Naphthyridinyloxy(or thio)phenoxy propanoic acids, derivatives thereof and methods of herbicidal use

Novel 2-naphthyridinyloxy(or thio)phenoxy propanoic acid compounds of the formula ##STR1## wherein ##STR2## represents a 6 membered nitrogen containing an aromatic ring which forms a 1,5-, 1,6-, 1,7- or 1,8-naphthyridinyl moiety with the adjoining pyridine ring, said naphthyridinyl moiety optionally substituted at the 6 position of the naphthyridinyl moiety with a chloro, bromo, iodo, CF.sub.3, or fluoro atom; PA1 A represents O or S; and PA1 agriculturally acceptable salts, esters, ethers, and amides thereof, are useful as fungicides and herbicides, particularly effective against grassy weeds.

BACKGROUND OF THE INVENTION 
The present invention relates to novel 2-(naphthyridinyloxy(or 
thio)phenoxy)propanoic acids and agriculturally acceptable salts, amides, 
ethers and esters thereof, optionally substituted in the 6 position of the 
naphthyridine ring system. The present invention also relates to 
herbicidal and fungicidal compositions of such novel compounds and methods 
of using such compounds for the control of grassy weeds and fungi. 
Various aryloxy(or thio)phenoxy alkanoic acids are known as herbicides. 
U.S. Pat. No. 4,236,912 discloses quinolinyloxy(or thio)phenoxy alkanoic 
acids and derivatives thereof. European Patent Application No. 483, 
published Feb. 7, 1979, discloses 2-pyridyloxy(or thio)phenoxy alkanoic 
acids and derivatives thereof. Belgian Pat. No. 834,495, issued Feb. 2, 
1976, as well as the published German patent application equivalent 
thereto, viz., No. 2,546,251, published Mar. 29, 1976, describe 
2-((4-pyridinyl-2-oxy)phenoxy)alkanoic acids, salts and esters having a 
halo substitution in the 3 and/or 5 ring positions in the pyridine ring. 
Published Japanese Patent Application No. 129,313/75, filed in Japan on 
Oct. 29, 1975 teaches pyridyloxyphenoxypropanols and esters thereof, while 
published Japanese Patent Application No. 064,160/75, filed on May 30, 
1975, teaches pyridyloxyphenoxy-propionitrile compounds. 
Heretofore, naphthyridinyloxy(or thio)phenoxy propanoic acids and 
agriculturally acceptable salts, amides, ethers and esters thereof have 
not been disclosed. 
SUMMARY OF THE INVENTION 
The present invention is directed to 2-naphthyridinyloxy(or thio)phenoxy 
propanoic acids corresponding to the formula 
##STR3## 
wherein 
##STR4## 
represents a six-membered nitrogen-containing aromatic ring which when 
fused to the above shown pyridyl ring forms a 1,5-, 1,6-, 1,7- or 
1,8-naphthyridinyl moiety optionally substituted at the 6 position of the 
naphthyridinyl moiety with a chloro, iodo, CF.sub.3, bromo, or fluoro atom 
with the proviso that said substitution occurs only when the 6-position of 
said naphthyridinyl moiety is occupied by a carbon atom; 
A represents O or S; and agriculturally acceptable salts, amides, ethers, 
and esters thereof. 
The compounds of the above Formula I, hereinafter referred to as "active 
ingredients", have been found to be active as herbicides and fungicides. 
Accordingly, the present invention also encompasses compositions 
containing one or more active ingredients as well as methods of 
controlling unwanted vegetation and fungi. Such methods comprise, for 
example, applying a herbicidally effective amount of one or more active 
ingredients preemergently or post-emergently to the locus of the undesired 
vegetation, and particularly to the locus where a valuable crop is to 
germinate and grow. 
DETAILED DESCRIPTION 
The term "herbicide" is used herein to mean an active ingredient which 
controls or adversely modifies the growth of plants. By "growth 
controlling" or "herbicidally-effective" amount is meant an amount of 
active ingredient which causes an adversely modifying effect and includes 
deviations from natural development, killing, regulation, dessication, 
retardation, and the like. The term "plants" is meant to include germinant 
seeds, emerging seedlings and established vegetation. 
The term "plants", when used herein, is meant to include germinant seeds, 
emerging seedlings, as well as established vegetation. 
The term "agriculturally acceptable salts, amides, ethers and esters", when 
used to describe the active ingredients disclosed herein, is meant to 
encompass any salt, amide, ether or ester of said active ingredients 
(acids) which does not substantially affect the herbicidal activity of 
said active ingredients. Agriculturally acceptable salts, amides, ethers 
and esters of the active ingredients include compounds of the formula 
##STR5## 
wherein 
##STR6## 
and A are as hereinbefore defined; Z represents --CO.sub.2 H (the acids), 
--CO.sub.2 M, --CO.sub.2 R, --COSR, --CONR'.sub.2, --CSNH.sub.2, --CN, 
--CH.sub.2 OR' or --CH.sub.2 O.sub.2 CR'; 
M represents Na, K, Mg, Ca or N(R").sub.4 ; 
R represents C.sub.1 -C.sub.8 alkyl or C.sub.3 -C.sub.6 alkoxyalkyl; 
each R' independently represents H or C.sub.1 -C.sub.4 alkyl; and 
R" independently represents H, C.sub.1 -C.sub.4 alkyl or C.sub.2 -C.sub.3 
hydroxyalkyl. 
