PRIOR ART 
Polyhalopyridyloxy compounds are well-known in the prior art. Various 
6-fluoro pyridyloxy compounds are taught in British Pat. No. 1,161,492. 
Polyfluoro pyridyloxy compounds are taught in British Pat. No. 1,159,036. 
Various halogenated 2-pyridyloxy-acetic acids are taught by Cava et al., 
J. Org. Chem. 1958 1614-1616; Wain et al. "The Chemistry and Mode of 
Action of Plant Growth Substances" (1956) Butterworths Scientific 
Publications, London, pages 117-133; Cava, "Final Report by The Ohio State 
University Research Foundation" on Synthesis of Heterocyclic Compounds 
(1957) pages 1-27; and Gorter, Physiologia Plantarium, 10 1957, pages 
858-868. U.S. Pat. Nos. 3,249,419; 3,251,849; 3,545,955 and 3,256,290 
teach various halogenated pyridyloxy compounds. U.S. Pat. No. 3,249,619 is 
directed to various halopyridyloxy carbamates and U.S. Pat. No. 3,535,328. 
Other references of interest include U.S. Pat. No. 2,676,926 which broadly 
teaches halopyridyloxyalkyl; U.S. Pat. Nos. 3,249,619 and 3,409,624; 
Hertog et al., Rec. Trav. Chem 70 (1951) pages 182-190; Belgian Patent No. 
630,125; and Chemical Abstracts 68 21842v. 
SUMMARY OF THE INVENTION 
The present invention is directed to novel compounds corresponding to the 
formula 
##STR4## 
wherein X represents chloro, bromo or iodo; R' represents hydrogen or 
methyl and R represents carboxy (--COOH), the alkyl esters thereof 
(--COOR.sup.6 wherein R.sup.6 represents alkyl of 1 to 8 carbon atoms, 
(2-alkoxyethoxy)carbonyl (--COOCH.sub.2 CH.sub.2 OR.sup.2) or 
(1-methyl-2-alkoxyethoxy)carbonyl 
##STR5## 
wherein R.sup.2 represents loweralkyl of 1 to 4 carbon atoms) or the 
metal salts thereof (--COOMe wherein Me represents ammonium or substituted 
ammonium ion (N+H(R.sup.6).sub.3 wherein each R.sup.6 independently 
represents hydrogen, alkyl of 1 to 4 carbon atoms or hydroxyalkyl of 2 to 
3 carbon atoms), alkali metal, alkaline earth metal, aluminum or a 
transition group metal); alkanoyloxymethyl (--CH.sub.2 OCOR.sup.2); 
(2,2-dichloropropionyloxy)methyl (--CH.sub.2 OCOC(Cl).sub.2 CH.sub.3); 
alkoxymethyl (--CH.sub.2 OR.sup.2); phenoxymethyl (--CH.sub.2 O.phi.); 
(2-alkoxyethoxy)-methyl (--CH.sub.2 OCH.sub.2 CH.sub.2 OR.sup.2); 
hydroxyalkyl (--R.sup.3 OH wherein R.sup.3 represents alkylene of from 1 
to 6 carbon atoms); 3-hydroxy-1-propenyl (--CH.dbd.CHCH.sub.2 OH); 
1,2-dihydroxyethyl 
##STR6## 
1-(2-hydroxyethoxy)methyl (--CH.sub.2 --O--CH.sub.2 CH.sub.2 OH); 
(2-(2-hydroxyethoxy)ethoxy)methyl (--CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2 
CH.sub.2 OH); carbamoyl (--CONHR.sup.4 R.sup.4 wherein each R.sup.4 
independently represents hydrogen or alkyl of 1 to 8 carbon atoms); 
(carboxymethyl)carbamoyl (--CONHCH.sub.2 COOH); (2-hydroxyethyl)carbamoyl 
(--CONR.sup.4 CH.sub.2 --CH.sub.2 OH); or (carbamoyloxy)--methyl 
(--CH.sub.2 OCONHR.sup.5 wherein R.sup.5 is alkyl of 1 to 4 carbon atoms 
or phenyl). 
The 6-fluoro-3,5-dihalo-2-pyridyloxy compounds of the present invention are 
crystalline solids or oils which are of low solubility in water and of 
moderate solubility in common organic solvents. These compounds have been 
found to be very effective pre- and post-emergent herbicides or as 
intermediates in the preparation of compounds which are effective pre- and 
post-emergent herbicides and as active agents in compositions employed as 
herbicides. 
The term "alkyl" as employed in the present specification and claims 
designates either straight or branched chain alkyl radicals. 
The 6-fluoro-3,5-dihalo-2-pyridyloxy compounds of the present invention can 
be prepared by a variety of methods as set forth hereinbelow. 
Those compounds wherein R is alkyl carboxylic acid ester (--COOR.sup.6 
wherein R.sup.6 is alkyl of 1 to 8 carbon atoms) can be prepared by the 
reaction of an appropriate .alpha.-bromo (or chloro) acetic or propionic 
acid ester with an appropriate 6-fluoro-3,5-dihalo-2-pyridinol in the 
presence of sodium or potassium metal, a loweralkanol and a co-solvent 
such as, for example, dimethyl formamide or dimethyl sulfoxide. 
In carrying out this reaction, one mole of the sodium or potassium metal is 
first dissolved in a loweralkanol and one mole of the pyridinol added 
thereto, followed by the addition of an excess of the ester reactant in 
one of the co-solvents listed hereinabove. The mixture is refluxed for 
about 1 to about 8 hours and at the completion of the reaction, the 
solvent is removed and the residue quenched with water. The product 
precipitates out and can be recovered by filtration or other conventional 
separatory procedures, and if desired, it can be purified by 
recrystallization from a solvent such as benzene or hexane. 
Those compounds wherein R is carboxy (--COOH) can be prepared by the 
hydrolysis of the corresponding alkyl ester. 
In carrying out this reaction, the ester reactant in a reaction medium or 
solvent is treated, under reflux conditions, with an alkali metal 
hydroxide for a period of time of from about 1 to about 4 hours. 
Thereafter, the reaction product is acidified with a mineral acid such as 
hydrochloric or sulfuric acid and the desired product recovered by 
filtration or other conventional separatory procedure. 
The reaction consumes the reactants in stoichiometric proportions, i.e., 
one equivalent of the ester reactant per equivalent of the alkali metal 
hydroxide and mineral acid. However, due to the nature of the hydrolysis 
reaction, it is preferred that a slight excess of the alkali metal 
hydroxide and mineral acid be employed. If desired, the product can be 
purified by recrystallization from a solvent such as, for example, 
nitromethane, carbon tetrachloride, n-hexane, cyclohexane, chloroform, 
benzene, methanol, ethanol or a methanol-water mixture or by the use of a 
combination of any of these solvents and/or by the sequential use of one 
or more of these solvents. 
Representative reaction mediums, i.e., solvents for carrying out the 
reaction include, for example, water, dioxane, dimethylformamide, 
dimethylsulfoxide, tetrahydrofuran, and other conventional ether solvents. 
Representative alkali metal hydroxides for use as reactants are the 
hydroxides of sodium, potassium, cesium, lithium and rubidium. 
The compounds of the present invention wherein R is a carboxylic acid salt 
(--COOMe) are prepared by the reaction of the appropriate 
6-fluoro-3,5-dihalopyridyloxy carboxylic acid with an appropriate metal 
hydroxide or carbonate. The term "salt" as employed in the present 
specification and claims designates the reaction products of basic 
compounds with the acid functional group --COOH. Such salts can be 
represented by the formula --COOMe wherein Me represents ammonium and 
substituted ammonium such as, for example, methyl ammonium, ethyl 
ammonium, n-propyl ammonium, n-butyl ammonium, dimethyl ammonium, diethyl 
ammonium, di-n-propyl ammonium, diisopropyl ammonium, di-n-butyl ammonium, 
ethanol ammonium, diisopropanol ammonium, methylethyl ammonium, 
methyldiethyl ammonium, ethylbutyl ammonium, methylethanol ammonium, 
methyldiisopropanol ammonium and the like; the alkali metals such as 
sodium, lithium, potassium, cesium or rubidium; the alkaline earth metals 
such as calcium, barium or strontium; and the heavy metals including 
antimony, zinc, bismuth, cadmium, cerium, chromium, cobalt, copper and 
other metals having a density of above 4. 
In carrying out the reaction, substantially equivalent proportions of the 
acid and base are mixed together in a suitable solvent such as an 
alcohol-water mixture whereupon a reaction takes place with the formation 
of the desired salt product and water-by-product. The salt may or may not 
be soluble in the reaction medium. If insoluble, it may be recovered by 
filtration; if soluble, it may be recovered by vaporizing off the solvent 
and water. The salt may be purified, if desired, by conventional methods. 
Salts of metals which form difficultly soluble hydroxides, such as, for 
example, copper, may be prepared by an alternative procedure wherein an 
alkali metal salt of the desired compound is reacted with a soluble 
mineral acid salt of said metal, such as the chloride or nitrate to 
produce the said metal salts of acid compound. In such preparation, 
substantially equivalent proportions of the alkali metal salt compound and 
said metal salt of a mineral acid are stirred together in water or a 
water-alcohol solvent at room temperature or with gentle warming for from 
0.5 hour to several hours whereupon the desired metal salt compound 
usually precipitates in the reaction mixture. The latter may be recovered 
by filtration and purified, if desired, by conventional procedures. 
