Novel fungicidal pyridyl carboximides having the general structural formula ##STR1## wherein R is C.sub.1 -C.sub.6 alkyl, preferably methyl; PA0 R.sub.1 is selected from the group consisting of halogen such as chlorine, fluorine and bromine, C.sub.1 -C.sub.3 alkoxy such as propoxyethoxy and methoxy, preferably methoxy, and C.sub.2 -C.sub.4 alkenyloxy; PA0 R.sub.2 is selected from the group consisting of hydrogen, C.sub.1 -C.sub.6 alkyl, C.sub.4 -C.sub.6 cycloalkyl, heterocyclic moieties, aryl, preferably phenyl, substituted aryl, preferably substituted phenyl wherein the substitutions are chlorine, fluorine, bromine, trifluoromethyl and --NO.sub.3 ; PA0 X is --O or --S; and PA0 Y is --O or --S; and fungicidally acceptable organic and inorganic salts thereof which are highly effective fungicides for use both as preventive and curative fungicides are disclosed herein.

BACKGROUND OF THE INVENTION 
Fungal infection of crops such as barley, rice, tomatoes, wheat, beans, 
roses, grapes and other agriculturally important crops can cause heavy 
losses in both quantity and quality of agricultural products. It is 
therefore extremely desirable to have means of preventing, controlling or 
eliminating fungal growth. Much preventive spraying with commercial 
fungicides is conducted to attempt to prevent the establishment and growth 
of fungi on agriculturally important crops. It would also be desirable to 
have a curative fungicide which, on detection of fungal infection, could 
control the fungi and eliminate the deleterious effects by use of a 
postinfection curative spray. 
SUMMARY OF THE INVENTION 
Novel fungicidal N-pyridyl imides having the formula 
##STR2## 
wherein R is C.sub.1 -C.sub.6 alkyl, preferably methyl; 
R.sub.1 is selected from the group consisting of halogen such as chlorine, 
fluorine and bromine, C.sub.1 -C.sub.3 alkoxy such as propoxy, ethoxy and 
methoxy, preferably methoxy, and C.sub.2 -C.sub.4 alkenyloxy; 
R.sub.2 is selected from the group consisting of hydrogen, C.sub.1 -C.sub.6 
alkyl, C.sub.4 -C.sub.6 cycloalkyl, heterocyclic moieties, aryl, 
preferably phenyl, substituted aryl, preferably substituted phenyl wherein 
the substitutions are chlorine, fluorine, bromine, trifluoromethyl and 
--NO.sub.3 ; 
X is --O or --S; and 
Y is --O or --S; 
and fungicidally acceptable organic and inorganic salts thereof which are 
highly effective fungicides for use both as preventive and curative 
fungicides are disclosed herein. 
The term "fungicide" is used to mean a compound which controls fungal 
growth. "Controls" includes prevention, destruction and inhibition of 
fungal growth. The term "curative" is meant to refer to a post-infection 
application of a fungicide which establishes control of fungal infection 
and prevents development of deleterious effects of the fungi on the host 
crop.

DETAILED DESCRIPTION 
The novel fungicidal compounds of this invention are N-pyridyl imides 
having the general formula 
##STR3## 
wherein R is C.sub.1 -C.sub.6 alkyl, preferably methyl; 
R.sub.1 is selected from the group consisting of halogen such as chlorine, 
fluorine and bromine, C.sub.1 -C.sub.3 alkoxy such as propoxy, ethoxy and 
methoxy, preferably methoxy, and C.sub.2 -C.sub.4 alkenyloxy; 
R.sub.2 is selected from the group consisting of hydrogen, C.sub.1 -C.sub.6 
alkyl, C.sub.4 -C.sub.6 cycloalkyl, heterocyclic moieties, aryl, 
preferably phenyl, substituted aryl, preferably substituted phenyl wherein 
the substitutions are chlorine, fluorine, bromine, trifluoromethyl and 
--NO.sub.3 ; 
X is --O or --S; and 
Y is --O or --S; 
and fungicidally acceptable organic and inorganic salts thereof which are 
highly effective fungicides for use both as preventive and curative 
fungicides are disclosed herein. 
The compounds of this invention can be generally prepared by a multi-step 
reaction process. The first step comprises reacting an appropriate 
aminopyridine with the appropriate acid chloride in an inert solvent such 
as dichloromethane in a suitable reactor such as a glass reaction flask. 
It is desirable to maintain an acid scavenger such as pyridine in the 
reaction vessel. The reaction generally will proceed at room temperature 
but will operate at a temperature range from -30.degree. to 80.degree. C. 