The terms "C.sub.1 -C.sub.4 alkyl" and "C.sub.1 -C.sub.8 alkyl" refer to 
different size alkyl groups which may be straight, branched, or cyclic, 
when the group contains at least three carbon atoms, and, contain 1-4 or 
1-8 carbon atoms respectively. 
The terms "C.sub.2 -C.sub.3 hydroxyalkyl" and "C.sub.3 -C.sub.6 
hydroxyalkyl" refer to different size hydroxyalkyl groups having 2-3 or 
3-6 carbon atoms, respectively, and the alkyl portion may be straight or 
branched, or cyclic when the group contains at least three carbon atoms. 
The active ingredients of the present invention are generally crystalline 
solids at ambient temperatures which are generally soluble in many organic 
solvents commonly employed as herbicidal carriers such as alcohols, 
acetone, chloroform, aromatic petroleum solvents and methylene chloride. 
Active ingredients within the scope of the present invention include 
2-(1,5-naphthyridinyl)oxy(or thio)phenoxy propanoic acids; 
2-(1,6-naphthyridinyl)oxy(or thio)phenoxy propanoic acids; 
2-(1,7-naphthyridinyl)oxy(or thio)phenoxy propanoic acids; 
2-(1,8-naphthyridinyl)oxy(or thio)phenoxy propanoic acids and 
agriculturally acceptable salts, amides, ethers and esters thereof. These 
active ingredients include compounds represented by the following 
formulas: 
##STR7## 
wherein Y represents H, Cl, I, CF.sub.3, Br or F, and A represents O or S. 
The active ingredient of the above Formula I which is 
2-(4-((6-chloro-2-(1,5-naphthyridinyl))oxy)phenoxy)propanoic acid and its 
agriculturally acceptable salts, amides, ethers, and esters constitute 
preferred compounds of the present invention. 
The 2-naphthyridinyloxyphenoxy propanoic acids are prepared by reacting an 
appropriately substituted 2-halonaphthyridine with the disodium or 
dipotassium salt of 2-(4-hydroxyphenoxy)propanoic acid in a suitable 
solvent medium, such as, dimethylsulfoxide (DMSO), dimethylformamide 
(DMF), hexamethylpyrophosphoramide or tetrahydrofuran (THF). 
Alternatively, a monosodium or monopotassium salt of 
2-(4-hydroxyphenoxy)propanoic acid alkyl ester is reacted with an 
appropriately substituted 2-halonaphthyridine to form the alkyl ester 
derivative. The reaction is advantageously carried out at a temperature in 
the range of from about 60.degree. C. to about 150.degree. C. and 
preferably from about 75.degree. C. to about 110.degree. C. under ambient 
atmospheric pressure. 
The 2-naphthyridinylthiophenoxy propanoic acids are prepared by reacting an 
appropriately substituted 2-halonaphthyridine with 
2-(4-mercaptophenoxy)propanoic acid in a suitable solvent medium, such as, 
DMSO, DMF, hexamethylpyrophosphoramide or THF. The reaction is 
advantageously carried out at a temperature in the range of from about 
60.degree. C. to about 150.degree. C. and preferably from about 75.degree. 
C. to about 110.degree. C. under ambient atmospheric pressure. 
The reaction between the naphthyridine and the hydroxy- or mercapto-phenoxy 
propanoic acid starting materials is carried out in a polar solvent such 
as, DMSO, to which has been added about 2 molar equivalents of a base such 
as sodium hydroxide or potassium carbonate. The reaction is usually 
carried out at a temperature in the range of from about 70.degree. to 
about 150.degree. C. and usually the reaction is complete in about 1/2 to 
about 8 hours. The pressure at which the reaction is carried out is not 
critical and the reaction is generally conducted at ambient atmospheric 
pressure. After the reaction is substantially complete, the reaction 
mixture is allowed to cool to room temperature and then poured into cold 
water and thereafter acidified by the addition of HCl. The desired 
product, i.e. naphthyridinyloxy(or thio)phenoxy propanoic acid compound, 
is then extracted and purified, employing known extraction and 
purification techniques, such as, for example, extraction with methylene 
chloride and thereafter evaporating the methylene chloride under vacuum 
resulting in a solid or an oil which is then triturated with water to give 
a solid product. 
Once the naphthyridinyloxy(or thio)phenoxy propanoic acid compounds of the 
present invention are prepared, the agriculturally acceptable salts, 
amides, ethers and esters thereof, hereinbefore described, are readily 
made in accordance with well known procedures relating to the preparation 
of salts, amides, ethers and esters of propanoic acid and substituted 
propanoic acid compounds. U.S. Pat. No. 4,236,912, which discloses the 
preparation of quinolinyloxy(or thio)phenoxy alkanoic acids and 
derivatives thereof, describes methods analogous to those employed in 
making the agriculturally acceptable salts, amides, ethers and esters of 
the active ingredients and is hereby incorporated by reference and made a 
part hereof. 
