58 (3H, d); '

¹⁹ F NMR (CDCl ₃ , ppm field up from "CgFg) 27.2 (d).

Analysis:

calculated for C ₁₅ H ₁₃ ClFNO _4: C, 55.31; H, 4.02; N, 4.30.

Found: C, 55.04; H, 3.85; N, 4,24.

The optical purity of the sample was determined as

i. 76% ee

Eu (tfc) ₃ .

76% ee by H NMR analysis in the presence of

Example 12

Preparation of 4 - ((3-fluoro-5- (trifluoromethyl) -2-pyridinyl) oxy) phenol

Hydroquinone (4.4 g, 0.04 mol) was dissolved in 65 ml of dimethylsulfoxide and finely-milled sodium hydroxide (1.4 g, 0.035 mol) was added all at once and the mixture was stirred under a nitrogen atmosphere for 10 minutes to convert it to the sodium salt , 2,3-difluoro-5- (trifluoromethyl) pyridine (6.0 g, 0.033 mol) were then added and the mixture was stirred for 1.5 hours at 50 ⁰ C, then at 6O ⁰ C for a moment

heated, allowed to cool for 15 minutes and then poured into 500 ml of cold water. Additional sodium hydroxide (^ 5g in water) was added to turn the desired product into its sodium salt. The insoluble bis derivative was then removed by extraction with hexane, the clear aqueous phase was separated, cooled and acidified with concentrated hydrochloric acid. The solid which settled was collected on a filter, washed, dried in a vacuum funnel and taken up in hot hexane. After treatment with decolorizing carbon, filtering, concentrating and cooling, "a white, crystalline product separated

 Yield; 2.6 g. Melting point: 97.5 to 98.5.

Analysis: % C to to %H 5 5 % N calculated: found: 52.76 52.71 , 58, 57 , 12, 12

Example 13 Preparation of 5-chloro-2,3-difluoropyridine

Cesium fluoride (125 g, 0.82 mol) and DMSO (300 ml) were placed in a fluorination flask equipped with a mechanical stirrer, a thermometer, and a distillation head. About 50 ml of DMSO was distilled off under vacuum to dry the system. 2,3,5-trichloro-pyridine (50 g, 0.27 mol) and potassium carbonate (2.5 g, 0.018 mol) were added and the mixture was heated to 130 to 14O ⁰ C for 7 hours with vigorous stirring. The product was distilled directly from the reaction mixture under vacuum. The DMSO was poured out and the product was distilled back to give a clear, colorless liquid (11.9 g, 29% of theory, b.p. 70-73 ° C @ 85 mmHg).

Analysis: % C% H% N% C1. calculated: 40.16 1.35 9.37 23.71 found: 39.54 1.36 9.44 2.3.92

B ei s ρ i e 1 14. ; .

Preparation of 5-bromo-2,3-difluoropyridine

Cesium fluoride (28.8 g, 0.19 mol), potassium carbonate (1.0 g, 0.007 mol), and sulfoarane (190 mL) were added to a fluorination flask equipped with a mechanical stirrer, thermometer and distillation head. About 20 ml of sulfolane was distilled off under vacuum to dry the system. 2,3,5-tribromopyridine (20 g, 0.063 mol) was added and the mixture was heated to 180 ^° C. for 2 1/2 days. The product was distilled directly from the reaction mixture to give a clear, colorless liquid (3.94 g, 32%) containing 80% 5-bromo-2,3-difluoropyridine and 20% the 3-bromo- 2,5-difluoropyridine isomers.

Analysis: % C 1 1 %H 7 7 % N calculated: found: 30,95 31,36 , 04, 14 , 22, 32

Example .15

Preparation of 4- (5-chloro-3-fluoro-2-pyridinyloxy) -phenol,.

A solution of, JNaOH (1.76 g, 0.044 mol) in a few ml of water was added to hydroquinone (4.86 g, 0.040 mol) in 250 ml of DMSO. The mixture was stirred under

Nitrogen for 20 minutes. 5-Chloro-2,3-difluoropyridine (6.0 g, 0.040 mol) was added. The reaction mixture was heated to 60 to 70 ^° C. for 3 hours, then poured over ice. Aqueous NaOH was added to pH 12 and the solid diethene by-product was filtered off. The filtrate was acidified, extracted with ether, treated with Norite Absorbent, and the solvent was removed by rotary evaporation to give a yellow oil which precipitated on standing and was purified by high performance liquid chromatography (HPLC) (80% hexane / 20% ethyl acetate). to give a white solid (2.5 g, 26% yield, mp 90-92 ° C). '..