The reaction should go to completion within 1 to 3 hours. The resulting 
intermediate product is recovered in a conventional manner by washing with 
an alkali solution such as sodium hydroxide and water, drying over 
conventional drying agents such as magnesium sulfate and crystallizing in 
hexane. The resulting carboxamide is then reacted with a properly 
substituted acid chloride in the presence of sodium hydride or other 
strong base in an inert solvent such as tetrahydrofuran (THF). An 
alternate procedure is to react the carboxamide or carbamate with a 
trialkylsilyl halide wherein the alkyl groups are C.sub.1 -C.sub.6 alkyl 
in the presence of an acid scavenger such as triethylamine to silylate the 
amide, followed by reaction with a properly substituted acid chloride or 
chloroformate. 
Salts of the various pyridyl imides can be conventionally prepared by 
reacting at least a molar amount of a Lewis acid with the carboxamide. 
Preferably the reaction is run in a solvent for the carboxamide. The 
prepared salt is recovered from the reaction mixture by conventional 
techniques. 
Pyridyl carboxamides of the invention are basic. The unprotonated nitrogen 
atom of the pyridyl ring can be protonated by an acid, either organic or 
inorganic. Representative inorganic acids are hydrochloric, nitric, 
hydrobromic, sulfuric, sulfamic and phosphoric. Representative organic 
acids are acetic, trifluoroacetic, benzoic, benzenesulfonic, 
p-toluenesulfonic, naphthalenesulfonic, phenylphosphonic and 
organophosphonic. The salts so formed are also fungicidal. 
EXAMPLE 1 
Preparation of N-(2-Methoxy-5-pyridyl)formamide 
5-Amino-2-methoxy pyridine (25 g, 0.2 mol) was added to ethylformate (50 
ml). This solution was refluxed for eight hours. The volatiles were 
removed on a rotary evaporator at 30.degree. C. and at aspirator vacuum. 
The resultant product was pink solid, 30.2 g, 99% of theory, m.p. 
81.degree.-83.degree. C. The structure was confirmed by mass spectroscopy 
(MS), infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy. 
EXAMPLE 2 
N-(2-Methoxy-5-pyridyl) N-formyltrimethylsilaneamine 
N-(2-Methoxy-5-pyridyl)formamide (30.4 g, 0.2 mol) was added to 200 ml 
benzene. This was stirred with a mechanical stirrer under argon at 
10.degree. C. Trimethylsilyl chloride (25 g, 0.23 mol) was added. While 
stirring at 10.degree. C., triethylamine (21 g, 0.21 mol) dissolved in 50 
ml benzene was added dropwise over 0.5 hour. The slurry was warmed to room 
temperature and after 0.5 hour filtered. The salt cake was washed with 100 
ml benzene and the combined filtrates concentrated on a rotary evaporator 
at 30.degree. C. under aspirator vacuum. The dark liquid product was 
distilled under reduced pressure. A clear liquid, 39 g, 87% yield, (b.p. 
87.degree. C./0.25 mmHg). The product was stored under argon. 
EXAMPLE 3 
Preparation of S-Methyl-N-formyl-N-(2-methoxy-5-pyridyl) thiolcarbamate 
N-(2-Methoxy-5-pyridyl)-N-formyl-trimethylsilane amide (2.28 g, 0.01 mol) 
was added to methylene chloride (25 ml) containing methyl 
chlorothiolformate (1.25 g, 0.011 mol). This solution was allowed to stand 
at room temperature overnight. This was then evaporated in vacuo and the 
residue purged with dry nitrogen at 50.degree. C. for several hours. This 
gave 1.8 g of white solid as the title compound, m.p. 
74.degree.-77.degree. C. The structure was confirmed by mass spectroscopy 
and its infra-red and nuclear magnetic resonance spectra. 
Representative compounds of this invention and their properties are shown 
in Table I. 
TABLE I 
______________________________________ 
##STR4## 
n.sub.D.sup.30 or 
Cmpd. melting 
No. R R.sub.1 R.sub.2 
X Y point .degree.C. 
______________________________________ 
1 CH.sub.3 OCH.sub.3 
H O S 74.0-77.0.degree. C. 
2 CH.sub.3 OCH.sub.3 
H O O 1.5292 
n-C.sub.4 H.sub.7 
OCH.sub.3 
H O O 1.5646 
4 C.sub.2 H.sub.5 
OCH.sub.3 
H O S 83.0-85.0.degree. C. 