The following examples illustrate the present invention and the manner in 
which it can be practiced but, as much, are not to be construed as 
limitations upon the overall scope of the same.

EXAMPLE 1 
Preparation of 2-(4-((6-chloro-2-(1,5-naphthyridinyl))oxy)phenoxy)propanoic 
acid 
##STR8## 
To a stirred, nitrogen flushed mixture of 270 mg (1.5 m moles) of 
2-(4-hydroxy)phenoxy propanoic acid and 420 mg (3 m moles) of powdered 
anhydrous potassium carbonate in 15 ml of DMSO was added 300 mg (1.5 m 
moles) of 2,6-dichloro-1,5-naphthyridine. The mixture was slowly warmed to 
105.degree.-110.degree. C. and maintained at this temperature range for 
one hour. The mixture was cooled to room temperature, poured into water 
and then extracted with methylene chloride. The aqueous layer was then 
made acidic by the addition of 6N HCl and then extracted twice with 
methylene chloride. The methylene chloride phases were then combined, 
washed twice with water and then evaporated to dryness under vacuum. The 
resulting oil was triturated with water to give an off-white solid. The 
solid was recrystallized once from toluene/pentane and once from 
toluene/hexane to give 327 mg of white crystals having a melting point of 
139.degree.-143.degree. C. Upon analysis, the prepared compound exhibited 
a carbon, hydrogen and nitrogen content of 58.67, 3.84 and 7.76 percent, 
respectively, as compared to the theoretical contents of 59.22, 3.80 and 
8.13 percent, respectively, calculated for C.sub.17 H.sub.13 ClN.sub.2 
O.sub.4. 
EXAMPLE 2 
Preparation of 2-(4-(1,8-naphthyridin-2-yloxy)phenoxy)propanoic acid 
##STR9## 
A 3-necked flask was equipped with a thermometer, a magnetic stirrer, a 
reflux condenser and a nitrogen line and flushed with nitrogen. The flask 
was charged with 15 ml of hexane and 1.38 gm (28.8 m moles) of 50% NaH/oil 
dispersion. After stirring for 10 minutes the hexane was decanted and 
replaced with 5 ml of DMSO followed by the dropwise addition of a solution 
of 2.18 gm (12 m moles) of 2-(4-hydroxyphenoxy)propanoic acid in 5 ml of 
DMSO. The mixture was warmed to 60.degree. C. and a solution of 1.97 gm of 
2-chloro-1,8-naphthyridine in 10 ml of DMSO was added. After warming the 
reaction mixture at 95.degree. C. for one hour, the mixture was cooled to 
room temperature and water cautiously added. The solution was extracted 
with methylene chloride and the aqueous phase neutralized with acetic acid 
to give a white precipitate. The aqueous mixture was extracted with 
CH.sub.2 Cl.sub.2 and the organic layer washed twice with water, dried 
over Na.sub.2 SO.sub.4 and evaporated to dryness to give 3.3 gm of yellow 
solid which could not be redissolved in ether or CH.sub.2 Cl.sub.2. 
EXAMPLE 3 
Preparation of 2-(4-(2-(1,8-naphthyridinyl)oxy)phenoxy)propanic acid, 
methyl ester 
##STR10## 
Thionyl chloride (15 ml) was added to 3.1 gm of 
2-(4-(1,8-naphthyridin-2-oxy)phenoxy)propanic acid and this solution was 
heated at reflux for 3 hours. After cooling, the solution was diluted with 
25 ml of toluene. The solvent was then removed by vacuum distillation. The 
residual solid was diluted with 50 ml of toluene and then 5 ml of methanol 
was slowly added. After 3 hours of stirring at room temperature, the 
mixture was poured into water and the aqueous layer made basic with NaOH. 
The aqueous layer was then extracted twice with CH.sub.2 Cl.sub.2. The 
combined organic layers were then washed twice with water, dried over 
Na.sub.2 SO.sub.4 and evaporated to dryness. The residue was purified by 
silica gel chromatography, eluting with 50% ethyl acetate/hexane, to give 
a brown gum (0.5 gm) which was pure by thin layer chromatography (TLC) and 
nuclear magnetic resonance (NMR) criteria. Carbon, hydrogen and nitrogen 
content by weight percent calculated for C.sub.18 H.sub.16 N.sub.2 O.sub.4 
is C, 66.85; H, 4.97; N, 8.64; which compared to that actually found of 
C, 65.41; H, 5.06; and N, 8.43. 
