CA1058632A - Substituted n-phenylcarbamates and their use to inhibit pupa metamorphosis - Google Patents
Substituted n-phenylcarbamates and their use to inhibit pupa metamorphosisInfo
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- CA1058632A CA1058632A CA267,477A CA267477A CA1058632A CA 1058632 A CA1058632 A CA 1058632A CA 267477 A CA267477 A CA 267477A CA 1058632 A CA1058632 A CA 1058632A
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- metamorphosis
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Abstract
ABSTRACT OF THE DISCLOSURE
Disclosed are certain novel substituted N-phenylcarbanates which can be applied to the habitat of insect larvae to inhibit the metamorphosis of the subsequently formed pupae. Also disclosed are compositions for the control of insects by the chemical inhibition of the metamorphosis of insect pupae. These compositions comprise pupae metamorphosis inhibiting material selected from the group of the new substituted phenylcarbanates.
Disclosed are certain novel substituted N-phenylcarbanates which can be applied to the habitat of insect larvae to inhibit the metamorphosis of the subsequently formed pupae. Also disclosed are compositions for the control of insects by the chemical inhibition of the metamorphosis of insect pupae. These compositions comprise pupae metamorphosis inhibiting material selected from the group of the new substituted phenylcarbanates.
Description
This invention relates to novel compounds useful for the control of insects by the chemical inhibition of the metamorphosis of pupae.
The term "insect" is used herein in its strict biological sense.
It does not include other arthropods commonly and loosely referred to as insects.
The invention is based on the discovery that certain compounds that have no noticeable effect on adult or mature insects (when applied at ordin-ary insecticidal concentrations) nevertheless inhibit the metamorphosis of the pupae when applied to insect larvae, especially when the larvae are in the late instar stages.
According to the invention novel compounds which can be used in a method for the control of insects by applying the compounds to the habitat of insect larvae material are selected from the following group of substitut-ed N-phenylcarbamates:
Isopropyl N-(p-bromophenyl)carbamate Isopropyl N-(p-iodophenyl)carbamate l-Butyn-3-yl N-(p-chlorophenyl)carbamate l-Butyn-3-yl N-(3,4-dichlorophenyl)carbamate l-Butyn-3-yl N-(p-bromophenyl)carbamate l-Butyn-3-yl N-(p-iodophenyl)carbamate.
A preferred compound is l-butyn-3-yl N-(p-chlorophenyl)carbamate.
Each of the N-phenylcarbamates of this invention can be made by two general processes. One process is based on the reaction:
H O
RNCO + HOR' ~ R-N- C-O-Rt catalyst in which R is the substituted phenyl moiety and R' is the corresponding alcohol residue. The other process is based on the reaction:
O H O
R' ~ R-N_ C-O-R' + HX
base in which X is halo. These general processes are well known and the reactants in these processes are either commer dally available or obtainable by well-known reactions from commercially available chemicals.
The substituted N-phenylcarbamates of this invention are generally applied to the habitat of insect larvae in a dispersible composition contain-ing application aid material.
In some embodiments of this composition the pupa metamorphosis in-hibiting material selected from the above group of substituted N-phenylcar-bamates comprises only one compound. In other embodiments the material com-prises two or more compounds of the above group.
Specific embodiments of the composition of this invention range from concentrates of the metamorphosis inhibiting material to the ultimate composition applied to the habitat of the larva of the insect to be controll-ed. Accordingly, concentration of the pupa metamorphosis inhibiting material in the compositions of this invention is in a broad range, generally being from about 0.1 to about 95% by weight of the composition. In concentrates, the concentration generally is in a range from about 1 to about 95% by weight of the composition and preferably in a range from about S to about 80% by weight of the composition. In the ultimate use composition, the concentra-tion generally is in a range from about 0.1 to about 50% by weight of the composition and preferably in a range from about 0.1 to about 20% by weight of the composition.
Application aid material is generally inert material that facili-tates distribution or dispersion of the insect pupa metamorphosis iohibiting material when it is applied to the habitat of the larva of the insect to be controlled. It encompasses diluents, carriers, extenders, surfactants, spreading agents, sticking agents, wind drif~ control agents, and the like.
It also includes inert gas of the kind employed in aerosol sprays, when the metamorphosis inhibiting material is to be applied by aerosol spraying.