Those compounds wherein R is alkoxy alkyl carboxylic esters (--COOR.sup.6) 
wherein R.sup.6 is (2-alkoxyethoxy)--carbonyl (--COOCH.sub.2 CH.sub.2 
OR.sup.2) or (1-methyl-2-alkoxyethoxy)--carbonyl 
##STR7## 
can be prepared by the reaction of an appropriate 
6-fluoro-3,5-dihalo-2-pyridyloxy carboxylic acid with an appropriate alkyl 
ether of ethylene glycol or propylene glycol in the presence of a solvent 
such as, for example, toluene and a catalyst, such as, for example, 
p-toluene sulfonic acid. 
The reaction scheme can be exemplified as follows: 
##STR8## 
In carrying out this reaction, substantially equimolar amounts of the acid 
and glycol reactants are mixed in the solvent with about 2 to 3 weight 
percent of the catalyst and the mixture heated under reflux conditions for 
a period of from about 2 to about 10 hours or more. The water is 
azeotroped out as formed under these conditions and the speed of its 
removal controls the overall reaction time. Thereafter, the reaction 
product is washed with a dilute alkaline solution such as, for example, 
sodium bicarbonate, potassium bicarbonate or the like, followed by a water 
wash. The mixture is dried over magnesium sulfate and filtered under 
vacuum. The solvent is thereafter removed by evaporation under reduced 
pressure or other such conventional separatory procedures. 
The compounds wherein R is alkoxymethyl (--CH.sub.2 OR.sup.2); 
phenoxymethyl (--CH.sub.2 O.phi.); (2-alkoxyethoxy)methyl (--CH.sub.2 
OCH.sub.2 CH.sub.2 OR.sup.2) or (2-(2-hydroxyethoxy)ethoxy)methyl 
(--CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH) can be prepared by 
reacting an appropriate 2,6-difluoro-3,5-dihalopyridine with an 
appropriate glycol ether in the presence of sodium hydride. 
The reaction is initiated by slowly bringing together a mixture of the 
pyridine and glycol ether reactants and solvent washed alkali hydride (as 
a solvent slurry). The reaction mixture, at room temperature, is stirred 
until the foaming which occurs ceases and then stirred for an additional 
.about.10 minutes and diluted with water. This mixture is extracted with a 
solvent such as, for example, methylene chloride, and diluted with water. 
This mixture is extracted with a solvent such as, for example, methylene 
chloride, ether, hexane, benzene or chloroform. The extract is dried, 
filtered and concentrated under a reduced pressure. The reaction consumes 
the reactants in substantially stoichiometric proportions, i.e. one 
equivalent of the pyridine reactant per equivalent of the glycol ether and 
alkali hydride. However, since the glycol ether can act as a reaction 
medium, it is preferred to use a sufficient excess of this reactant so 
that it can function as the reaction medium. 
The compounds wherein R is alkanoyloxymethyl (--CH.sub.2 OCOR.sup.2) or 
(2,2-dichloropropionyloxy)methyl (--CH.sub.2 OCOC(Cl).sub.2 CH.sub.3) can 
be prepared by reacting an appropriate 
2-(3,5-dihalo-6-fluoro-2-pyridyloxy) ethanol and an appropriate acid 
chloride 
##STR9## 
in the presence of a base such as pyridine or a tertiary amine to act as a 
reaction medium and an acid acceptor. 
The reaction is initiated by slowly bringing together a mixture of the base 
and pyridyloxyethanol reactant and the acid chloride, at room temperature. 
The mixture is stirred for from about 1 to about 16 hours and filtered to 
remove any insoluble materials. The mixture is concentrated under a 
reduced pressure and the residual material crystallized with a 
loweralkanol-water mixture. The reaction consumes the reactants in 
substantially stoichiometric proportions, i.e. one equivalent of the 
pyridyloxy ethanol reactant per equivalent of the acid chloride and the 
use of such proportions is preferred. 
The compounds wherein R is hydroxyalkyl (--R.sup.3 OH), 
3-hydroxy-1-propenyl (--CH.dbd.CHCH.sub.2 OH), 1,2-dihydroxyethyl 
(--CH--OH--CH.sub.2 OH) or (2-hydroxyethoxy)methyl (--CH.sub.2 
--O--CH.sub.2 --CH.sub.2 OH) can be prepared by reacting an appropriate 
2,6-difluoro-3,5-dihalopyridine with an appropriate diol (HO-M-OH wherein 
M is loweralkylene, vinylene, 1-propenylene, 2-hydroxy propylene or 
oxydiethylene in the presence of an alkali metal hydroxide and a diol as a 
solvent. 
The reaction is initiated by slowly bringing the reactants together in the 
presence of a base and a diol as a solvent for a period of time of from 
about 5 minutes to about 1 hour. The reaction consumes the reactants in 
substantially stoichiometric proportions, i.e., one equivalent of the 
pyridine reactant per equivalent of the diol and alkali metal hydroxide. 
However, since the diol compound can act as a reaction medium (solvent), 
it is preferred to use a sufficient excess of this reactant so that it can 
function as the reaction medium. The reaction is carried out at a 
temperature of about 65.degree.-90.degree. C. At the completion of the 
reaction, the reaction mixture is cooled and diluted with water. The 
insoluble by-products are removed using conventional separatory techniques 
and the remaining mixture extracted with a solvent such as, for example, 
methylene chloride, ether, hexane, benzene or chloroform. The extract is 
dried, if desired, and the solvent removed by conventional techniques such 
as, for example, evaporation under a reduced pressure. The product can be 
purified by recrystallization from a solvent such as one of those listed 
hereinbefore. 
The compounds wherein R is carbamoyl (--CONR.sup.4 R.sup.4) can be prepared 
by the direct amination of the corresponding carboxylic acid alkyl ester 
compound with ammonia or an amine. 
In carrying out the reaction, the ester and ammonia or amine reactants in a 
solvent or reaction medium are contacted together in any suitable fashion 
and maintained together, under agitation, for a period of time of from 
about 1 to about 20 hours. When one of the reactants is a highly volatile 
material, it is preferred that a closed reaction vessel be employed to 
prevent loss of this reactant. The reaction can be carried out at a 
temperature of from about room temperature to about 100.degree. C. Upon 
completion of the reaction, the excess ammonia or amine reactant is 
removed by flashing or evaporation under reduced pressure. The solid 
material is thereafter recrystallized from solvents listed hereinbefore. 
The compounds wherein R is (carboxymethyl) carbamoyl (--CONHCH.sub.2 COOH) 
can be prepared by the reaction of the acid chloride of the appropriate 
6-fluoro-3,5-dihalo-pyridyloxy acetic acid with sodium or potassium salt 
of glycine in an aqueous solution. 
In carrying out this reaction, one mole of glycine and 3 moles of an alkali 
metal hydroxide such as sodium or potassium hydroxide are dissolved in 
about 36 moles of water. A solution of one mole of the acid chloride of 
the appropriate pyridyloxy acetic acid in 750-800 milliliters of benzene 
is thereafter added with vigorous stirring over a 10 to 15 minute period. 
During the addition the temperature is held at about 2.degree.-5.degree. 
C. and thereafter the reaction mixture is allowed to come to room 
temperature and stirred at this temperature for about 2-3 hours. At the 
end of this time, the aqueous layer is separated and acidified. The 
product is a solid and precipitates out and is recovered by filtration and 
washed and dried. 
The compounds wherein R is (2-hydroxyethyl)-carbamoyl(--CONR.sup.4 CH.sub.2 
CH.sub.2 OH) can be prepared by the reaction of the acid chloride of the 
appropriate 6-fluoro-3,5-dihalopyridyloxy acetic acid with an appropriate 
amino ethanol in an organic solvent such as benzene or hexane. 
In carrying out the reaction, a solution of about one mole of the acid 
chloride reactant in about 1.5 liters of a benzene-hexane mixture (50 
percent each) is added at a temperature of about 25.degree. C. over a 
20-30 minute period to a solution of 2 moles of the aminoethanol in 1.0 
liter of the same solvent mixture. The reaction mixture is held with 
stirring at 25.degree. C. for about 1.0 hour. At the completion of the 
reaction, the insoluble amine hydrochloride by-product is removed by 
decantation or other conventional separatory procedures and the solvent 
phase cooled to precipitate the desired product. The product is washed and 
dried and if desired can be further purified by recrystallization from 
hexane. 
The compounds wherein R is (carbamoyloxy)-methyl (--CH.sub.2 OCONHR.sup.5) 
can be prepared by reacting an appropriate 
2-(3,5-dihalo-6-fluoro-2-pyridyloxy) ethanol and an appropriate loweralkyl 
or phenyl isocyanate in the presence of a reaction medium such as 
dichloromethane and a catalytic amount of an amine such as triethylamine 
to act as a reaction medium and an acid acceptor. 
The reaction is initiated by slowly bringing together a mixture of the base 
and pyridyloxyethanol reactant and the isocyanate, at room temperature. 
The mixture is stirred for from about 1 to about 16 hours, filtered and 
concentrated. The mixture is thereafter extracted with a solvent such as a 
loweralkanol-water mixture and dichloromethane or dried. The reaction 
consumes the reactants in substantially stoichiometric proportions, i.e. 
one equivalent of the pyridyloxyethanol reactant per equivalent of the 
isocyanate and the use of such proportions is preferred.

DESCRIPTION OF SOME PREFERRED EMBODIMENTS 
In order that the present invention may be more fully understood, the 
following examples are given primarily by way of illustration and should 
not be construed as limitations upon the overall scope of the present 
invention. 
EXAMPLE I 
Ethyl(3,5-dichloro-6-fluoro-2-pyridyloxy)-acetate 
##STR10## 
A solution was prepared by dissolving 6.9 grams (0.3 mole) of sodium metal 
in 700 milliliters of 95 percent ethanol. To this solution was added with 
stirring 54.5 grams (0.3 mole) of 3,5-dichloro-6-fluoro-2-pyridinol. 