5 CH.sub.3 OCH.sub.3 
CH.sub.3 
O O 60.0-63.0.degree. C. 
6 CH.sub.3 OCH.sub.3 
CH.sub.3 
O S semi-solid 
______________________________________ 
EXAMPLE 4 
Preventative Spray Evaluation Procedures 
Barley Powdery Mildew (PM) 
Northrup King Sunbar 401 barley seed is planted (12 seeds/2" pot) in a 
sandy-loam soil seven days prior to testing. The test compound is diluted 
in a 50/50 acetone/water solution to produce concentrations decreasing 
from 2250 ug/ml. Twelve ml of test solution are sprayed onto the barley 
plants with atomizing sprayers. 
Twenty-four hours later, test plants are placed in an inoculation box 
equipped with a circulating fan. Barley plants with heavily sporulating 
Erysiphe graminis lesions are placed in front of the fan to dislodge and 
distribute the spores. After two minutes the fan is shut off and the 
chamber is left closed five minutes for the spores to settle. Inoculated 
plants are then placed on an automatic sub-irrigation greenhouse bench. 
Results are recorded seven days following inoculation as percent disease 
control based on the percent reduction in infected area as compared to the 
untreated control plants. Compound concentrations which provide 90% 
disease control (EC 90) are determined from dosage/dilution curves. 
Botrytis Bud Blight (BB) 
Two white rose petals are placed in a petri dish lined with wet filter 
paper. The compound to be tested is diluted with a 50/50 acetone/water 
solution to produce concentrations decreasing from 2250 ug/ml. One-half ml 
of test solution is atomized onto the petals, and allowed to dry. 
Inoculum is prepared by adding a 5 mm plug from a two-week old Botrytis 
cinerea culture grown on Elliot's V-8 agar, to 10 ml sterile distilled 
water plus 0.5 ml grape juice. A 20 ul drop of this inoculum suspension is 
placed on each petal. Petri dishes with inoculated petals are stored in 
sealed plastic boxes to maintain saturated humidity. 
Results are read four days following inoculation as a percent reduction in 
necrotic area compared to the acetone/water controls. Compound 
concentrations which provide 90% disease control (EC 90) are determined 
from dosage/dilution curves. 
The results are presented in Table II as an approximate EC 90 in parts per 
million. The entry (*) indicates no control at 750 ppm. 2250 ug/ml is 
equal to 2250 ppm. The entry (750) indicates partial control at 750 ppm. 
The entry (2250) indicates partial control at 2250 ppm. Only selected 
compounds were tested at 2250 ppm. 
TABLE II 
______________________________________ 
Cmpd. No. PM BB 
______________________________________ 
1 * 250 
2 * 25 
3 2250 (2250) 
4 (2250) 2250 
5 (750) 250 
6 * 25 
______________________________________ 
The compounds of this invention are particularly effective against Botrytis 
bud blight and are particularly effective as preventative foliar sprays 
and curative foliar sprays when compared to standard commercial compounds 
used as Botrytis preventative and curative sprays. The compounds of the 
present invention are also particularly effective against Erysiphe 
graminis. 
The compounds of the present invention are useful as fungicides, especially 
as preventative or curative fungicides, and can be applied in a variety of 
ways at various concentrations. In general, these compounds and 
formulations of these compounds can be applied directly to the crop 
foliage, the soil in which the crop is growing or in the irrigation water 
for the crop or soil. In practice, the compounds herein defined are 
formulated into fungicidal compositions, by admixture, in fungicidally 
effective amounts, with the adjuvants and carriers normally employed for 
facilitating the dispersion of active ingredients for agricultural 
applications, recognizing the fact that the formulation and mode of 
application of a toxicant may affect the activity of the materials in a 
given application. Thus, these active fungicidal compounds may be 
formulated as wettable powders, as emulsifiable concentrates, as powdery 
dusts, as dusts, as solutions or as any of several other known types of 
formulations, depending upon the desired mode of application. Preferred 
formulations for preventative or curative fungicidal applications are 
wettable powders and emulsifiable concentrates. These formulations may 
contain as little as about 0.1% to as much as about 95% or more by weight 
of active ingredient. A fungicidally effective amount depends upon the 
nature of the seeds or plants to be treated and the rate of application 
varies from about 0.05 to approximately 25 pounds per acre, preferably 
from about 0.1 to about 10 pounds per acre. 