In those embodiments of the composition of this invention, which are normally solid, the application aid material generally comprises an inert solid in a divided condition.
Some embodiments of the solid composition are granular, while others are dispersible powders or dusts.
The granular compositions are of the coated type, the impregnated type or the incorporated type.
The coated type of granular composition is made by dusting a wett-able powder or ground powder camprising the pupa metamorphosis inhibiting material onto granular carried material which either before or after the dusting has been a~miyed with an adhesive or a sticker. Water, oils, alco-hols, glycols, aqueous gums, waxes and the l;ke including m;xtures thereof, are used as stickers. E~amples of granular carrier material include attaclay, ground corn cobs, vermiculite, ground walnut hulls and almost any granular mineral or organic material screened to the desired particle si~e (generally 15-60 mesh, preferably about 30 mesh, United States screen si~e). Generally the pupa metamorphosis inhibiting material is about 2-20% by weight of the composition and the granular carrier material is generally about 60-93% by weight of the composition.
In the case of the impregnated type of grsnular composition, the pupa metamorphosis inhibiting material is dissolved in a solvent or melted, and then sprayed on or poured into the granular carrier material. The sol-vent can be removed by evaporation, or permitted to remain. In either case, the pupa metamorphosis inhibiting material impregnates the particles of the granular carrier material. Examples of the granular carrier material include those just mentioned with respect to the coated type of granular composition.
The pupa metamorphosis inhibiting material is generally about 2-20~ by weight of the composition, while the granular carrier material is generally about 80-98% by weight of the composition.
The incorporated type of granular composition is made by admixing the pupa metamorphosis ;nh;biting material with an inert finely divided solid such as, for example, clay, carbon, plaster of paris and the like, and made ~058632 into a mud with water or other inert evaporable liquid. The mud is then dried to a solid sheet or cake, broken up or comminuted, and screened to the desired particle size (g~neraIly 15-60 mesh, preferably about 30 mesh, United States screen size). In other embodiments, the mud is put into a granular pan and granules are formed therein with subsequent removal of the water or solvent. In still another procedure, the mud is extruded through a die into rods which are cut into small pieces. In the incorporated type of granular composition, the pupa metamorphosis ;nh;biting material generally is about 2-50% by weight of the composition, and the solid carrier material is about 50-98% by weight of the composition.
In some embodiments of the granular composition of this invention the carrier material comprises a polymeric substance which effects a slow constant rate of release of the pupa metamorphosis inhibiting material when the composition is applied to the-insect larva habitat. In some instances, for example, when the substance is rubber or the l;ke~ the release comes about because of incompatibility of the pupa metamorphosis inhibiting mater-ial or solution thereof with the polymeric substance, and the material or solution thereof bleeds or oo~es from the polymeric substance. In other instances, the release comes about because of degradation of the polymeric substance by water, ultraviolet light, or other exterior or interior agency.
Those embodiments that effect slow control of release of the pupa metamor-phosis inhibiting material, when they are introduced into water, are particu-larly effective in controlling insects such as mosquitoes and the like, the habitat of the larva of which is water.
In all granular embodiments of the composition of this invention the carrier is usually a dispersible inert solid. A typical dispersible solid of this type is clay. Other suitable solids (dispersible solid) in-clude talc, attapulgite, pyropylite, diatomaceous earth, kaolin, aluminum magnesium silicate, montmorillonite, Fullers earth, sawdust and the like.
The solid dispersible composition can be air dispersible, in which case it is ~05863Z
usually referred to as wettable powder. Generally, when it is intended that the composition be water dispersible, the composition preferably contains emulsifying material (one or more surfactants) at a concentration sufficient to enable a suspension of the desired degree of stability to be formed when the composition is admixed with a suitable quantity of water. A typical di-spersible solid composition of this invention generally comprises about 10-50% by weight of pupa metamorphosis inhibiting material, about 50-90~ by weight of solid carrier material and, when emulsifying material is present, about 1-10% by weight of emulsifying material.
