CA1182459A - Pyridine intermediates for the preparation of pyridyl(oxy/thio)phenoxy compounds - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Certain novel pyridinyloxyphenoxy alkanoic acids, pyridinylthiophenoxy alkanoic acids, derivatives thereof and related compounds exhibit surprising preemergent and postemergent activity in the control of grassy weeds. They are prepared from novel pyridine intermediates having the general formula:- wherein W' is F, Br or

Description

5~
~693-3301D
This invention relates to certain novel pyridine compounds useful in the preparation of pyridyl(oxy/thio)phenoxy compounds.
This application is divided from applicant's copending application Serial No. 430,592 filed June 17, 1983 and relating (a) to navel pyridyl(oxy/thio)phenoxy compounds, (b) to herbicidal compositions of such novel compounds and (c) to methodsof using such compounds for the preemergent and postemergent control of grassy weeds in non-crop areas as well as in the presence of certain valuable crops such as soybeans, cotton and wheat.
Belgian Patent No. 834,495, issued February 2, 1976 as well as the published German patent application equivalent -thereto, viz., No.2,546,251, published April 29, 1976, describe

2-((4-pyridinyl-2-oxy)phenoxy)-alkanoic acids, salts and esters having halo substitution in the 3- and/or 5-ring positions in the pyridine ring. Later references, e.g. published Brltish Patent application 2,026,865 disclose such compounds having trifluoro-methyl substitution on thepyridine ring and European Patent Applica-tion 0002800 describes the enhanced effect of the D-steroisomers of such compounds.
The pyridyl(oxy/thio)phenoxy compounds of aforementioned application Serial No. 430,592 have herbicidal activity and corres-pond to the ~ormula -~ T~ O-Z

., g wherein X is CF3, CHF2 or CClF2; T is 0 or S; and z is an organic moiety containing N, O or S atoms or a metallic, ammonium or organic amine cation and is or can be hydrolyzed and/or oxidized in plants or soil to a carboxyl moiety that is in undissociated and/or dissociated form. The invention is also directed to the novel stereoisomers of such compounds, the R-isomers having exceptional activity.
The aforementioned application Serial No. 430,592 is also directed to a process for making a compound having the formula: F

X--~T {~ O- Z

wherein X is CF3, CHF2 or CClF2; T is 0 or S; and Z is an organic moiety containing N, 0 or S atoms or metallic or ammonium ions which comprises (A) reacting a compound having the formula ~ ~ F
X~O~W' wherein W' is F, Cl or Br and X is as above defined with a compound having the formula MT ~ o-z wherein M is hydrogen or a metallic cation, and T and Z are as above defined, in the presence of a base or (B) reacting a compound having the formula `3 X ~ O ~ - - T- - ~ OM

wherein 1~ is H or a metallic cation and T and X are as above defined with a compound having the formula WIZ wherein W' is Cl or Br and Z is as above defined, :Ln the presence o~ a base.
In accordance with the present invention, there is now provided a compound having the general formula:

F

lQ ~
X~O,,~W' wherein W' is F, Br or -O ~ OH, and X is CF3, Cl or Br and its alkali metal salts, except that when W' is F, ~ is not CF3.
The novel pyridine compounds of the present invention are listed specifically as follows: 2-bromo-3-fluoro-5-(tri-fluoromethyl)pyridine, 5-chloro-2,3-difluoropyridine or 5-bromo-2,3-difluoro-pyridine, 4-((3-fluoro-5-(trifluoromethyl)-2-pyri-dinyl)oxy)phenol and its alkali metal salts, 4-(5-chloro-3-fluoro-2-pyridinyloxy)phenol and its alkali metal salts~
The present invention, together with that of applicant's aforementioned application Serial No. 430,592, will now be described in more detail.
A variety of herbicidal compounds containing substituted pyridyl and phenoxy moieties joined via a bivalent -O- and -S-are described in the art. For example, United States Patent Nos.
4,046,553; 4,317,913, 4,267,336; 4,213,774; 4,324,627 and 4,309,547 - 2a -and European Patent 483 all describe such compounds, methods ofmaking them, compositions containi:ng them and methods of u-tilizing said compositions. In general, thle moieties bonded -to the pendant -O- group of the phenoxy in the herbicidal com~ounds described in these references will also be suitable as the monovalent organic radical represented by Z in the formula for the aforementioned novel compounds and, given the appropriate pyridine starting material, the compounds of this invention can be prepared by methods described in the above-mentioned prior art, and can be utilized in compositions as described in said prior art.

- 2b -~ I

-3~

Z moieties include, but are not limited to Rl -C- (Y )nR2 H

wherein Y is a saturated or unsaturated alkyl group containing an even number of carbon atoms, preferably from 2 to 18 carbon atoms, n is 0 or 1, R1 is H or a Cl-C3 alkyl group and R2 is a group corresponding to one of the following formulae:

-CN, N~
//

NH~
/ N
~N~

-C-X, wherein X is halogen, or CN, o -C O M , wherein M is a me-tallic cation, ammonium or an organic amine cation typically, but not exclusively, containing alkyl (saturated or unsaturated), alicyclic, heterocyclic or aromatic groups, all unsub-stituted or substi-tuted with various other groups not limited to, but including, halo, cyano, ni-tro and unsubstituted or substituted -thiol, hydxoxy, amino or : 30,864-F -3~

