Note: Descriptions are shown in the official language in which they were submitted.
~086~
0-PIIOS~ I'r3 OXIMI~S
SUMMI~RY or" TIIEJ LNVlENTION
Thi.s invention relates to novel chemlcal com-
pounds, and is more particularly directed to 0-phosphate oximes
of the formula: I
X~ N-0-P--R
where X and Y are selected from the group consisting of hydrogen,
halo, lower alkyl, cyano, and nitro Z is oxygen or sulfur, R
is lower alkyl or cyano, R] is oxygen or sulfur, and R and
R3 are lower alkyl or lower alkoxv.
This invention is also directed to a new use
of the phosphate oximes falling within the just-outlined
. . .
structural formula for controlling insects and acarid pests ~ -
and to new pesticidal formulations comprising the O-phospha-te
oxime as an essential active ingredient in combination with
various diluent carriers.
:'s~
.i` DETAILED DESCRIPTION OF THE INVENTION
.~. ..
` The new 0-phosphate oximes representated by
the above general structural formula may be prepared by a
;, variety of methods. ~lowever, they are most conveniently
prepared as follows. A substituted or unsubstituted thiophene
,j . .
or furan is halomethylated. Thereafter, in order to produce
the, compounds where R is cyano, the halomethyl derivative is
then reacted with potassium cyanide to produce the corresponding
:
::, :.-: :
, : ~
i: : ;
~ )86~754
,yano methyl d~rivative. This deriv.ltive in turn i~ r~acted
with a base and a nitrosating agent such as butyl nitrite
to produce an alpha-oximino-heteryl acetonitrile. This
class of compounds is then in turn reacted with a substituted
chlorophosphate to produce the final compounds of the invention.
The overall reaction sequence then is as follows:
~ HCl > X ~ ~ CH2Cl Acetone)
X ~ CH~ C- N -Buty~-~No > X ~ ~ C- NON
_ N
The other sequence of reaction involves synthesis -~
o~ those compounds where R is lower alkyl. Here a substituted
or unsubstituted thiophene or furan is reacted with an acyl
chloride or an alkyl anhydride to produce the corresponding
2-keto furan or thiophene. This derivative in turn is reacted
with hydroxyl amine hydrochloride to produce the ketoximes
which again in turn are reacted with a substituted chlorophosphate
to yield the final products. The general reaction scheme is
¦ 15 as follows where R is lower alkyl.
I ' .'
` '.
; .'
~ 2
., .
~0 ~ 67 5
R-C-Cl ~ X~ ~ C--R
~r ~ c =NOH 5~ X lr~ ~C =N--O -- P~
~ .
A number of the intermediates used in preparing
the final compound of the invention here are believed to be
novel. These are the oximes which have the following general
~ structural formula:
'`, ' Y ,'.''
.. : ., ~
~; X ~ ~ C- N -OH
Z C- N
" S wherei~ X.and Y are selected from the group consisting of
hydrogen, halo, lower alkyl, cyano and nitro and Z is oxygen
.~ or sulfur. :
. ~ .
~, . .
~ ,1 .
"~ .
' `:
':"'` : ' ' '
. . .
. `:
l` . .
7S4
Th~ foLlowillg ex~mples -illus~rclte typicnl ~ompounds
of the invention and their mode of preparation. lt Ls under-
stood that these examples are merely illustrative, and that
the invent;on is not to be limited thereto.
EXAMPLE I
2-Acetyl Thiophene O(-Diethylthiophosphoryl) Keto-Oxime
A mixture of 7.05 g. (0.05 mole) of 2-acetyl thiophene
ketoxime, 2 g. (0.05 mole) of sodium hydroxide and 9.4 g.
(0.05 mole) of diethyl chlorothiophosphate was stirred together
- 10 for 16 hours in 100 ml. of water and 10 ml. of ethanol. 300 ml.of water was then added and the mixture was ex~racted with
diethyl ether. The ether solution in turn was then successively
washed with water, dilute potassium hydroxide and water again.
A~ter drying the etheral solution over magnesium sulfate the
fiLtrate was concentrated to an oil which then crys~allized.
Onè recrystallization from cyclohexane gave a white solid which ~
I melted at 55-56.5C. ~ -
The compound which had the formula
,l , .. ..
