CA1086754A

CA1086754A - O-phosphate oximes

Info

Publication number: CA1086754A
Application number: CA157,195A
Authority: CA
Inventors: Robert G. Stein; Terry L. Couch; Aldo J. Crovetti
Original assignee: Abbott Laboratories
Current assignee: Abbott Laboratories
Priority date: 1971-12-20
Filing date: 1972-11-22
Publication date: 1980-09-30
Also published as: FR2169825B1; JPS5118503B2; PH9458A; DE2262189A1; GB1390839A; FR2169825A1; AU4949072A; AU470171B2; JPS4867438A; DE2262189B2; CH561020A5; GB1390840A; ZA728481B; IT972533B

Abstract

ABSTRACT OF THE DISCLOSURE

Novel chemical compounds, particularly 0-phosphate oximes of the formula:
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, R1 is oxygen or sulfur, and R2 and R3 are lower alkyl or lower alkoxy.
The compounds having this formula are useful as pesticides.

Description

~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 .
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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.
.
:

. .

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 , ~-.

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]~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 ;.: . . - .
, .~ , .. .. -. .. - . .- . . .. .. .- - -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.

. ~

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.. - : . : : .

~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, ~ ' ' '' :.

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 .

'.

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 .

' ' . . : . . : -, . .. .
~ . . .: : . -: . .

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.

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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

, .
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

~ - 19---- 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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:

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compound of the formula:

wherein 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, R1 is oxygen or sulfur, and R2 and R3 are lower alkyl or lower alkoxy with the proviso that R is not cyano when either R1 or Z is sulfur.

2. The compound of claim 1 where Z and R1 are sulfur.

3. The compound of claim 2 where R2 and R3 are alkoxy.

4. The compound of claim 3 where R2 and R are ethoxy.

5. The compound of claim 2 wherein at least one of X and Y is halo.

6. The compound of claim 2 where X is halo and Y is hydrogen.

7. The compound of claim 2 where R is alkyl.

8. The compound of claim 1 where R1 is oxygen and Z is sulfur.

9. The compound of claim 8 wherein X and Y are hydrogen.

10. A method of controlling insects and acarid pests which comprises contacting such pests with at least an effective amount of compound of the formula:

where X and Y are selected from the group of consisting of hydrogen, halo, lower alkyl, cyano, and nitro, Z is oxygen or sulfur, R is lower alkyl or cyano, R1 is oxygen or sulfur, and R2 and R3 are lower alkyl or lower alkoxy, with the proviso that R is not cyano when either R1 or Z is sulfur.

11. The method of claim 10 wherein Z and R1 are sulfur.

12. The method of claim 11 wherein R2 and R3 are alkoxy

13. The method of claim 12 wherein R2 and R3 are ethoxy

14. The method of claim 11 wherein at least one of X
and Y is halo.

15. The method of claim 11 wherein X is halo and Y is hydrogen.

16. The method of claim 11 wherein R is alkyl.

17. The method of claim 10 wherein R1 is oxygen and Z is sulfur.

18. The method of claim 17 wherein X and Y are hydrogen

19. An oxime selected from those having the following formulae:

and wherein 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, R1 is oxygen or sulfur, and R2 and R3 are lower alkyl or lower alkoxy, with the proviso that in the O-phosphate oximes R is not cyano when either R1 or Z is sulfur.

20. A cyano oxime according to claim 19 having the following general structural formula:

wherein X and Y are selected from the group consisting of hydrogen, halo, lower alkyl, cyano and nitro and Z is oxygen or sulfur.

21. The compound of claim 20 wherein X and Y are hydrogen and Z is sulfur.

22. The compound of claim 20 wherein X is halo, Y
is hydrogen and Z is sulfur.

23. The compound of claim 20 wherein X and Y are hydrogen and Z is oxygen.