Other specific embodiments of the pupa metamorphosis inhibiting composition of this invention comprise solutions of pupa metamorphosis inhib-iting material in inert, preferably volatile, usually water immiscible sol-vents for the metamorphosis inhibiting material. Examples of suitable sol-vents include isophorone, cyclohexanone, methyl isobutyl ketone, xylene, and the like. Such a solution, which can be regarded as a concentrate, typically comprises about 10~50% by weight of pupa metamorphosis inhibiting material and about 50-90~0 by weight of solvent. The solution can be applied as is, or diluted with more solvent, or dispersed in water, or water dispersed in it.
Preferably, when it is intended that the solution be dispersed in water or water dispersed in it, the mixture of solution and water also comprises emul-sifying material at a concentration sufficient to enable a dispersion of the desired degree of stability to be formed. A typical emulsifying material concentration is about 1-10% by weight of the concentrate. The water concen-tration is such that the pupa metamorphosis inhibiting material concentration is about 0.5-lO~o by weight of the total composition.
Examples of the surfactants employed in both the liquid and solid compositions of this invention comprise the well-known surface active agents of the anionic, cationic and non-ionic types and include alkali metal (sodium or potassium) oleates and similar soaps, amine salts of long chain fatty acids (oleates), sulfonates, animal and vegetable oils (fish oils and castor oil), sulfonated acyclic hydrocarbons, sodium salts of lignin sulfonic acids, alkylnaphthalene sodium sulfonates, sodium lauryl sulfonate, disodium mono-lauryl phosphate, sorbitol laurate, pentaerythritol monostearate, glyce~yl monostearate, poly(ethylene oxides), ethylene oxide condensates of stearic acid, stearyl alcohol, stearyl amine, rosin amines, dehydroabietyl amine and the like, lauryl amine salts, dehydroabietyl amine salts, lauryl pyridinium bronide, stearyl trimethylammonium bromide, and cetyl dimethylbenzylammonium chloride. StiIl other examples are listed in "Detergents and Emulsifiers -1968 Annual" by John W. McCutcheon.
In addition to the pupa metamorphosis inhibiting material and application aid material, a number of specific embodiments of the dispersible composition of this invention comprise one or more other components, examples of which include insecticides, acaricides, herbicides, fungicides, plant nutrients, and the like.
The insect pupa metamorphosis ;nhibiting composition of t_is inven-tion is used by applying it by conventional ways and means to the habitat of the larva of the insect to be controlled.
The rate of application of the composition of this invention is such as to provide about 0.1-10 pounds of pupa metamorphosis ;nh;biting ma-terial per acre. Higher and lower effective rates, however, are within thebroader concepts of this invention.
Typical results obtained in controlling insect larvae with the sub-stituted N-phenylcarbamates of this invention are illustrated by the follow-ing tabulated data.
These are actual data obtained in laboratory tests in which the test compound was incorporated into an emulsifiable concentrate consisting essentially of the test compound, toluene and polyoxyethylene (20) sorbitan monolaurate (an emulsifier in which the oxyethylene content averages about 20 mole per cent) at a ratio of 1 w:l v:l v in which w represents parts by weight, v represents parts by volume, and w is to v as the kilogram is to the liter The concentrate was then admixed with distiIled water to give 100 v of emulsion. Aliquot portions of the emulsion were then further diluted to give emulsions containing the test compound at the concentration specified in the following tables.
The test procedures and typical data obtained when the test com-pound is a compound of this invention are as follows.
Yellow Fever Mosquito (Aedes aevPti) - Larvae Ten late 4th instar larvae are exposed to the emulsion containing the test compound at a specified concentration in a smaIl container covered with a plastic bag. A control container with larvae is also provided. A
smsIl amount of ground guinea pig pellets is added to each container to feed the larvae to the pupal stage. When aIl of the adults have emerged in the control container, the container with the test compound is inspected and the number of dead larvae, dead pupae and nonmal adults determined.
Table 1 presents the data obtained when the substituted N-phenyl-carbamates of this invention were employed in this test.