Thereafter 58.5 grams (0.35 mole) of ethyl bromoacetate was added and the 
mixture refluxed for 5 hours. At the completion of the reaction, the 
ethanol was distilled off and the residue poured into water. The solid 
which precipitated was filtered off and taken up in hexane and dried with 
activated carbon and anhydrous sodium sulfate. The mixture was filtered 
and the hexane removed and the ethyl-(3,5-dichloro-6-fluoro-2-pyridyloxy) 
acetate product was recovered by distillation. The product was a white 
waxy solid which boiled at 135.degree.-170.degree. C. (M.P. 
63.5.degree.-64.degree. C.) 
EXAMPLE II 
(3,5-Dichloro-6-fluoro-2-pyridyloxy) acetic acid 
##STR11## 
A mixture of 17 grams (0.06 mole) of 
ethyl-(3,5-dichloro-6-fluoro-2-pyridyloxy)acetate in 90 milliliters of 
commercial grade ethanol and 2.8 grams of sodium hydroxide in 25 
milliliters of water was refluxed for .about.20 minutes. Thereafter 5.9 
cubic centimeters of concentrated hydrochloric acid was added thereto and 
the mixture stirred and cooled for 15 minutes. The mixture was filtered to 
recover the solid which precipitated and the solid was extracted 
exhaustively with boiling hexane followed by extraction with a 
hexane-benzene mixture. After drying, the 
(3,5-dichloro-6fluoro-2-pyridyloxy) acetic acid product was recrystallized 
from hexane and was recovered in a yield of .about.6 grams and melted at 
140.degree.-144.degree. C. Upon analysis, the product was found to have 
carbon, hydrogen, chlorine and nitrogen contents of 36.04, 2.11, 29.28 and 
5.64 percent, respectively, as compared with the theoretical contents of 
35.03, 1.67, 29.54 and 5.83 percent, respectively, calculated for the 
above-named compound. 
EXAMPLE III 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)ethanol 
##STR12## 
To a solution of 12 grams (0.065 mole) of 3,5-dichloro-2,6-difluoropyridine 
in 35 milliliters of ethylene glycol was added over a 10 minute period 2.7 
grams of anhydrous sodium hydroxide in 40 milliliters of ethylene glycol. 
The reaction mixture was maintained at .about.70.degree. C. with agitation 
for 10 minutes, cooled and poured into water. The insoluble material is 
removed by filtration and the filtrate extracted with methylene chloride 
and dried. The solid 2-(3,5-dichloro-6-fluoro-2-pyridyloxy) ethanol 
product was crystallized from hexane and recovered in a yield of 9 grams 
(61 percent of theoretical). The product melted at 65.degree.-67.degree. 
C. and was found by analysis to have carbon, hydrogen, chlorine and 
nitrogen contents of 37.4, 3.1, 31.5 and 6.4 percent, respectively, as 
compared with the theoretical contents of 37.2, 2.7, 31.4 and 6.2 percent, 
respectively, calculated for the above-named compound. 
EXAMPLE IV 
Mixture of 2-(3,5-dichloro-6-fluoro-2-pyridyloxy)-1-propanol and 
1-(3,5-dichloro-6-fluoro-2-pyridyloxy)-2-propanol 
##STR13## 
To a solution of 14 grams (0.076 mole) of 3,5-dichloro-2,6-difluoropyridine 
in 40 milliliters of propylene glycol was added in .about.5 minutes 3.12 
grams (0.078 mole) of sodium hydroxide in 50 milliliters of propylene 
glycol. The reaction mixture was maintained at .about.70.degree. C. with 
agitation for .about.10 minutes. The mixture was cooled and poured into 
300 milliliters of water and thereafter extracted thoroughly with 
methylene chloride. The extract was dried and the methylene chloride 
removed by evaporation. The residue was taken up in boiling hexane, passes 
over activated charcoal, dried and cooled. The solid product, a mixture of 
2-(3,5-dichloro-6-fluoro-2-pyridyloxy)-1-propanol and 
1-(3,5-dichloro-6-fluoro-2-pyridyloxy)-2-propanol, which precipitated, was 
recovered by filtration in a yield of 10.5 grams (56.1 percent of 
theoretical). The product melted at 47.degree.-50.degree. C. and was found 
by analysis to have carbon, hydrogen, chlorine and nitrogen contents of 
40.5, 3.6, 29.1 and 6.5 percent, respectively, as compared with the 
theoretical contents of 40.0, 3.4, 29.5 and 5.8 percent, respectively, 
calculated for the above-named compounds. 
EXAMPLE V 
3-(3,5-Dichloro-6-fluoro-2-pyridyloxy)-1,2-propanediol 
##STR14## 
To a solution of 12.9 grams (0.07 mole) of 
3,5-dichloro-2,6-difluoropyridine in 50 milliliters of glycerol was added 
over an 8 minute period 2.9 grams of sodium hydroxide in 25 milliliters of 
glycerol. The mixture was maintained at .about.85.degree. C. for .about.17 
minutes, cooled and poured into 200 milliliters of cold water. The solid 
which precipitated was air dried and taken up in benzene, dried and most 
of the benzene was removed by evaporation under reduced pressure. The 
residue was mixed with hexane and cooled and the crystalline 
3-(3,5-dichloro-6-fluoro-2-pyridyloxy)-1,2-propanediol product which 
precipitated was recovered by filtration. The product was covered in a 
yield of 10 grams (56 percent of theoretical). The product melted at 
78.degree.-80.degree. C. and was found upon analysis to have carbon, 
hydrogen, chlorine and nitrogen contents of 37.5, 2.9, 27.6 and 5.6 
percent, respectively, as compared with the theoretical contents of 37.5, 
3.2, 27.7 and 5.5 percent, calculated for the above-named compound. 
EXAMPLE VI 
4-(3,5-Dichloro-6-fluoro-2-pyridyloxy)-2-buten-1-ol 
##STR15## 
To a solution of 11 grams (0.06 mole) of 3,5-dichloro-2,6-difluoropyridine 
in 35 milliliters of ethylene glycol was added over a 15 minute period 
2.44 grams of sodium hydroxide in 35 milliliters of 
butenediol(2-butene-1,4-diol). The mixture was heated to .about.70.degree. 
C. and agitated for .about.31/2 hours. Thereafter the mixture was poured 
into water and extracted with hot hexane. Most of the hexane was removed 
and upon cooling the 4-(3,5-dichloro-6-fluoro-2-pyridyloxy)-2-buten-1-ol 
product precipitated out. The product was recovered in a yield of 9 grams 
(60 percent of theoretical) and melted at 30.degree. C. Upon analysis, the 
product was found to have carbon, hydrogen, chlorine and nitrogen contents 
of 43.3, 2.8, 27.8 and 5.6 percent, respectively, as compared with the 
theoretical contents of 42.9, 3.2, 28.1 and 5.6 percent, respectively, as 
calculated for the above named structure. 
EXAMPLE VII 
Ethyl[2-(3,5-Dichloro-6 -fluoro-2-pyridyloxy)]-propionate 
##STR16## 
A solution was prepared by dissolving 1.84 grams (0.08 mole) of sodium 
metal in 140 milliliters of 28 percent ethanol. To this solution was added 
14.6 grams (0.08 mole) of 3,5-dichloro-6-fluoro-2-pyridinol. The solution 
was warmed and 60 milliliters of N,N-dimethylformamide was added thereto. 
The solution was further heated to remove about 3/4 of the ethanol. To the 
remaining solution was added 15.5 grams (0.85 mole) of ethyl 
bromopropionate followed by an additional 40 milliliters of 
N,N-dimethylformamide. The mixture was refluxed at 118.degree. C. for 20 
minutes, cooled and poured into water. The mixture was extracted with 
hexane and the hexane thereafter removed by evaporation. The residue was 
distilled under reduced pressure and the 
ethyl[2-(3,5-dichloro-6-fluoro-2-pyridyloxy)]propionate was recovered as 
an oil in a yield of 17.7 grams (78.3 percent of theoretical) and had a 
boiling point at 2.4 millimeters of mercury at 127.degree. C. Upon 
analysis, the product was found to have carbon, hydrogen, chlorine and 
nitrogen contents of 42.0, 3.1, 25.1 and 5.2 percent, respectively, as 
compared with the theoretical contents of 42.6, 3.6, 25.1 and 4.9 percent, 
respectively, calculated for the above named compound. 
EXAMPLE VIII 
4-(3,5-Dichloro-6-fluoro-2-pyridyloxy)-1-butanol 
##STR17## 
To a solution of 11 grams (0.06 mole) of 3,5-dichloro-2,6-difluoropyridine 
in 35 milliliters of 1,4-butanediol was added over a 10 minute period 2.44 
grams of sodium hydroxide in 35 milliliters of ethylene glycol. The 
temperature was maintained at between 50.degree.-60.degree. C. during the 
addition. The mixture was stirred for 13/4 hours while the temperature was 
maintained between 60.degree.-65.degree. C. The reaction mixture was 
cooled and poured into water and thereafter extracted three times with 135 
milliliter portions of hot hexane. The mixture was heated to remove most 
of the hexane by evaporation, cooled and filtered to remove the solid 
4-(3,5-dichloro-6-fluoro-2-pyridyloxy)-1-butanol product. The product was 
recovered in a yield of 11 grams (73 percent of theoretical) and melted at 
38.degree.-39.degree. C. Upon analysis, the product was found to have 
carbon, hydrogen, chlorine and nitrogen contents of 43.2, 3.7, 27.9 and 
5.7 percent, respectively, as compared with the theoretical contents of 
42.5, 3.9, 27.9 and 5.5 percent, respectively, as calculated for the above 
named compound. 