Analysis: % C% H% N

Calculated: 55.14 2.94 5.85 Found: 55.05 2.93 5.65

Be i spie 116

Preparation of methyl 2- (4- (3-fluoro-5-chloro-2-pyridinyloxy) -phenoxy) -propionate

A solution of NaOH (2.7 g, 0.068 mol) in a few ml of water was added to 2- (4-hydroxyphenoxy) -propionic acid (6.09 g, 0.033 mol) in 55 ml of DMSO and the mixture was stirred for 20 minutes under nitrogen. 5-chloro-2,3-difluoropyridine (5.0 g, 0.033 mol) was added and the mixture was heated to 7O ⁰ C for 5 hours. The reaction was then poured over ice and extracted with CH ₂ Cl ₂ . The organic layer was washed with water; dried over Na ₃ SO ₄ and the solvent was removed by rotary evaporation.

55 , 31 4 , 02 4 30 54 91 4 , 05 4 , 21

The residual oil was dissolved in 130 ml of dry methanol, p-toluene sulphonic acid (0.5 g, 0.003 mmol) was added and the mixture was stirred at room temperature for 24 hours. The methanol was removed by rotary evaporation. The residue was taken up in ether, washed with dilute aqueous NaOH and dried over Na ₃ SO ₄ . The ether was removed by rotary evaporation to give a tan oil which solidified on trituration with methylcyclohexane to give a white solid (6.4 g, 59%, mp 53-56 ° C).

Analysis:. % C% H% N calculated: Found:

Example 17

Preparation of 2- (4- (5-bromo-3-fluoro-2 ^ -pyridinyloxy) phenoxy) propionic acid

A solution of NaOH (0.54 g, 0.013 mol) in a few ml of water was added to 2- (4-hydroxyphenoxy) -propionic acid (1.22 g, 0.0067 mol) in 20 ml of DSMO and the mixture was allowed to stand for 20 minutes stirred under nitrogen. 5 ~ bromo-2,3-difluoropyridine (1.3 g, 0.0067 mol) was added and the mixture was stirred for 5 1/2 hours at 80 to 9O ⁰ C. The reaction mixture was poured into water, acidified to pH 1 with concentrated HCl and extracted into CH ₂ Cl ₂ . The solution was dried over Na ₂ SO ₄ and the solvent was removed by rotary evaporation to give a gum which became a true white solid on standing (0.78 g,%, m.p. 94-97 ⁰ C). .

3 , U 3 , 93 22 , 43 3 12 3 , 94 22 , 34

Analysis: % C % H % N% B r calculated: 47.21 found: 46.88

The compounds of the present invention have been found to be suitable for use in methods for the selective preemergence and post-interference control of annual and perennial grassy weeds. These compounds, the active ingredients of the present invention, have demonstrated an advantage over known compounds in the control of annual and perennial grassy weeds in that the present compounds control such weeds at much lower dose rates. In addition, the present compounds are sufficiently tolerant to most broadleaf crops to maintain the control of grassy weeds therein at a substantially commercially viable level, especially with the preferred compounds. In addition, some of the compounds have sufficient tolerance to seriferous crops such as wheat to allow selective control of grassy weeds in these crops as well.

For such purposes, unmodified active ingredients of the present invention may be employed. However, the present invention also encompasses the use of the compounds in composite form with an inert material known in the art as an agricultural adjuvant or carrier in solid or liquid form. Therefore, the active ingredient z. B. be dispersed in a finely divided solid and used as

Dust or granules. Also, the active ingredients, as liquid concentrates or solid compositions comprising one or more of the active ingredients, may be dispersed in water, typically with the aid of a wetting agent, and the resulting aqueous dispersion may be applied as a spray. In other processes, the active ingredients may be employed as part of organic, liquid compositions, oil-in-water and water-in-oil emulsions or water dispersions, with or without the addition of wetting, dispersing or emulsifying agents. Suitable adjuvants for the foregoing types are well known in the art.