S~ ~ N O- P (-OC2H5)2
i was then analyzed as follows:
~j .- ,
Calcd: C, 40-94; H, 5.49; N~ 4.77
Found: C, 40.78 H, 5.55; N, 4.79
EXAMPLE II
2-Acetyl~5-Chlorothiophene OT~iethylthiophosphorYl) Keto-Oxime
A mixture of 17.5 g. (0.L0 mole) o~ 2-acetyl-5-
~l 25 chlorothiophene ketone oxime, 18.8 g. (0.10 mole) of diethyl
chlorothiophosphate, and 4.8 g. (0.12 mole) of sodium hydroxide
was stirred at room temperature in 200 ml. of water, in 25 ml.
i : :
¢ . '
: :
. :' , -'-.
_4_
. .
:~L01~i7~
ethanol for l6 ho~lrs. Thercafter, 250 ml. o~ wa~er was
~dded and the mixt~lre extr~cted with diethyl ether. The
ether solution was then washed successively with water, 5%
potassium hydroxide solution and water and then drled over
magnesium sulfate. The drying agent was removed and the filtrate
concentrated in oil. The oil was dried under high vacuo, and
was demonstrated to be essentially pure by resort to nuclear
magnetic resonance.
The compound had the following structure:
Cl ~ o P (-OC2H5)2
The compound was analyzed as ~ollows:
Calcd: N, 4.27
Found: N, 4.24
EXAMPLE III
Alpha-Oximino~~Thi~cL~ ton~trll-
Here the just-named compound was prepared as an
intermediate to synthesis a number of the final compounds of
the invention.
To a stirred solution of 2.3 g, (0.10 mole) of
t sodium metal dissolved in 50 ml. of ethanol and cooled to
20 0C. in an ice bath was added 12.3 g. (0.10 mole) of 2-
thienylacetonitrile. After the addition was complete 10.3 g.
¦ (0.10 mole) of butylnitrite was added. The reaction mixture was
stirred 1 hour at 0C. and 3 hours at room temperature before
the mixture was concentrated to dryness in vacuo. The residue
was`washed with ether. The sodium salt of the product was
~ dissolved in water and acidified with concentrated hydrochloric
`l a~id to a pH of 3. The solid was filtered, washed with water,
dried and recrystallized from chloroform to yield the final
product (Mp-136-138C) having the formula: -
: :
_5_
~ . .
~ ~ .
C= N- OH
C-N
The compound was analyzed as follows:
Calcd:C, 47.37; H, 2.65; N, 18.42;
Found:C, 47.51; H, 2,63; N, 18.60;
EXAMPLE IV
Alpha-Oximino-5-~hT~ ~Thienylacetonitrile
The above entitled compound was prepared essentially
utilizing the procedure of Example III, with the starting
material here being 5-chloro-2-thienylacetonitrileO A tan ~-
solid was obtained which was recrystallized from chloroform
and had a melting point of 174-176 C.
The compound having the formula was analyzed as
follows: -
~lr~c=~O~ :
Cl S
C_N
Calcd: C, 38.61; H, 1.61; N, 15.00
Found: C, 38.82; H, 1.61; N, 15.27
EXAMPLE V
Alpha-Oximino-~-Fu~Tacetonitrile
Yet another intermediate was prepared here as just
named. To a cooled solution of 6.9 g. (0.30 mole~ of sodium
metal dissolved in 200 ml. of ethanol at 10Cu was added 30.9 g.
(0.30 mole) of butylnitrite dropwise, followed by addition of
32.1 g. ~0~30 mole) of 2-furanacetonitrile. The mixture was
stirred one hour at 10C. and then 3 hours at room te~lperature.
The-dark mixture was then concen-trated n vacuo. The sodium
.
,
. .
~ .
6'75 4
,alt w~s tll~n wash~d ~7ith ~:h~r, ~I:i.sso l.v~ in wntc~r clllcl ~Ic~ ied
with concentral~d hyclroclllorLc ac-l~l to n ptl o~ 3. 'rhc solid
was ~iltered, washed with wa-ter~ driecl .Ind reCL'yStal1iZed ~rom
chloroform to give 21 g. of product which melted at 122-124C,
This product analy~ed as follows:
Calcd: C, 52.9h; H, 2.96; N, 20.58
Fo~md:C, 53.18; H, 2.91; N, 20.8
This intermediate had a formula as follows:
11 J--C~N OH
o I .
