Fungicidal tin salts of thienyl and furyl hydroxamic acids, compositions, and method of use therefor

Compounds of the formula: ##STR1## wherein Z is sulfur or oxygen; R is alkyl of 1 to 7 carbon atoms; R.sup.1 is aryl of 6 to 10 carbon atoms, lower alkyl of 1 to 6 carbon atoms or cycloalkyl of 3 to 8 carbons, all optionally substituted with 1 to 3 halogen atoms; a is 0 or 1; b is 0, 1, or 2; X is independently halo, nitro, trihalomethyl, lower alkyl of 1 to 3 carbon atoms, or lower alkoxy of 1 to 3 carbon atoms are useful as fungicides and insecticides.

BACKGROUND OF THE INVENTION 
The present invention relates to tin salts of thiophene- and 
furan-containing hyroxamic acids which are active as fungicides. 
Various organo-tin compounds have been disclosed as having biocidal 
activities. See, e.g., U.S. Pat. Nos. 3,657,451; 3,906,103; 3,987,191; and 
4,224,338. 
U.S. Pat. No. 4,061,764 discloses certain O-substituted thiophene oxime 
carbamates as antibacterial and antifungal agents. 
SUMMARY OF THE INVENTION 
The present invention relates to novel tin salts of thiophene- and 
furan-containing hydroxamic acids of the formula: 
##STR2## 
wherein Z is sulfur or oxygen; R is alkyl of 1 to 7 carbon atoms; R.sup.1 
is aryl of 6 to 10 carbon atoms, lower alkyl of 1 to 6 carbon atoms or 
cycloalkyl of 3 to 8 carbons, all optionally substituted with 1 to 3 
halogen atoms; a is 0 or 1; b is 0, 1, or 2; X is independently halo, 
nitro, trihalomethyl, lower alkyl of 1 to 3 carbon atoms, or lower alkoxy 
of 1 to 3 carbon atoms. These compounds are active as fungicides; they 
also exhibit insecticidal and acaracidal activity. In addition, some of 
these compounds show bactericidal and/or bacteristatic activity. 
Among other factors, the present invention is based on my surprising 
finding that these compounds are surprisingly effective as fungicides. In 
particular, they are useful in controlling botrytis. 
Preferred R groups include methyl, ethyl, propyl, benzyl, propenyl, and 
halopropenyl. 
Preferred R.sup.1 groups include n-butyl, cyclohexyl, and phenyl. 
Preferred trihalomethyl groups include trifluoromethyl. 
Preferred X groups include chloro, bromo, nitro, trifluoromethyl, ethoxy, 
and methoxy. 
Particularly preferred R groups include methyl and ethyl. 
Particularly preferred R.sup.1 groups include n-butyl, cyclohexyl, and 
phenyl. 
Preferred are compounds where Z is sulfur. 
Also preferred are compounds where a is 0. 
Representative compounds of this invention are found in Table I. 
DEFINITIONS 
As used herein, the following terms have the following meanings unless 
expressly stated to the contrary. 
The term "alkyl" refers to both straight- and branched-chain alkyl groups. 
The term "lower alkyl" refers to both straight- and branched-chain alkyl 
groups having a total of from 1 to 6 carbon atoms and includes primary, 
secondary and tertiary alkyl groups. Typical lower alkyls include, for 
example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 
n-pentyl, n-hexyl, and the like. 
The term "cycloalkyl" refers to cyclic alkyl groups. The term "lower 
cycloalkyl" refers to groups having from 3 to 6 carbon atoms in the ring, 
and includes cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. 
The term "alkylene" refers to the group --(CH.sub.2).sub.m -- wherein m is 
an integer greater than zero. Typical alkylene groups include, methylene, 
ethylene, propylene and the like. 
The term "alkylthio" refers to the group R'S-- wherein R' is alkyl. The 
term "lower alkylthio" refers to akylthio groups having 1 to 6 carbon 
atoms; examples include methylthio, ethylthio, n-hexylthio, and the like. 
The term "alkylthioalkylene" refers to an alkyl group substituted with an 
alkylthio group. The term "lower alkylthioalkylene" refers to groups 
having up to a total of 8 carbon atoms and includes, for example, 
ethylthiomethylene, methylthiomethylene, 2-methylthiopropylene, and the 
like. 
The term "alkoxy" refers to the group --OR' wherein R' is an alkyl group. 
The term "lower alkoxy" refers to alkoxy groups having from 1 to 6 carbon 
atoms; examples include methoxy, ethoxy, n-hexoxy, n-propoxy, isopropoxy, 
isobutoxy, and the like. 
The term "alkoxyalkylene" refers to an alkyl group substituted with an 
alkoxy group. The term "lower alkoxyalkylene" refers to groups having up 
to a total of 8 carbon atoms and includes, for example, ethoxymethylene, 
methoxymethylene, 2-methoxypropylene, and the like. 
The term "alkenyl" refers to unsaturated alkyl groups having a double bond 
[e.g., CH.sub.3 CH.dbd.CH(CH.sub.2).sub.2 --] and includes both straight- 
and branched-chain alkenyl groups. "Lower alkenyl" refers to groups having 
a total of from 3 to 6 carbon atoms. Typical lower alkenyl groups include, 
for example, propenyl, but-3-enyl, hex-4-enyl, 2-methyl-pent-4-enyl, and 
the like. 
The term "halo" or "halogen" refers to the groups fluoro, chloro, bromo and 
iodo. 