EXAMPLE 4 
Preparation of 2-(4-(2-(1,6-Naphthyridinyl)oxy)phenoxy)propanoic acid, 
methyl ester 
##STR11## 
A nitrogen flushed flask was charged with 1.18 gm (6 m moles) of 
2-(4-hydroxyphenoxy)propanoic acid, methyl ester, 20 ml of dry DMSO, 0.99 
gm (7.2 m moles) of dry powdered potassium carbonate and 0.99 gm (6 m 
moles) of 2-chloro-1,6-naphthyridine. This mixture was warmed at 
80.degree. C. for one hour. After cooling to room temperature the mixture 
was poured into water and extracted 3 times with ether. The combined ether 
layers were washed with 5% aqueous NaOH, dried over MgSO.sub.4 and 
evaporated to dryness. The residual solid was recrystallized from 
methylcyclohexane to give 1.58 gm (81%) of the product as white platelets 
having a melting point of 88.degree.-90.degree. C. Carbon, hydrogen and 
nitrogen analysis calculated for C.sub.18 H.sub.16 N.sub.2 O.sub.4 is C, 
66.65; H, 4.97; N, 8.64, which compares to that actually found of C, 
66.41; H, 4.99; and N, 8.60. 
EXAMPLE 5 
Preparation of 2-(4-((6-chloro-2-(1,7-naphthyridinyl))oxy)phenoxy)propanoic 
acid, methyl ester 
##STR12## 
Step 1: Preparation of 2,2-dimethyl-N-(2-chloro-5-pyridinyl)propanamide 
##STR13## 
To an ice-cooled solution of 45 g (0.35 mole) of 5-amino-2-chloropyridine 
and 42.4 g (0.42 mole) of triethylamine in 300 ml of CH.sub.2 Cl.sub.2 was 
added, dropwise, a solution of 44.3 g (0.368 moles) of trimethyl acetyl 
chloride in 60 ml of dichloromethane over a period of 1.5 hours. This 
mixture was stirred at room temperature for 2 hours, poured into 5% 
aqueous NaOH and the dichloromethane layer separated. The organic layer 
was washed with 5% aqueous NaOH, dried over Na.sub.2 SO.sub.4 and 
evaporated to leave a brown oil which solidified on standing. This solid 
was taken up in hot ethyl acetate, treated with charcoal, filtered and 
diluted with hexane. Cooling this solution resulted in the precipitation 
of 58.7 g (79% of theoretical) of white crystals having a melting point of 
120.degree.-123.degree. C. Carbon, hydrogen and nitrogen content 
calculated for C.sub.10 H.sub.13 ClN.sub.2 O is C, 56.47; H, 6.16; and N, 
13.17 percent by weight which compared to that actually found of C, 56.31; 
H, 6.14; and N, 13.02 percent by weight. 
Step 2: Preparation of 2,2-dimethyl-N-(2-chloro-4 
-formyl-5-pyridinyl)propanamide 
##STR14## 
A three-necked flask, equipped with a thermometer, a magnetic stirrer and a 
nitrogen inlet, was flushed with nitrogen. The flask was charged with 
10.63 g of 2,2-dimethyl-N-(2-chloro-5-pyridinyl)propanamide (50 mmoles) 
and stoppered with a rubber septum. 100 Ml of THF was added to the flask. 
The flask was cooled in a liquid N.sub.2 /MeOH slush bath and 52.4 ml (110 
mmoles) of 2.1M t-butyllithium was slowly added maintaining the 
temperature .ltoreq.75.degree. C. by the rate of addition. The flask was 
transferred to a dry-ice/isopropanol (IPA) bath and stirred for 1.5 hours 
when a solution of 10.95 g (150 mmoles) of dimethylformamide in 5 ml of 
THF was added. The mixture was stirred at -78.degree. C. for 30 minutes, 
40 ml of 6N HCl was then added to the flask and the reaction mixture was 
allowed to warm to room temperature. After stirring for 30 minutes at room 
temperature, water and ether were added and the organic layer was 
separated. The aqueous layer was washed twice with ether and the combined 
organic layers washed with saturated NaCl, dried over MgSO.sub.4 and 
evaporated to leave an oil. The oil was triturated sequentially with water 
and ether and filtered to remove precipitated solids. The ethereal 
filtrate was recovered and dried over MgSO.sub.4 and the ether evaporated. 
Chromatography of the oil residue by preparative liquid chromatography 
(eluting with 20% EtOAc (ethyl acetate)/hexane) gave 3.5 g of the aldehyde 
(29 % of theoretical) as a pale yellow solid. The solid was recrystallized 
from hexane to give yellow needles having a melting point of 
105.degree.-106.5.degree. C. Carbon, hydrogen, nitrogen and chlorine 
content calculated for C.sub.11 H.sub.13 ClN.sub.2 O is C, 54.89; H, 5.44; 
N, 11.64 and Cl, 14.73 percent by weight which compares to that actually 
found upon analysis of C, 54.79; H, 5.38; N, 11.63; and Cl, 14.74. 