% % %
Conc. Dead Dead Normal Test Compound (p.p.m.)karvaePuPae Adults Isopropyl N-(p-bromophenyl)car- 1.0 0 100 0 bamate O.S 0 100 0 Isopropyl N-(p-iodophenyl)car- 0.5 20 80 0 bamate 0.1 0 50 50 0.05 0 0 100 l-Butyn-3-yl N-(p-chlorophenyl)- 0.5 0 100 0 carbamate 0.05 0 100 0 0.005 0 100 0 0.0005 0 70 30 0.5 0 100 0 0.05 0 0 100 l-Butyn-3-yl N-(3~4-dichloro- 0.5 0 100 0 phenyl)carbamate 0.05 0 70 30 0.005 0 0 100 l-Butyn-3-yl N-(p-bromophenyl)- 1.0 0 100 0 carbamate l-Butyn-3-yl N-(p-iodophenyl)- 0.5 10 90 0 carbamate 0.1 0 40 60 0.05 0 0 100 The dead larvae and dead pupa are believed to result from arrested development or metamorphosis, and not from a toxic reaction.
Plum Curculio (Conotrachelus nenuphar) - Larvae A one ounce plastic container is filled with fine vermiculite admixed with a quantity of an aqueous emulsion of the concentrate, which quantity is selected to give the desired concentration of the test compound in the venmiculite. Into the container are placed S mature plum curculio larvae and the containers are covered. The same thing is done with a coated container except that water only is admixed with the vermiculite. After three weeks the containers are inspected.
Typical results when two of the compounds of this invention are employed in this test are given in Table 2.
~1 ~8 oo oo oo oo CO~ ~ CO~ CO~ c~oJ o o o o o o ~o o o o o g O ~ ~ ~ e p ~
_~ _ _ _ _ ~ U~ U~
~ ~, o o ~ o รด o O, .
H P, ~Z;
_ 9 _ ~05863Z
The dead larvae, dead pupae and dead abnormal adults are believed to be the result of arrested development, and not the result of a toxic reaction.
In the laboratory, tes~s have shown that at least one or two of the N-phenyl carbamates of this invention not only inhibit metamorphosis of lar-vae and pupa of various insects, but also inhibit metamorphosis of insect ova such as, for example, the ova of the Yellow Fever Mosquito (Aedes aegypti).
However, the emphasis in this specification is in inbibiting metamorphosis of at least the pupae of the insect to be controIled, and if it happens that metamorphosis of insect larvae and even of insect ova are inhibited at the same time, such is a side advantage of the practice of the method of this invention.
Thus, this invention provides a new method and composition for the control of insects.
E~LE;
This example iIlustrates one way of how to make l-butyn-3-yl N-(p-chlorophenyl)carbamate.
A solution of p-chlorophenyl isocyanate (1919 w) in acetone (S00 v) is added slowly (3 hours when w is in grams) to a solution of 3-butyn-2-ol (875 w), triethylamine (5 v), stannous octoate (5 v) and acetone (1000 v).
In the foregoing w is parts by weight, v is parts by volume with w being to v as the kilogram is to the liter.
The resulting solution is refluxed for 1 1/2 hours to give a reac-tion ~ixture.
While still hot the reaction miyture is filtered. Acetone is then stripped from the filtrate to give a slightly yellow solid product (2149.8 w).
This product, the typical melting point of which is 97-100C., consists essentially of l-butyn-3-yl N-(p-chlorophenyl)carbamate at a typical concen-tration of 92% by weight s measured by NMR.
Recrystallization of the product from benzene gives a clean white solid, the melting point of which is 101-103C.
Other features, advantages and specific embodiments of this inven-tion will become readily apparent to those exercising ordinary skill in the art after reading the foregoing disclosures. Such specific embodiments are within the scope of the claimed subject matter unless expressly indicated to the contrary by claim language. Moreover, while specific embodiments of this invention have been described in considerable detail, variations and modifi-cations of them can be effected without departing from the spirit and scope of the invention as disclosed and claimed.
The language "consisting essentially of" as used in this specifi-cation excludes any unrecited substance at a concentration sufficient to sub-stantially adversely affect the essential properties and characteristics of the composition being defined, while permitting the presence of one or more unrecited substances at concentrations insufficient to substantially adverse-ly affect said essential properties and characteristics.
The term "insect" is used herein in its strict biological sense.
It does not include other arthropods commonly and loosely referred to as insects.
The invention is based on the discovery that certain compounds that have no noticeable effect on adult or mature insects (when applied at ordin-ary insecticidal concentrations) nevertheless inhibit the metamorphosis of the pupae when applied to insect larvae, especially when the larvae are in the late instar stages.