The term "haloalkenyl" refers to alkenyl groups substituted with from 1 to 
2 halogen atoms. "Lower haloalkenyl" refers to groups having a total of 
from 3 to 5 carbon atoms, and includes, for example, 1-chloro-propenyl, 
2,3-dibromo-but-3-enyl, and the like. 
The term "alkynyl" refers to unsaturated alkyl groups having a triple bond 
(e.g., CH.sub.3 C.tbd.CCH.sub.2 CH.sub.2 --) and includes both straight- 
and branched-chain alkynyl groups. "Lower alkynyl" refers to groups having 
a total of from 3 to 5 carbon atoms. Typical lower alkynyl groups include 
propynyl, butynyl, and the like. 
The term "hydroxy alkyl" refers to the group --R" OH wherein R" is branched 
or unbranched alkylene and the hydroxy can be on a primary, secondary or a 
tertiary carbon. Examples include hydroxy ethyl and 2-hydroxy-propyl and 
2-hydroxy-2-methyl butyl. 
The term "aryl" refers to aryl groups having from 6 to 10 carbon atoms and 
includes, for example, phenyl, p-chlorophenyl, m-methylphenyl, 
p-butylphenyl, m-trifluoromethylphenyl, naphthyl, and the like. 
The term "aralkyl" refers to an alkyl group of 1 to 4 carbons substituted 
with an aryl group of from 6 to 10 carbons and includes, for example, 
benzyl, p-chlorobenzyl, p-methylbenzyl and 2-phenylethyl. 
The term "arylthio" refers to the group R"'S-- wherein R"' is an aryl 
group; examples include phenylthio, naphthylthio, and the like. 
The term "arylthioalkyl" refers to an alkyl group of 1 to 4 carbon atoms 
substituted with an arylthio group and includes, for example, 
phenylthiomethylene, naphthylthiomethylene, phenylthioethylene, and the 
like. 
The term "alkylamino" refers to the group R'R"N-- wherein R' is alkyl and 
R" is hydrogen or alkyl. The term "lower alkylamino" refers to alkylamino 
groups having 1 to 6 carbon atoms. Typical alkylamino groups include 
methylamino, ethylamino, diethylamino, dimethylamino, and the like. 
Pests are any insect, rodent, nematode, fungus, weed, or any form of 
terrestrial or aquatic plant or animal life or virus, bacterial organism 
or other microorganism (except those viruses, bacteria or other 
microorganisms existing in living humans or other living animals) 
considered injurious to health, the environment or man's economic 
well-being. 
Pesticides are chemical entities or mixtures thereof intended for 
preventing, destroying, repelling or mitigating any pest. 
The term, "pesticide", when not specifically modified or delimited by other 
words, sometimes includes any one or a combination of the following: the 
active ingredient, the pesticide formulation or the pesticide product. It 
may also include baits for attracting and ultimately killing amphibian and 
reptile pests. 
The terms "insecticide" and "insect" as used herein refer to their broad 
and commonly understood usages rather than to those creatures which, in 
the strict biological sense, are classified as insects. Thus, the term 
"insect" is used not only to include small invertebrate animals belonging 
to the class "Insecta", but also to other related classes of arthropods, 
whose members are segmented invertebrates having more or fewer than six 
legs such as spiders, mites, ticks, centipedes, worms, and the like. 
Miticides prevent, inhibit or destroy any of the acarine arachnid 
arthropods (except ticks) which are common pests to cotton, pecans, 
mushrooms, avocados, wheat, apples, chickens and other life forms. 
Nematocides prevent, repel, inhibit or destroy any members of the class 
Nematoda. These animals, often called threadworms, roundworms and 
eelworms, are injurious to plants. They feed on roots, stems, leaves or 
flowers. 
DETAILED DESCRIPTION OF THE INVENTION 
The compounds of the present invention may be conveniently prepared 
according to the following reaction scheme: 
##STR3## 
wherein Z, R, R.sup.1, X, a and b are as previously defined in conjunction 
with formula I, b.sub.1 is a base, M is a basically reacting metal 
compound which is capable of removing the proton from the hydroxyl of V, 
and Y is halogen. 
Reaction (1) is conducted by combining II, III, and IV in solvent. It is 
preferred to add II in solvent to a precooled mixture (to about 0.degree. 
C. to about -5.degree. C.) of III and IV in water/organic solvent, 
maintaining the cooling during the addition. Suitable organic solvents 
include methylene chloride, chloroform, ether, toluene, and the like. 
Certain acid chlorides, II, are commercially available, others may be 
conveniently prepared from the corresponding carboxylic acid by 
conventional procedures. Suitable bases, b.sub.1, include inorganic bases 
such as potassium carbonate, sodium carbonate, sodium hydroxide, and the 
like. It is preferred to add an excess of III and IV relative to II, on 
the order of about 1.10 to about 1.25 equivalents III per equivalent II 
and about 1.15 to about 1.30 equivalents IV per equivalent II. The 
reaction is conducted at a temperature of about -15.degree. C. to about 
10.degree. C., preferably from about -5.degree. C. to about 0.degree. C., 
and is generally complete within about 4 to about 6 hours. The product, 
V, is isolated by conventional procedures such as extraction, filtration, 
washing, stripping, and the like. 
Reaction (2) is conducted by combining approximately equimolar amounts of V 
and VI in solvent. It may be preferred to add a slight excess of VI 
relative to V, on the order of about 1.02 to about 1.05 equivalents VI per 
equivalent V. It is preferred to add VI to V in solvent. Suitable 
basically reacting metal compounds, M, include alkali (Group IA) metals 
such as sodium and potassium, also sodium hydride, butyllithium, and the 
like. Suitable solvents include low molecular weight alcohols such as 
methanol and ethanol, also dimethoxy ethane, tetrahydrofuran, ether, and 
the like. The reaction is conducted at a temperature of from about 
0.degree. C. to about reflux, preferably from about 0.degree. C. to about 
20.degree. C. or for convenience at ambient temperature, and is generally 
complete within about 0.5 to about 1.5 hours. The product, VII, is 
isolated by conventional procedures such as stripping and the like. 