-4- ~ 5~

carboxyl groups and, additionally, alicyclic, hetero-cyclic and aromatic groups substituted with unsubsti-tuted or substituted satural_ed or unsaturated alkyl groups, for example, trifluoromethyl, chloromethyl, cyanomethyl and vinyl, -CH20R3, C-R3, ~CH20-C-R

- C -oR3, --C - S~

-C-N
\ R3 " /

O/S .R5 C-N
~02R6 '' /
-C-N \
CN

30,864-F 4-_5_ O~S /R3 -CH20-C-N ~
CN
W

- C=N- R3, R4\ /R3 -C=N-R3, O ~I~alkyl -C-NOR

Il , / .
-C - N --- N\

15-C--N - - N\
CN

~C--N--N
\ S02R6 " ' " 3 -C--N--C R, o~6 C~OR6 oR6 30, 864-F -5--6- `~

-C(SR6)3 -C(OR6)2 H
-C(SR6)2 (R~
.
-C-H

fR~
~) ~
-C-~

~R~
~S O

o/ N(R )2 -C N-C

~R7~N(R )2 : 25 X N-R3 where X is S or 0, -CH~

where W is halogen; R3 is H or R6; R4 is H, alkoxy or R6; R5 is H, a metallic cation or R~; and R6 is an alkyl (saturated or unsaturated), alicyclic, heterocycl.ic or aromatic group, unsubstituted or substituted with various other groups not limited to, but including, halo, cyano, nitro and unsubstituted or substituted thiol, hydroxy, 30,864-F -6-amino or carbo~yl groups and, additionally, alicyclic, heterocyclic and aromatic groups substituted with unsubstituted or substituted saturated or unsaturated alkyl groups, for example, trifluoromethyl, chloro-methyl, cyanomethyl and vinvl, O/S
" f--~ 7 -C-N R , ~ .
O/S
" ~ 7 -CH2-O-C-N R , (R) N
-C=N-R3, ~ 7 A R
-C = N where A is O, S or N, or ,, , '~~` 7 -C - N - N R , where R7 completes an unsubstituted or substituted saturated heterocyclic ring system.

The above derivatives can be made by processes generally known -to those skilled in the art and as des cribed in the-above-mentioned patents. For example, the corresponding acid chlorides can be reacted with a Grignard reager.t to make the desired aldehyde or ketone derivative. Similarly, reaction of an acid chloride with KSH will provide the desired thiol acid. Thio-amides may be prepared from the corresponding amide by reaction with P2S5 or, if hydrogen is presen-t on the nitroyen atom, the carbonyl may be converted to, e.g., 30,864-F -7-chloride, with removal of HCl, followed by reaction with hydrogen sulfide. Carbamoyl chlorides are avail-able in the art or they may be prepared from-the desired amine and phosgene or thiophosgene for use in making compounds containing the -C - N \ group.

- The reaction of an amine with a sulfonyl chloride, e.g., R5NH~ + R6S02Cl provides the group HN

for use in reacting with an appropriate acid chloride.

The reaction of an amine with BrCN provides, e.g., R3 NH
NC

which reacts with the appropriate acid chloride to provide compounds con~aining the O ~3 C - N
CN

moiety. P~S5 is employed to make the corresponding S-containing compound.

30,864-F -8-g ~ 3 Reaction of the above cyanoamine with phosgene or thiophosgene provides R O~S
N - C - Cl CN

for use in making the correspondin~ derivatives.

The reaction of the compounds having the moiety o Il 3 -C-~HR

with PCl5 will provide compounds havlng the moiety Cl ' 3 -C=NR

The reaction of the corresponding acid chloride with RONH2 will provide compounds having the group O H

ll l -C - N - OR

Various hydrazine derivatives can be made, e.g.~ from trimethyl hydrazine by reaction with the acid chlorides. The reaction of the amides, e.g., ~ C-NHR3 with dicarboxylic anhydrides will provide compounds having the group 30,864-F -9-.

o o 1, " 3 -C-N-C-R

R is preferably a carboxylic acid group, an alkali or alkaline earth metal salt thereof, an ammonium or organic amine salt thereof or a lower alkyl ester thereof, wherein "lower alkyl" includes straight, brancned or cyclic saturated or unsaturated alkyl groups containing no more than 6 carbon atoms. Preferably, n is 0.

In the above formulae 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 hetero-cyclic ring systems, may be employed if desired.

In the formula for the aforementioned novel compounds, T is preferably O and X is preferably CF3, Cl or Br. Most preferred are the compounds in which X
is CF3 or Cl, T is O, and Z is CH3 o - CH - C - O - R"

wherein R" is methyl, ethyl, propyl, isopropyl, iso-butyl or n-butyl.

The compounds of the above formula, herein-after referred to for convenience as "active ingredients", have been found to be especially active as herbicides ~or the control of und~sired vegetation, for example, 30,864-F -10 grassy or graminaceous weeds and are unexpectedly more r effective than the compounds of the known art.
Especially surprising is the finding that the unexpected activity of the presently claimed compounds

5 is specifically related to fluorine substituted in the 3-position of the pyridine ring; fluorine sub-stitution in other positions on the pyridine ring, e.g., the 5-position, does not cause unusually beneficial acti~ity to result. With the compounds of this 10 invention, it is possible to employ lower dosage rates and still obt~in effective control, thus reducing plant residues and any potential environmental contamination and/or toxicological effect on fish and warm blooded animals. Accordingly, the present invention also 15 encompasses herbicidal compositions containing one or more of these active ingredients as well as preemergent and postemergent methods of controlling undesired plant growth, especially in the presence of valuable crops.
Such methods comprise applying a herbicidally-effective 20 amount of one or more of said active ingredients to the locus of the undesired plants, that is, the seeds, foliage, rhizomes, stems and roots or other parts of the growing plants or soil in which the plants are growing or may be found.