The herbicidally active concentration of the active ingredient in solid or liquid compositions is generally between 0.0003 and 95% by weight or more. Concentrations of 0.05 to 50% by weight are often used. In compositions used as concentrates, the active ingredient may be present at a concentration between 5 and 98% by weight. The active ingredient composition may also contain other compatible additives, ζ. Phytotoxic agents, plant growth regulators and other biologically active compounds used in agriculture. ι

In other embodiments, the compounds of the present invention or the compositions containing them may preferably be used in combination with one or more additional pesticidal compounds. Such additional pesticidal compounds may be insecticides, nematocides, miticides, arthropodicides, herbicides, fungicides or bactericides,

which are compatible with the compounds of the present invention in the medium chosen for the application and are not antagonists to the activity of the present compounds. Accordingly. In such embodiments, the pesticidal compound is used as a supplemental toxicant for the same or for a different pesticidal application or as an adjunct. The compounds in combination may generally be present in a ratio of 1: 100 parts of the compound of the present invention with 100 to 1 part of the additional compound. ': "' '... ... · /. , , - ·. ·. , , The active ingredients of the present invention exhibited desirable herbicidal activity generally against grassy weeds such as foxtail, barnyard grass, wild oats, seedling Johnson grass and crab grass in pre-emergence pre-emergence procedures and also against the same grasses in post-operative procedures while tolerant important broadleaf crops such as cotton, soybeans, sugar beet and oilseed rape and, in the case of certain compounds, certain cereal crops such as wheat. These compounds are also uniquely effective in the selective control of perennial grass weeds such as Johnson grass. : Quack grass, Bermuda grass and Dallis grass.

In particular, the active ingredients of the present invention aimed to have desirable herbicidal activity against wild oats, foxtail, barnyard grass, crab grass, and seedling Johnson grass in post-operative methods as well as a desirable broad spectrum of activity against perennial grassy

Weeds listed above, and at lower dose rates than the prior art substituted propanoates and propanols, while exhibiting high selectivity over the broadleaf crops and in the case of certain compounds to wheat.

The present compounds, which are substituted propanols or propyl ethers, are more effective in preemergence processes than in post-emient applications.

The exact rate that must be applied depends not only on the specific active ingredient being used, but also on the specific action desired, the type of plant to be affected and the degree of its growth, as well as the part of the plant Plant that comes in contact with the toxic active ingredient. Therefore, all of the active ingredients of the present invention and the composition containing them may not be equally effective at equal concentrations or against the same plant species.

In postemergic procedures, a dose of about 0.05 to about 20 pounds / acre (0.056 to 22.4 kg / hectare) is generally used, although not all compounds are equally effective and some weeds are more difficult to control. Therefore, a dpsis rate in the range of about 0.01 to about 0. 0 pound / acre (0.01 to 1 ', 12 kg / hectare) is preferred in the post-emptive control of annual grassy weeds, while about 0.05 to about 5 pounds / acre (0.056 to 5.6 kg / hectare) a preferred dose range for the '

postemergent control of perennial grassy weeds. In applications with tolerant crops, a weed controlling, but not fodder-damaging, amount of about 0.005 to 1.0 lb / acre (0.0056 to 1.12 kg / hectare) is generally employed. , ..; -. , , / ·

In pre-emptive procedures, a dose rate of 0.01 to 10 lbs / acre (0.011 to 11.2 kg / ha), preferably 0.05 to 2.0 lbs / acre (0.056 to 2.25 kg / ha) and most preferably 0.1 to 1 lb / acre (0.11 to 1.12 kg / hectare) in general.

The following examples illustrate the effect of the compounds of this invention.

B e i s ρ i e 1 18

In representative procedures, each compound used in a series of tests was dissolved in acetone at half the final volume (twice the final concentration) applied and in each case the acetone solution was mixed with the same volume of water containing 0, 1% by weight of the nonionic surfactant).

R surfactant TWEEN 20 (a polyoxyethylene sorbitan monolaurate

The compositions, generally in the form of an emulsion, were used to spray various individual plant species grown to a height of 2 to inches (50.8 to 152.4 mm) in a nutritious soil in a greenhouse. Sufficient quantities were used to provide different rates of application, as listed in the table. The different beds were side by side

placed and exposed to substantially identical conditions of temperature and light. Each bed was kept in such a way as to prevent any interference with test compounds in other seedbeds. ' Other parts of the plants were left untreated to serve as controls. After treatment, the plants were kept under greenhouse conditions for about 2 weeks, which are conducive to good plant growth and watered as needed. The individual plant species, test compounds and doses, and percent post-negative control obtained are set forth in the table below. The control refers to the reduction of growth compared to the observed results of the same untreated species. "NT" means "not tested".