Alternatively, after stripping and chasing of the solvent, product VII may 
be used directly in Reaction (3) without further isolation. 
Reaction (3) is conducted by combining approximately equimolar amounts of 
VII and VIII in solvent. It is preferred to add VIII to VII in solvent, in 
order to obtain improved yields. Suitable solvents include organic 
solvents such as dimethoxyethane, tetrahydrofuran, low molecular weight 
dialkyl ethers, and the like. The reaction is conducted at a temperature 
of from about 0.degree. to about 35.degree. C., preferably from about 
5.degree. C. to about 35.degree. C. or at reflux, and is generally 
complete within about 6 to about 10 hours. The product, I, is isolated by 
conventional procedures such as stripping, extraction, washing, 
filtration, and the like. 
Utility 
The compounds of the present invention are useful in controlling a wide 
variety of pests. 
These compounds are active as fungicides and are particularly effective in 
controlling a variety of fungi which are deleterious to plants, including 
plant fungal infections. These compounds are particularly effective in 
controlling leaf blights caused by organisms such as Phytophthora 
infestans and Septoria apii. In addition, some of these compounds are 
useful in controlling early blights caused by organisms such as Alternaria 
solani, and powdery mildew such as that caused by Erisiphe polygoni. 
However, some of the compounds of this invention may be more fungicidally 
active than others against particular fungi. 
In addition, some of the compounds of this invention show antibacterial 
activity and may inhibit bacterial growth. 
These compounds are also effective as insecticides and acaracides and may 
be used in controlling a variety of insect and arthropod pests. In 
particular, these compounds are especially effective as miticides. 
However, some of these compounds may be more insecticidally and 
acaricidally active than others against particular pests. 
Like most insecticides, they are not usually applied full strength, but are 
generally incorporated with conventional biologically inert extenders or 
carriers normally employed for facilitating dispersion of active 
ingredients for agricultural chemical application, recognizing the 
accepted fact that the formulation and mode of application may affect the 
activity of a material. The toxicants of this invention may be applied as 
sprays, dusts, or granules to the insects, their environment or hostages 
susceptible to insect attack. They may be formulated as granules of large 
particle size, powdery dusts, wettable powders, emulsifiable concentrates, 
solutions, or as any of several other known types of formulations, 
depending on the desired mode of application. 
Wettable powders are in the form of finely divided particles which disperse 
readily in water or other dispersants. These compositions normally contain 
from about 5% to 80% insecticide, and the rest inert material, which 
includes dispersing agents, emulsifying agents and wetting agents. The 
powder may be applied to the soil as a dry dust, or preferably as a 
suspension in water. Typical carriers include fuller's earth, kaolin 
clays, silicas, and other highly absorbent, readily wettable, inorganic 
diluents. Typical wetting, dispersing or emulsifying agents include, for 
example: the aryl and alkylaryl sulfonates and their sodium salts; 
alkylamide sulfonates, including fatty methyl taurides; alkylaryl 
polyether alcohols, sulfated higher alcohols and polyvinyl alcohols; 
polyethylene oxides; sulfonated animal and vegetable oils; sulfonated 
petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene 
oxide addition products of such esters; and the addition products of 
long-chain mercaptans and ethylene oxide. Many other types of useful 
surface-active agents are available in commerce. The surface-active agent, 
when used, normally comprises from 1% to 15% by weight of the insecticidal 
composition. 
Dusts are freely flowing admixtures of the active insecticide with finely 
divided solids such as talc, natural clays, kieselguhr, pyrophyllite, 
chalk, diatomaceous earths, calcium phosphates, calcium and magnesium 
carbonates, sulfur, lime, flours, and other organic and inorganic solids 
which act as dispersants and carriers for the toxicant. These finely 
divided solids have an average particle size of less than about 50 
microns. A typical dust formulation useful herein contains 75% silica and 
25% of toxicant. 
Useful liquid concentrates include the emulsifiable concentrates, which are 
homogeneous liquid or paste compositions which are readily dispersed in 
water or other dispersant, and may consist entirely of the insecticide 
with a liquid or solid emulsifying agent, or may also contain a liquid 
carrier such as xylene, heavy aromatic naphthas, isophorone, and other 
nonvolatile organic solvents. For application, these concentrates are 
dispersed in water or other liquid carrier, and are normally applied as a 
spray to the area to be treated. 
Other useful formulations for insecticidal applications include simple 
solutions of the active insecticide in a dispersant in which it is 
completely soluble at the desired concentration, such as acetone, 
alkylated naphthalenes, xylene, or other organic solvents. Granular 
formulations, wherein the insecticide is carried on relatively coarse 
particles, are of particular utility for aerial distribution or for 
penetration of cover-crop canopy. 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. All of those techniques for formulating 
and applying insecticides are well known in the art. 
The percentages by weight of the insecticide may vary according to the 
manner in which the composition is to be applied and the particular type 
of formulation, but in general comprise 0.5% to 95% of the toxicant by 
weight of the insecticidal composition. 
The insecticidal compositions may be formulated and applied with other 
active ingredients, including nematocides, insecticides, fungicides, 
bactericides, plant-growth regulators, fertilizers, etc. In applying the 
chemical, an effective amount and concentration of the toxicant of this 
invention is, of course, employed. 