C~N
EXAMPLE VI
O~ O-Diethylphosphoryl- a-Oximino~2-Thienylacetonitrile
To a stirred solution of 4 g. (0.026 mole) of a-
oximino-2-thienylacetonitrile an~ 2 .1 g . (0 . 027 mole) of
triethylamine in 200 ml. of diethyl ether was added 4.47 g.
(0.026 mole) of diethyl chlorophosphate in 25 ml. of diethyl
15 ether. The triethylamine hydrochIoride was washed from the
mixture with water and the organic layer was then successively
washed wi~h dilute sodium hydroxide and water. The ether was
dried over magnesium sulfate, ~iltered and concentrated to an
oil. After drying under a high vacuo the brown oil solidified.
The product melted at 37 40 C. The compound had the following
structural ~ormula
r~ c N- O-P (-0C2Hs)2 ~
~ ;
C-N
and analyzed as Eollows:
Calcd:~ N, 9.71
Fo~md: ~ N~ 9.h8
' ,' ~ .
~7-
. ~ .
'75~
F. X~\M l'T ,1~ V r I
2, 5 Di.CIll.OrO CY,-O~Y:ill;.LtlU_ 3~ace~ton~ rilc
To a stirr~d solution of 3.~5 g. (0.l5 moLe) oE
sodium dissolved in 200 ml. e~hanol and coolecl to 0C. in
an ice bath was added 29 g (0.15 mole) of 2,5 dichloro 3-
thienylacetonitrlle. After the addition was complete 15.5 g.
(0.15 mole) butyl nitrite was added. The reaction was stirred
at 0C~ and 3 hours at room temperature. The solid was
removed by ~iltration and dried and gave 15 g. o~ the sodium
10 salt of the product. The filtrate was concentrated to dryness -
_ vacuo and the residue washed with ether. The sodium salt
from the filtrate was dissolved in water and acidified with
concentrated hydrochlorlc acid to a pH of 3. The solld was
fil~ered, washed with water, dried and recrystallized from
chloroform to give 8.6 g. which melted at 163 165C.
The compound which had the formula
_C =N-- OH
~ C- N
Cl ~ S ~ Cl
was then analyzed as follows:
Calcd: C, 32.60; H, .90; N, 12.66 -
Found: C, 32.51 H, .96; N, 12.90
. . ' .': '
EXAMPLE VIII
I-a-oximino-2-Furvl~ce~onitri
To a stirred mixture of 6.8 g. (0.05 mole) of
a~oximino-2-furylacetonitrile and 5.05 g. (0.05 m~le) of
triethylamine in 200 ml. oE diethylether was added 9.4 g.
(0.G5 mole) of diethyl chlorothiophosphate in 25 ml. of
dièthylether. The reaction mixture was stirred 8 hours, and
then successively washed with water, dilute sodium hydroxide
solution and water, and therea~ter dried over magnesium sul:fate.
.
:
-8
. .
S4
The drying agent ~/as then removecl by ~iltration ~nd th~
filtrate concentrated Ln v - ~lCttO to yield a solicl. Recrystalliæation
from pentane gave a solid which melted at 46-48C. :
The product had the following structural formula
~ C= ;~- o- p(OC~15)2
C- N . .
and analyzed as follows:
Calcd: C, 41.66; H, 4O54; N, 9 a 71
Found: C, 41.83; H, 4.58; N, 9.81
., ' ' .
EXAMPLE IX
O,O-Diethylthionopho ~ lmino-2-Thienyl Acetonitrile
To an etheral solution of 5.05 g. (0.05 mole) of ..
triethylamine and 7.6 g. (0.05 mole) a-oximino-2-thienylacetonitrile
was add~d 9.4 g. (0.05 mole) of diethyl chlorothiophasphate
in 25 ml. of diethyl ether. The mixture was stirred for 4
hours. Thereater, the reaction mixture was washed successively :
.. . .
15 wlth water, dilute sodium hydroxide solution and water. The i~
diethyl ether solution was dried over magnesium sulfate,
~iltered and concentrated -to an oil which solidified upon ; ~
cooling. The residue was recrystallized ~rom pen~ane and .~ .
gave a whi~e solid which melted at 62-63C, .