EXAMPLE IX 
(3,5-Dichloro-6-fluoro-2-pyridyloxy)-acetyl chloride 
##STR18## 
A solution was prepared by admixing 8.6 grams (0.036 mole) of 
3,5-dichloro-6-fluoro-2-pyridyloxy acetic acid in 15 milliliters of 
thionyl chloride. The mixture was refluxed for about 50 minutes. At the 
completion of the reaction, the excess thionyl chloride was removed by 
distillation. The liquid residue was cooled and the crystals which formed 
were separated. The (3,5-dichloro-6-fluoro-2-pyridyloxy)acetyl chloride 
product was recovered in a yield of 8.4 grams (92 percent of theoretical). 
Upon analysis, the product was found to have carbon, hydrogen, chlorine 
and nitrogen contents of 32.9, 0.9, 41.9 and 5.3 percent, respectively as 
compared with the theoretical contents of 32.8, 0.4, 41.4 and 5.5 percent, 
respectively, as calculated for the above-named compound. 
EXAMPLE X 
N-[(3,5-Dichloro-6-fluoro-2-pyridyloxy)-acetyl]glycine 
##STR19## 
A solution was prepared by admixing 2.93 grams (0.039 mole) of glycine with 
4.67 grams (0.117 mole) of sodium hydroxide in 117 milliliters of water. 
To this solution was added 10.0 grams of 
(3,5-dichloro-6-fluoro-2-pyridyloxy)acetyl chloride in 30 milliliters of 
benzene. The mixture was allowed to stand at a temperature of 
.about.2.degree.-5.degree. C. for about 10 minutes and the mixture was 
warmed to room temperature and stirred for about 30 minutes. The reaction 
mixture was diluted with additional benzene and the aqueous layer which 
formed was removed and acidified. The solid which precipated was removed 
by filtration, dried and recrystallized from 50 percent ethanol. The 
N-[(3,5-dichloro-6-fluoro-2-pyridyloxy)acetyl]glycine product was 
recovered in a yield of 5.0 grams and melted at 155.degree.-157.degree. C. 
and upon analysis was found to have carbon, hydrogen, chlorine and 
nitrogen contents of 35.7, 2.1, 24.2 and 8.7 percent, respectively as 
compared with the theoretical contents of 36.5, 2.4, 23.9 and 9.4 percent, 
respectively, calculated for the above named compound. 
EXAMPLE XI 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)-ethyl 2,2-dichloropropionate 
##STR20## 
A solution was prepared by admixing 250 milliliters of acetonitrile, 55.3 
grams (0.4 mole) of potassium carbonate, 42.5 grams (0.16 mole) of 
2-(3,5-dichloro-6-fluoro-2-pyridyloxy)ethanol and 32.3 grams (0.2 mole) of 
2,2-dichloropropionyl chloride. This mixture was stirred at room 
temperature for 4 days. The solids which formed were removed by filtration 
and the filtrate was concentrated under a reduced pressure. The residual 
material which remained was dissolved in hexane and washed with water. The 
hexane was removed under a reduced pressure to yield a pale-orange liquid 
having a refractive index of n/25D=1.5239. The product was confirmed to be 
2-(3,5-dichloro-6-fluoro-2-pyridyloxy)ethyl 2,2-dichloro propionate by its 
infrared and nuclear magnetic resonance spectrums. 
EXAMPLE XII 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)ethyl acetate 
##STR21## 
A solution was prepared by admixing 80 milliliters of pyridine and 11.25 
grams (0.05 mole) of 2-(3,5-dichloro-6-fluoro-2-pyridyloxy)ethanol to this 
solution was added dropwise 3.93 grams (0.05 mole) of acetyl chloride. The 
reaction mixture was stirred at room temperature overnight and thereafter 
poured into a mixture of crushed ice and concentrated hydrochloric acid. 
The resulting mixture was extracted twice with 100 milliliter portions of 
dichloromethane. The extracts were combined and dried over anhydrous 
sodium sulfate, filtered and concentrated under reduced pressure. The oil 
which remained as a residue was vacuum distilled yielding 6.45 grams (48 
percent of theoretical) of 2-(3,5-dichloro-6-fluoro-2-pyridyloxy) ethyl 
acetate as a light amber oil. The product had a boiling point of 
93.degree.-106.degree. C. at 0.4 millimeters of mercury (mm). Upon 
analysis, the product was found to have carbon, hydrogen and nitrogen 
contents of 40.47, 3.14 and 5.42 percent, respectively, as compared with 
the theoretical contents of 40.32, 3.01 and 5.22 percent, respectively, 
calculated for the above named structure. 
EXAMPLE XIII 
2-[2-(2-Butoxyethoxy)ethoxy]-3,5 -dichloro-6-fluoropyridine 
##STR22## 
A mixture was prepared by admixing 12.9 grams (0.07 mole) of 
3,5-dichloro-2,6-difluoropyridine, 100 milliliters of diethyleneglycol 
n-butyl ether and 3.3 grams (0.75 mole) of a hexane slurry of sodium 
hydride. The sodium hydride was a 53 percent oil dispersion and had been 
washed 3 times with 10 milliliter portions of hexane. Considerable foaming 
occurred and after foaming ceased, the reaction mixture was stirred for 
.about.10 minutes at room temperature and thereafter diluted with 200 
milliliters of water. The mixture was extracted 3 times with 100 
milliliter portions of hexane, the extracts combined and dried over 
anhydrous sodium sulfate, filtered and concentrated under reduced 
pressure. The oil which remained as a residue was vacuum distilled to 
yield 14.3 grams of 
2-[2-(2-butoxyethoxy)ethoxy]-3,5-dichloro-6-fluoropyridine as a 
water-white product. The product had a boiling point of 
113.degree.-124.degree. C. at 0.3 millimeters of mercury (mm). Upon 
analysis, the product was found to have carbon, hydrogen and nitrogen 
contents of 47.55, 5.37 and 4.36 percent, respectively, as compared with 
the theoretical contents of 47.87, 5.56 and 4.29 percent, respectively, as 
calculated for the above named compound. 
EXAMPLE XIV 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)-ethyl-N-phenyl carbamate 
##STR23## 
A mixture was prepared by admixing 80 milliliters of dichloromethane, 5.95 
grams (0.05 mole) of phenyl isocyanate and 11.25 grams (0.05 mole) of 
2-(3,5-dichloro-6-fluoro-2-pyridyloxy)ethanol and 5 drops of 
triethylamine. The mixture was allowed to sit overnight at room 
temperature. The solid precipitate which occurred was removed by 
filtration and the filtrate was concentrated under a reduced pressure. The 
oil which remained as a residue was crystallized from an ethanol-water 
mixture. Two additional recrystallizations were carried out and the 
crystals were dried yielding 7.84 grams of 
2-(3,5-dichloro-6-fluoro-2-pyridyloxy)ethyl-N-phenyl carbamate as the 
product. The product melted at 70.degree.-75.5.degree. C. An additional 
recrystallization was given as above and after drying the product melted 
at 75.degree.-76.5.degree. C. Upon analysis, the product was found to have 
carbon, hydrogen and nitrogen contents of 48.64, 3.27 and 7.98 percent, 
respectively, as compared with the theoretical contents of 48.71, 3.21 and 
8.12 percent, respectively, calculated for the above named compound. 
The following compounds of the present invention are prepared in accordance 
with the methods hereinbefore set forth: 
__________________________________________________________________________ 
##STR24## 
X M.P. .degree.C./B.P. .degree.C. or 
(both) 
R' R M.W. Refractive indices 
__________________________________________________________________________ 
Cl H COOCH.sub.3 254.07 
64.degree.-65.degree. 
Br H COOH 328.94 
165.degree.-166.degree. 
I H COOH 422.93 
Br H COOCH.sub.3 342.94 
Br H COOC.sub.2 H.sub.5 
356.96 
69.degree.-70.degree. 
Br CH.sub.3 
COOH 342.97 
Br H CN 309.94 
I CH.sub.3 
COOC.sub.4 H.sub.9 
488.02 
Cl CH.sub.3 
COOH 254.08 
152.degree.-153.degree. 
Br CH.sub.3 
CONH.sub.2 341.98 
Cl H CONH.sub.2 239.05 
134.degree.-136.degree. 
Cl H COONa 262.03 
Cl H COO).sub.3 Al .about.744.09 
Cl H COO).sub.2 Cu .about.541.61 
Cl H COOK 278.14 
Br CH.sub.3 
COO).sub.2 Ca .about.724.00 
Br CH.sub.3 
COO).sub.2 Co .about.742.86 
I H COO).sub.2 Zn .about.909.22 
I CH.sub.3 
COO).sub.3 Sb .about.1277.78 
I CH.sub.3 
CN 417.95 
Cl H CN 221.04 
29.degree.-33.degree. 
Cl CH.sub.3 
COOC.sub.4 H.sub.9 
310.17 
Cl H COO(CH.sub.2).sub.2 OCH.sub.3 
298.10 
Cl H COO(CH.sub.2).sub.2 OC.sub.4 H.sub.9 
340.18 
Cl CH.sub.3 
##STR25## 326.15 
Cl CH.sub.3 
##STR26## 368.24 
I H COCl 441.38 
Cl H (CH.sub.2).sub.4 CH.sub.2 OH 
282.16 
Cl H CHCHOH 238.07 
Cl CH.sub.3 
COCl 271.47 
Cl H CHCHCH.sub.2 OH 
252.09 
.about.30.degree. 