The terms "insecticide" and "insect" as used herein refer to their broad 
and commonly understood usage rather than to those creatures which, in the 
strict biological sense, are classified as insects. Thus, the term 
"insect" is used not only to include small invertebrate animals belonging 
to the class "Insecta", but also to other related classes of arthropods, 
whose members are segmented invertebrates having more or fewer than six 
legs, such as spiders, mites, ticks, centipedes, worms, and the like. 
When used as fungicides, the compounds of the invention are applied in 
fungicidally effective amounts to fungi and/or their habitats, such as 
vegetative hosts and non-vegetative hosts, e.g., animal products. The 
amount used will, of course, depend on several factors such as the host, 
the type of fungus, and the particular compound of the invention. As with 
most pesticidal compounds, the fungicides of the invention are not usually 
applied full strength, but are generally incorporated with conventional, 
biologically inert extenders or carriers normally employed for 
facilitating dispersion of active fungicidal compounds, recognizing that 
the formulation and mode of application may affect the activity of the 
fungicide. Thus, the fungicides of the invention may be formulated and 
applied as granules, as powdery dusts, as wettable powders, as 
emulsifiable concentrates, as solutions, or as any of several other known 
types of formulations, depending on the desired mode of application. 
Wettable powders are in the form of finely divided particles which disperse 
readily in water or other dispersants. These compositions normally contain 
from about 5% to 80% fungicide, and the rest inert material, which 
includes dispersing agents, emulsifying agents and wetting agents. The 
powder may be applied to the soil as a dry dust, or preferably as a 
suspension in water. Typical carriers include fuller's earth, kaolin 
clays, silicas, and other highly absorbent, readily wettable, inorganic 
diluents. Typical wetting, dispersing or emulsifying agents include, for 
example: the aryl and alkylaryl sulfonates and their sodium salts; 
alkylamide sulfonates, including fatty methyl taurides; alkylaryl 
polyether alcohols, sulfated higher alcohols and polyvinyl alcohols; 
polyethylene oxides; sulfonated animal and vegetable oils; sulfonated 
petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene 
oxide addition products of such esters; and the addition products of 
long-chain mercaptans and ethylene oxide. Many other types of useful 
surface-active agents are available in commerce. The surface-active agent, 
when used, normally comprises from 1% to 15% by weight of the fungicidal 
composition. 
Dusts are freely flowing admixtures of the active fungicide with finely 
divided solids such as talc, natural clays, kieselguhr, pyrophyllite, 
chalk, diatomaceous earths, calcium phosphates, calcium and magnesium 
carbonates, sulfur, lime, flours, and other organic and inorganic solids 
which act as dispersants and carriers for the toxicant. These finely 
divided solids have an average particle size of less than about 50 
microns. A typical dust formulation useful herein contains 75% silica and 
25% of toxicant. 
Useful liquid concentrates include the emulsifiable concentrates, which are 
homogeneous liquid or paste compositions which are readily dispersed in 
water or other dispersant, and may consist entirely of the fungicide with 
a liquid or solid emulsifying agent, or may also contain a liquid carrier 
such as xylene, heavy aromatic naphthas, isophorone, and other nonvolatile 
organic solvents. For application, these concentrates are dispersed in 
water or other liquid carrier, and are normally applied as a spray to the 
area to be treated. 
Other useful formulations for fungicidal applications include simple 
solutions of the active fungicide in a dispersant in which it is 
completely soluble at the desired concentration, such as acetone, 
alkylated naphthalenes, xylene, or other organic solvents. Granular 
formulations, wherein the fungicide is carried on relatively coarse 
particles, are of particular utility for aerial distribution or for 
penetration of cover-crop canopy. 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. All of those techniques for formulating 
and applying fungicides are well known in the art. 
The percentages by weight of the fungicide may vary according to the manner 
in which the composition is to be applied and the particular type of 
formulation, but in general comprise 0.5% to 95% of the toxicant by weight 
of the fungicidal composition. 
The fungicidal compositions may be formulated and applied with other active 
ingredients, including other fungicides, insecticides, nematocides, 
bactericides, plant-growth regulators, fertilizers, etc. 
A further understanding of the invention can be had in the following 
non-limiting Examples. Wherein, unless expressly stated to the contrary, 
all temperature ranges refer to the Centigrade system and the term 
"ambient" or "room temperature" refers to about 20.degree. C. to about 
25.degree. C. The term "percent" refers to gram moles. The term 
"equivalent" refers to a quantity of reagent equal in moles, to the moles 
of the preceding or succeeding reagent recited in that example in terms of 
finite moles or finite weight or volume. Also, unless expressly stated to 
the contrary, geometric isomer and racemic mixtures are used as starting 
materials and correspondingly, isomer mixtures are obtained as products.

EXAMPLES 
Example 1 
Preparation of 2-Thiophenecarboxylic Acid Chloride 
##STR4## 
To a stirred solution of 100 g. (0.78 moles) 2-thiophenecarboxylic acid 
chloride in about 350 ml methylene chloride in which a small amount of 
pyridine (about 2 ml) had been added as a catalyst, 116 g (0.98 moles) 
thionyl chloride was added dropwise. The reaction mixture was refluxed 
about 24 hours. The solvent and excess thionyl chloride were removed under 
reduced pressure and heat. Fresh methylene chloride was added to the 
residue. The resulting solution was divided into two equal portions, one 
of which was used in Example 2. 