Step 3: Preparation of 
2-chloro-3-((2,2-dimethyl-1-oxopropyl)amino)-.beta.-hydroxy-4-pyridine 
propanoic acid, 1,1-dimethyl ethyl ester 
##STR15## 
An oven-dried, 3-necked flask, equipped with a magnetic stirrer, a 
thermometer and a nitrogen inlet, was flushed with nitrogen. The flask was 
stoppered with a rubber septum and charged with 100 ml of ether and 7.9 ml 
(56.7 mmoles) of diisopropylamine. The solution was cooled in a 
dry-ice/IPA bath while 34.3 ml (56.7 mmoles) of 1.65M n-butyllithium in 
hexane was added. After stirring at -78.degree. C. for 15 minutes, a 
solution of 3.45 g (29.7 mmoles) of t-butylacetate in 5 ml of ether was 
slowly added. After 15 minutes a solution of 6.5 g (27 mmoles) of 
2,2-dimethyl-N-(2-chloro-4-formyl-5-pyridinyl)propanamide in 20 ml of 
ether and 5 ml of THF was slowly added to immediately give a yellow 
precipitate. The reaction mixture was stirred at -78.degree. C. for 15 
minutes, slowly warmed to room temperature and poured into water. The 
ether layer was separated and the aqueous phase extracted twice with 
ether. The combined organic layers were washed with saturated NaCl, dried 
over MgSO.sub.4 and evaporated to dryness. The residual gum was purified 
by preparative liquid chromatography eluting with 30% ethyl 
acetate/hexane. After removal of solvent, the resulting gum was taken up 
in hot hexane containing a trace of acetone. Upon cooling, 6.24 g (65% of 
theoretical) of white crystals of the above-captioned compound formed 
having a melting point of 123.degree.-125.degree. C. The carbon, hydrogen, 
nitrogen and chlorine content calculated for C.sub.17 H.sub.25 ClN.sub.2 
O.sub.4 is C, 57.21; H, 7.06; N, 7.85; and Cl, 9.94 percent by weight 
which compares to that actually found upon analysis of C, 56.91; H, 7.03; 
N, 7.83; and Cl, 10.19. 
Step 4: Preparation of 6-chloro-1,7-naphthyridine-2-one 
##STR16## 
A solution of 4.63 g (13 mmoles) of 
2-chloro-5-((2,2-dimethyl-1-oxopropyl)amino)-.beta.-hydroxy-4-pyridine 
propanoic acid, 1,1-dimethylethyl ester in 70 ml of dioxane and 30 ml of 
3N HCl in water was warmed at reflux for a period of 4 hours. The solution 
was diluted with 100 ml of water and cooled to give a white precipitate. 
The crystals were filtered, washed with water and dried in a vacuum oven 
to give 2.18 g (93% of theoretical) of the above-captioned compound having 
a melting point of 304.degree.-306.degree. C. The carbon, hydrogen and 
nitrogen content calculated for C.sub.8 H.sub.5 ClN.sub.2 O is C, 53.20; 
H, 2.79; and N, 15.52 percent by weight which compares to that actually 
found upon analysis of C, 53.55; H, 2.79; and N, 15.47. 
Step 5: Preparation of 2,6-dichloro-1,7-naphthyridine 
##STR17## 
A mixture of 1.08 g (6 mmoles) of 6-chloro-1,7-naphthyridin-2-one and 10 ml 
of POCl.sub.3 were warmed at reflux for one hour to give a clear solution. 
Upon cooling, a precipitate formed and the mixture was poured cautiously 
over ice. CH.sub.2 Cl.sub.2 was added and the mixture was neutralized with 
solid K.sub.2 CO.sub.3. The CH.sub.2 Cl.sub.2 layer was separated and the 
aqueous layer washed twice with CHCl.sub.3. The combined organic layers 
were washed with water, dried over K.sub.2 CO.sub.3 and evaporated to give 
a white solid. The solid was recrystallized from hexane/acetone to give 
1.14 g (95% of theoretical) of the desired product as short, white needles 
having a melting point of 213.degree.-216.degree. C. Analysis calculated 
for C.sub.8 H.sub.4 Cl.sub.2 N.sub.2 : C, 48.27; H, 2.03; N, 14.08. Found: 
C, 48.80; H, 2.09; N, 14.55. 
Step 6: Preparation of 2-(4-((6-chloro-2-(1,7-naphthyridinyl))oxy)phenoxy) 
propanoic acid, methyl ester 
##STR18## 
An oven-dried, three-necked flask, equipped with a thermometer, a magnetic 
stirrer and a reflux condenser attached to a nitrogen inlet, was flushed 
with nitrogen. The flask was charged with 0.83 g (6 mmoles) of anhydrous 
powdered K.sub.2 CO.sub.3, 1.08 g (5.5 mmoles) of 
2-(4-hydroxphenoxy)propanoic acid, methyl ester, 1 g (5 mmoles) of 
2,6-dichlor-1,7-naphthyridine and 20 ml of DMSO. The mixture was warmed 
with an oil bath at 80.degree.-85.degree. C. for 1.5 hours, cooled to room 
temperature and poured into 2% aqueous NaOH. The mixture was extracted 
three times with ether and the combined organic layers were washed twice 
with water, dried over MgSO.sub.4 and evaporated to dryness to give a 
white solid. The solid was recrystallized from methylcyclohexane to give 
1.57 g (88% of theoretical) of white crystals having a melting point of 
126.degree.-128.degree. C. Analysis calculated for C.sub.18 H.sub.15 
ClN.sub.2 O.sub.4 : C, 60.25; H, 4.21; N, 7.81. Found: C, 60.11; H, 4.16; 
N, 7.70. 