The term "herbicide" is used herein to mean an active ingredient which controls or adversely modifies the g~owth of plants because of phytotoxic or other effects substantial enough to seriously retard the growth of -the plant or further to damage the plant sufficiently to kill the plant.

By "growth controlling" or "herbicidally--effective" amount is meant an amount of active ingre-dient which causes a modifying effect and includes 30,864-F -11-12~

deviations from natural development, killing, regu-lation, desiccation, retardation, and the like.

The term "plants" is meant to include germinant seeds, emerging seedlings, rhizomes, stolons and other underground propagules, and established vegetation.

The active ingredients, i.e., new compounds, of the present invention are readily prepared by processes described in the above cited prior art by choosing the appropriate starting materials. The stereoisomers are readily ~eparated as described in European 0002800 referred to above.

Certain of the pyridine reactants employed to make the novel pyridinyloxyphenoxy compounds of this invention are themselves novel compounds and such reactants may be made as generally described hereafter and as specifically set forth in the following examples or by methods analagous .hereto, starting with known compounds.

We have unexpectedly found that the fluorine atom in 3-chloro-2-fluoro-5-(trifluoromethyl)pyridine can be readily replaced with a 2-cyano group by reacting said pyridine compound wlth an alkali metal cyanide, preferably potassium cyanide, in a polar aprotic solvent, preferably dimethylsulfoxide, at a temperature of 10-50C., preferably 20-30C. We have further found that the chlorine atom in the resulting product, ie., 3-chloro-2-cyano 5-~trifluoromethyl)pyridine is readily selectively replaced with fluorine by reaction with, e.g., cesium or potassium fluoride in a polar aprotic solvent, preferably dimethyl sulfoxide, at a temperature of 80-140C., preferably 90-100C. The cyano group in 30,~64-F -12-., -13~

the resulting 2 cyano-3-fluoro-5-(trifluoromethyl)pyridine can be readily converted, by known procedures, to the corresponding acid or amide, as desired. The resulting acid may be readily converted to the corresponding bromine derivative by the Hunsdiecker reaction, as shown in the following Example 4, or the amide may be converted to the corresponding amine and then hydroxy compound by the Hoffmann hypobromite reaction followed by diazotization and replacement by hydroxide as known in the art. The latter is then treated with POC13 plus PC15, as known in the art, to prepare, for example, 2-chloro-3-fluoro-5-(tri1uoromethyl)pyridine.

Alternatively, ~,3-difluoro-5-(trifluoro-methyl)pyridine may be prepared by contacting 2,3-dichloro-5-(trifluoromethyl~pyridine or 3-chloro-- -2-fluoro-5-(trifluoromethyl)pyridine with a fluorinating agent and the 2,3-difluoro-5-(tri-fluoromethyl)pyridine may be used directly to make 2-~4-((3-fluoro-5-(trifluoromethyl)-2-pyridinyl)oxy)-phenoxy)alkanoic acids and derivatives.

The following examples further illustrate thepresent invention.

Example 1 - PREPARATION OF 3-CHLOR0~2-CYAMO-5-(TRI-FLUOROMETHYL)PYRIDINE

F3C ~Cl 'l N CN

30,864-F 13-/
3-Chloro-2-fluoro-5-(trifluoromethyl)pyridine (obtained as a by-product from the fluorine exchange reaction when converting 2,3-dichloro-5-trichloromethyl pyridine to 2,3-dichloro-5-(trifluoromethyl)pyridine) (40.0 g, 0.2 mole) was put into 270 ml of dimethyl sulfoxide and stirred while potassium cyanide ~14.4 g, 0.221 mole) was spooned in over a 20-minute period.
The mixture was then stirred for another 20 minutes.
The temperature was held between 23 and 28C -throughout 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 activa-ted charcoal and distilled on a Vigreaux-Claisen still at 198-110C at 30 mm Hg to yield 31.45 g of colorless oil with an analysis of, in percent 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 (TRI-FLUOROMETHYL)PYRIDINE
3 ~ F
'l N CN

A flask fitted with an air s-tirrer and a takeoff head was set up. Cesium fluoride ~45.6 g, 0.3 mole), potassium carbonate (1.2 g) and 350 ml of dimethyl sulfoxide were put into the flask and heated and stirred under vacuum (30 mm). 120 Ml of dimethyl sulfoxide was distilled off to dry the system. The reaction mix-ture was cooled to 80C, the vacuum was released and 3-chloro-2~cyano-5-~trifluoromethyl)pyridine 30,864 F 14--15~ 5~

(41.6 g - 0.201 mole) was aclded over a 7-minute period.
The reaction mixture was then warmed to 93C and held at 93-111C for about 20 minutes. The mixture was then cooled to 54C, 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 90-94C to yield 29.6 g of colorless oil which had an a:nalysis of, in percent by weight:

Calculated: C=44.22; H=].06; N=14.74.
Found: C=43.53; H=1.11; N=14.44.