The co~pound had the following structure
C= N -O- P(OC2H5)2
C- N .:-~
' ':
and analyzed as follows: .
.
Calcd: C, 36.46; H, 4730; N~ 9.21
: ~Found: : C, 36.70; H, 4.36 . N, 9.31 :.
' : ~: ', :,:,
` ;~ 9 , ~-.
s~
]~XI\MI'I 1~ Y
O,O-Diel:llylthiono~ ~r ~ o 5-Chl.oLo-2~'rh:Lcny1 Acc~oni~rlle
~ solutioll o~ 11.3 g. (0.06 mole) o~ cliethyl
chlorothiophosph~te was addecl dropwise to a stirred soLution
of 11.16 g. (0.06 mole) of a-oximino-5-chloro-2-thienyl
acetonitrile and 6.06 (0.06 mole) of triethylamine in 200 ml.
of diethyl ether. The mixture was stirred ~our hours and
successively washed with water, dilute sodium solution and
water. The solution was dried over magnesium sulfate, filtered
and concentrated to an oil. Upon standing the oil was induced
to crystallize. A recrystallization from pentane gave a pure
material which melted at 46-47C.
The compound had the following structural formula
Cl ~ C- N -O- P(OC2Hs)2
C~-N
and analyzed as follows:
Calcd: C~ 35.45; H, 3.56; N, 8.26
Found: C~ 36.19; H, 3.69 N, 8.21
EXAMPLE XI
O~O-Dimethylthionophosphoryl-a-Oximino-2-Thienyl Acetonitrile
8.0 g. (0.05 mole) of dimethyl chlorothiophosphate
20 in 25 ml. of diethyl ether was added dropwise to a stirred `
solution of 5.05 g. (0.05 mole) of triethylamine and 7.6 g.
(0.05 mole) of a-oximino-2-thienyl acetonitrile in 200 ml.
of diethyl ether. After 4 hours the reaction mixture was
successively washed with water, dilute sodium hydroxide solution
and water. This solution was dried over magnesium sulfate,
~iltered and concentrated to an oil. On drying under high ;~ -~
~acuo the yellow oil was essentially pure as shown by thin
layer chromatography.
. ' '
'.
` ~ :
~0 8 ~'~S ~
'l'lle compo~lnd h.l~ tll~ Eollowlllg s~ruc~llral Eormllla
___
l l S
` S ' C=-N--0--P(0CH3)2
C-- N
and analy~ed as ~ollows:
Calcd: C, 34.77; H, 3.28; N, 10.13
Found: C, 34.16; H, 3.30; N, 10.04
O,O-Dimethylthionophosphoryl~ ximino-5-Chloro-2-Thienyl Aceto~le
To 6.1 g. (0.033 mole) of a-oximino-5-chloro-2- -
thienyl acetonitrile and 3.4 g. (0.033 mole) of triethyl amine
in 200 ml. of diethyl ether was added 5.2 g. (0.033 mole~ of
dimethyl chlorothiophosphate in 25 ml. of diethyl ether. The
resulta~t mixture was successively ~ashed with water, dilute
sodium hydroxide solution and water. Ater drying the solution ; `
over magnesium sul~ate, it was fil~ered and concentrated to
.
~ an oil which was induced to erystallize. After crystallization
from pentane the product melted at 48-50Co
The compound had the following structural formula
~ : '
cl/~S ~L~=N--O--P(0CH3)
C~----N
' '
and analyzed as follows:
. :
Calcd: C, 30.92; H, 2.59; N, 9.01 ~ : .
:: ~Found: C, 31.07; H, 2.57; N, 9.06
:
: : ~ : ~: :
6'7
~M~ x r.-c~
2,5 Dichloro, 0, O-Dlc~T~lionoï;~losphoryl-a-oxLmino-
3-r['hlen~l Aceto~ rilc
To a stirring mixture of 1~.58 g. (0.06 mole) the
sodium salt o~ 2,5 dichloro-alpha ox-imino-3 thienylacetonitrile
in 150 ml. acetone was added 9.4 g. (0.05 mole) diethyl
chlorothiophosphate in 10 ml. acetone. The mixture was
stirred 2 hours and then poured in-to 400 ml. water. The
precipitated oil is taken up with benzene. The benzene solu~ion
is washed with wa~er and a 2N sodium hydroxide solution to
remove the unreacted oximino compound and subsequently dried
over magnesium sulfate. After distîlling the solvent
9.8 g. 2,5 dichloro 0,0-diethylthionophosphoryl-a, oximino- -
. 3-thienyl acetonitrile was obtained as orange oil of re~ractive --
index nD 1.5625.
