Note: Descriptions are shown in the official language in which they were submitted.
1058632
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
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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
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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
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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
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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
105863Z
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.
TABLE 1
% % %
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
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1058632
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.
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~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 ô 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
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1058632
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.
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