Example 3 - PREPARATION QF 3-FLUORO-5-(TRIFLUORO-METHYL)PICOLINIC ACID

F3C ~ F

COOH

2-Cyano-3-1uoro-5-(trifluoromethyl)-pyridine (11.1 g, 0.0584 mole) was put into 87 ml of 90% sulfuric acid in a beaker. The mixture was stirred and heated ~t 100-112C for 1-1/4 hours. The reaction mixture was then cooled, poured over ice and the solids that came down were filtered off. The solids were dissolved in a dilute solu-tion of NaOH. Any material that didn't go into solution was filtered out and the filtrate was acidified with aqueous HCl and the precipitate was filtered off and dried. This yielded 6.47 g of solid product with an analysis of, in percent by weight:

Calculated. C=40.20; H=1.45i N-6.70.
Found: C=39.29; H=1.35; N=6.98.

30,864-F -15-1.05 g of a second crop of solids was obtained on standing which exhibited the same IR spectrum as the first solids out. These were combined and used to make the following bromo compouncl.

Example 4 - PRE~ARATION OF 2-BROMO-3-FLUORO-S-(TRI-FLUOROMETHYL)PYRIDINE

F3C ~ F
~O l N Br The 3-fluoro-5-(trifluoromethyl~-picolinic acid ~7.35 g, 0.035 mole) starting material was put into 150 ml of dry carbon tetrachloride and then red mercuric oxide ~9.1 g, 0.042 mole) was added and the mixture was stirred and refluxed 1 hour and 25 minutes.
A solution of bromine (6.7 g, 0.042 mole) in 20 ml of dry carbon tetrachloride was added slowly with the mixture at reflux over the next 2-1/3 hours. Light from a W lamp was directed on the reaction mixture during the addition and the reaction mixture was refluxed for another hour. 25 Ml more of dry carbon tetrachloride was added and the refluxing was continued for about 16 hours more while UV radiation was applied. The reaction was then filtered throu~h CELITE diatomaceous earth to remove the mercury salt. The carbon tetrachloride was removed on a still and the product was distilled over to yield 2.45 g of yellow oil with an analysis of, in per-cent by weight:

Calculated: C=29.53; H=0.83; ~-5O74.
Found: C=29.36; H=0.77; N-5.82.

30,864-F -16-~ -17~ 5~

The gas chromatograph shQwed the oil to be a r 99~% pure compound.

Example 5 - PREPARA~ION OF ~'-(4-((3-FLUORO-5-(TRIFLUORO-METHYL)-2-PYRID]:NYL)OXY)PHENOXY)PROPANOIC ACID

F3C ~ F oCCHCo2H

2-~4~Hydroxyphenoxy) propanoic acid (1.80 g, 0.00988 mole) was dissolved in 15 ml of dimethyl sulfoxide. A solution of sodium hydroxide (0.8 g, 0.02 mole in 1 ml of water) was added and the reaction mixture was heated under nitrogen to 48C over a 27 minu~e period. 2-Bromo-3-fluoro-5-(trifluoromethyl)-pyridine (2.40 g, 0.00984 mole) dissolved in 5 ml of dimethyl sulfoxide was added and the reaction mixture was heated at 75-78C for 40 minutes. The mixture was poured into 150 ml o cold water and acidified with aqueous HCl. A gum came down. Upon work-up and puri-fication, a fraction (0.45 g) was obtained which had an elemental analysis of, in percent by weight:

Calculated: C-52.18; ~=3.21; N=4.06.
Found- C=51.89; H=3.19; N-4.02.

This material had a melting point of 130-132C.

~ PREPARATION OF 2-(4-((3-FLUORO-5-TRI-- ~5 FLUOROMETHYL) -2-PYRIDINYL)OXY)PHENOXY)-PROPIONAMIDE

A~ A fresh sample of 2-(4-(~3-fluoro-5-(trifluoro-methyl)-2-pyridinyl)oxy)phenoxy propanoic acid was 30,864-F -17--18~

prepared by the reaction of 2,3-difluoro-5-(trlfluoro-methyl~pyridine with 2-(4-hydroxyphenoxy)propanoic acid in the presence of 2 moles of sodium hydroxide as above described and 9.0 g (0.026 mole) was refluxed in excess SOC12 for about 1/2 hour to prepare the corresponding acid chloride. The excess SOC12 was removed by heating to 115C under an aspirator vacuum. The resulting acid rhloride was added to a mixture of concentrated ammonium hydroxide (30 ml) lQ and methanol ~60 ml). The flask was rinsed with an additional 15 ml ammonium hydroxide mixed with about - 25-ml of methanol and the two fractions were combined.
The acid amide formed as a solid which was filtered out, rinsed with water, slurried in water, filtered, dried and analyzed. M.P. 140-141C.

Analysis: %C %H ~oN
Calculated: 52.33 3.51 8.14 Found: 52.54 3.46 8.09 B. Other propionamides of the invention, as set forth below, were prepared using similar procedures:

CF3 ~ ~ CH3 ,O, A M. P. C Analysis ~,OC ~ %Cl -N ~ Cl 142-143.5 Calc... 55.45 3.32 6.16 7.80 Found: 55.88 3.34 6.11 7.70 30,864-F -18~

-19~ 5~

Example 7 - PREPARATION OF 2-(4-((3-FLUORO-5-(TRI-- FLUOROMETHYL)-2-PYRIDINYL)OXY)PHENOXY)-PRQPIONITRILE

-A portion of the amide prepared in Example 6A
(5.68 g, 0.0165 mole) was refluxed with an èxcess of POCl3 for about 2 hours after which the excess POCl3 was removed by dlstillation under an aspirator 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 gummy material formed which was again placed on the evaporator leaving an oil which was recovered and analyzed .

