Claims
- 1. A compound of the formula ##STR8## wherein R.sup.1 is alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 3 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, phenyl or benzyl substituted with 1 to 2 of the same or different substituents selected from fluoro, chloro, bromo and alkyl of 1 to 4 carbon atoms; R.sup.2 is alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 3 carbon atoms, benzyl or benzyl substituted with 1 to 2 of the same or different substituents selected from fluoro, chloro, bromo and alkyl of 1 to 4 carbon atoms; and R.sup.3, R.sup.4 and R.sup.5 individually are alkyl of 1 to 6 carbon atoms, phenyl or benzyl.
- 2. The compound of claim 1 wherein R.sup.1 is alkyl of 1 to 4 carbon atoms, R.sup.2 is alkyl of 1 to 4 carbon atoms and R.sup.3, R.sup.4 and R.sup.5 individually are alkyl of 1 to 6 carbon atoms.
- 3. The compound of claim 1 wherein R.sup.1 and R.sup.2 are methyl, and R.sup.3, R.sup.4 and R.sup.5 are n-butyl.
- 4. The compound of claim 1 wherein R.sup.3, R.sup.4 and R.sup.5 individually are alkyl of 1 to 6 carbon atoms.
- 5. The compound of claim 1 wherein R.sup.1 is alkyl of 1 to 4 carbon atoms.
- 6. The compound of claim 1 wherein R.sup.2 is alkyl of 1 to 4 carbon atoms.
RELATED APPLICATION
This application is related to applicant's copending application Ser. No. 617,871, filed Sept. 29, 1975, which is directed to fungicidal 1-halohydrocarbylthio-3-hydrocarbylthio-4-substituted-1,2,4-delta.sup.2 -triazolidin-5-ones.
The present invention is directed to organotin compounds. Organotin compounds have been found to be useful in a variety of applications, such as for wood preservation, food packaging, marine anti-fouling paints, and as fungicides. A recent review of organotin compounds and their applications is found in an article by P. Smith and L. Smith, in Chem. Brit. 11, 208-211 (1975).
U.S. Pat. No. 3,907,818 of Buchel et al. discloses insecticidal and acaricidal trialkyl- and tricycloalkyl-stannyl-1,2,4-triazoles. The compounds of the invention are triorganostannyl-substituted 1,2,4-trazolidin-5-ones.
U.S. Pat. No. 3,767,666 of Zielinski discloses 3-hydrocarbylthio-1,4-disubstituted 1,2,4-triazol-2-in-5-ones, which are related to the 3-organothio-4-substituted-1,2,4-delta.sup.2 -triazolidin-5-ones (3-organothio-4-substituted-1,2,4-triazol-2-in-5-ones) used as intermediates for the preparation of the compounds of the invention.
Arndt et al., Chemical Abstracts, Vol. 16 (1922), pg. 2509, discloses the methylation product of 4-phenylthiourazole (3-methylthio-4-phenyl-1,2,4-delta.sup.2 -triazolidin-5-one), which is an intermediate for the preparation of the compounds of the invention.
The 1,2,4-delta.sup.2 -triazolidin-5-ones of the invention are represented by the formula ##STR2## wherein R.sup.1 is alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 4 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, phenyl, benzyl, or phenyl or benzyl substituted with 1 to 3 of the same or different substituents selected from fluoro, chloro, bromo, alkyl of 1 to 4 carbon atoms, haloalkyl of 1 to 4 carbon atoms and 1 to 3 chloro, bromo or fluoro, alkoxy of 1 to 3 carbon atoms, and nitro; R.sup.2 is alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 4 carbon atoms, haloalkyl of 1 to 4 carbon atoms and 1 to 5 of the same or different halogen atoms selected from fluoro, chloro and bromo, benzyl or benzyl substituted with 1 to 2 of the same or different substituents selected from fluoro, chloro, bromo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 3 carbon atoms or nitro; and R.sup.3, R.sup.4 and R.sup.5 individually are alkyl of 1 to 6 carbon atoms, phenyl, benzyl, or phenyl or benzyl substituted with 1 to 2 of the same or different substituents selected from fluoro, chloro, bromo or alkyl of 1 to 4 carbon atoms.