Example 2 
Preparation of N-Methoxy-2-Thienylhydroxamic Acid 
##STR5## 
To a stirred mixture of 82 g (0.98 moles) methoxamine hydrochloride and 140 
g (1.0 mole) potassium carbonate in water/methylene chloride (about 600 
ml) maintained at about -5.degree. C., one portion of the 
2-thiophenecarboxylic acid chloride (in methylene chloride) from Example 1 
was dropped in slowly. After the addition was complete, the reaction 
mixture was allowed to come to room temperature and stirred at room 
temperature for about 6 hours. The aqueous and methylene chloride layers 
were phase separated. The methylene chloride layer was dried over 
magnesium sulfate, filtered, and stripped to give 31 g of the 
above-identified product. 
Elemental analysis for C.sub.6 H.sub.7 NO.sub.2 S showed: calculated %C 
45.8, %H 4.49, and %N 8.91; found %C 46.1, %H 4.63, and %N 9.12. 
Example 3 
Preparation of Tri-n-butylstannyl-O-(N-methoxy-2-thienyl Carboximidoate) 
##STR6## 
(a) To a solution of 3.9 g (0.0248 moles) N-methoxy-2-thienylhydroxamic 
acid in methanol which had been stirred several minutes, 0.6 g (0.026 
moles) sodium metal were added slowly, stirring until each piece the 
sodium metal had dissolved. The methanol was removed under reduced 
pressure and heat. Toluene was used to chase the methanol. 
The resulting sodium salt was used in step (b) without further isolation. 
(b) Dimethoxy ethane (about 100 ml) was added to the sodium salt from step 
(a) and the resulting mixture was stirred. Into that stirred mixture, 7.8 
g (0.024 moles) tri-n-butyl tin chloride were dropped in slowly. The 
reaction mixture was refluxed 8 hours. The solvent (dimethoxy ethane) was 
removed under reduced pressure and heat. Water (about 100 ml) and 
methylene chloride (about 125 ml) were added to the residue. The methylene 
chloride layer was separated and washed 3 times with water. The methylene 
chloride layer was dried over magnesium sulfate, filtered, and stripped to 
give the above-identified product, as a yellow liquid. 
Elemental analysis for C.sub.18 H.sub.33 NO.sub.2 SSn showed: calculated %C 
48.5, %H 7.45, and %N 3.14; found %C 48.2, %H 7.7, and %N 2.78. 
Example 4 
Preparation of N-Ethoxy-2-Furylhydroxamic Acid 
##STR7## 
To a stirred mixture of 43 g (0.44 moles) ethoxyamine hydrochloride and 70 
g (0.5 moles) potassium carbonate in about 100 ml (1:1) water/methylene 
chloride maintained at about -5.degree. C., 50 g (0.38 moles) 2-furoic 
acid chloride were dropped in slowly. The reaction mixture was allowed to 
come to room temperature. Methylene chloride (about 150 ml) was added to 
the reaction mixture which was then stirred an additional 2 to 3 hours. 
The aqueous and methylene chloride layers were phase separated. The 
methylene chloride layer was dried over magnesium sulfate, filtered, and 
stripped to give a solid. The solid was washed with hexane and ethyl ether 
and suction filtered to give the above-identified product as a cream 
solid. 
Elemental analysis for C.sub.7 H.sub.9 NO.sub.3 showed: calculated %C 54.2, 
%H 5.85, and %N 9.03; found %C 55.6, %H 6.14, and %N 9.43. 
Example 5 
Preparation of Tri-n-butylstannyl-O-(N-ethoxy-2-furyl Carboximidoate) 
##STR8## 
(a) To a mixture of 3.9 g (0.025 moles) N-ethoxy-2-furylhydroxamic acid 
(the product of Example 4) in methanol (about 100 ml) which had been 
stirred several minutes, 0.6 g (0.026 moles) sodium metal was added slowly 
until all the sodium metal was dissolved. The mixture was then put on a 
rotovac to remove the methanol, chasing with toluene to give the 
corresponding sodium salt which was then used in step (b) without further 
isolation. 
(b) Dimethoxyethane (about 100 ml) was added to the sodium salt from step 
(a). Into the resulting stirred solution, 6.5 g (0.02 moles) tri-n-butyl 
tin chloride in a small amount of dimethoxy ethane was dropped in slowly. 
The reaction mixture was refluxed 8 hours. The dimethoxy ethane was 
removed under reduced pressure and heat. Water (about 25 ml) and methylene 
chloride (about 150 ml) were added to the residue and the resulting 
mixture was stirred. The layers were phase separated. The methylene 
chloride layer was washed 2 times with water, dried over magnesium 
sulfate, filtered, and stripped to give about 9.1 g of the 
above-identified product as a liquid. 
Elemental analysis for C.sub.19 H.sub.35 NO.sub.3 Sn showed: calculated %C 
51.4, %H 7.94, and %N 3.15; found %C 51.21, %H 8.53, and %N 2.9. 
Compounds made in accordance with the methods disclosed in the Detailed 
Description of the Invention and Examples 1 to 5 and using the appropriate 
starting materials are found in Table I. 