Analysis: %C %H /~
Calculated: 55.22 3.09 8.59 Found: 55.64 3.00 8.81 Refractive Index = 1.5067 at 25C.

Example 8 - PREPA~ATION OF 2-~4-((3-FLUORO-5-(TRI-FLUOROMETHYL)-2-PYRIDINYL)OXY)PHENOXY)-METHYL PROPANOATE

Following the procedure of Example 6A the acid chloride was prepared by refluxing a portion of the acid from Example 6A with thionyl chloride. The resulting acid chloride (3.45 g, 0.01 mole) was then reacted with methanol (l.0 g, 0.0312 mole) in the presence of triethylamine (2.0 g, 0.02 mole) in 20 ml of toluene at 80 88C. The salt was removed by filtration, then rinsed with hexane, the filtrate combined and solvent removed by evaporation. The crude product was taken up in hexane, some solids 30,864-F -19~

-20~ 5~

removed by filtration and the solution decolorized with charcoal after which solvents were removed under vacuum. The product gradually solidified and was recovered and analy2ed. M.P. 50-52C.

Analysis: %C %H %N
Calculated: 53.49 3.63 3.90 Found: 53.82 3.68 3.87 Following the above procedure except to . employ other alcohols or thioalcohols as the esterifying agent the following compounds were prepared having the general formula:

F

~ ~ ,CH3 ,O, 30,864-F -20-U~ I 0 ~ ~ Lr) O U~
.~ I" ~
~1 ta a~ ~1 ~ ~ ~D CS~
O ~ L') ~ ~ ~) ~'1 Q ~Z;
O ;~
r~ r~
m~ t~ L" ~ L') Lr) ~ d' ~
0 c~ ~ r~ ~ OD
~ V .. .. ..
aJ ~ ~D
P I~) Lr) L~') L') Ll-) Ll') .. .. .. .. .. ..
. ~ . ~ ' ~
(d O ~ O ~ O
V ~4 C,3 kl C) ~4 L') lR ~ ~
~ ~ ~ O
.,1 ~ ~ ~
~ ~ L') ~ . .
a~ ~ ,~
O 11 11 ~
~LI . . ~1 r--lH ~ I C)h . ,,1 . O O O
Q, OP:~ Il-) ~; Lrl ~.) ~I) t~
X
~@1 .,1 .
. O O
-~
~ r~
C~ ~

~ h O
N t~
~ c~
o o u~ -30, 864-F -21--2~ S ~

Example 9 - PREPARATION OF 2-(4-((3-FLUORO-5-(TRI-FLUOROMETHYL)-2-PYRIDINYL)OXY)PHENOXY-The methyl ester of Example 8 ~5.7 g, 0.0159 mole) was dissolved in methanol (75 ml) and a solution of sodium borohydride (3.5 g, 0.0954 mole) was added dropwise to the cooled ~19C) solution, maintaining the temperature at about 25C. The mixture was stirred for about 1~ hours after which the temperature was down to 18C. On standing 30 minutes, the temperature increased to 23.5C after which the reaction mixture was warmed to 42C ~30 minutes), continued stirring without heat for 30 minutes, poured into a beaker and added ice water (200 ml). Extracted with hexane and then twice -with methylene chloride. Combined extracts, removed solvents and ob-tained 4.94 g of the above indicated product as a light yellow oil. R.I. = 1.5144 @ 25C.

Analysis: ~C y~ %N
Calculated: 54.38 3.96 4.23 Found: 54.25 3.98 4.44 Example 10 - PREPARATION OF THE R-ENANTIOMER OF
2-(4-((3-FLUORO-5-(TRIFLUOROMETHYL)-2--PYRIDINYL)OXY)PHENOXY)PROP I ON I C AC I D-, METHYL ESTER

A mixture of 2.11 g (7.72 mmol) of 4-(3-fluoro-S [trifluoromethyl)~-2-pyridyloxyphenol ~prepared as in Example 12) 1.07 g (7.72 mmol) of anhydrous K2CO3 and 14.1 g (77.2 mmol) of the methane sulfonate of the methyl ester of L-(+)-lactic acid in 16 ml of dry dlmethylsul-foxide (DMSO) was stirred at room temperature for 43 hours. The reaction mix-ture was paxtitioned between 30,864-F -22-S~

diethylether and water. The organic phase was separated, dried (Na2SO4) and evaporated at reduced pressure to give a colorless liquid. Pu:rification by high pressure liquid chromatography on silica gel eluting S with ethyl acetate-hexane (3:22, v/v) gave 2.15 g ~78%) of the R-enantiomer of the desired product as a colorless oil: [N ] 25 ~ 31.4 (CHC13, C 0.0110 g/ml)i IR (CC14) 1766 and 1741 cm 1; lH NMR (CDC13) ~ 8.0-8.2 (lH, m), 7.5-7.8 (lH, m), 6.7-7.2 (4H, m), 4.71 (lH, q), 3.73 ~3H, s) and 1.59 (3~, d); 19F NMR
(CDC13, ppm upfield from C6F6) 102.1 (s) and 26.3 (d) Anal. Calculated for C16H13F4NO4: C, 53.49; H, 3.65;
N, 3.90. Found: C, 53.61; ~, 3.53; N, 3.86. The optical purity of the ~ample was determined to be 15 > 90% ee by lH NMR analysis in the presence of Eu(tfc)3.