Preferably R.sup.1 is alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 3 carbon atoms, cycloalkyl of 5 to 6 carbon atoms, phenyl, benzyl, or phenyl or benzyl substituted with 1 to 2 substituents, either the same or different, selected from fluoro, chloro, bromo or alkyl of 1 to 4 carbon atoms. Most preferably R.sup.1 is alkyl of 1 to 4 carbon atoms.
Preferably R.sup.2 is alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 3 carbon atoms, benzyl or benzyl substituted with 1 to 2 of the same or different substituents selected from fluoro, chloro, bromo or alkyl of 1 to 4 carbon atoms. Most preferably R.sup.2 is alkyl of 1 to 4 carbon atoms.
Preferably R.sup.3, R.sup.4 and R.sup.5 individually are alkyl of 1 to 6 carbon atoms, phenyl or benzyl.
Representative alkyl groups which R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 may represent are methyl, ethyl, propyl, isobutyl and n-butyl.
Representative alkenyl groups which R.sup.1 and R.sup.2 may represent are vinyl, allyl and 2-butenyl.
Representative cycloalkyl groups which R.sup.1 may represent are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl and cyclooctyl.
Representative phenyl groups which R.sup.1 may represent are:
o-fluorophenyl,
p-fluorophenyl,
p-chlorophenyl,
o-chlorophenyl,
m-chlorophenyl,
m-bromophenyl,
3,4-dichlorophenyl,
3-chloro-4-bromophenyl,
2,4,6-trichlorophenyl, and
1,3,5-tribromophenyl;
p-tolyl,
2,4-dimethylphenyl,
3,5-diethylphenyl,
4-isopropylphenyl, and
3-n-butylphenyl;
2-chloromethylphenyl,
3-(1',2'-dichloroethyl)phenyl,
o-trichloromethylphenyl,
p-trifluoromethylphenyl,
n-tribromoethylphenyl, and
2,4-ditrifluoromethylphenyl;
2-methoxyphenyl,
4-ethoxyphenyl, and
2,4-dipropoxyphenyl;
o-nitrophenyl,
2,4-dinitrophenyl,
p-nitrophenyl, and
m-nitrophenyl;
2-nitro-4-chlorophenyl,
2-methyl-4-nitrophenyl,
3-methoxy-4-methylphenyl,
2,6-dimethyl-4-methoxyphenyl,
2-methyl-4-chlorophenyl,
2-bromo-4-ethylphenyl, and
3-chloro-4-isopropylphenyl.
Representative benzyl groups which R.sup.1 and R.sup.2 may represent are
4-chlorobenzyl,
2,4-dibromobenzyl,
4-methylbenzyl,
3-trifluoromethylbenzyl,
2-ethoxybenzyl, and
4-nitrobenzyl.
Representative haloalkyl R.sup.2 groups are
chloromethyl,
difluoromethyl,
dichloromethyl,
dibromomethyl,
dichlorofluoromethyl,
trifluoromethyl,
tribromomethyl,
1,1,2,2-tetrafluoroethyl,
2,2,2-trichloroethyl,
1,2,2-trichloroethyl,
2,2,2-trichloroethyl,
1,1,2,2-tetrachloroethyl,
1-bromo-2,2,2-trichloroethyl,
pentachloroethyl,
pentabromomethyl,
3,4-dichlorobutyl, etc.
Representative alkenyl R.sup.2 groups are allyl, 2-butenyl, 2-hexenyl, etc.
Representative phenyl and benzyl groups which R.sup.3, R.sup.4 and R.sup.5 may represent are
o-fluorophenyl,
2,4-dichlorophenyl,
p-tolyl,
2-chloro-4-methylphenyl,
p-bromobenzyl, and
2,4-dimethylbenzyl.
The compounds of the present invention are prepared from an appropriate 1,2,4-delta.sup.2 triazolidin-5-one by reaction with a triorganotin halide, thus: ##STR3## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 have the same meaning as stated before, and X is chloro or bromo, preferably chloro.