The compounds of the present invention have been found to be suitable for 
use in methods for the pre-emergent and post-emergent control of grasses, 
such as, barnyard grass, crabgrass, yellow foxtail and johnson grass, in 
the presence of broadleaf crops, such as, cotton, soybeans and sugar 
beets. 
For all such uses, unmodified active ingredients of the present invention 
can be employed. However, the present invention embraces the use of a 
herbicidally-effective amount of the active ingredients in composition 
form with an inert material known in the art as an agricultural adjuvant 
or carrier or solid or liquid form. Such adjuvants or carriers must not be 
phytotoxic to valuable crops particularly at the concentration employed in 
applying the composition in attempting selective weed control in the 
presence of crops. If weed control is desired in the absence of crops, it 
is generally sufficient to employ adjuvants or carriers which do not leave 
a persistent phytotoxic residue. 
Thus, for example, an active ingredient can be dispersed on a 
finely-divided solid and employed therein as a dust. Also, the active 
ingredients, as liquid concentrates or solid compositions comprising one 
or more of the 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 constituent of organic liquid compositions, oil-in-water and 
water-in-oil emulsions or 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 methods of applying the solid or liquid herbicidal 
formulations similarly are well known to the skilled artisan. 
Organic solvents that can be employed include toluene, xylene, kerosene, 
diesel fuel, fuel oil, and petroleum naphtha, ketones such as acetone, 
methylethyl ketone and cyclohexanone, chlorinated hydrocarbons such as 
trichloroethylene, and perchloroethylene, esters such as ethyl acetate, 
amyl acetate and butyl acetate, ethers e.g., ethylene glycol monomethyl 
ether and diethylene glycol monomethyl ether, alcohols, e.g., methanol, 
ethanol, isopropanol, amyl alcohol, ethylene glycol, propylene glycol, 
butylcarbitol acetate and glycerine. Mixtures of water and organic 
solvents, either as emulsions or solutions, can be employed. 
The active ingredients of the present invention can also be applied as 
aerosols, e.g., by dispersing them by means of a compressed gas such as 
one of the hydrocarbon successors to the fluorocarbons which are shortly 
to be banned. 
The active ingredients of the present invention can also be applied with 
solid adjuvants or carriers such as talc, pyrophyllite, synthetic fine 
silica, attapulgus clay, kieselguhr, chalk, diatomaceous earth, lime, 
calcium carbonate, bentonite, Fuller's earth, cotton seed hulls, wheat 
flour, soybean flour, pumice, tripoli, wood flour, walnut shell flour, 
redwood flour and lignin. 
As stated, it is frequently desirable to incorporate a surface-active agent 
in the compositions of the present invention. Such surface-active or 
wetting agents are advantageously employed in both the solid and liquid 
compositions. The surface-active agent can be anionic, cationic or 
nonionic in character. 
Typical classes of surface-active agents include alkyl sulfonate salts, 
alkylaryl sulfonate salts, alkylaryl polyether alcohols, fatty acid esters 
of polyhydric alcohols and the alkylene oxide addition products of such 
esters, and addition products of long-chain mercaptans and alkylene 
oxides. Typical examples of such surface-active agents include the sodium 
alkylbenzene sulfonates having 10 to 18 carbon atoms in the alkyl group, 
alkyl phenol ethylene oxide condensation products, e.g., p-isooctylphenol 
condensed with 20 ethylene oxide units, soaps, e.g., sodium stearate and 
potassium oleate, sodium salt of propylnaphthalene sulfonic acid, 
di(2-ethylhexyl)ester of sodium sulfosuccinic acid, sodium lauryl sulfate, 
sodium decyl sulfonate, sodium salt of the sulfonated monoglyceride of 
coconut fatty acids, sorbitan sesquioleate, lauryl trimethyl ammonium 
chloride octadecyl trimethyl ammonium chloride, polyethylene glycol lauryl 
ether, polyethylene glycol esters of fatty acids and rosin acids, e.g., 
Ethofat 7 and 13, sodium N-methyl-N-oleyl taurate, Turkey Red Oil, sodium 
dibutylnaphthalene sulfonate, sodium lignin sulfonate, polyethylene glycol 
stearate, sodium dodecyl benzene sulfonate, tertiary dodecyl polyethylene 
glycol thioether (nonionic 218), long-chain ethylene oxide-propylene oxide 
condensation products e.g., Pluronic 61 (molecular weight about 1000), 
polyethylene glycol ester of tall oil acids, sodium octophenoxyethoxyethyl 
sulfate, tris(polyoxyethylene)sorbitan monostearate (Tween 60), and sodium 
dihexylsulfosuccinate. 
The concentration of the active ingredients in solid or liquid compositions 
generally is from about 0.003 to about 95 percent by weight or more. 