In addition, by following the procedures disclosed in the Detailed 
Description of the Invention and in Examples 1 to 5 and using the 
appropriate starting materials and reagents, the following compounds are 
made: 
Tricyclohexylstannyl-O-(N-methoxy-2-thienyl carboximidoate); 
Tricyclohexylstannyl-O-(N-ethoxy-2-thienyl carboximidoate); 
Triphenylstannyl-O-(N-methoxy-2-thienyl carboximidoate); 
Triphenylstannyl-O-(N-ethoxy-2-thienyl carboximidoate); 
Tricyclohexylstannyl-O-(N-methoxy-2-furyl carboximidoate); 
Tri-n-butylstannyl-O-(N-methoxy-2-furyl carboximidoate); 
Triphenylstannyl-O-(N-methoxy-2-furyl carboximidoate); 
Triphenylstannyl-O-(N-ethoxy-2-furyl carboximidoate); 
Tri-n-butylstannyl-O-[N-methoxy-2-(5-trifluoromethylthienyl)carboximidoate] 
; 
Tri-n-butylstannyl-O-[N-ethoxy-2-(5-nitrothienyl)carboximidoate]; 
Tricyclohexylstannyl-O-[N-methoxy-2-(3-nitrothienyl)carboximidoate]; 
Tricyclohexylstannyl-O-[N-methoxy-2-(5-chlorothienyl)carboximidoate]; 
Tri-n-butylstannyl-O-[N-ethoxy-2-(5-chlorofuryl)carboximidoate]; and 
Triphenylstannyl-O-[N-methoxy-2-(3-nitrofuryl)carboximidoate]. 
Example A 
Bacterial Inhibition 
Compounds of this invention were evaluated for in vitro bactericidal 
effectiveness by means of a bacterial inhibition test. This test is 
designed to measure the antibacterial activity of compounds in terms of 
degree of inhibition bacterial multiplication. The representative bacteria 
used were Erwinia amylovora, Pseudomonas syringae and Xanthomonas 
vesicatoria. Each compound to be tested was dissolved in acetone to give a 
500 ppm concentration. Agar plates were inoculated using a micro sprayer 
with an suspension of the particular bacteria shortly (3 to 5 seconds) 
before treatment. The inoculated agar plates were then treated with the 
compound to be tested by spraying with a micro sprayer. The treated plates 
were incubated at 23.5.degree. C. and the data was taken 24 hours after 
treatment. Antibacterial activities are measured by a zone of inhibited 
bacterial growth from the center of the agar plate and the deposit 
concentration in mg/cm.sup.2 at the edge of the zone of inhibition 
(ED.sub.99). The effectiveness of the compounds for antibacterial activity 
are reported in Table II in terms of the percent of the ED.sub.99 of each 
compound of the ED.sub.99 of the standard PMA (phenyl mercuric acetate). 
Example B 
Mycelial Inhibition 
Compounds were evaluated for in vitro fungicidal effectiveness by means of 
a mycelial inhibition test. This test is designed to measure the 
fungitoxic activity of fungicidal chemicals in terms of their degree of 
inhibition of mycelium growth. Fungi used were Pythium ultimum, 
Rhizoctonia solani, Fusarium moniloforme, Botrytis cinerea, Aspergillus 
niger and Ustilago hordeii. Each compound to be tested was dissolved in 
acetone to 500-ppm concentration. Paper strips were infused with the 
particular mycelium growth by covering the paper with a potato dextrose 
broth culture of mycelial suspension. The papers were then placed on 
potato dextrose agar plates and sprayed by means of a micro sprayer with 
the fungicidal solution. The treated paper strips were incubated at 
25.degree. C. and the data is taken after 24 hours. Fungicidal activities 
are measured by a zone of inhibited mycelial growth from the center of the 
paper strip in terms of mg/cm.sup.2 needed for 991/2 control of the fungus 
(ED.sub.99). The effectiveness of the compounds for fungicidal activity 
are reported in Table III in terms of the percent of the ED.sub.99 of the 
test compound of the ED.sub.99 of the standard Difolatan.RTM.. 
Example C 
Grape Downy Mildew 
Compounds were tested for the control of the Grape Downy Mildew organism, 
Plasmopara viticola. Seedlings of Vitis vinifera var. Emperor (7+ weeks 
old) were used as hosts. The plants were sprayed with a 200 ppm solution 
of the test compound in an acetone and water solution containing a small 
amount of nonionic emulsifier. The treated plants were inoculated one day 
later by spraying them with a spore suspension of the organism. The 
treated plants were then held in a greenhouse at a temperature of about 
68.degree. F. to about 72.degree. F. (relative humidify varied between 
about 30 and about 99%) for 4 days. The plants were then placed in an 
environmental chamber at 100% relative humidity to induce sporulation. On 
removal from the chamber and after drying, the plants were evaluated for 
disease development. The percent disease control provided by a given test 
compound was based on the percent disease reduction relative to untreated 
check plants. The results are reported in Table III. 
Example D 
Tomato Late Blight 
Compounds were tested for the preventative control of the Tomato Late 
Blight organism Phytophthora infestans. Five- to six-week-old tomato 
(cultivar Bonny Best) seedlings were used. The tomato plants were sprayed 
with a 200-ppm suspension of the test compound in acetone, water and a 
nonionic emulsifier. The sprayed plants were then inoculated 1 day later 
with the organism, placed in an environmental chamber and incubated at 
66.degree. F. to 68.degree. F. and 100% relative humidity for at least 16 
hours. Following the incubation, the plants were maintained in a 
greenhouse for approximately 7 days. The percent disease control provided 
by a given test compound was based on the percent disease reduction 
relative to untreated check plants. The results are tabulated in Table 
III. 
Example E 
Rice Blast 
Compounds of this invention were tested for control of the Rice Blast 
organism Piricularia oryzae, using 10- to 14-day-old rice plant seedlings 
(Calrose M-9 variety). Seedling plants were sprayed with a 625-ppm 
solution of the test compound in acetone, water and a non-ionic emulsifier 
(ORTHO X-77 spreader). The sprayed plants were inoculated 1 day later with 
the organism in an environmental chamber. After inoculation, the plants 
were kept in an environmental chamber for about 48 hours under conditions 
of about 72.degree. F. to 75.degree. F. and about 100% relative humidity. 