Br CH.sub.3 
CHCHCH.sub.2 OH 
355.02 
Cl H CH.sub.2 OCH.sub.2 CH.sub.2 OH 
260.11 
oil 
Cl H 
##STR27## 263.08 
139.5.degree.-140.5.degree. 
I H 
##STR28## 295.16 
77.degree.-78.degree. 
Cl CH.sub.3 
##STR29## 309.18 
Cl H 
##STR30## 351.27 
75.degree.-77.degree. 
Cl H 
##STR31## 255.09 
Br H 
##STR32## 385.95 
Cl H 
##STR33## 297.13 
125.degree. 
Br CH.sub.3 
##STR34## 386.03 
Cl H 
##STR35## 283.10 
114.degree.-116.degree. 
Cl H 
##STR36## 282.02 
97.degree.-107.degree. at 0.5 mm 
Cl H 
##STR37## 296.03 
91.degree.-97.degree. at 0.3 mm 
Cl H 
##STR38## 310.04 
90.degree.-109.degree. at 0.3 mm 
Cl H CH.sub.2 OCH.sub.3 
240.00 
85.degree.-95.degree. 
at 0.5 mm 
Cl CH.sub.3 
CH.sub.2 OCH.sub.3 
254.01 
n/25D=1.5055 
Cl H CH.sub.2 OC.sub.4 H.sub.9 -n 
282.03 
n/25D=1.4994 
Cl H CH.sub.2 O.phi. 
302.05 
n/25D=1.5631 
Cl H CH.sub.2 OC.sub.2 H.sub.5 
235.01 
80.degree.-95.degree. 
at 0.6 mm 
Cl H CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 
284.02 
120.degree.-130.degree. 
at 0.5 mm 
Cl H CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 
298.03 
108.degree.-120.degree. 
at 0.7 mm 
Cl H CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH 
314.03 
135.degree.-150.degree. 
at 0.5 mm 
Cl H 
##STR39## 283.01 
80.5.degree.-87.degree. 
Cl CH.sub.3 
##STR40## 325.05 
Cl CH.sub.3 
##STR41## 507.95 
__________________________________________________________________________ 
The following compounds are all quaternary ammonium compounds wherein R 
represents --COO.sup.(-) N.sup.(+) H(R.sup.6).sub.3. For brevity, the 
positive and negative charges are not being placed on the ammonium salts. 
It is to be understood that such charges are encompassed herein. 
______________________________________ 
M.P..degree.C./ 
B.B. .degree.C. or 
X Refractive 
(both) 
R' R M.W. indices 
______________________________________ 
Br H --COONH.sub.4 345.97 
Cl H --COONH.sub.3 CH.sub.3 
271.08 
Cl H --COONH.sub.3 C.sub.4 H.sub.9 
312.31 
Br H --COONH.sub.2 (CH.sub.3).sub.2 
522.75 
Cl CH.sub.3 
--COONH.sub.2 (C.sub.4 H.sub.9).sub.2 
383.29 
Cl H --COONH.sub.2 (i-C.sub.3 H.sub.6 OH).sub.2 
373.21 
I H --COONH(C.sub.4 H.sub.9).sub.3 
624.28 
Cl H --COONH.sub.2 C.sub.2 H.sub.4 OH 
301.10 
Cl H --COONH.sub.2 (CH.sub.3)C.sub.2 H.sub.5 
299.13 
Cl H --COONH(CH.sub.3)(C.sub.4 H.sub.9).sub.2 
383.29 
Cl CH.sub.3 
--COONH(CH.sub.3)(C.sub.3 H.sub.6 OH).sub.2 
401.27 
______________________________________ 
In accordance with the present invention, it has been discovered that the 
6-fluoro-3,5-dihalopyridyloxy compounds of the present invention are 
useful as pre- and post-emergent herbicides. In accordance with this 
invention, a method for controlling or inhibiting the growth of 
undesirable plant species is provided which comprises applying to plants, 
plant parts or their habitat, an effective or growth inhibiting amount of 
at least one of the 6-fluoro-3,5-dihalopyridyloxy compounds as set forth 
hereinabove. 
An outstanding feature of the present invention is the ability of the 
presently claimed compounds to control, either by post-emergent or 
pre-emergent application, the growth of grasses and broadleaf plants, such 
as, for example, barnyard grass, crabgrass, yellow foxtail, Johnson grass, 
wild oats, bindweed, pigweed, ragweed, wild mustard, beans, cotton, 
sorghum, corn, rice, soybeans and wheat. 
The application of the compounds of the present invention to plants and 
plant parts and their habitats, gives rise to varying degrees of response 
to the compounds depending upon the nature of the plant or seed, the stage 
of growth or maturity of the plant, the specific compound employed, and 
the dosage at which plant or plant part or habitat exposure to the 
compound is carried out, as well as environmental conditions. When large 
dosages of many of the compounds are applied to the foliage of undesirable 
plants, a substantially complete kill is obtained. Soil or foliar 
applications of more dilute dosages of many of the compounds suppress the 
growth of the germinant seeds and seedlings of many undesirable grasses 
while having little or no effect upon the seeds, emerging seedlings or 
established plants of many desirable crop plants. Thus, many of the 
compounds can be employed for the selective control of emerging seedlings 
of undesirable weeds in plantings or stands of desirable crop plants. 
The minimum amount of active compound applied should be that which is 
effective in controlling and/or killing undesirable plant growth. 
Ordinarily, for pre-emergent control, good results are obtained when from 
0.06 to 4 pounds or more of at least one of the active pyridyloxy 
compounds are applied per acre. In foliage treatment, good results are 
obtained when from 0.02 to 4 pounds of active compound per acre are 
employed. In selective applications to foliage for the control of many 
undesirable weeds in the presence of desired crop plants, a uniform dosage 
of from about 0.02 to 2 pounds of active compound can be employed. In all 
selective applications, the exact dosage to be employed is dependent upon 
the resistance of the crop plant or their seeds to the active compounds. 
The present invention can be carried out by directly employing the claimed 
compounds singly or in combination with each other. However, the present 
invention also embraces the employment of liquid, granular, encapsulated 
or dust compositions containing at least one of said compounds. In such 
usage, the compound or compounds can be modified with one or more of a 
plurality of chemically inert additaments or pesticidal materials 
including solvents or other liquid carriers, surface active dispersing 
agents or coarsely or finely divided inert solids. The augmented 
compositions are also adapted to be employed as concentrates and 
subsequently diluted with additional inert carrier, to produce other 
compositions in the form of dusts, sprays, granules, washes or drenches. 
In compositions where the additament is a coarsely or finely divided 
solid, a surface active agent or the combination of a surface active agent 
and a liquid additament, the added material cooperates with the active 
component so as to facilitate the invention. Whether the composition is 
employed in liquid form, as a wettable powder, or as a granular or 
encapsulated material, the active compound will normally be present in an 
amount of from about 5 to about 95 percent by weight of the total 
composition. 
In the preparation of dust compositions, the toxicant products can be 
compounded with any of the finely divided solids, such as, for example, 
pyrophyllite, talc, chalk, gypsum, fuller's earth, bentonite, attapulgite, 
and the like. In such operations, the finely divided carrier is ground or 
mixed with the toxicant or wet with a solution of the toxicant in a 
volatile organic solvent. Also, such dust compositions when employed as 
concentrates can be dispersed in water, with or without the aid of 
dispersing agents to form spray mixtures. 
Granular formulations are usually prepared by impregnating a solution of 
the toxicant in a volatile organic solvent onto a bed of coarsely divided 
clays, such as, for example, attapulgite, bentonite, diatomite, or the 
like. 
Similarly, the toxicant products can be compounded with a suitable 
water-immiscible organic liquid and a surface active dispersing agent to 
produce an emulsifiable concentrate which can be further diluted with 
water and oil to form spray mixtures in the form of oil-in-water 
emulsions. In such compositions, the carrier comprises an aqueous 
emulsion, i.e., a mixture of water-immiscible solvent, emulsifying agent 
and water. Preferred dispersing agents which can be employed in these 
compositions, are oil-soluble materials including non-ionic emulsifiers 
such as, for example, the condensation products of alkylene oxides with 
the inorganic acids, polyoxyethylene derivatives or sorbitan esters, 
complex ether alcohols and the like. Also, oil-soluble ionic emulsifying 
agents such as mahogany soaps can be used. Suitable organic liquids which 
can be employed in the composition include, for example, petroleum oils 
and distillates, toluene, liquid halohydrocarbons and synthetic organic 
oils. The surface-active dispersing agents are usually employed in liquid 
compositions and in the amount of from 0.1 to 20 percent by weight of the 
combined weight of the dispersing agent and active compound. 
In addition, other liquid compositions containing the desired amount of 
effective agent can be prepared by dissolving the toxicant in an organic 
liquid such as, for example, acetone, methylene chloride, chlorobenzene 
and petroleum distillates. The preferred organic solvent carriers are 
those which are adapted to accomplish the penetration and impregnation of 
the environment and particularly soil with the toxicant compounds and are 
of such volatility as to leave little permanent residue thereon. 
Particularly desirable carriers are the petroleum distillates boiling 
almost entirely under 400.degree. F. at atmospheric pressure and having a 
flash point above 80.degree. F. The proportion of the compounds of this 
invention employed in a suitable solvent may vary from about 2 to about 50 
percent or higher. 