The compolmd had the following structural formula
S
r_~c~_PI(c2~l5)2
Cl Cl
and analyzed as follows:
Analysis: N, 8.18
Found: N, 7.83
-12-
;.: . . - .
, .~ , .. .. -
. .. - . .- . . .. .. .- - -
36'7S~
~ lv~nt~-lr,~ ly! tl~ c~;vc co~ c~ c~7r~ o
the present invention exl~ s~OIl~ insccticicl~l an~l
acaricidal ac~ivities, with comparativcly low ~oxicity
to warm-blooded animals and concomitently low phytot:oxicit$~.
The efEects set in rapidly and are long-lasting. The
instant active compounds can therefore be used with favor~ble
results for the control o noxious sucking and biting insects,
Diptera and mi~es (Acarina).
Among the insects which can be effectiveLy controlled
10 by the compounds-of the present invention are the chewing --
insects such as the Mexican bean beetle, and the Southern
armyworm; the piercing-sucking insects, such as ~he pea aphid,
.the cereal leaf beetle, the housefly, the grape leafhopper,
the chinch bug, the lygus bugs, oyster shell scale, the
Caliornia red scale, the Florida red scale, the soEt scale
and mosquitoes; the internal feeders, including borers
such as the E~ropean~corn borer, the peach twig borer and the
corn earworm; worms or weevils such as the codling moth,
alfalfa weevil, cotton boll weevil, pink boll WO~Q, plltm
curculio, red band lea roller, melon worm, cabbage looper,
-and apple maggott; leafminers such as the apple lear miner,
birch miner and beet J.eaf miner; and gall insects such as
the wheat joint worm and the grape phylloxera. Insects
which attack below the surface of the ground are classified
as subterranean insects and include such destructive pests
as the woolly apple aphid, the Japanese beetle, the onion
maggott and the corn root wonm.
Mi~es and ~icks are not true insects. Many
economically important species of mites and ticks c~n be
controlled-by the compounds of this present invention such
as the red spider mite, the two spotted spider mite, the strawberry
spider mite, the citrus red mite and the European red mite.
. ~
-13- -:
.. - : . : : .
~o~ s~
~ aemicals use~lL for th~ con~roL ol mitc~ arc O~Ctl C;llled
miticides whi.le those ~se~ul for tlle control of l~otll mites
and ~icks are known specifically clS ~CclrlCiCIC9~
The ncw compounds of this invention c~ be uced
5 in many ways Eor the contol of insects or acarids. Insécticides
or acaricides w'~lich are to be ~Ised as stomach poisons or
protective materials can be applied to the surface on which
the insects or acarids feed or travel. Insecticides or
acarcides which are to be used as contact poisons or eradicants
can be applied directly to the body of the insect or acarid,
as a residual trea~ment to the surface on which the insect
or acarid may walk or crawl, or as a fumigant treatment of
the air which the insect or acarid breathes. In some cases,
the compounds applied to the soil or plan~ surfaces are
taken up by the plant, and ~he insects or acarids are poisoned
systemically. In essence then, the just-described methods
o using the insecticides or acar~cicles are based on the
~. .
fact tha~ almost all the injury done by insects or acarids
is a direct or indirect r sul~ of their attempts to secure food. `
The act~ve compounds according to the instant
invention can be utilized, if desired, in the form of the
usual formulatîons or compositions with conventional inert
pesticidal diluents or extenders, i.e. conventional pesticidal
dispersible carrier vehicles, such as solutions, emulsions,
suspensions, emulsifiable concentrates, spray powders,
pastes, soluble powders, dusting agents, granules etc.
These are prepared in known manners, ~or instance by
extending the actiye compounds with conventional pesticidal
dispersable liquid diluent carriers and/or dispersible solid
carriers, optiunally witn the use of carrier vellicle assis~an~s,
e.g. conventional pesticidal surface-active agents, including
emulsifying agents, dispersing agents, whereby, for example,
~ ' ' '' :.