This reaction proceeds readily at temperatures in the range 0.degree.-150.degree. C, preferably 20.degree.-100.degree. C. Substantially equal molar quantities of the reactants are mixed in an inert solvent, preferably a chlorinated aliphatic hydrocarbon such as chloroform, dichloroethane or dichloromethane. Dichloromethane is preferred. A substantially equivalent amount of a base material is also present in the reaction medium to scavenge the hydrogen halide by-product. Such bases include triethylamine, pyridine, triethylene diamine, etc. The quantity of solvent varies, but is preferably sufficient to dissolve the triazolidin-5-one. In the case of compounds having low solubility, slurries in the solvent are satisfactory. Reaction times vary from 1 to 24 hours.
The product is isolated and purified by conventional procedures such as extraction, filtration and crystallization.
The 3-organothio-4-substituted-1,2,4-delta.sup.2 -triazolidin-5-one (II) utilized in the above reaction is in turn obtained from the cyclization of an appropriate 1-carbomethoxy-4-substituted thiosemicarbazide (IV) under the influence of a base and subsequent alkylation, thus: ##STR4##
wherein R.sup.1 and R.sup.2 are as indicated above.
The preferred base is potassium carbonate, and for satisfactory yields it is necessary that an exact equivalent, (i.e., one half mol) be used. This reaction is carried out in a polar solvent, preferably methanol or ethanol. The temperature of the reaction is in the range 50.degree.-100.degree. C; preferably it is the atmospheric pressure reflux temperature of the solvent. Reaction is carried out until all of the carbonate has reacted, as indicated by its disappearance. Then a slight molar excess of the iodide reactant (R.sup.2 I) is added. The crude reaction mixture is concentrated, mixed with water and extracted with dichloromethane. After drying, the dichloromethane is removed by distillation under reduced pressure. The crude product obtained in this way is satisfactory for the next step of the synthesis. However, it may be purified by crystallization from a benzene/hexane mixed solvent system.
The starting material (IV) for reaction (2) is readily obtained from the room-temperature reaction of methylhydrazinocarboxylate (V) with an appropriate isothiocyanate (VI) in a solvent such as diethylether: ##STR5##
After a reaction time of 15 to 150 minutes, the product precipitates from the ether solvent and is readily recovered by cooling and filtration. No purification other than drying is required; the product is ready for use in reaction (2).
The compounds of the invention have exhibited pesticidal activity against a variety of microbiological organisms, such as fungi, molds and bacteria. The compounds of the invention are particularly effective for the control of fungi.
When used as pesticides against microbiological organisms and pests such as fungi and bacteria, the compounds are applied in pesticidally (fungicidally or bactericidally) effective amounts to the organism and/or their habitats, such as vegetative hosts and non-vegetative hosts, e.g., animal products. Generally, some pesticidal compounds will be more pesticidally active than others against particular fungi or bacteria. The amount of pesticidal compound 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 pesticides 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 pesticidal compounds, recognizing that the formulation and mode of application may affect the activity of the pesticide. Thus, the pesticides 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 dispersant. These compositions normally contain from about 5-80% pesticide, 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 pesticidal composition.
Dusts are freely flowing admixtures of the active pesticide 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 the toxicant. Useful liquid concentrates include the emulsifiable concentrates which are homogeneous liquid or paste compositions which are readily dispersed in water or other dispersants, and may consist entirely of the pesticide 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 pesticidal applications include simple solutions of the active pesticide 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 pesticide 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 pesticides are well known in the art.
The percentages by weight of the pesticide 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 pesticide by weight of the pesticidal composition.
The pesticidal compositions may be formulated and applied with other active ingredients, including other fungicides, insecticides, nematocides, bactericides, plant growth regulators, fertilizers, etc.
The compounds of this invention are also toxic to a variety of crop and household insects. It is generally desirable to apply the compounds in insecticidal compositions comprising one or more of the insecticidal compounds intimately admixed with a biologically inert carrier. The carrier may be a liquid or a solid, e.g., the compounds of the invention may be formulated as solutions, emulsifiable concentrates, wettable powders, powdery dusts or granules, as hereinbefore described for other pesticidal compositions of the compounds of the invention. In insecticidal compositions, the insecticidal compounds can be from about 0.01 to 95% by weight of the entire composition.