Wettable powders are in the form of finely divided particles which disperse 
readily in water or other dispersants. The wettable powder is ultimately 
applied to the soil or plants either as a dry dust or as a dispersion in 
water or other liquid. Typical carriers for wettable powders include 
Fuller's earth, kaolin clays, silicas and other readily wet organic or 
inorganic diluents. Wettable powders normally are prepared to contain 
about 5% to about 95% of the active ingredient and usually also contain a 
small amount of wetting, dispersing, or emulsifying agent to facilitate 
wetting and dispersion. 
Dry flowables or water dispersible granules are agglomerated wettable 
powders made by either pan granulation or by fluidized bed. The dry 
flowable is ultimately applied to the soil or plants as a dispersion in 
water or other liquid. These granules are dust-free and free flowing when 
dry and yet upon dilution in water, form homogeneous dispersions. Typical 
carriers for dry flowables include fuller's earth, kaolin clays, silicas 
and other readily wet organic or inorganic diluents. The dry flowables 
normally are prepared to contain from about 5% to about 95% of the active 
ingredient and usually contain a small amount of wetting, dispersing or 
emulsifying agent to facilitate wetting and dispersion. 
Emulsifiable concentrates are homogeneous liquid compositions which are 
dispersible in water or other dispersant, and may consist entirely of the 
active compound with a liquid or solid emulsifying agent, or may also 
contain a liquid carrier, such as xylene, heavy aromatic naphtha, 
isophorone and other non-volatile organic solvents. For fungicidal 
application, these concentrates are dispersed in water or other liquid 
carrier and normally applied as a spray to the area to be treated. The 
percentage by weight of the essential active ingredient may vary according 
to the manner in which the composition is to be applied, but in general 
comprises about 0.1% to 95% of active ingredient by weight of the 
fungicidal composition. 
Typical wetting, dispersing or emulsifying agents used in agricultural 
formulations include, for example, the alkyl and alkylaryl sulfonates and 
sulfates and their sodium salts; polyhydroxy alcohols; and other types of 
surface-active agents, many of which are available in commerce. The 
surface-active agent, when used, normally comprises from 0.1% to 15% by 
weight of the fungicidal composition. 
Dusts, which are free-flowing admixtures of the active ingredient with 
finely divided solids such as talc, clays, flours and other organic and 
inorganic solids which act as dispersants and carriers for the toxicant, 
are useful formulations for many applications. 
Pastes, which are homogeneous suspensions of a finely divided solid 
toxicant in a liquid carrier such as water or oil, are employed for 
specific purposes. These formulations normally contain about 5% to about 
95% of active ingredient by weight, and may also contain small amounts of 
a wetting, dispersing or emulsifying agent to facilitate dispersion. For 
application, the pastes are normally diluted and applied as a spray to the 
area to be affected. 
______________________________________ 
EXAMPLES OF TYPICAL FORMULATIONS 
______________________________________ 
Oil 
Ingredient Weight % 
______________________________________ 
Compound 1 1 
Oil solvent-heavy aromatic naphtha 
99 
Total 100 
Emulsifiable Concentrate 
Compound 2 50 
Kerosene 45 
Emulsifying agent (mixture of long 
5 
chain ethoxylated polyethers with 
long chain sulfonate) 
Total 100 
Emulsifiable Concentrate 
Compound 3 90 
Kerosene 5 
Emulsifying agent (mixture of long 
5 
chain ethoxylated polyethers with 
long chain sulfonate) 
Total 100 
______________________________________ 
Dusts and/or Powders 
Ingredients Wt. % Wt. % Wt. % 
______________________________________ 
Compound 4 0.5 50.0 90.0 
Attapulgite Clay Powder 
93.5 44.0 4.0 
Sodium lignin sulfonate 
5.0 5.0 5.0 
Sodium dioctyl sulfosuccinate 
1.0 1.0 1.0 
Total 100.0 100.0 100.0 
______________________________________ 
Other useful formulations for fungicidal applications include simple 
solutions of the active ingredient in a dispersant in which it is 
completely soluble at the desired concentration, such as acetone, 
alkylated naphthalenes, xylene and other organic solvents. Pressurized 
sprays, typically aerosols, wherein the active ingredient is dispersed in 
finely divided form as a result of vaporization of a low boiling 
dispersant solvent carrier, such as the Freons, may also be used. 
The fungicidal compositions of this invention are applied to the plants in 
the conventional manner. Thus, the dust and liquid compositions can be 
applied to the plant by the use of power-dusters, boom and hand sprayers 
and spray dusters. The compositions can also be applied from airplanes as 
a dust or a spray because they are effective in low dosages.