Plant species in these tests were as follows: '.' '

'· · · · · ·. General name Scientific name e

Barnyard grass Echinochloa crusgalli (water grass)

Crabgrass Digitaria sanquinalis

Yellow foxtail Setaria l \ itescens

Johnson Grass Sorghum halepense Wild Oats. Avena fatua

Cotton Gossypium hirsutum

Oilseed Brassica napus

Soybean Glycine max

Sugar beet Beta vulgaris

Wheat Triticum aestivum

Tested connection XYZ

Postemergent control of plant species

CiL

0 '- C-COZ

ι. .

Dose in ppm

OH

OCH.

plant species

Cotton rapeseed

Soybean sugar beet

barnyardgrass

crabgrass

Yellow foxtail

Johnson grass

Wild oats

wheat

cotton

rape

Soybean

sugar beet

barnyardgrass

crabgrass

Yellow foxtail

Johnson grass

Wild oats

Wheat 125 62.5 31.25 15.6 7.8

100 100 100 100 100 100

100 100 10.0 100 100 30

0 0 0 0

100 100 100 100 .100 100

0 0 0 0

100 100 100 100 100 0

Ö 0 0 0

100

100

100

100

80

90

  ο

0 0 0

100

100

100

100

20

0 0 0 0

80 90 65 100 40 40

0 0 0 0

95

100

90

100

0 0 0 0

30

80

20

50

0 0 0 0

10

100

100 0 0

Postemergent control of plant species

Tested connections

X. YZ Br F OH

_CF F OCH ₃ (R-enantiomers% optical purity)

plant species

cotton

rape

Soybean

sugar beet

Barnyard Grass 100 100

Crab grass 100 100

Yellow Foxtail 100 100

Johnson grass 100 100

Wild oat 100 100

Wheat 100 90

Cotton rapeseed

Soybean sugar beet

0 0 0 0

Barnyard Grass 100 100

Crabcfras iuu iuu

Yellow Foxtail 100 100

Johnson grass 100 100

Wild oat 100 100

Wheat. ^{90 10} °

Dose in pp m

, 25 15,6 7,8

100 100 100 100 0 20

0 0 0 0

0 0 0 0

100 100

9.5 90

100 100 55

10

100

100

70

0 0 0 0

95

100

40

70

65

- V3T-

'(Continued) Postemergent control of 125 plant species Dose in ppm 7.8 · - 3.9 ω ο co 0 5 31.25 15.6 0 0 I τι Tested connection Pflsn ^ PTiarf-fln 0 62nd 0 0 0 0 X Y Z cotton 0 0 0 Ό 0 0 , · CF- ν F 'OCH- rape 0 0 0 0 0 0 • Soybean 100 0 0 0 10 • 0 sugar beet 100 O 100 100 90 50 Barnyarägras 100 100 100 100 10. 0 crabgrass 100 100 40 50 90 .50      : Yellow foxtail 100 100 100 90. 0 0 Johnsonqras 100 100 90 20 NT   NT Wild i'af he 0 100 20 ϋ 0 0 wheat 0 100 0 '0 0 0 cotton ο 0 0 0 0 0 CF ₃ F OC ₂ H ₄ OC ₂ H ₅ rape 0 0 0 0 0 '0 Soybean 100 0 "0 0 90 70 sugar beet 100 0 100 100 100 90th Barnyard grass. 100 100 100.. 100 85 • 10 crabgrass 100 100 100 100 100 90 Yellow foxtail 100 100 100 100 40 • 0 Johnson grass 100 100 90 80 40 0 Wild oats 100 90 85 Wheat. , 100