The insecticidal compositions may be formulated and applied with other active ingredients, including other nematocides, insecticides, fungicides, bactericides, plant growth regulators, fertilizers, etc. In applying the chemical, an insecticidally effective amount and concentration of the compounds 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.
The compounds of the present invention are also useful as herbicides in both pre- and post-emergent applications. For pre-emergent control of undesirable vegetation, the herbicidal compounds will be applied in herbicidally effective amounts to the locus or growth medium of the vegetation, e.g., soil infested with seeds and/or seedlings of such vegetation. Such application will inhibit the growth of or kill the seeds, germinating seeds and seedlings. For post-emergent applications, the herbicidal compounds will be applied directly to the foliage and other plant parts. Generally, the herbicidal compounds of the invention are effective against weed grasses as well as broadleaved weeds.
The compounds of the present invention can be used alone as herbicides. However, it is generally desirable to apply the compounds in herbicidal compositions comprising one or more of the herbicidal compounds intimately admixed with a biologically inert carrier. The carrier may be a liquid diluent or a solid, e.g., in the form of dust powder or granules. In the herbicidal composition, the active herbicidal compounds can be from about 0.01 to 95% by weight of the entire composition.
Suitable liquid diluent carriers include water and organic solvents, e.g., hydrocarbons such as benzene, toluene, kerosene, diesel oil, fuel oil, and petroleum naphtha. Suitable solid carriers are natural clays such as kaolinite, atalpulgite and montmorillonite. In addition, talcs, pyrophillite, diatomaceous silica, synthetic fine silicas, calcium aluminosilicate and tricalcium phosphate are suitable carriers. Organic materials such as walnut-shell flour, cottonseed hulls, wheat flour, wood flour or redwood-bark flour may also be used as solid carriers.
The herbicidal composition will also usually contain a minor amount of a surface-active agent. Such surface agents are those commonly known as wetting agents, dispersing agents and emulsifying agents, and can be anionic, cationic or nonionic in character. The herbicidal compositions may also contain other pesticides, adjuvants, stabilizers, conditioners, fillers, and the like.
The amount of herbicidal compound or composition administered will vary with the particular plant part or plant growth medium which is to be contacted, the general location of application -- i.e., sheltered areas such as greenhouses, as compared to exposed areas such as fields -- as well as the desired type of control. Generally, for both pre- and post-emergent control, the herbicidal compounds of the invention are applied at rates of 0.2 to 60 kg/ha, and the preferred rate is in the range 0.5 to 40 kg/ha.
The compounds of the invention are also useful for controlling microbiological organisms such as algae, bacteria, molds and occasionally aquatic weeds which foul aqueous industrial effluents and cooling streams, such as those occurring in the paper and food processing industries. They may also be used to control such organisms in other aqueous bodies such as lakes, streams, canals, pools and the like. When so used, a biocidal quantity of one or more of the compounds of this invention is added to the aqueous growth environment of the organisms. Usually, this dosage will range between about 0.1 to 50 ppm. In any given instance, the optimum dosage will depend upon the particular organism and aqueous body involved. For instance, when used to control algae, these compounds will usually be employed at concentrations of about 0.1 to 10 ppm. In terms of pounds of compound per acre of water 1 foot deep, 0.1 to 10 ppm is equal to about 0.3 to 30 pounds per acre of water 1 foot deep. These compounds may be applied to the aqueous growth environments of such organisms as dispersible powders or in solution with water-miscible solvents.
US Referenced Citations (3)
| Number |
Name |
Date |
Kind |
|
3701784 |
Seidel et al. |
Oct 1972 |
|
|
3767666 |
Zielinski |
Oct 1973 |
|
|
3907818 |
Buchel et al. |
Sep 1975 |
|
Foreign Referenced Citations (2)
| Number |
Date |
Country |
| 2,259,983 |
Dec 1971 |
DE |
| 2,250,572 |
Apr 1974 |
DE |
Patent Grant
4110332