14
n~
. . ~ . . ,
~ S 4
.~ the casc wllerc wa~cr is usc(l as a dilucllt, or~-,allic soJvcnts
may be add~d as a~ ry solv~n~s. rl~ ollowing may be
chi~fly considered for use as convenl:ion~ll carrier vellicl~s
for this purpose: inert dispe~sible liquid diluent carriers,
5 including inert organic solvents such as aromatic hydrocarbons
(e.g. benzene, toluene, ~ylene, etc.), h~logenated, especially
chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes,
etc.)5 paraf~ns (e.g. petroleum fractions), chlorinated -
aliphatic hydrocarbons (e.g.methylene chloride, etc.), alcohols
(e.g. methanol, ethanol, propanol, butanol, etc.), amines
(e.g. ethanol amine, etc.), ethers, ether-alcohols (e.g.
glycol monomethyl ether, etc.), amides (e.g. dimethy~ormamide,
.etc.), sulfoxides (e.g. d-imethyl sulfoxide, etc.), ketones
(e.g. acetone, etc.), and or water; as well as inert dispersible
lS finely di~ided solid carriers such as ground na~ural minerals
(e.g. kalines, alumina, silica, chalk (i.e. calcium carbonate,
talc, ~ieselg~hr, etc), and ground synthetic minerals (e.g.
highly dispersed silicic acid, silic~tes, e.g. alkali
silicates, etc.); whereas the following may be chiefly considered
for use as conventional carrier vehicle assistants, e.g.
sur~ace-acti~e agents~ for ~his purpose; emulsifying agents,
such as non-ionic and/ ~ anionic emulsifying agents (e.g.
polyethylene oxide esters of fatty acids~ polyethylene
oxide ethers of fatty alcohols, alkyl surfonates, aryl sulfonates,
etc. and especially alkyl arylpolyglycol ethers, magnesium
stearate~ sodium oleate, etc.); andJor dispersing agen~s, such
as llgnin, sulfite waste liquors~ methyl cellulose, etc.
The active compounds of the invention may be employed
alone or in the form of mixtures with one another and/or
with such solid and/or liquid dispersible carrier vehicles
and/or witn other known compatable active agents, especially
plant;protection agents, such as otller acaricides, insecticides
.
-15-
'.
8ti'7S~
Tl. .l-lSCiC:iCl(~S, tlOnl;ll:iCil.l~S, Cllll~':i.C~ !I'i)ici.(l(:'sJ ~ Ct~1'3C~ '.S,
etc. if desired, or -in the EoLm oE p.~rticul.lr closa~c pr~ r;ltiolls
f~r speciflc application mad~ ther~Eron~, s~lch ~s solu~ions,
emulsions, suspellsions, pow~lers, pastes and g~anules wllich
5 are thus ready for use. . -
Typical insecticides or acaricides with which the
compounds of the invention can be used in the insecticidal
or acaricidal compositions to control insects or acarids.
include halogenated compounds such as DDT, methoxychlor~ :
10 TDE, lindane, chlordane, isobenzan, aldrin, dieldrin, hepthchlor,
endrin, mirex, endosulfon, dicofol, and the like; organic
phosphorus compounds such as TEPP, schradan, ethion, parathion,
~ethyl parathion~ EPN, demeton, carbonphenothion, phorate, ~-
zinophos, diazinon, malathion, mevinphos, dimethoate, DB~,ronnel,
1.5 oxydemet~n-methyl,'dicapthon, chlorothion phosphamidon, naled
enthion, trichorofon, DDVP, and the like; organic nitrogen
compounds such''as dinitro-o-cresol, dinitrocyclohexylphenol,
~NB, DNP, binapacril~ azobenzene~ and the like; organic
carbamate compounds, such'as carbary' and the like; organic sulfur
20 compounds such as phenothiazine, phenoxathin, lauryl ~hiocynate,
bis (2 thiocyanoethyl)-ether, iosbornyl thiocyanoacetate,
and the ~.ike; as well as such substances usually referred to
as f~umigants, as hydrogen cyanide, carbon tetrachloride, -
calcium cyanide~ carbon disul~ide, ethylene dichloride,
25 propylene dichloride, ethylene dibromide, ethylene oxide,
methyl bromide~ paradichlorobenzene, and the like. ..