In further embodiments, the compounds as employed in accordance with the 
present invention, or compositions containing the same, can be 
advantageously employed in the present invention in combination with one 
or more pesticidal or preservative compounds. In such embodiments, the 
pesticidal or preservative compound is employed either as a supplemental 
toxicant or as an additament. Representative operable pesticidal or 
preservative compounds include substituted phenols, cresols, substituted 
cresols and their metal salts, bisphenols and thiobisphenols; halogenated 
salicylanilides, organo sulfur compounds, carbamate compounds, quaternary 
ammonium compounds, organometallic compounds, inorganic salts and 
miscellaneous other compounds, such as phenol, cresol, trichlorophenols, 
tetrachlorophenols, pentachlorophenol, P-chloro-m-cresol, sodium 
pentachlorophenol and other sodium, potassium, etc. salts of the phenols, 
substituted phenols, cresols and substituted cresols, di- and 
tribrominated salicylanilides, 2,2'-methylenebis(3,4,6-trichlorophenol), 
2,2'-thiobis(4,6-dichlorophenoxide), halogenated trifluoromethyl 
salicylanilide, disodium ethylenebisthiocarbamate, sodium 
N-methyldithiocarbamate, zinc dimethyldithiocarbamate, 
2-mercaptobenzothiazole, 
3,5-dimethyltetrahydro-1,3,5-2H-thioadiazine-2-thione, 
2,3-dinitro-1,4-dithia-anthraquinone, dodecyl pyridinium chloride, alkyl 
dimethyl benzyl ammonium chloride, dialkyl dimethylammonium chloride, 
bis-tributyltin oxide, bis-tripropyltin oxide, copper pentachlorophenate, 
copper 8-hydroxyquinolate, sodium borate, 9-undecylenic acid, 
10,10'-oxybisphenoxarsine, 
1-(3-chloroallyl)-3,5,7-triaza-1-azonia-adamantane chloride, 
1,4-bromobisacetobutene and substituted phosphorothioates (soil applied 
insecticides). 
In application to an area to be treated, the compounds of this invention 
may be applied by spraying or by the use of mechanical spreaders in 
accordance with conventional practice. With respect to application, 
however, it will be noted that, depending upon the particular 
circumstances encountered, one method of application may be preferable 
over others. Thus, for example, for preferred pre-emergence application it 
has been found very satisfactory to apply the active compound in a liquid 
spray or on granules and incorporate it into the soil. 
In a further method, the distribution can be accomplished by introducing a 
toxicant or toxicants into the water employed to irrigate the soil. In 
this method, the amount of water can be varied in accordance with the 
moisture equivalent or field capacity of the soil in order to obtain the 
desired depth of distribution of the toxicant. 
The following embodiments are illustrative of the present methods. 
EXAMPLE XV 
Forty--five parts by weight of 
4-(3,5-dichloro-6-fluoro-2-pyridyloxy)-1-butanol is mixed and ground with 
5 parts by weight of Triton X-155 surfactant (an alkylated aryl polyether 
alcohol) to prepare a water-dispersible concentrate composition containing 
90 percent by weight of the ester compound. 
In a further operation, 25 parts by weight of 
methyl(3,5-dichloro-6-fluoro-2-(pyridyloxy)acetate, 10 parts by weight of 
Triton X-155 surfactant and 65 parts by weight of xylene are mixed 
together to prepare an emulsifiable concentrate composition containing 25 
percent by weight of said ester compound. 
A mixture of 10 parts by weight of 
6-(3,5-dichloro-6-fluoro-2-pyridyloxy)-1-hexanol, 10 parts by weight of 
2-[2-(3,5-dichloro-6-fluoro-2-pyridyloxy)ethoxy]ethanol, 0.1 part of 
Nacconol NR detergent (alkyl sulfonate), 0.1 part of Daxad No. 27 (a 
polymerized sodium salt of benzoid alkyl sulfonic acids) and 200 parts of 
water are ball-milled together to prepare a water dispersible liquid 
concentrate composition containing 20 parts by weight of the mixed 
pyridine compounds. The concentrate compositions thus prepared can be 
dispersed in water to prepare aqueous compositions which have very 
desirable wetting and penetrating properties and are adapted to distribute 
growth inhibiting amounts of the 6-fluoro-3,5-dihalo-2-pyridyloxy 
compounds on plant parts. 
EXAMPLE XVI 
In separate operations, aqueous compositions containing 
6-fluoro-3,5-dihalopyridyloxy compounds are prepared as follows: 
Four parts by weight of one of the ester compounds, 0.08 part of sorbitan 
trioleate (Span 85), and 0.02 part of a sorbitan monoleate polyoxyethylene 
derivative (Tween 80) are dispersed in 40 milliliters of acetone to 
produce a concentrate composition in the form of a water-soluble liquid 
containing one of the ester compounds as the sole active agent. The 
compounds employed in these procedures include the following: 
(3,5-Dichloro-6-fluoro-2-pyridyloxy) acetonitrile; 
(3,5-Dichloro-6-fluoro-2-pyridyloxy) acetic acid; 
Methyl(3,5-dichloro-6-fluoro-2-pyridyloxy) acetate; 
Ethyl(3,5-dichloro-6-fluoro-2-pyridyloxy) acetate; 
(3,5-Dibromo-6-fluoro-2-pyridyloxy) acetic acid; 
Ethyl(3,5-dibromo-6-fluoro-2-pyridyloxy) acetate; 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)propionic acid; 
Ethyl[2-(3,5-dichloro-6-fluoro-2-pyridyloxy)]propionate; 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)acetamide; 
2-Methoxyethyl(3,5-dichloro-6-fluoro-2-pyridyloxy)acetate; 
Ammonium(3,5-dibromo-6-fluoro-2-pyridyloxy)acetate; 
Methyl ammonium(3,5-dichloro-6-fluoro-2-pyridyloxy)-acetate; 
Butyl ammonium(3,5-dichloro-6-fluoro-2-pyridyloxy)-acetate; 
Dimethyl ammonium(3,5-dibromo-6-fluoro-2-pyridyloxy)-acetate; 
Dibutyl ammonium[2(3,5-dichloro-6-fluoro-2-pyridyloxy)]propionate; 
Diisopropanol ammonium(3,5-dichloro-6-fluoro-2-pyridyloxy)acetate; 
Tributyl ammonium(6-fluoro-3,5-diiodo-2-pyridyloxy)-acetate; 
Ethanol ammonium(3,5-dichloro-6-fluoro-2-pyridyloxy)-acetate; 
Methylethyl ammonium(3,5-dichloro-6-fluoro-2-pyridyloxy)acetate; 
Methylbutyl ammonium(3,5-dichloro-6-fluoro-2-pyridyloxy)acetate; 
Methyldiisopropanol 
ammonium[2(3,5-dichloro-6-fluoro-2-pyridyloxy)]propionate; 
2-n-Butoxyethyl(3,5-dichloro-6-fluoro-2-pyridyloxy)acetate; 
2-(2-Methoxyethyl(3,5-dichloro-6-fluoro-2-pyridyloxy))-propionate; 
2-(1-Methyl-2-n-butoxyethyl(3,5-dichloro-6-fluoro-2-pyridyloxy))propionate; 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy) ethyl 2,2-dichloropropionate; 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy) ethyl acetate; 
3,5-Dichloro-6-fluoro-2-(2-phenoxyethoxy)-pyridine; 
2-[2-(2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)ethoxy)-ethoxy]ethanol; 
3,5-Dichloro-2-(2-ethoxyethoxy)-6-fluoropyridine; 
3,5-Dichloro-6-fluoro-2-(2-(2-methoxyethoxy)ethoxy)pyridine; 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)ethyl N-methyl carbamate; 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)ethyl N-phenyl carbamate; 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)ethyl propionate 
2-[2-(2-Butoxyethoxy)ethoxy]-3,5-dichloro-6-fluoropyridine; 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy) ethyl 2,2-dimethylpropionate; 
3,5-Dichloro-6-fluoro-2-(2-phenoxyethoxy)pyridine; 
2-(2-Butoxyethoxy)-3,5-dichloro-6-fluoropyridine; 
3,5-Dichloro-6-fluoro-2-(2-methoxyethoxy)pyridine; 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy) ethyl 2-methylpropionate; 
3,5-Dichloro-6-fluoro-2-(2-(2-ethoxyethoxy)ethoxy)-pyridine; 
3,5-Dichloro-6-fluoro-2-(2-methoxy-1-methylethoxy)-pyridine; 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy) N-methyl acetamide; 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy) N-butyl acetamide; 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy) N-octyl acetamide; 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy) N-(2-hydroxyethyl)-N-methyl 
acetamide; 
N-[(3,5-Dichloro-6-fluoro-2-pyridyloxy)acetyl]-glycine; 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy) N-(2-hydroxy ethyl)acetamide; 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)ethanol; 
Mixture of 2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)-1-propanol and 
1-(3,5-dichloro-6-fluoro-2-pyridyloxy)-2-propanol; 
4-(3,5-Dichloro-6-fluoro-2-pyridyloxy)-1-butanol; 
4-(3,5-Dichloro-6-fluoro-2-pyridyloxy)-2-buten-1-ol; 
2-[2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)ethoxy]ethanol; 
6-(3,5-Dichloro-6-fluoro-2-pyridyloxy)-1-hexanol and 
3-(3,5-Dichloro-6-fluoro-2-pyridyloxy)-1,2-propanediol. 
Portions of these concentrate compositions are dispersed in separate 
portions of water to provide aqueous compositions, each containing 0.44 
pound of one of the pyridyloxy compounds per 100 gallons of ultimate 
aqueous mixture. The diluted compositions have very desirable wetting and 
penetrating properties and are adapted to distribute growth inhibiting 
amounts of the compound on plant parts. 