Example 11 - PREPARATION OF TEE R-ENANTIOMER OF
2-(4-((3-FLUORO-5-CHLORO-2 PYRIDINYL)-OXY)PHENOXY)PROPIONIC ACID-, MET~YL ESTER

A mixture of 1.80 g (7.50 mmol) of 4-(3--fluoro-5-chloro~-2-pyridyloxyphenol, 1.04 g (7.50 mmol3 of anhydrous K2CO3 and 13.7 g (75.0 mmol) of the methane sulfonate of the methyl ester of L-(~)-lactic acid in 16 ml of dry DMSO was stirred at room temperature for 4~ hours. The reaction mixture was partitioned between diethylether and water. The organic phase was separated, dried (Na2SO4) 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: [a]25 + 34,4o (CHC13, 0.0112 g/ml);
IR (CC14~ 1762 and 1740 cm 1; lH NMR (CDC13) ~ 7.82 30, 864-F -23-(lH, d), 7.43 (lH, d of d), 6.7-7.3 (4H, m), 4.69 (lH, q), 3.72 (3H, s) and 1.58 (3H, d); 19F NMR (CDC13, ppm upfield from C6F6) 27.2 (d). Analysis: Calculated for C15H13ClFNO4: 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 to be > 76% ee by 1H NMR analysis in the presence of Eu(tfc)3.

Example 12 - PREPARATION OF 4-((3-FLUORO-5-(TRI-FLUOROMETHYL)-2-PYRIDINYL)OXY)PHENOL

19 Xydroquinone (4.4 g, 0.04 mole) was dissolved in 65 ml of dimethylsulfoxide and powdered sodium hydroxide (1.4 g, 0.035 mole) was added in one portion and the mixture stirred under nitrogen atmos-phere fox 10 minutes to convert to the sodium salt.
2,3-Difluoro-5-(trifluoromethyl)pyridine (6.0 g, 0.033 mole) was then added and the mixture stirred at 50C for 1.5 hours then warmed to 60C for a moment, let cool for 15 minutes and then poured into 500 ml of cold water. Additional sodium hydroxide (~3 g in water) was added to convert the desired product to 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 hydro-chloric acid. The solid which separated was collected on a filter, washed, dried on a vacuum furmel and taken up in hot hexane. After treating with decolorizing carbon, filtering, concentrating and cooling the white crystal-line product separated. Yield: 2.6 g. M.P. 97.5-98.5.

Analysis: ~OC ~H ~
Calculated: 52.76 2.58 S.12 Founcl: 52.71 2.57 5.12 30,864-F -24-Example 13 - PREPARATION OF 5-CHLORO-2,3-DIFLUORO-r PYRIDINE

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 distilling head. About 50 ml DMSO were 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 at 130-140C for 7 hours, with vigorous stirring. The product was distilled directly out of the reaction mixture, under vacuum. The DMSO was watèred out and the product was xedistilled to give a clear, colorless li~uid (11.9 g, 29% of theoretical, b.p. 70-73C @ 85 mmHg).

Analysis: %C ~ Cl Calculated: 40.16 1.35 9.37 23.71 Found: 39.54 1.36 9.44 23.92 Exam~le 14 - PREPARATION OF 5-BROMO-2,3-DIFLUORO-PYRIDINE
Cesium fluoride (28.8 g, 0.19 mol), potas-sium carbonate (1.0 g, 0.007 mol) and sulfolane (190 ml) were placed in a fluorination flask equipped with a mechanical stirrer, a thermometer, and a distilling head. About 20 ml sulfolane were distilled off, under vacuum, to dry the system. 2,3,5-Tri-bromopyridine (20 g, 0.063 mol) was added and the mixture was heated at 180C for 2l-2 days. The product was dis-tilled directly out of the reaction mixture to 30,864-F -25--26~ f~ 5~

yield a clear, colorless liquid (3.94 g, 32%) that was 80% 5-bromo-2,3-difluoropyri,ine and 20% 3-bromo-2,5--difluoropyridine isomer.

Analysis: %C /~I /~
Calculated: 30.95 1.04 7.22 Found: 31.36 1.14 7.32 Example 15 - PREPARATION OF 4-(5-CHLORO-3-FLUORO--2-PYRIDINYLOXY)PHENOL

A solution of NaOH (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 DMSO. The mixture was stirred under nitrogen for 20 minutes. 5-Chloro-2,3-difluoro-pyridine (6.0 g, 0.040 mol) was added. The reaction mixture was heated at 60-70C for 3 hours, then poured over ice. Aqueous NaOH was added to pH 1~ and the solid diether side-product was filtered off. The filtrate was acidified, extrac-ted with ether, treated with Norite adsorbent, and the solvent was removed by rotary eVapQration to give a yellow oil which solidified on s-tanding and was purified by high pressure liquid chromatosraphy ~HPLC) (80% hexane/20% ethyl acetate) to give a white solid (2.5 g, 26% yield, m.p. 90-92C).