According to the invention novel compounds which can be used in a method for the control of insects by applying the compounds to the habitat of insect larvae material are selected from the following group of substitut-ed N-phenylcarbamates:
Isopropyl N-(p-bromophenyl)carbamate Isopropyl N-(p-iodophenyl)carbamate l-Butyn-3-yl N-(p-chlorophenyl)carbamate l-Butyn-3-yl N-(3,4-dichlorophenyl)carbamate l-Butyn-3-yl N-(p-bromophenyl)carbamate l-Butyn-3-yl N-(p-iodophenyl)carbamate.
A preferred compound is l-butyn-3-yl N-(p-chlorophenyl)carbamate.
Each of the N-phenylcarbamates of this invention can be made by two general processes. One process is based on the reaction:
H O
RNCO + HOR' ~ R-N- C-O-Rt catalyst in which R is the substituted phenyl moiety and R' is the corresponding alcohol residue. The other process is based on the reaction:
O H O
R' ~ R-N_ C-O-R' + HX
base in which X is halo. These general processes are well known and the reactants in these processes are either commer dally available or obtainable by well-known reactions from commercially available chemicals.
The substituted N-phenylcarbamates of this invention are generally applied to the habitat of insect larvae in a dispersible composition contain-ing application aid material.
In some embodiments of this composition the pupa metamorphosis in-hibiting material selected from the above group of substituted N-phenylcar-bamates comprises only one compound. In other embodiments the material com-prises two or more compounds of the above group.
Specific embodiments of the composition of this invention range from concentrates of the metamorphosis inhibiting material to the ultimate composition applied to the habitat of the larva of the insect to be controll-ed. Accordingly, concentration of the pupa metamorphosis inhibiting material in the compositions of this invention is in a broad range, generally being from about 0.1 to about 95% by weight of the composition. In concentrates, the concentration generally is in a range from about 1 to about 95% by weight of the composition and preferably in a range from about S to about 80% by weight of the composition. In the ultimate use composition, the concentra-tion generally is in a range from about 0.1 to about 50% by weight of the composition and preferably in a range from about 0.1 to about 20% by weight of the composition.
Application aid material is generally inert material that facili-tates distribution or dispersion of the insect pupa metamorphosis iohibiting material when it is applied to the habitat of the larva of the insect to be controlled. It encompasses diluents, carriers, extenders, surfactants, spreading agents, sticking agents, wind drif~ control agents, and the like.
It also includes inert gas of the kind employed in aerosol sprays, when the metamorphosis inhibiting material is to be applied by aerosol spraying.
In those embodiments of the composition of this invention, which are normally solid, the application aid material generally comprises an inert solid in a divided condition.
Some embodiments of the solid composition are granular, while others are dispersible powders or dusts.
The granular compositions are of the coated type, the impregnated type or the incorporated type.
The coated type of granular composition is made by dusting a wett-able powder or ground powder camprising the pupa metamorphosis inhibiting material onto granular carried material which either before or after the dusting has been a~miyed with an adhesive or a sticker. Water, oils, alco-hols, glycols, aqueous gums, waxes and the l;ke including m;xtures thereof, are used as stickers. E~amples of granular carrier material include attaclay, ground corn cobs, vermiculite, ground walnut hulls and almost any granular mineral or organic material screened to the desired particle si~e (generally 15-60 mesh, preferably about 30 mesh, United States screen si~e). Generally the pupa metamorphosis inhibiting material is about 2-20% by weight of the composition and the granular carrier material is generally about 60-93% by weight of the composition.
In the case of the impregnated type of grsnular composition, the pupa metamorphosis inhibiting material is dissolved in a solvent or melted, and then sprayed on or poured into the granular carrier material. The sol-vent can be removed by evaporation, or permitted to remain. In either case, the pupa metamorphosis inhibiting material impregnates the particles of the granular carrier material. Examples of the granular carrier material include those just mentioned with respect to the coated type of granular composition.
The pupa metamorphosis inhibiting material is generally about 2-20~ by weight of the composition, while the granular carrier material is generally about 80-98% by weight of the composition.