30.81 Tested connection Y Z Postemergent control 125 the plant species .Dose in ppm 7.8 3.9 54-F X F N ^ Cl 0 31.25 15.6 0 0 ^CF 3 I H P-Fl an7Pnarten 0 62.5 0 0   O 0 cotton 0 0 0 0 0 0 rape 0 0 0 0 0 0 Soybean 100 0 0 0 20 '0 Zuckerrühe 100 0 90 70 90 40 barnyardgrass 100 100 100 100 80 10 crabgrass 100 100 100 100 95 80 Yellow foxtail 100 100 100 100 20 Ό Johnson grass 100 100 30 50 10 0 F SC ₄ H ₉ Wild oats 0 100 80 40 0 , 0 CF ₃ wheat 0 100 0 0 ' 0 0 Cotton · 0 0 0   , 0 · 0 0 rape 0 0 0 0 0 Ö Soybean 100 100 .0. , '°' 0 80 100 40 90 Sugar beet , 100 0 100 100 70oo 95 65 Barnyard grass Crabgrass 100 100 100 100 100 100 100. 0 75 NT Yellow foxtail 100 100 100 90 - 95 10 10 0 Johnsongrass Wild Oats 100 100 90 80 100

- 4-f. -

30.86 Postemergent control of Tested connection cotton 125 plant species Dose in 15.6 ppm 3.9 ι XY Z rape 0 31.25 0 7.8 0 CF-F NH, Soybean 0 62.5 0 0 0 0 sugar beet 0 0 0 0 0 0 barnyardgrass 0 o · 0 0 0 ο crabgrass 100 0 Ό 95 0 20 Yellow foxtail 100 0 100 100 95 90 Johnson grass 100 100 100 .100 100 15 Wild oats 100 100 100 100 90 90 wheat 100 100 100 80 95 0 '-'.- sugar beets 100 100 90 80 70 50 barnyardgrass NT 100 90 0 75 0 Cl F OCH ₃ • crabgrass NT 100 0 100 0 25 (R-enantiomer - Yellow foxtail NT 0 100 100 100 100 2 & 75% optical & ohnsongras NT 100 100 100 100 50 Purity) Wild oats NT 100 100 100 100 10 wheat NT 100 100 70 90 0 NT 100 80 0 70 0 100 20 0 75

Example 19

In order to clearly demonstrate the phytotoxic properties of the various active ingredients of the present invention when used preemergently, a controlled greenhouse experiment was described below. , '; · '/ ·,'. '.. .. .-

The seeds of various plant species were planted in beds of good agricultural soil in a greenhouse. A number of compositions of the present invention, generally in the form of an aqueous emulsion, were used at rates listed in the table so that a predetermined amount of the active ingredients were uniformly deposited over the surface of the bed. Another seedbed was treated with water only to serve as a control. After the treatment, the seed beds were kept under greenhouse conditions for two weeks, which are conducive to good plant growth and watered as much as necessary. The specific plant species, test compounds, and doses, and the percent accurate control are set forth in the table below. The control refers to the reduction in growth compared to the observed results of the same untreated species.

Pjra-emergent control of plant species

CH-

Tested connection XY Z '

plant species

CF,

OH

Cotton rapeseed

Soybean sugar beet

barnyardgrass

crabgrass

Gelbar foxtail

Johnson grass

Wild oats

wheat

C-COZ dose   , '., .035 .018 H .14 (Kg / ha) 0 0 0 .07 0 0 .28 0 0 0 O· 0 0 0 0 .0 0 O 0 85 10 0 100 0 60 5 0 ioo 97 30 10 100 100 100 ' 65 25 100 98 ' 85 65 10 100 99 97 20 0 100 97 80 100 40 100

30.81 tested compound CF ₃ F OCH ₃ Preamplifiers control of plant species (Kg / ha) • .035 .018 54-F X Y Z dose .07 0 0 CF 'F OCH plant species .28 .14 0 0 0 0 Ό 0 0 (B enantiomer 1 90% optical purity) cotton 0 0 0 0 Ö 95 50 Rapeseed soybean sugar beet 0 0 0 0 0 0 100 100 100 barnyardgrass 100 100 100 90 70 Crabr: as 100 100 100 100 90 Yellow foxes 100 100 100 40 • 30 Johnr- ^ nqras 100 , 100 98 90 4.0 Wild oat · 100 100 100 30 10 wheat 100 100 80 100 90 barnyardgrass 100 100 100 40 10 Crabqras .... 100 100 50 90 50 Yellow foxtail. 100 • ioo, 100 30 0 Johnsonqras 100 100 95 40 10 Wild oats loo 100 98th wheat ioo 100

At 0.28 kg / hectare, there was no injury to cotton, rapeseed, soybean or sugar beet. ,

O tested Verbinduna co XY ___2 1 CF ₃ F OC ₄ H ₉ '' I

Preemerqente control of plant species

Dose (kg / hectare)