nalysis: %C
Calculated: 55.14 2.94 5.85 Found: 55.05 2.93 5.65 30,864-F -26-, , -27~ 5~

Example 16 - PREPARATION OF 2-(4-( 3- FLUORO-5-CHLORO--2-PYRIDINYLOXY)PHENOXY)PROPIONIC ACID, METHYL ESTER

A solution of NaOFI (2.7 g, 0.068 mol) in a few ml of water was added to 2-(4-hydroxyphenoxy)pro-pionic acid (6.09 g, Q.033 mol) in 55 ml 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 at 70~C for 5 hours.
The reaction was then poured over ice and extracted with CH2Cl2. The organic layer was washed with water, dried over Na2SO4 and the solvent removed ~y rotary evaporation. The residual oil was dissolved in 130 ml dry methanol, p-toluene sulfonic acid (0.5 g, 0.003 mmol) was added and the mixture was stirred at room tempera-ture 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 Na2SO~. The ether was removed by rotary evaporation to yield a tan oil which solidified on trituration with methylcyclohexane to give a white solid ~6.4 g, 59%, m.p. 53-56C).

Analysis: %C /~ /~
._ Calculated: 55.31 4.02 4.30 Found: 54.91 4.05 4.21 Example 17 - PREPARATION OF 2-(4-(5-BROMO-3-~LUORO--2-PYRIDINYLOXY)PHENOXY)PROPIONIC ACID

A solution of NaOH (0.54 ~, 0.013 mol~ in a few ml o~ water was added to 2-(4-hydroxyphe~oxy)pro-pionic acid (1.22 g, 0.0067 mol) in 20 ml DMSO and the mixture was stirred for 20 minutes under N2. 5-Bromo--2,3-difluoropyridine (1.3 g, 0.0067 mol) ~Jas added 30,864-F -27-. , 28~ 5~

and the mixture was stirred for 51-2 hours at 80-90C.
The reaction mix-ture was poured into water, acidified with concentrated HCl to pH 1 and extracted into CH2C12. The solution was dried over Na2SO4 and the solvent was removed by rotary evaporation to yield a gum which became an off-white solid (0.78 g, 33%, m.p. 94-97C) upon standing.

Anal~ysis: %C /~ y~ ~OBr Calculated: 47.21 3.11 3.93 22.43 Found: ~6.88 3.12 3.94 22.34 The compounds of the present invention have been found to be suitable for use in methods for the selective pre- and postemergent control of annual and perennial grassy weeds. These compounds, -the active ingredients of the present invention, have been found to have advantage over prior art compounds in the control of annual and perennial grassy weeds in that the present compounds control such weeds at substan-tially lower dosage rates. In addition, the present compounds are sufficiently tolerant towards most broad leafed crops to contemplate control of grassy weeds therein at substantially commercially practicable levels, particularly so with the preferred compounds.
In addition, certain of the compounds have sufficient tolerance towards cereal crops such as wheat to enable selective grassy weed control in these crops as well.

For such uses, unmodified active ingredients of the present invention can be employed. However, the present invention embraces the use of the compounds in composition form with an inert material, known in the 30,864-F -28--29~

art as an agricultural adjuvant or carrier, in solid or liquid form. Thus, for exam'ple, an active ingredient can be dispersed on a finely-divided solid and employed therein as a dust or granule. Also, the active ingredients, as liquid concentrates or solid compositions comprising one or more of thle active ingredients can be dispersed in water, typically with aid of a wetting agent, and the resulting aqueous dispersion employed as a spray. In other procedures, the active ingredients can be employed as a constituen-t 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 of the foregoing type are well known to those skilled in the art.

- The herbicidally effective concentration of the active ingredients in solid or liquid compositions generally is from 0.0003 to 95 percent by weight or more. Concentrations from 0.05 to 50 percent by weight are often employed. In compositions to be employed as concentrates, the active ingredient can be present in a concentration from 5 to 98 weight percent. The active ingredient compositions can also con-tain other compatible additaments, for example, phytotoxicants, plant growth regulants and other biologically active compounds used in agriculture.

In further embodiments, the compounds of the present invention or compositions containing the same, can be advantageously employed in combination with one or more additional pesticidal compounds. Such additional pesticidal compounds may be insecticides, nematocides, miticides, arthropodicides, herbisides, fungicides or 30,864-F -29 _30_ ~ 5~
.

bactericldes that are compatible with the compounds of the present invention in the medium selected for application and not antagonistic to the activity of the present compounds. Accordingly, in such embodiments, the pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use or as an additament. The compounds in combination can generally be present in a ratio of from 1 to 100 parts o the compound of the present invention with from lO0 to 1 parts of the additional compound(s).

The active ingredients of the present invention have been found to possess desirable herbicidal activity in general against grassy weeds such as foxtail, barnyard-grass, wild oats, seedling johnsongrass and crabgrass in preemergent operations and also against the same grasses in postemergent operations while being tolerant to important broadleaf crops such as cotton, soybeans, sugarbeets and rape and in the case of certain cf the compounds, certain cereal crops such as wheat. These compounds are also uni~uely effective in selectively controlling perennial grassy weeds such as johnsongrass, quackgrass, bermudagrass and dallisgrass.