The incorporated type of granular composition is made by admixing the pupa metamorphosis ;nh;biting material with an inert finely divided solid such as, for example, clay, carbon, plaster of paris and the like, and made ~058632 into a mud with water or other inert evaporable liquid. The mud is then dried to a solid sheet or cake, broken up or comminuted, and screened to the desired particle size (g~neraIly 15-60 mesh, preferably about 30 mesh, United States screen size). In other embodiments, the mud is put into a granular pan and granules are formed therein with subsequent removal of the water or solvent. In still another procedure, the mud is extruded through a die into rods which are cut into small pieces. In the incorporated type of granular composition, the pupa metamorphosis ;nh;biting material generally is about 2-50% by weight of the composition, and the solid carrier material is about 50-98% by weight of the composition.
In some embodiments of the granular composition of this invention the carrier material comprises a polymeric substance which effects a slow constant rate of release of the pupa metamorphosis inhibiting material when the composition is applied to the-insect larva habitat. In some instances, for example, when the substance is rubber or the l;ke~ the release comes about because of incompatibility of the pupa metamorphosis inhibiting mater-ial or solution thereof with the polymeric substance, and the material or solution thereof bleeds or oo~es from the polymeric substance. In other instances, the release comes about because of degradation of the polymeric substance by water, ultraviolet light, or other exterior or interior agency.
Those embodiments that effect slow control of release of the pupa metamor-phosis inhibiting material, when they are introduced into water, are particu-larly effective in controlling insects such as mosquitoes and the like, the habitat of the larva of which is water.
In all granular embodiments of the composition of this invention the carrier is usually a dispersible inert solid. A typical dispersible solid of this type is clay. Other suitable solids (dispersible solid) in-clude talc, attapulgite, pyropylite, diatomaceous earth, kaolin, aluminum magnesium silicate, montmorillonite, Fullers earth, sawdust and the like.
The solid dispersible composition can be air dispersible, in which case it is ~05863Z
usually referred to as wettable powder. Generally, when it is intended that the composition be water dispersible, the composition preferably contains emulsifying material (one or more surfactants) at a concentration sufficient to enable a suspension of the desired degree of stability to be formed when the composition is admixed with a suitable quantity of water. A typical di-spersible solid composition of this invention generally comprises about 10-50% by weight of pupa metamorphosis inhibiting material, about 50-90~ by weight of solid carrier material and, when emulsifying material is present, about 1-10% by weight of emulsifying material.
Other specific embodiments of the pupa metamorphosis inhibiting composition of this invention comprise solutions of pupa metamorphosis inhib-iting material in inert, preferably volatile, usually water immiscible sol-vents for the metamorphosis inhibiting material. Examples of suitable sol-vents include isophorone, cyclohexanone, methyl isobutyl ketone, xylene, and the like. Such a solution, which can be regarded as a concentrate, typically comprises about 10~50% by weight of pupa metamorphosis inhibiting material and about 50-90~0 by weight of solvent. The solution can be applied as is, or diluted with more solvent, or dispersed in water, or water dispersed in it.
Preferably, when it is intended that the solution be dispersed in water or water dispersed in it, the mixture of solution and water also comprises emul-sifying material at a concentration sufficient to enable a dispersion of the desired degree of stability to be formed. A typical emulsifying material concentration is about 1-10% by weight of the concentrate. The water concen-tration is such that the pupa metamorphosis inhibiting material concentration is about 0.5-lO~o by weight of the total composition.
Examples of the surfactants employed in both the liquid and solid compositions of this invention comprise the well-known surface active agents of the anionic, cationic and non-ionic types and include alkali metal (sodium or potassium) oleates and similar soaps, amine salts of long chain fatty acids (oleates), sulfonates, animal and vegetable oils (fish oils and castor oil), sulfonated acyclic hydrocarbons, sodium salts of lignin sulfonic acids, alkylnaphthalene sodium sulfonates, sodium lauryl sulfonate, disodium mono-lauryl phosphate, sorbitol laurate, pentaerythritol monostearate, glyce~yl monostearate, poly(ethylene oxides), ethylene oxide condensates of stearic acid, stearyl alcohol, stearyl amine, rosin amines, dehydroabietyl amine and the like, lauryl amine salts, dehydroabietyl amine salts, lauryl pyridinium bronide, stearyl trimethylammonium bromide, and cetyl dimethylbenzylammonium chloride. StiIl other examples are listed in "Detergents and Emulsifiers -1968 Annual" by John W. McCutcheon.