CF ₃ F NH ₂

plant species At 0.28 , 28 .14 100 .07 .035 20 .018 '- - ... Bamyardgrass cotton NT 100 100 90 50 100 0 Crabaras Bamyardgras NT 100 100 100 100 30 40 Yellow foxtail crabgrass NT 100 100 · 100 30 60 .0 Johnsonqras Yellow foxtail NT 100 100 100 100 30 '20 Wild oats ~ Johnson grass NT 40 100 30 0 70 0 wheat Wild oats NT 100 100 60 10 wheat kg / hectare, there were none Damage of , Rans, Soybean or Sugar beet. 100 .70 0 100 100 30 100 100 0 100 80 10 100 100 0 100 97 0

At 0.25 lb / acre, there was no injury to cotton, oilseed rape, soybean or sugarbeet.

Pre-eminent control of plant species

Tested compound XY 2

plant species

Dose (kg / hectare)

CF.

Cl

CF,

SC ₄ H ₉

CF,

CN *

* replaces COZ

Bamyardgras

crabgrass

Yellow foxtail

Johnson grass

Wild oats

wheat

100 100 100 100 100 100

.14

100 100 100 - 100 100 50

.07

.035

At 0.28 kg / ha there was no damage from rape, soybean or sugar beet

Bamyard grass - 100 100

Crabqras 100 100

Yellow Foxtail 100 100

Johnsonqras 100 100

Wild oat 100 100

Wheat__ 100 100

At 0.28 kg / ha there was no damage from. "Rape, soybean or sugar beet.

Bamyardgras

Craboras

Yellow foxtail

Johnsonqras. - ^; _

Wild oats

Wheat - -

At 0.2.8 kg / ha, there were none. Damage to rapeseed, soybean or sugar beet.

100 100 100 100 100 100 100 100 NT 100 100 30

70 20 0 0 0 7 100 100 40 100 100 3.0 100 95: 30 30 30 100 30 '0 80 20 60 20 0 70 30 0. NT 70 10 from cotton I cotton 30 100 30 50 30 100 100 2Ό 100; 90 0 90 60 0 100 20 100 0 from cotton 80 100 90 95 100 40 from

30.8 Pre-eminent control of plant species tested compound barnyardgrass .28 Dose (kq / hectare) .07 100 100 100 80 .035 70 ·. 64-F χ YZ plant species Grabqras .14. 100 100 100 100 100 .018 'CF ₃ F OC ₂ H ₄ OC ₂ H ₅ - Yellow foxtail 100 100 100 100 100 90 20 100 Johnsonqras 100 100 100 90. 80 80 90 50 20 0 Wild oats 100 100 90 100 40 100 98 20 10 10 wheat 100 100 80 100 100 10 0 20 50 0 At 0.28 kg / ha 100 90 70 Damage of 30 cotton 0 - ..-; Rapeseed, · soybean 100 100 100 or sugar beet. 50 0 CF ₃ F CH ₂ OH * Barnyard grass There were none 100 Damage of 100 cotton 30 20th * replaces the rest of Crabgrass or sugar beet. 100 * 98 -COZ Yellow Foxtail 100 · 100 30 Johnson grass. 100 l 100 40 40 · · · Wild Oats 100 100 40 100 wheat 100 20 0 50 At 0.28 kg / ha 100 0 Raos, soybean 100 0 Cl F OCH ₃ Barnyard grass There were none 40 crabgrass Yellow foxtail Johnson grass 10 Wild oats 30 wheat 10 20 10 0

At 0.28 kg / ha there was no injury to cotton, oilseed rape, soybean or sugar beet.

Pre-emptive control of plant species

OO Tested connection • Appoint Pf 1 .28 Dose (kg / hectare) .07 .035 .018 64 XYZ , Earnyardgras 100 .14 100 40 10 Br F OH crabgrass 100 100 100 40 0 Yellow foxtail 70 100 40 10 0 Johnson grass 100 90 98 60 10 Wild oats 100 100. 10 0 NT wheat 100 30 20 0 NT 70

At 0.28 kg / ha, there was no damage to cotton, rapeseed, soybean or sugarbeet.

Other compounds within the scope of the present invention, e.g. The various metal salts, amine salts and other derivatives of the compounds described above can also be used to control certain plant species that produce results that correspond to the results described above.