Following the incubation period, the plants were placed in a greenhouse 
with a temperature of about 72.degree. F. and maintained with bottom 
watering for about 12 to 16 days. The percent disease control provided by 
a given test compound is based on a comparison of the percentage disease 
relative to the percent disease development on the untreated check plants: 
##EQU1## 
The results are tabulated in Table III. 
Example F 
Tomato Early Blight 
Compounds were tested for the control of the Tomato Early Blight organism 
Alternaria solani. Tomato (variety Bonny Best) seedlings of 6- to 7-weeks 
old were used. The tomato plants were sprayed with a 200-ppm solution of 
the test compound in an acetone-and-water solution containing a small 
amount of a nonionic emulsifier. The sprayed plants were inoculated 1 day 
later with the organism, placed in the environmental chamber and incubated 
at 66.degree. F. to 68.degree. F. and 100% relative humidity for 24 hours. 
Following the incubation, the plants were maintained in a greenhouse for 
about 12 days. Percent disease control was based on the percent disease 
development on untreated check plants. The results are tabulated in Table 
III. 
Example G 
Celery Late Blight 
The Celery Late Blight tests were conducted using celery (Utah) plants 11 
weeks old. The Celery Late Blight organism was Septoria apii. The celery 
plants were sprayed with 200-ppm solutions of the candidate toxicant mixed 
with acetone, water and a nonionic emulsifier. The plants were then 
inoculated with the organism and placed in an environmental chamber and 
incubated at 66.degree. F. to 68.degree. F. in 100% relative humidity for 
an extended period of time (approximately 48 hours). Following the 
incubation, the plants were allowed to dry and then were maintained in a 
greenhouse for approximately 14 days. The percent disease control provided 
by a given test compound is based on the percent disease reduction 
relative to untreated check plants. The results are reported in Table III. 
Example H 
Bean Powdery Mildew 
Compounds were tested for the control of the Bean Powdery Mildew organism 
Erysiphe polygoni. Seedling bean plants were sprayed with a 250-ppm 
solution of the test compound in acetone, water and a nonionic emulsifier. 
The sprayed plants were then inoculated 1 day later with the organism. The 
plants were maintained for 10 days at temperatures of 68.degree. F. at 
night with daytime temperatures of 72.degree. F. to 80.degree. F.; 
relative humidity was maintained at 40% to 60%. The percent disease 
control provided by a given test compound was based on the percent disease 
reduction relative to the untreated check plants. The results as percent 
control are tabulated in Table III. 
Example I 
Bean Rust 
Compounds were evaluated for their ability to eradicate Bean Rust caused by 
Uromyces phaseoli typica on pinto beans. 
Pinto bean plants, variety Idaho 1-11, 16 (summer) or 19 (winter) days old 
were inoculated with a 50-ppm suspension of uredospores in water 
containing a small amount of nonionic surfactant. The inoculated plants 
were placed in an environmental chamber immediately after inoculation and 
incubated 20 hours. Following the incubation period, the plants were 
removed from the chamber and placed in a greenhouse maintained at 
66.degree.-68.degree. F. and 60-80% relative humidity. Two days after 
inoculation, the plants were treated by spraying with a 200-ppm solution 
of test compound in an acetone and water carrier formulation containing a 
small amount of nonionic surfactant. One or two replicate pots (each 
containing two plants) were used for each compound. In addition one or two 
replicate pots were sprayed with the same carrier formulation (without a 
test compound) as a control (hereinafter "untreated Checks"). The plants 
were kept in the greenhouse until evaluated. The plants were evaluated for 
disease control when disease symptoms were well developed on the untreated 
Checks, normally about 14 days after treatment. The percentage disease 
control (or eradication) provided by a test compound was based on the 
percent disease reduction relative to the untreated Checks. The results 
are reported in Table III. 
Example J 
Aphid Control 
The compounds of this invention were tested for their insecticidal activity 
against cotton aphids (Aphis gossypii Glover). An acetone solution of the 
test compound containing a small amount of nonionic emulsifier was diluted 
with water to give a concentration of 40 ppm. Cucumber leaves infested 
with cotton aphids were dipped in the test compound solution. Mortality 
readings were taken after 24 hours. The results are tabulated in Table II 
in terms of percent control. 
Example K 
Aphid Systemic Evaluation 
This procedure is used to assess the ability of a candidate insecticide to 
be absorbed through the plant root system and translocate to the foliage 
and thus to show insecticidal activity against the cotton aphid (Aphis 
gossypii Glover). 
Two cucumber plants planted in a 4-inch fiber pot with a soil surface area 
of 80 cm.sup.2 are used. Forty ml of an 80-ppm solution of the candidate 
insecticide is poured around the plants in each pot. (This corresponds to 
40 gamma/cm.sup.2 of actual toxicant.) The plants are maintained 
throughout in a greenhouse at 75.degree.-85.degree. F. Forty-eight hours 
after the drenching, the treated plants are infested with aphids by 
placing well-colonized leaves over the treated leaves so as to allow the 
aphids to migrate easily from the inoculated leaf to the treated leaf. 
Three days after infestation, mortality readings were taken. The results 
are tabulated in Table IV in terms of percent control. 
Example L 
Mite Adult 
Compounds of this invention were tested for their insecticidal activity 
against parathion-resistant Two-spotted Spider Mite (Tetranychus urticae 
Koch). An acetone solution of the candidate toxicant containing a small 
amount of nonionic emulsifier was diluted with water to 40 ppm. Lima bean 
leaves which were infested with mites were dipped in the toxicant 
solution. The results are tabulated in Table IV in terms of percent 
control. 