EXAMPLE XVII 
Representative products of the present invention were evaluated for the 
post-emergent control of barnyard grass, wild mustard, crabgrass, pigweed, 
yellow foxtail and bindweed. In these evaluations, plots of the above 
plant species grown to a height of about 4 inches were used. Aqueous spray 
compositions, each containing 4,000 parts of a given 
6-fluoro-3,5-dihalopyridyloxy compound per million parts of ultimate 
composition, were prepared in accordance with the procedures of Example 
XVI, and each separate composition was applied to a separate plot. The 
application was made to the point of run-off and was carried out with 
conventional spraying equipment. Other plots were sprayed with similar 
compositions containing no toxicant to serve as controls. Thereafter, the 
plots were maintained under conditions conducive for plant growth. Two 
weeks after treatment, the plots were examined for plant growth and 
evaluated. The results of the examination of the treated plots are set 
forth below in Table A. 
Table A 
__________________________________________________________________________ 
Percent Kill and Control of 
Bardyard 
Wild Crab- 
Pig- Yellow 
Bind- 
Compound Employed Grass 
Mustard 
grass 
weed Foxtail 
weed 
__________________________________________________________________________ 
N-[(3,5-Dichloro-6-fluoro-2-pyridyloxy)- 
acetyl]glycine 100 100 90 100 95 100 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)-N- 
(2-hydroxyethyl)acetamide 
100 100 90 100 90 100 
Methyl(3,5-dichloro-6-fluoro-2-pyridyloxy) 
acetate 100 N.R..sup.(1) 
80 100 100 100 
(3,5-Dichloro-6-fluoro-2-pyridyloxy) aceta- 
mide 50 90 85 100 100 100 
(3,5-Dichloro-6-fluoro-2-pyridyloxy) acetic 
acid 100 85 90 100 95 100 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)- 
ethanol 100 100 100 
100 100 100 
(3,5-Dichloro-6-fluoro-2-pyridyloxy) aceto- 
nitrile 90 90 90 100 90 100 
2-[2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)- 
ethoxy]ethanol 80 60 80 100 70 90 
6-(3,5-Dichloro-6-fluoro-2-pyridyloxy)-1- 
hexanol 100 100 95 100 90 100 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)- 
N-methyl-acetamide 90 100 90 100 100 100 
2-(3,5-Dichloro-6-fluoro-2-pyridyl 
oxy) ethyl acetate 90 N.R..sup.(1) 
80 100 80 N.R..sup.(1) 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy) 
ethyl-N-methyl carbamate 
80 N.R..sup.(1) 
80 100 80 N.R..sup.(1) 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)- 
ethyl propionate 95 N.R..sup.(1) 
90 100 90 N.R..sup.(1) 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)- 
ethyl-N-phenyl carbamate 
80 N.R..sup.(1) 
80 100 80 N.R..sup.(1) 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)- 
ethyl 2,2-dimethylpropionate 
95 N.R..sup.(1) 
50 100 60 N.R..sup.(1) 
2-[2-(2-Butoxyethoxy)ethoxy] -3,5-dichloro- 
6-fluoropyridine 60 N.R..sup.(1) 
70 80 40 N.R..sup.(1) 
3,5-Dichloro-6-fluoro-2-(2-methoxyethoxy)- 
pyridine 20 N.R..sup.(1) 
70 60 70 N.R..sup.(1) 
3,5-Dichloro-2-6-fluoro-(2-ethoxyethoxy)- 
pyridine 40 N.R..sup.(1) 
80 70 90 N.R..sup.(1) 
3,5-Dichloro-6-fluoro-2-(2-methoxy-1- 
methylethoxy)pyridine 
70 N.R..sup.(1) 
60 100 60 N.R..sup.(1) 
Control 0 0 0 0 0 0 
__________________________________________________________________________ 
.sup.(1) N.R. = Not run 
EXAMPLE XVIII 
Additional products of the present invention were evaluated for the 
post-emergent control of barnyard grass, wild mustard, crabgrass, pigweed, 
yellow foxtail and bindweed. In these evaluations, plots of the above 
plant species grown to a height of about 4 inches were used. Aqueous spray 
compositions, each containing 3,000 parts of a given 
6-fluoro-3,5-dihalopyridyloxy compound per million parts of ultimate 
composition, were prepared in accordance with the procedures of Example 
XVI, and each separate composition was applied to a separate plot. The 
application was made to the point of run-off and was carried out with 
conventional spraying equipment. Other plots were sprayed with similar 
compositions containing no toxicant to serve as controls. Thereafter, the 
plots were maintained under conditions conducive for plant growth. Two 
weeks after treatment, the plots were examined for plant growth and 
evaluated. The results of the examination of the treated plots are set 
forth below in Table B. 
TABLE B 
__________________________________________________________________________ 
Percent Kill and Control of 
Barnyard 
Wild Crab- 
Pig- Yellow 
Bind- 
Compound Employed Grass 
Mustard 
grass 
weed Foxtail 
weed 
__________________________________________________________________________ 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)- 
propionic acid 90 95 90 80 90 N.R..sup.(1) 
(3,5-Dibromo-6-fluoro-2-pyridyloxy) acetic 
acid 90 85 85 80 70 80 
Ethyl(3,5-dibromo-6-fluoro-2-pyridyloxy) 
acetate 85 85 80 70 60 95 
Control 0 0 0 0 0 0 
__________________________________________________________________________ 
.sup.(1) N.R. = Not run 
EXAMPLE XIV 
Aqueous compositions of various ester compounds prepared in accordance with 
Example XVI were employed for pre-emergent applications on plots 
immediately after they were seeded with crabgrass, wild oats, barnyard 
grass, wild mustard, pigweed, yellow foxtail and bindweed. Other plots 
similarly seeded with the above plant species were treated with like 
compositions containing no toxicant to serve as control plots. The 
treating applications were carried out by drenching the soil with the 
aqueous compositions to obtain a treating rate of 2.0 pounds per acre. 
Thereafter, the plots were maintained under conditions conducive for good 
plant growth. Two weeks after treatment, the plots were examined to 
determine the percent plant growth and evaluated. The results of the 
examinations are set forth below in Table C. 
TABLE C 
__________________________________________________________________________ 
Percent Kill and Control of 
Johnson 
Barnyard 
Wild Crab- 
Pig- Yellow 
Bind- 
Wild 
Rag- 
Compound Employed Grass 
Grass 
Mustard 
grass 
weed Foxtail 
weed Oats 
weed 
__________________________________________________________________________ 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)- 
propionic acid 90 90 100.sup.(1) 
100.sup.(2) 
NR.sup.(3) 
75 100.sup.(2) 
50 70 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)- 
N-methyl acetamide 100 90 90 95 90 100 100 50 100 
6-(3,5-Dichloro-6-fluoro-2-pyridyloxy)- 
1-hexanol 90 85.sup.(2) 
100 90.sup.(1) 
50.sup.(2) 
90 80 90.sup.(4) 
100 
2-[2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)- 
ethoxy]ethanol 80 100.sup.(2) 
100.sup.(1) 
100.sup.(2) 
100.sup.(4) 
70 100.sup.(4) 
50 100.sup.(2) 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)- 
ethanol 100 100 100 100 100 100 100 70 100 
(3,5-Dichloro-6-fluoro-2-pyridyloxy) 
acetic acid 100 90 100 100 100 100 100 -- 100 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)- 
acetamide 95 95 100 100 NR.sup.(3) 
85 100 75 100 
Methyl(3,5-dichloro-6-fluoro-2-pyridyloxy) 
acetate 100 100 NR.sup.(3) 
100 100 100.sup. 