Claims (3)

invention claim , Herbicidal composition, characterized in that it comprises an inert carrier in admixture with a herbicidally effective amount of a compound or its separate optically active isomers of the formula: , ·. F. ' · · O - Z wherein X is QF ₃ , CHF ₂ , CClF ₂ or Br means j TO or S; and Z is an organic moiety containing N, O or S atoms or a metallic or ammonium or organic amine cation and is hydrolyzed and / or oxidized or may be present in plants or in the soil to a carboxylate in undissociated and / or dissociated form present * 2 »Composition according to item 1 _#, characterized in that'z · - - '. '. '. , ; ; ' wherein Y is a saturated or unsaturated alkyl group having an even number of carbon atoms, preferably 2 to 18 carbon atoms, η is O or is R is H or a C ₁ to C 1-4 alkyl group and R ^{2 is} 63 257 18 a carboric acid group or its alkali metal * alkaline earth metal ammonium or amine salts or one of its lower alkyl esters is 3 »Composition according to item 2», characterized in that η is 0. Composition according to item 3, characterized in that it contains a herbicidally effective amount of methyl 2- (4- (3-fluoro-5- (trifluoromethyl) * 2-pyridyloxy) -phenoxy) -propanoate. Composition according to item 3, characterized in that it contains a herbicidally effective amount of 2- (4- (3-fluoro-5-chloro-2-pyridinyloxy) -phenoxy) -propanoic acid methyl ester. Composition according to item 3, characterized in that it contains a herbicidally effective amount of 2- (4- (3-fluoro-5-bromo-2-pyridinyloxy) -phenoxy) -propanoic acid methyl ester. A method of controlling undesired plant growth characterized by using, at the site of said plants, a composition comprising an inert carrier in admixture with a herbicidally effective amount of a compound or its resolved optically active isomers of the formula o-z 63 257 18 , ''^; . ", '-52 -.; · ..,.'. '^;_:;' wherein X is CF ₃ , CHF ₃ , CClF ₂ or Br;
TO or S means; and Z is an organic fraction
containing N, O or S atoms or a metallic
Ammonium or organic amine cation and is hydrolyzed and / or oxidized, may be barren in plants or in the soil to a carboxylate present in undissociated and / or dissociated form. 8 · Method according to item 7, characterized in that Z - C- (Y) _n R ² wherein Y is a saturated or unsaturated alkyl group having an even number of carbon atoms, preferably 2 to 18 carbon atoms, η 0 or 1 · 2 Is ₁ , R is H or a C ₁ to C ₁ alkyl group and R. a carboxylic acid group whose alkali, alkaline earth or ammonium or amine salts or their lower alkyl esters. ·, '. '; , '' ν. ν. , 9 _t Method according to item 8, characterized in that the compound is used »in which η is Ö. 10 # Process according to item 9, characterized in that as compound 2- (4- (3-fluoro-5- (trifluoromethyl) -2-pyridyloxy) phenoxy) propanoic acid or one of its salts or
Ester is used » 63 257 18 - ';; .., ^: . "-. ν V - .53 -' · .. 11. The method according to item 9, characterized in that the compound 2- (4- (3-fluoro-5-chloro-2-pyridinyloxy) -phenoxyj-propanoic acid or its salt or ester is applied * Method according to item 9, characterized in that the compound 2- (4- (3-fluoro-5-bromo-2-pyridinyloxy) -phenoxy) -propanoic acid or its salt or its ester is applied. '. , ; : '. , , \ '.. · .-. , ... ... 13 · Method according to item 7, characterized in that the compound is applied postemergence for grass weeds « 14 _e Method according to item 13 *, characterized in that the compound is applied at a dose rate in the range from 0 to 20 pounds per acre (0.01 to 22.4 kg / ha). '. .... .,: .. · .-. :: '·' 15 »Method according to item 14, characterized in that the compound is used for perennial grassy weeds. 16 · method according to item 7, characterized in that the connection is applied preemergent · 17, method according to item 16, characterized in that the compound is incorporated into the soil in front of the plant, before planting a broadleaf crop, in an effective amount but less than 63 257 18   , , , t a phytotoxic amount in relation to the broadleaf crop to control grassy weeds in the broadleaf crops » 18. The method according to item 17, characterized in that the compound is postemergent applied to control unwanted grassy vegetation in the presence of wheat.