In addition to the pupa metamorphosis inhibiting material and application aid material, a number of specific embodiments of the dispersible composition of this invention comprise one or more other components, examples of which include insecticides, acaricides, herbicides, fungicides, plant nutrients, and the like.
The insect pupa metamorphosis ;nhibiting composition of t_is inven-tion is used by applying it by conventional ways and means to the habitat of the larva of the insect to be controlled.
The rate of application of the composition of this invention is such as to provide about 0.1-10 pounds of pupa metamorphosis ;nh;biting ma-terial per acre. Higher and lower effective rates, however, are within thebroader concepts of this invention.
Typical results obtained in controlling insect larvae with the sub-stituted N-phenylcarbamates of this invention are illustrated by the follow-ing tabulated data.
These are actual data obtained in laboratory tests in which the test compound was incorporated into an emulsifiable concentrate consisting essentially of the test compound, toluene and polyoxyethylene (20) sorbitan monolaurate (an emulsifier in which the oxyethylene content averages about 20 mole per cent) at a ratio of 1 w:l v:l v in which w represents parts by weight, v represents parts by volume, and w is to v as the kilogram is to the liter The concentrate was then admixed with distiIled water to give 100 v of emulsion. Aliquot portions of the emulsion were then further diluted to give emulsions containing the test compound at the concentration specified in the following tables.
The test procedures and typical data obtained when the test com-pound is a compound of this invention are as follows.
Yellow Fever Mosquito (Aedes aevPti) - Larvae Ten late 4th instar larvae are exposed to the emulsion containing the test compound at a specified concentration in a smaIl container covered with a plastic bag. A control container with larvae is also provided. A
smsIl amount of ground guinea pig pellets is added to each container to feed the larvae to the pupal stage. When aIl of the adults have emerged in the control container, the container with the test compound is inspected and the number of dead larvae, dead pupae and nonmal adults determined.
Table 1 presents the data obtained when the substituted N-phenyl-carbamates of this invention were employed in this test.
% % %
Conc. Dead Dead Normal Test Compound (p.p.m.)karvaePuPae Adults Isopropyl N-(p-bromophenyl)car- 1.0 0 100 0 bamate O.S 0 100 0 Isopropyl N-(p-iodophenyl)car- 0.5 20 80 0 bamate 0.1 0 50 50 0.05 0 0 100 l-Butyn-3-yl N-(p-chlorophenyl)- 0.5 0 100 0 carbamate 0.05 0 100 0 0.005 0 100 0 0.0005 0 70 30 0.5 0 100 0 0.05 0 0 100 l-Butyn-3-yl N-(3~4-dichloro- 0.5 0 100 0 phenyl)carbamate 0.05 0 70 30 0.005 0 0 100 l-Butyn-3-yl N-(p-bromophenyl)- 1.0 0 100 0 carbamate l-Butyn-3-yl N-(p-iodophenyl)- 0.5 10 90 0 carbamate 0.1 0 40 60 0.05 0 0 100 The dead larvae and dead pupa are believed to result from arrested development or metamorphosis, and not from a toxic reaction.
Plum Curculio (Conotrachelus nenuphar) - Larvae A one ounce plastic container is filled with fine vermiculite admixed with a quantity of an aqueous emulsion of the concentrate, which quantity is selected to give the desired concentration of the test compound in the venmiculite. Into the container are placed S mature plum curculio larvae and the containers are covered. The same thing is done with a coated container except that water only is admixed with the vermiculite. After three weeks the containers are inspected.
Typical results when two of the compounds of this invention are employed in this test are given in Table 2.
~1 ~8 oo oo oo oo CO~ ~ CO~ CO~ c~oJ o o o o o o ~o o o o o g O ~ ~ ~ e p ~
_~ _ _ _ _ ~ U~ U~
~ ~, o o ~ o รด o O, .
H P, ~Z;
_ 9 _ ~05863Z
The dead larvae, dead pupae and dead abnormal adults are believed to be the result of arrested development, and not the result of a toxic reaction.
In the laboratory, tes~s have shown that at least one or two of the N-phenyl carbamates of this invention not only inhibit metamorphosis of lar-vae and pupa of various insects, but also inhibit metamorphosis of insect ova such as, for example, the ova of the Yellow Fever Mosquito (Aedes aegypti).