Concentrations from about 0.05 to about 50 percent by weight are often 
employed. In compositions to be employed as concentrates, the active 
ingredient can be present in a concentration from about 5 to about 98 
weight percent, preferably 15-50 weight percent. The active ingredient 
compositions can also contain other compatible additaments, for example, 
phytotoxicants, plant growth regulants, pesticides and the like and can be 
formulated with solid particulate fertilizer carriers such as ammonium 
nitrate, urea and the like. 
The present compositions can be applied by the use of power dusters, boom 
and hand sprayers, spray dusters, by addition to irrigation water, and by 
other conventional means. The compositions can also be applied from 
airplanes as a dust or spray since the active ingredients are effective at 
very low application rates. 
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 amd crabgrass in pre-emergent operations and also 
against the same grasses in post-emergent operations. The active 
ingredients possess desirable herbicidal activity against the grassy 
weeds, described above, while at the same time are tolerant or selective 
to broadleaf crops such as cotton, soybeans and sugar beets. 
The exact rate to be applied is dependent not only on a specific active 
ingredient being applied, but also on a particular action desired (e.g., 
general or selective control), the plant species to be modified and the 
stage of growth thereof as well as the part of the plant to be contacted 
with the toxic active ingredient. Thus, it is to be understood that all of 
the active ingredients of the present invention and compositions 
containing the same may not be equally effective at similar concentrations 
or against the same plant species. In non-selective pre-emergence and 
foliar treatments, the active ingredients of the invention are usually 
applied at an approximate rate of from about 0.5 to about 5 pounds/acre, 
but higher rates may be appropriate in some cases such as 20 pounds/acre 
or more. In pre-emergent operations for selective uses a dosage of about 
0.01 to about 10 pounds/acre or more is generally applicable, a rate of 
0.05 to 4 pounds/acre being preferred and about 0.1 to about 2 pounds/acre 
being most preferred. For controlling an infestation of annuals, a dosage 
of about 0.1 to 0.5 pound/acre is generally utilized. When the infestation 
consists largely of perennials, a dosage of from 0.1 to 4, preferably 0.5 
to 2.0 pounds/acre should be employed. 
In post-emergent operations a dosage of about 0.01 to about 20 pounds/acre 
or more is generally applicable, although not all compounds are equally 
effective and some weeds are more difficult to control. A dosage rate in 
the range of about 0.05 to about 0.75 pounds/acre is preferred in 
selective post-emergent control of annual grassy weeds, while about 0.5 to 
about 5 pounds/acre is preferred and more preferably about 0.5 to about 2 
pounds/acre for the selective post-emergent control of perennial grassy 
weeds. 
EXAMPLE 6 
Representative compositions of the present invention were evaluated for the 
post-emergence control of species of plants listed in Table A. In these 
evaluations, plots of the plant species listed in Table A, grown to a 
height of about 4 inches, were used. Aqueous spray compositions, 
containing various amounts of 
2-(4-((6-chloro-2-(1,5-naphthyridinyl))-oxy)phenoxy) propanoic acid, i.e., 
250 ppm, 125 ppm, 62.5 ppm, 31.25 ppm, 15.6 ppm and 7.8 ppm, respectively, 
were applied to separate plots. The spray compositions were made by mixing 
the active ingredient and an emulsifier or dispersant with about 1:1 
water/acetone solution to provide spray compositions containing the 
aforementioned concentrations of active ingredient. The application to the 
plants was made to the point of run-off (250 ppm provides approximately 
0.625 lb active ingredient per acre) 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 on a 
scale of 0 to 100 where 0 represents no effect and 100 represents complete 
kill. The results of the examination of the treated plots are set forth 
below in Table A. 
TABLE A 
______________________________________ 
Percent Kill and Control of Plants at Various 
Concentrations (ppm) of 2-(4-((6-chloro-2-(1,5- 
naphthyridinyl))oxy)phenoxy)propanoic acid 
Plant Control 250 125 62.5 31.25 
15.6 7.8 
______________________________________ 
Corn 0 90 80 50 20 0 --* 
Rice 0 50 50 60 30 15 0 
Sorghum 0 60 75 60 70 65 15 
Wheat 0 50 80 40 10 20 0 
Barnyard 
0 100 95 80 55 15 0 
Grass 
Crab- 0 95 95 95 90 75 30 
grass 
Yellow 0 90 100 95 60 0 -- 
Foxtail 
Johnson 0 100 95 95 95 75 40 
Grass 
Wild Oats 
0 40 10 0 -- -- -- 
______________________________________ 
*"--" denotes not tested 
At 250 ppm 2-(4-((6-chloro-2-(1,5-naphthyridinyl))-oxy)phenoxy) propanoic 
acid was inactive against cotton, rape, soybeans, sugar beets, jimson 
weed, morning glory, pigweed, velvet leaf and cockleburr. 
When employing substantially the same procedure as that described in 
Example 5, 2-(4-((6-chloro-2-(1,7-naphthyridinyl))oxy)phenoxy)propanoic 
acid, methyl ester, at a concentration of 2,000 ppm (approximately 5 
lbs/acre) completely killed sugar beets and barnyard grass and reduced the 
growth by 95 percent in johnson grass, 99 percent in corn, 90 percent in 
crabgrass, 70 percent in wheat and 50 percent in sorghum. 