The active ingredients of the present invention have been found to possess particularly desirable herbicidal activity against wild oats, ~oxtail, barnyard-grass, crabgrass and seedling johnsongrass in postemergent operations as well as desirable broad spectrum activity against the perennial grassy weeds listed above and at lower dosage rates than the substituted propanoates and propanols of the prior art while showing high selectivity to broadleaf crops and, in the case of certain of the compounds, wheat.

30,86~-F -30--31~ S~

The present compounds which are substituted propanols or propyl et~ers are more effective in pre-emergent operations than in postemergent applications.

l'he exact rate to be applied is dependent not only on a specific active ingredient being applied, but also on a particular action desired, the plant species to be modified and the stage of g owth thereof as well as the part of the plant to be contacted with the toxic active ingredient. Thus, all of the active ingrediencs of the present invention and compositions containing the same may not be equally e~fective at similar concen-~xa-tions or against the same plant species.

In postemergent operations a dosage of about 0.05 to about 20 pounds/acre (0.056-22.4 kg/-15- hectare) is generally applicable, although not all compounds are equally effective and some ~eeds are more difficult to control. Thus, a dosage rate in the range of about 0.01 to about 1.0 pound/acre (0.01-1.12 kg/-hectare) is preferred in postemergent control o~ annual grassy weeds, while about 0.05 to about 5 pounds/acre (0.056-5.6 kg/hectare) is a preferred dosage range for the postemergent control of perennial grassy weeds. In applications to tolerant crops a ~eed controlling bu~
less than crop damaglng amount of from about .005 to about 1.0 lb/acre (0.0056 to 1.12 kgs/hectare~ is generally employed.

In preemergent operations a dosage rate of 0.01 to 10 lbs/acre (0.011 to 11.2 kgs/hectare), pre-~erably 0.05 to 2.0 lbs/acre ~0.056 to 2.25 kgs/hectare) and most pre~erably 0.1 to 1 lb/acre (0.11 -to 1.12 kgs/-hectare) is generally employed.

30,864-F 31--32~ 59 The following examples illustrate effects of the compounds of this invention.

Exam~le 18 In representative operations, each compound to be utilized in a series of tests is dissolved in acetone to one-half of ~he final volume (twice the final concentration~ to be used and the acetone solution in each case is admixed with an equal volume of water containing 0.1 percent by weight of the non-ionic surfactant TWEEN~ 20 (a polyoxyethylene sorbitan monolaurate). The compositions, generally in the nature of an emulsion, were employed to spray separate respective plant species which had been grown to a height of 2-6 inches in soil of good nutrient content in a greenhouse.
Sufficient amounts were employed to provide various application rates as listed in the table. The various beds were positioned side by side and exposed to sub-stantially identical conditions of temperature and light. Each bed was maintained so as to prevent any interaction with test compounds in different seed beds.
Other portions of the plants were left untxeated to serve as controls~ After treatment, the plants were maintained for about two weeks under greenhouse condi-tions conducive for good plant growth and watered as necessary. The specific plant species, test compound and dosage and the percen-t postemergent control obtained are set forth in the table below. Control refers to the reduction in growth compared to the observed results of the same untreated species. Note the "NT" means "not tested".

30,864-F -32-:
. ,, -33~ f~ 3 Plant species in these tests were the following:

Common Name Scientific Name Barnyardgrass (Watergrass) Echinochloa crusgalli Crabgrass Di~__aria sanquinalis Yellow foxtail Setaria lutescens Johnson grass Sor~hum halepense Wild Oats Avena fatua Cotton Gossypium hirsu-tum Rape Brassica ~
. _ Soybeans Gl~cine max Sugarbeet B _ vulgarls Wheat Triticum aestivum . _ 30,864-F -33-o o o o c~ Ln o o o E~ o o o o o o E~ o E~ E~
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30, 864-F ~38-Ex~mDle 19 So as to clearly illustrate -the phytotoxic properties of the various active ingredients of the present invention applied preemergently, a controlled greenhouse experiment is described below.

The seeds of various species of plants were planted in beds of good agricultural soil in a green-house. A number of compositions o~ the present invention, generally in the nature of an aqueous emulsion, were applied at rates listed in the table so as to deposit a predetermined amount of active ingredients uniformly throughout the surface of the bed.
Another seed bed was treated only with water to serve as a control. After treatment the seed beds were maintained for two weeks under greenhouse conditions conducive for good plant growth and watered as necessary.
The specific plant species, test compound, and dosage and the percent preemergent control are set forth in the table below. Control refers to the reduction in growth compared to the observed results of the same untreated species.

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30, 864-F -45--46~

Other compounds within the scope of the present invention, e.g., the various metal salts, amine salts and other derivatives of the ahove des~
cribed compounds may also be employed to control certain plant species with results commensurate to the above described results~

30,864-F -46- -

Claims (4)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound having the general formula:
wherein W' is F, Br or , and X is CF3, Cl or Br and its alkali metal salts, except that when W' is F, X is not CF3.

2. A pyridine compound which is 2-bromo-3-fluoro-5-(tri-fluoromethyl)pyridine, 5-chloro-2,3-difluoropyridine or 5-bromo-2,3-difluoro-pyridine.

3. 4-((3-Fluoro-5-(trifluoromethyl)-2-pyridinyl)oxy)phenol and its alkali metal salts.

4. 4-(5-Chloro-3-fluoro-2-pyridinyloxy)phenol and its alkali metal salts.