As concerns commercially-marketed preparations,
these generally contemplate carrier composition mixtures in
which the active compound is present in an amount substantially
30 between 0.1-95% by weight, and preferably 0'.5-9C% by weigh~
of the mixture, whereas carrier composition mixtures suitable
. for direct appllcati.on or field application generally contemplates
.
- -16-
' '
. . : . . : -
, . .. .
~ . . .: : . -
: . .
YS~
llOSC' ill whicll lhe .-lcl:lve compo-lncl is l~rl~s(~ n .llno~lnt
substantially betwcen 0.00001-20'~oJ preEcral)Ly 0,0002-20'~,
and most preferably O.Ol-2% by ~eight oE tlle mixture. Thus,
the present invention contemplates over-~ll compositions
which comprise mixtures of the conventional dispersible
carrier vehicle such as (1) a dispersible inert finely
divided solid~ and/or (2) a dispersible carrier liquid such
as an inert organic solid and/or water, preferable including
a surface-active effective amount of a carrier vehicle
assistant, e.g. a surface-active agent, such as an emulsifying
agent and/or a dispersing agent, and an amount of the ac~ive
compound which is effective for the purpose in question
which is generally between about O.00001-95% and preferably
0.01 9570.
': ' ' '
. . "
:. :
'
,
'.,...,, . -
.
- 17 ~:
~ . . .. . ... .
1(18~;754
Represel~Latlve compo~lnds oE the -Ln-vc~nL:Lon werc ~cst~d
as to their insectlcidal activity u~ilizing as tesl: insect~
the housefly (Mnsca dome_tica Linnaeu~), th~ two-5potted spi-Jer
mite (Tetran~_hus _rticae) and ~he beet armyworm (Spodoptera
exigu,;) and in each instance the compounds were ~ested at a
number of varying dosages. The ratings are as follows:
VA indicates greater than 80% kill; A indicates a 50-80% ~'
kill; SA indicats25-~9% kill; and I indicates a 0-25% kill.
In more detail, the following test procedures were
used to screen the insecticides o the invention. With respect
to the test on the housefly, three day old adult houseflies
are used. Approximately 50 flies are used for each dilution
of the chemical tested. Flies are anesthetized with carbon
dioxide and placed in a Buchner funnel. The appropriate
dilution is then poured onto the flies. Contact time is
approximately 5 seconds. The chemical is then removed by
suction and the flies are transferred to glass beakers and
mortality noted after one hour.
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With re~lpecl: I:o thc~ spider mlt:e) n lec~E dL~;c
bioassay procedure is usecl to cleterrnine tlle mi~icid.ll activity
of the compounds Oe the invention. Speci~ically, l~aE discs
approximately 15 mm. in diameter cut from fresh Henderson
5 Bush Lima Bean plan~s. The discs are then dipped in the
appropriate dilution of the chemical being tested. The leaf
discs are allowed to dry a~id are ~hen placed on moistened
filter paper and appropriate labeled petri dishes. Ten adult
mites are placed on each disc. Nine discs are used for each
10 compound. Percent mortality is then determîned after 48 hours.
The immersion technique described for the housefly
was modiEied and used for the beet armyworm. - 5 to 7 day old
larvae of S. exi~ua are emersed in the appropriate dilution of
the insecticide candidate for five seconds. The chemical
15 is removed by suction and the worms are placed in petri dishes.
24\ hours later mortality is determined.
Results of insecticidal activity are given in Tables
I, II and III. The compound number relates to the corresponding
example number.
TABLE
_wo-Spotted Spider Mite
C~d. No. 2500_~ _500 ppm 250 ppm I25 ppm
XI VA VA VA SA
XII VA VA VA SA
~5 IX VA VA VA VA
X ~A VA VA VA
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TABLE Il
Housefly
~_o. 5000 ppm 500 ppm 250 ppm 125_~pm 62~ 30 ppm
XI- ~ VA VA VA A SA
XII VA VA VA A SA I
IX VA SA SA
X ~A VA VA A A SA
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-- 1086~S4
TABLE I I :[
Beet Arm~wonn
Cpd. No.50 O ppm 500 _E~. 250 ppm _25 ppm
XI VA
XII VA
IX VA
X VA VA VA VA
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