In a representative operation, 
2-(4-((6-chloro-2-(1,5-naphthyridinyl)oxy)phenoxy)propanoic acid to be 
utilized in a series of tests is dissolved in acetone to one half of the 
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 Tween-20 surface active material (Tween-20 is a 
trademark of Atlas Chemical Company). The composition, generally in the 
nature of an emulsion, was employed to treat separate respective seed beds 
of sandy loam soil of good nutrient content wherein each seed bed 
contained separate groups of good viable seeds, each group being of one of 
a known plant species. The various beds were positioned side by side and 
exposed to substantially identical conditions of temperature and light. 
Each bed was maintained so as to prevent any interaction with the test 
compound in different seed beds. Each seed bed was treated with the 
composition as a soil drench applied at one of two predetermined rates to 
deposit a predetermined amount of the compound uniformly throughout the 
surface of the bed. Another seed bed was treated only with the 
acetone-Tween-20 water mixture with no chemical added 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, dosage and the percent preemergent 
control obtained are set forth in Table 8 below. Control refers to the 
reduction in growth of the test species in the presence of the test 
chemical relative to the observed growth of the same species in the 
absence of the test chemical. 
TABLE B 
__________________________________________________________________________ 
Premergence Control of Plant Species (%) 
Exhibited by 2-(4-((6-Chloro-2-(1,5- 
naphthyridinyl)oxy)phenoxy)propanoic Acid 
Plant Species 
Dosage Barn- 
in Lbs. yard 
Crab 
Johnson 
Wild 
Yellow 
Per Acre 
Corn 
Rice 
Sorghum 
Wheat 
Grass 
Grass 
Grass 
Oats 
Foxtail 
__________________________________________________________________________ 
2 75 100 
100 100 100 80 100 70 100 
1 70 100 
90 80 100 100 100 40 100 
0.5 70 60 
20 20 10 70 80 0 40 
0.25 35 20 
0 0 0 0 10 .sup. --.sup.a 
0 
__________________________________________________________________________ 
.sup.a "--" denotes not tested 
The compounds of the present invention have also been found to exhibit 
antifungal properties. For example, 2-(4-(1,8-naphthyridinyl)oxy)phenoxy 
propanoic acid, when employed as the sole toxicant in a standard fungicide 
screening test at a concentration of 500 ppm by weight of the total 
composition, was shown to kill and control 90% of the grape downey mildew 
organisms. When 2-(4-(2-(1,6-naphthyridinyl)oxy)phenoxy)propanoic acid, 
methyl ester was employed as the sole toxicant in a standard fungicide 
screening test at a concentration of 25 ppm by weight of the total 
composition, 90% of tobacco black shank pathogen Phytophthora parasitica 
var. Nicotianeae were controlled. 
For all such fungicidal uses, unmodified active ingredients of the present 
invention can be employed. However, the present invention embraces the use 
of a fungicidally-effective amount of the active ingredients in 
composition form with an inert nonphytotoxic material known in the art as 
an adjuvant or carrier in solid or liquid form. 
The compounds of the present invention contain an optically active center 
as shown in Formula (I) (2 position of the propanoic acid) and can exist 
in optically active stereoisomeric forms such as the dextrorotatory and 
levorotatory forms of each of the above configurations. The various 
mixtures and racemates of the above isomers are within the scope of the 
present invention. 
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, 
arthropodicides, herbicides, fungicides or bactercides 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 
the ratio of from 1 to 100 parts of the compound of the present invention 
with from 100 to 1 parts of the additional compound(s). 
Starting Materials 
The halonaphthyridine starting materials, described herein, are prepared by 
employing procedures disclosed in Y. Hamada and I. Takeuchi, Chem. Pharm. 
Bull., 19, 1857 (1971); G. R. Newkome and S. J. Garbis, J. Heterocyclic 
Chem., 15, 685 (1978); W. Roszkiewicz and M. Wozniak, Synthesis, 691-692 
(1976); J. Heterocyclic Chem, Vol. 9, 703-706 (1972); Polish Journal of 
Chemistry, 52, 2369-2376, (1978); Chemical Pharm. Bull., Vol. 17 (5), 
1045-1050, (1969); J. Org. Chem, Vol. 36, No. 3, 450-454 (1971); 
Tetrahedron Letters, No. 12, 1233-1237, (1966); J. Org. Chem., Vol. 37, 
No. 20, 3101-3105 (1972); U.S. Pat. No. 4,308,273 (preparation of 
1,6-naphthyridine); CA 111959, Vol. 82, 503 (1975); J.A.C.S., Vol. 77, 
2438-2440, (1955); and E. M. Hawes and D. G. Wibberley, J. Chem. Soc., C., 
1564-1568 (1967); all of which are incorporated herein by reference and 
made a part hereof. The 2-(4-hydroxy (or mercapto)phenoxy)propanoic acid 
and derivatives thereof employed as starting materials are known 
compounds.