100 70 NR.sup.(3) 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)- 
N-(2-hydroxyethyl)acetamide 
90 95 100.sup.(1) 
100.sup.(2) 
100.sup.(4) 
100 100 90.sup.(4) 
100.sup.(1) 
N-[(3,5-Dichloro-6-fluoro-2-pyridyloxy)- 
acetyl]glycine 100 90 100.sup.(1) 
100.sup.(1) 
100.sup.(1) 
100.sup.(1) 
100.sup.(1) 
-- 100.sup.(1) 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)- 
N-(2-hydroxyethyl)-N-methyl acetamide 
100 90 100 100 100 90 90 65 100.sup.(2) 
2-(3,5-Dichloro-6-fluoro-2-pyridyloxy)- 
2-propanol in admixture with 3,5-Dichloro- 
6-fluoro-2-pyridyloxy-2-propanol 
80 70 90 85 100 90.sup.(4) 
100.sup.(4) 
50.sup.(5) 
100.sup.(5) 
3,5-Dichloro-6-fluoro-2(2-(2- 
methoxyethoxy)ethoxy)pyridine 
70 70 N.R..sup.(3) 
100 N.R..sup.(3) 
70 N.R..sup.(3) 
N.R..sup.(3) 
N.R..sup.(3) 
3,5-Dichloro-6-fluoro-2-(2-(2- 
ethoxyethoxy)ethoxy)pyridine 
70 70 N.R..sup.(3) 
100 N.R..sup.(3) 
70 N.R..sup.(3) 
N.R..sup.(3) 
N.R..sup.(3) 
2-[2-(2-(3,5-Dichloro-6-fluoro- 
2-pyridyloxy)ethoxy)ethoxy]ethanol 
40 50 N.R..sup.(3) 
70 N.R..sup.(3) 
70 N.R..sup.(3) 
N.R..sup.(3) 
N.R..sup.(3) 
Ethyl[2-(3,5-dichloro-6-fluoro-2- 
pyridyloxy)]acetate 99 90 N.R..sup.(3) 
100 N.R..sup.(3) 
90 N.R..sup.(3) 
N.R..sup.(3) 
N.R..sup.(3) 
3,5-Dichloro-6-fluoro-2-(2- 
ethoxyethoxy)pyridine 
70 50 N.R..sup.(3) 
70 N.R..sup.(3) 
70 N.R..sup.(3) 
N.R..sup.(3) 
N.R..sup.(3) 
2-(3,5-Dichloro-6-fluoro-2-pyridyl- 
oxy)ethyl N-phenyl carbamate 
90 80 N.R..sup.(3) 
100 N.R..sup.(3) 
80 N.R..sup.(3) 
N.R..sup.(3) 
N.R..sup.(3) 
2-(3,5-Dichloro-6-fluoro-2-pyri- 
dyloxy) ethyl 2-methylpropionate 
90 95 N.R..sup.(3) 
100 N.R..sup.(3) 
95 N.R..sup.(3) 
N.R..sup.(3) 
N.R..sup.(3) 
2-(3,5-dichloro-6-fluoro-2-pyri- 
dyloxy)]propionate 100 95 N.R..sup.(3) 
100 N.R..sup.(3) 
95 N.R..sup.(3) 
N.R..sup.(3) 
N.R..sup.(3) 
2-(3,5-Dichloro-6-fluoro-2-pyri- 
dyloxy)ethyl-N-methyl carbamate 
80 80 N.R..sup.(3) 
100 N.R..sup.(3) 
80 N.R..sup.(3) 
N.R..sup.(3) 
N.R..sup.(3) 
Control 0 0 0 0 0 0 0 0 0 
__________________________________________________________________________ 
.sup.(1) Actual treating rate 0.5 pound per acre 
.sup.(2) Actual treating rate 1.0 pound per acre 
.sup.(3) N.R. = not run 
.sup.(4) Actual treating rate 20.0 pounds per acre 
.sup.(5) Actual treating rate 10.0 pounds per acre 
EXAMPLE XX 
Aqueous compositions of various compounds prepared in accordance with 
Example XVI were employed for pre-emergent applications on plots 
immediately prior to their being seeded with seeds of barnyard grass, 
pigweed and bindweed. Other plots similarly to be seeded with the above 
plant species were treated with the like compositions containing no 
toxicant to serve as control plots. The treating applications were carried 
out by drenching the soil with the aqueous compositions to a depth of 
about one inch to obtain a treating rate of 10 pounds per acre. The plots 
were thereafter seeded with seeds of the above plant species and the seeds 
covered with a sand cap and watered with sufficient water to insure seed 
germination. Thereafter, the plots were maintained under conditions 
conducive for good plant growth. Four weeks after treatment, the plots 
were examined to determine the percent plant growth and evaluated. The 
results of the examinations are set forth below in Table D. 
TABLE D 
______________________________________ 
Percent Kill and Control of 
Pig- Barnyard Bind- 
Compound Employed weed Grass weed 
______________________________________ 
Ethyl(3,5-dibromo-6-fluoro- 
2-pyridyloxy) acetate 
100 98 100 
Ethyl[2-(3,5-dichloro-6- 
fluoro-2-pyridyloxy)]propionate 
100 90 100 
3-(3,5-Dichloro-6-fluoro-2- 
pyridyloxy)-1,2-propanediol 
98 95 98 
3,5-Dichloro-6-fluoro-2-(2-(2- 
methoxy)ethoxy)pyridine 
100 80 N.R..sup.(1) 
3,5-Dichloro-6-fluoro-2-(2-(2- 
ethoxyethoxy)ethoxy)pyridine 
100 70 N.R..sup.(1) 
Ethyl[2-(3,5-dichloro-6- 
fluoro-2-pyridyloxy)]acetate 
100 100 N.R..sup.(1) 
2-(3,5-Dichloro-6-fluoro- 
2-pyridyloxy) ethyl 2,2- 
dichloropropionate 
100 99 N.R..sup.(1) 
3,5-Dichloro-6-fluoro-2-(2- 
phenoxyethoxy)pyridine 
N.R..sup.(1) 
70 N.R..sup.(1) 
2-(2-(2-Butoxyethoxy)ethoxy)- 
3,5-dichloro-6-fluoropyridine 
100 80 N.R..sup.(1) 
3,5-Dichloro-6-fluoro-2-(2- 
methoxyethoxy)pyridine 
N.R..sup.(1) 
80 N.R..sup.(1) 
Ethyl[2-(3,5-dichloro-6- 
fluoro-2-pyridyloxy)]pro- 
pionate 100 99 N.R..sup.(1) 
3,5-DIchloro-6-fluoro-2-(2- 
ethoxyethoxy)pyridine 
100 80 N.R..sup.(1) 
3,5-Dichloro-6-fluoro-2-(2- 
methoxy-2-methylethoxy)- 
pyridine 100 70 N.R..sup.(1) 
2-(3,5-Dichloro-6-fluoro-2- 
pyridyloxy)ethyl-N-methyl 
carbamate 100 80 N.R..sup.(1) 
2-(2-Butoxyethoxy)-3,5-di- 
chloro-5-fluoropyridine 
N.R..sup.(1) 
80 N.R..sup.(1) 
2-(3,5-dichloro-6-fluoro- 
2-pyridyloxy) ethyl 2,2- 
dimethyl propionate 
100 90 N.R..sup.(1) 
2-(2-(2-(3,5-Dichloro-6- 
fluoro-2-pyridyloxy)- 
ethoxy)ethoxy)ethanol 
90 70 N.R..sup.(1) 
2-(3,5-Dichloro-6-fluoro- 
2-pyridyloxy)ethyl-N- 
phenyl carbamate 100 80 N.R..sup.(1) 
3,5-Dibromo-6-fluoro-2-pyridy- 
loxy acetic acid 100 98 100 
2-(3,5-Dichloro-6-fluoro-2- 
pyridyloxy)-N-butyl acetamide 
100 98 100 
2-(3,5-Dichloro-6-fluoro-2- 
pyridyloxy)-N-octyl acetamide 
100 98 100 
(3,5-Dichloro-6-fluoro-2-pyridyl- 
oxy)acetonitrile 100 100 100 
4-(3,5-Dichloro-6-fluoro-2- 
pyridyloxy)-2-buten-1-ol 
100 100 100 
4-(3,5-Dichloro-6-fluoro-2- 
pyridyloxy)-1-butanol 
100 100 100 
Control 0 0 0 
______________________________________ 
.sup.(1) N.R. = not run 
EXAMPLE XXI 
Preparation of Starting Materials 3,5-Dichloro-2,6-difluoro pyridine 
##STR42## 
A solution was prepared by adding 20 grams (0.092 mole) of 
2,3,5,6-tetrachloro pyridine and 16 grams (0.092 mole) of dried potassium 
fluoride to 40 milliliters of dimethylformamide. The mixture was refluxed 
at the reflux temperature of the mixture for 61/2 hours. The reaction 
mixture was poured into an equal amount of water with agitation. A dark 
precipitate formed which was separated and extracted with hexane. The 
hexane layer was separated and passed through activated charcoal and 
filtered through diatomaceous earth. The hexane was removed by aspiration 
leaving 16.9 grams (92 percent yield) of the 3,5-dichloro-2,6-difluoro 
pyridine product. Infrared analysis of the product confirmed the 
structure. 
EXAMPLE XXII 
6-Fluoro-3,5-dichloro-2-pyridinol 
##STR43## 
To a 500 milliliter nickel lined reaction bomb was added 10 grams (0.05 
mole) of 3,5-dichloro-2,6-difluoropyridine (prepared as above, Example I), 
4.4 grams (0.11 mole) of sodium hydroxide and 65 milliliters of water. The 
bomb was sealed and the reaction carried out at 125.degree. C. for 21/2 
hours. At the completion of the reaction, the bomb was opened and the 
contents, which consisted of a crystalline meterial and a dark liquid, 
were removed. The mixture was heated until the crystals went into 
solution. Activated charcoal was added and the mixture filtered through 
diatomaceous earth. The solution was acidified, cooled and filtered to 
recover the crude 6-fluoro-3,5-dichloro-2-pyridinol product as a solid. 
The product was purified by recrystallization from hot benzene and 
recovered as white crystals melting at 136.degree.-140.degree. C. The 
product was recovered in a yield of 3.2 grams (31.7 percent). The 
structure of the product was analyzed by infrared. Upon elemental 
analysis, the product was found to have carbon, hydrogen, chlorine, 
fluorine and nitrogen contents of 33.6, 1.3, 37.2, 10.7 and 7.7 percent, 
respectively, as compared with the theoretical contents of 33.0, 1.1, 
38.9, 10.5 and 7.7 percent, respectively, calculated for the above named 
compound. 
EXAMPLE XXIII 
6-Fluoro-3,5-dibromo-2-pyridinol 
##STR44## 
A solution was prepared by dissolving 10 grams (0.09 mole) of 
6-fluoro-2-pyridinol in 50 milliliters of glacial acetic acid. A solution 
consisting of 28.2 grams (0.18 mole) of bromine in 10 milliliters of 
glacial acetic acid was added thereto with stirring over a period of 45 
minutes. During the addition, the temperature was held at 
.about.25.degree. C. Upon the completion of the bromine addition, the 
mixture was stirred an additional 2 hours and allowed to stand overnight 
(.about.15 hours). The reaction mixture was poured into water and the 
solid which formed was removed by filtration, washed and partially dried. 
The crude 6-fluoro-3,5-dibromo-2-pyridinol was purified by 
recrystallization from hot benzene. The product was in the form of light 
yellow crystals melting at 175.degree.-176.degree. C. and was recovered in 
a yield of 16 grams (67 percent). Upon analysis, the product was found to 
have carbon, hydrogen, bromine and nitrogen contents of 22.8, 0.9, 58.7 
and 5.1 percent, respectively, as compared with the theoretical contents 
of 22.2, 0.7, 59.0 and 5.2 percent, respectively, calculated for the above 
named compound.