However, the emphasis in this specification is in inbibiting metamorphosis of at least the pupae of the insect to be controIled, and if it happens that metamorphosis of insect larvae and even of insect ova are inhibited at the same time, such is a side advantage of the practice of the method of this invention.
Thus, this invention provides a new method and composition for the control of insects.
E~LE;
This example iIlustrates one way of how to make l-butyn-3-yl N-(p-chlorophenyl)carbamate.
A solution of p-chlorophenyl isocyanate (1919 w) in acetone (S00 v) is added slowly (3 hours when w is in grams) to a solution of 3-butyn-2-ol (875 w), triethylamine (5 v), stannous octoate (5 v) and acetone (1000 v).
In the foregoing w is parts by weight, v is parts by volume with w being to v as the kilogram is to the liter.
The resulting solution is refluxed for 1 1/2 hours to give a reac-tion ~ixture.
While still hot the reaction miyture is filtered. Acetone is then stripped from the filtrate to give a slightly yellow solid product (2149.8 w).
This product, the typical melting point of which is 97-100C., consists essentially of l-butyn-3-yl N-(p-chlorophenyl)carbamate at a typical concen-tration of 92% by weight s measured by NMR.
Recrystallization of the product from benzene gives a clean white solid, the melting point of which is 101-103C.
Other features, advantages and specific embodiments of this inven-tion will become readily apparent to those exercising ordinary skill in the art after reading the foregoing disclosures. Such specific embodiments are within the scope of the claimed subject matter unless expressly indicated to the contrary by claim language. Moreover, while specific embodiments of this invention have been described in considerable detail, variations and modifi-cations of them can be effected without departing from the spirit and scope of the invention as disclosed and claimed.
The language "consisting essentially of" as used in this specifi-cation excludes any unrecited substance at a concentration sufficient to sub-stantially adversely affect the essential properties and characteristics of the composition being defined, while permitting the presence of one or more unrecited substances at concentrations insufficient to substantially adverse-ly affect said essential properties and characteristics.
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound selected from the group consisting of:
Isopropyl N-(p-bromophenyl)carbamate Isopropyl N-(p-iodophenyl)carbamate 1-Butyn-3-yl N-(p-chlorophenyl)carbamate 1-Butyn-3-yl N-(3,4-dichlorophenyl)carbamate 1-Butyn-3-yl N-(p-bromophenyl)carbamate l-Butyn-3-yl N-(p-iodophenyl)carbamate.
Isopropyl N-(p-bromophenyl)carbamate Isopropyl N-(p-iodophenyl)carbamate 1-Butyn-3-yl N-(p-chlorophenyl)carbamate 1-Butyn-3-yl N-(3,4-dichlorophenyl)carbamate 1-Butyn-3-yl N-(p-bromophenyl)carbamate l-Butyn-3-yl N-(p-iodophenyl)carbamate.
2. 1-Butyn-3-yl N-tp-chlorophenyl)carbamate.
3. A method for the control of an insect population which com-prises applying to the habitat of the larva of said insect, which habitat is infested with said insect larvae, a pupa metamorphosis inhibiting quantity of material which comprises a compound as claimed in claim 1.
4. A method according to claim 1 in which said quantity is about 0.1 - 10 pounds per acre.
5. A method according to claim 3 or 4 in which the insect is the mosquito.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA267,477A CA1058632A (en) | 1973-05-07 | 1976-12-09 | Substituted n-phenylcarbamates and their use to inhibit pupa metamorphosis |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US35819673A | 1973-05-07 | 1973-05-07 | |
| CA176,914A CA1022069A (en) | 1973-05-07 | 1973-07-19 | Inhibition of pupa metamorphosis by certain substituted n-phenylcarbamates |
| CA267,477A CA1058632A (en) | 1973-05-07 | 1976-12-09 | Substituted n-phenylcarbamates and their use to inhibit pupa metamorphosis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1058632A true CA1058632A (en) | 1979-07-17 |
Family
ID=27162941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA267,477A Expired CA1058632A (en) | 1973-05-07 | 1976-12-09 | Substituted n-phenylcarbamates and their use to inhibit pupa metamorphosis |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1058632A (en) |
-
1976
- 1976-12-09 CA CA267,477A patent/CA1058632A/en not_active Expired
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