Example M 
Mite Egg Control 
Compounds of this invention were tested for their ovicidal activity against 
eggs of the two-spotted spider mite (Tetranychus urticae Koch). An acetone 
solution of the test toxicant containing a small amount of nonionic 
emulsifier was diluted with water to give a concentration of 40 ppm. Two 
days before testing, 2 -week old lima bean plants were infested with 
spider mites. Two days after infestation, leaves from the infested plants 
are dipped in the toxicant solution, placed in a petridish with filter 
paper and allowed to dry in the open dish at room temperature. The treated 
leaves were then held in covered dishes at about 31.degree. C. to 
33.degree. C. for seven days. On the eighth day egg mortality readings are 
taken. The results, expressed as percent control, are tabulated in Table 
IV. 
Example N 
Housefly 
Compounds of this invention were tested for their insecticidal activity 
against the Housefly (Musca domestica Linnaeus). A 500-ppm acetone 
solution of the candidate toxicant was placed in a micro sprayer 
(atomizer). A random mixture of anesthetized male and female flies was 
placed in a container and 55 mg of the above-described acetone solution 
was sprayed on them. A lid was placed on the container. A mortality 
reading was made after 24 hours. The results are tabulated in Table IV in 
terms of percent control. 
Example O 
American Cockroach 
Compounds of this invention were tested for their insecticidal activity 
against Chlorodane-resistant American Cockroaches (Periplaneta americana 
Linnaeus). A 500-ppm acetone solution of the candidate toxicant was placed 
in a micro sprayer (atomizer). A random mixture of anesthetized male and 
female roaches was placed in a container and 55 mg of the above-described 
solution was sprayed on them. A lid was placed on the container. A 
mortality reading was made after 24 hours. The results are tabulated in 
Table IV in terms of percent control. 
Example P 
Alfalfa Weevil 
The compounds of this invention were tested for their insecticidal activity 
against Alfalfa Weevil (Hypera brunneipennis Boheman). A 500-ppm acetone 
solution of the candidate toxicant was placed in a micro sprayer 
(atomizer). A random mixture of male and female weevils was placed in a 
container and 55 mg of the above-described acetone solution was sprayed on 
them. A lid was placed on the container. A mortality reading was made 
after 24 hours. The results are tabulated in Table IV in terms of percent 
control. 
Example Q 
Cabbage Looper Control 
The compounds of this invention were tested for their insecticidal activity 
against Cabbage Looper (Trichoplusia ni Hubner). An acetone solution of 
the candidate toxicant containing a small amount of nonionic emulsifier 
was diluted with water to give a concentration of 500 ppm. Excised 
cucumber leaves were dipped in the toxicant solution and allowed to dry. 
The leaves were then infested with Cabbage Looper larvae. Mortality 
readings were taken after 24 hours. The results are tabulated in Table IV 
in terms of percent control. 
TABLE I 
__________________________________________________________________________ 
Compounds of the Formula: 
##STR9## 
ELEMENTAL ANALYSIS 
% C % H % N 
Compound 
Z R R.sup.1 
Physical State 
Calc. 
Found 
Calc. 
Found 
Calc. 
Found 
__________________________________________________________________________ 
1 44461 
S CH.sub.3 
(CH.sub.2).sub.3 CH.sub.3 
yellow liquid 
48.5 
48.2 
7.45 
7.7 3.14 
2.78 
2 44506 
S CH.sub.2 CH.sub.3 
(CH.sub.2).sub.3 CH.sub.3 
yellow liquid 
49.6 
48.3 
7.67 
8.14 
3.04 
3.74 
3 44569 
O CH.sub.2 CH.sub.3 
(CH.sub.2).sub.3 CH.sub.3 
yellow liquid 
51.4 
51.2 
7.94 
8.53 
3.15 
2.9 
4 44862 
O CH.sub.2 CH.sub.3 
##STR10## 
viscous opaque liquid 
57.5 
75.9 
7.91 
11.8 
2.68 
4.77 
__________________________________________________________________________ 
TABLE II 
______________________________________ 
BACTERICIDAL ACTIVITY 
Compound Pseudo. Erwin. Xanth. 
______________________________________ 
1 44461 0 0 63 
2 44506 0 0 63 
3 44569 0 0 100 
4 44862 0 0 0 
______________________________________ 
TABLE III 
__________________________________________________________________________ 
FUNGICIDAL ACTIVITY 
Mycelial Inhibition 
Compound 
Pyth. 
Rhiz. 
Fusar. 
Botry. 
Asper. 
Ustil. 
TLB 
RB TEB 
CLB 
BPM BR 
__________________________________________________________________________ 
1 44461 
25 38 162 67 214 50 98 0 0 100 
69 0 
2 44506 
25 25 80 25 255 28 95 0 0 93 0 0 
3 44569 
25 28 105 29 220 40 100 
57 0 97 0 0 
4 44862 
0 18 55 21 71 25 91 0 44 92 100 0 
__________________________________________________________________________ 
TABLE IV 
______________________________________ 
INSECTICIDAL ACTIVITY 
Com- 
pound AR AW HF MA ME Aph. AS CL 5-CL 
______________________________________ 
1 44461 
70 20 30 100 100 50 0 80 100 
2 44506 
40 0 30 70 100 0 0 0 100 
3 44569 
0 0 0 95 100 70 0 100 100 
4 44862 
0 0 0 40 60 0 0 40 100 
______________________________________